NL9500583A - Liquid-crystal polymeric compositions, method and products - Google Patents

Abstract

The invention relates to extended chain copolymers or chain block copolymers containing repeating units which are represented by one of the formulae IX-XVIII. The invention further relates, in the wider sense, to novel anisotropic (liquid-crystal) extended chain polymer/polyphosphoric acid compositions, to the preparation of the extended chain polymers of high molecular weight by polycondensation of selected monomers in specific polyphosphoric acids, and in particular to the preparation of highly concentrated copolymer compositions from which polymeric articles useful for industry such as fibres and films can readily be prepared.

Description

Liquid crystalline polymer compositions, method and products.

The invention relates to extended chain copolymers or block copolymers containing repeating units, which are represented by one of the formulas:

wherein Ar1, Ar3, Ar4, Ar5, Ar6 and Ar9 are aromatic organic groups, and X2 are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), is a bivalent organic radical, Y7 is an octavalent organic group is, (a ^ bj m / m + m '), (¾ m' / m + m '); and a ^ bj represent the molar ratios of the respective different repeating units present in their respective copolymers, and greater than 0 and less than 1, Y ^ ^ and Y ^ an average number of the successive repeating units present in their respective represents copolymers, and n is a positive integer.

The invention further relates broadly to novel anisotropic (liquid crystalline) extended chain copolymer polyphosphoric acid compositions, for the preparation of the high molecular weight extended chain copolymers by polycondensation of selected monomers in certain polyphosphoric acids, and in particular for the preparation of high highly concentrated copolymer compositions from which industrially useful polymeric articles such as fibers and films can be readily prepared.

Some of the most serious problems that arise in the preparation of thermally stable articles such as fibers and films from extended chain polymers are described in the background art given below.

Background of the prior art

In general, the classes of aromatic heterocyclic extended chain polymers are well known for their extremely good thermal, physical and chemical properties. Unfortunately, these polymers are non-melting ebb and have proved very difficult to economically convert into articles. In order to form such polymers into desirable marketable articles, for example, fibers, films, fibrids and the like, it is necessary that they be in solution or dop form. Although such polymers can be dissolved in the various acidic solvents, such as sulfuric acid, methanesulfonic acid, chlorosulfonic acid, polyphosphoric acid, and the like, a difficulty is often encountered in preparing and using the polymeric acid compositions or in doping due to poor polymeric acid solubility.

Under normal conditions, a precipitated or dried particulate form of the polymer is dissolved in strong acid solvent by mixing the (isolated) polymer particles at elevated temperature and / or high pressures over a period of from several hours to several days. If the polymer is insoluble in the particular solvent, other solvents or a variety of solvent mixtures are used. Usually heating and cooling cycles are used and repeated to obtain a more useful dope.

The resulting dopes often contain undissolved polymer and must be filtered before further processing into articles. Although spinning dips of polybenzo bisoxazole, polybenzimidazole and polybenzobisthiazole in sulfuric acid and / or methanesulfonic acid and / or chlorosulfonic acid with polymer concentrations above 10% are known in the art, the intrinsic viscosity of these polymers is usually below 5 dl / g and often less than 3 dl / g. The cohesive strength of such dopes is inextricably linked weakly and economically less desirable for use in dry-jet wet spinning. In the case of polybenzobisoxazole, numerous attempts at dry-jet spinning of an approximately 10% polybenzo bisoxazole / methanesulfonic acid dope to fibers have been unsuccessful (E.W. Choe, et al. In Macromolecules 1981, 14, 920-924).

In the case of polybenzimidazole, dopes of this prior art polymer lack adequate strength to maintain filament integrity as they pass through the air hole. In order to overcome this problem, U.S. Pat. 4,263,245 Dissolving a high concentration (up to 30%) of this polymer in suitable solvents such as concentrated sulfuric acid. At such high polymer concentrations, lithium chloride is required to prevent the polybenzimidazole from phase separation from the solution.

In the case of polybenzobisthiazole, U.S. Patent 4,225,700 teaches the formation of a liquid crystalline composition of this polymer at concentrations of nearly 10% in methanesulfonic acid and chlorosulfonic acid and at about 6% in polyphosphoric acid. Concentration of polybenzobisthiazole in polyphosphoric acid above about 10 wt. % are difficult to achieve, if at all. A difficulty encountered is that the solution of the 2,5-diamino-1,4-benzenedithiol monomer in polyphosphoric acid with U.S. Pat. 4,225,700 described content of P2O5, is very viscous and dehydrohalogenation is difficult. Significant foaming also occurs. Although solutions of precipitated polymer in solvents such as methanesulfonic acid and chlorosulfonic acid can be prepared, high concentrations of polymer are difficult or impossible to achieve. S.R. Allen et al., In Macromolecules 1981, 14, pp. 1135-1139 describes attempts to spin polybenzobisthiazole directly from the polymerization medium (polyphosphoric acid) containing 5-6% polymer.

As far as polybenzobisthiazole is concerned, it is possible to achieve compositions of almost 10% polymer in polyphosphoric acid with intrinsic viscosity equal to 26 dl / g (J.F. Wolfe et al., Macromolecules 1981, 14, 915-920). Attempt to increase the intrinsic viscosity of the polymer can only be achieved with a fairly large sacrifice (reduction) in polymer concentration. Liquid crystalline compositions of 10% polybenzobisthiazole in polyphosphoric acid are heretofore unknown in the art. Liquid crystalline compositions of polybenzobisthiazole with intrinsic viscosities greater than about 30.3 dl / g in polyphosphoric acid are heretofore unknown in the art.

In practical terms, this means that such polymer polyphosphoric acid compositions are severely limited in their potential utilization for the preparation of articles of highly ordered, high molecular weight polymers.

In general, liquid crystalline extended chain copolymer and block polymer compositions are heretofore unknown in the art.

Disclosure of the Invention 1. Objects of the Invention

Accordingly, it is an object of the invention to provide compositions that are substantially free of one or more of the drawbacks of prior art compositions.

Another object is to provide a process for preparing liquid crystalline extended chain copolymer compositions.

A further object is to provide liquid crystalline extended chain copolymer compositions with excellent cohesive strength.

Another object is to provide liquid crystalline extended chain copolymer compositions with excellent spin stretchability.

Another object is to provide liquid crystalline extended chain copolymer compositions capable of being drawn through long air gaps.

Yet another object is to provide liquid crystalline extended chain copolymer compositions that are capable of being drawn at high spin draw ratios.

A further object of the invention is to prepare a liquid crystalline spinning composition with a high extended chain copolymer content.

Another object is to provide liquid crystalline extended chain copolymer compositions.

Another object of the invention is to provide a process for the preparation of a high polymer content liquid crystalline polymer composition of an extended chain copolymer.

Another object of the invention is to provide a process for preparing liquid crystalline extended chain copolymer compositions from selected monomers.

Another object is to provide a process for the preparation of high molecular weight liquid crystalline extended chain copolymer compositions.

A further object of the invention is to provide a process for synthesizing high molecular weight extended chain copolymers and block copolymers.

Yet a further object is to provide a process in which the dehydrohalonation of certain hydrohalide monomers can be carried out more easily and quickly.

Yet another object is to provide a method in which a significantly higher concentration of monomeric reagents can be used, resulting in liquid crystalline elongated chain copolymer compositions of significantly greater polymer concentration than hitherto possible.

Another object is to reduce the foaming problem referred to above.

Another object is to provide articles such as fibers and films prepared from liquid crystalline extended chain copolymer compositions.

For the attainment of these purposes, the invention provides a copolymer according to claim 1, a method according to claim 9, and a polymer-polyphosphoric acid composition (baptismal solution) according to claims 2 and 3, as well as fibers and other articles obtained therefrom, in particular fibers according to claim 7 .

2. Explanation of the invention

The invention broadly encompasses novel polymer compositions useful as dopes in the preparation of high strength molded articles, comprising blends of certain polyphosphoric acids as described below, and a high concentration of one or more high molecular weight extended chain polymers or more mesogenic group or groups. The extended chain polymers can be copolymers or block polymers as will be illustrated by examples below. The extended chain copolymer is present in the mixture at a sufficient concentration to be able to exhibit an anisotropic polymer phase individually or in combination with one or more different polymers with or without mesogenic group or groups. The mixtures in accordance with the invention are polycondensation products obtained by reacting selected monomers in a suitable solution of phosphoric acid, as described below. These blends exhibit special properties that make them very useful as dopes in the preparation of fibers, films, fibrids and the like. In addition to being anisotropic (liquid crystalline), the blends have a new combination of properties including unexpectedly high spin stretchability and excellent cohesive strengths, and also have the ability to be drawn through both short and extremely long gap distances. , and that they are spun at low as well as exceptionally high tensile ratios. These properties are believed to be attributable to the combination of high polymer concentration, high polymer molecular weight, and high phosphorus pentoxide content comprising the blends of the present invention.

The invention further broadly encompasses a method of preparing new extended chain copolymer compositions useful as dopes in the preparation of fibers and films.

This method comprises: (a) mixing at least one of a selected first monomer (as described below) with or without oxidation-protecting atoms or groups with a prior solvent or phosphoric acid of relatively small phosphorus pentoxide content.

(b) heating and optionally bringing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups present and to provide a first mixture of the first monomer in the previous solvent, (c) adding at least one of a selected second monomer (as described below) in a resulting mixture of step (b) to provide a first mixture of the first and second monomer in the preceding solvent, (d) subsequently increasing the phosphorus pentoxide content of the mixture from step (b) or (c) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (e) polymerizing the first or first and second monomer at a temperature sufficient to allow reaction to be established at a rate to form a first homo-oligomeric product or a first co-oligomeric product with a preselected intrinsic viscosity, or (f) polymerizing the first or the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first homopolymeric product or a first copolymeric product, (g) mixing a selected amount of the first homo-oligomer product with a selected amount of at least one of a selected second homo-oligomeric product to form a first polyoligomeric product, while the second homo-oligomeric product is formed by equal steps (a) and (b) followed by: (1g) adding at least one of a selected second monomer into the resulting mixture of step (b) to provide a mixture of a first and second monomer in the preceding solvent, (2g) subsequently increasing the phosphorus pentoxy content of the mixture resulting from step (b) or (1g) to provide a first or a first e n second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (3g) polymerizing the first or first and second monomer at a temperature sufficient to effect reaction at the rate to form the second homoligomer product with a preselected intrinsic viscosity, with the general proviso that at least one of the selected monomers of step (a) or (Ig) forming the second homoligomer product is different from at least one of the selected monomers of step ( a) or (c) that the first homo-oligomeric product forms, or (h) mixing a selected amount of the first homo-oligomeric product with a selected amount of a second mixture of at least one of the selected first monomer or a first and second monomer in the preliminary solvent to form a monomer-oligomer mixture, and then increasing the phosphorus pentoxide content of a mono multi-oligomer mixture to provide a high phosphorus pentoxide monomer-oligomer reaction medium suitable for polymerization, wherein the first monomer of the second mixture is formed by equal steps (a) and (b) and the first and second monomer of the second mixture is formed by equal steps (a), (b) and (c), with the general proviso that in at least one of the selected monomers of step (a) or (c), that the first or first and second monomer of the second mixture, different from at least one of the selected monomers of step (a) or (c), which forms the first homoligomer product, (i) polymerizing the polyoligomer product resulting from step (g) or the monomer oligomer formed from step (h) at a temperature sufficient to effect reaction at a rate to form a first block oligomer product of a preselected intrinsic viscosity or a first block polymer product, ( j) spinning, drawing, extruding, or casting an article from said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said first poly-oligomeric product, said second homo-oligomeric product product, said first block oligomeric product, said first block polymer product, or mixtures thereof.

2a. Figures

The invention will be explained more fully with reference to the figures, in which:

Fig. 1 graphically illustrates the weight stability of spun polymer fibers of 4BIfn and -fAI} -n with time during isothermal maturation in air at 371 ° C;

Fig. 2 graphically illustrates the weight stability of precipitated polymers of dv3-n and fTtn over time during isothermal ripening in air at 371 ° C;

Fig. 2a graphically illustrates the weight stability of block copolymers AI-AN "and AI-AG" with the temperature in air at a heating rate of 5 ° C per minute;

Fig. 3 graphically illustrates the weight stability of polymers 4Τ] -η and -fV ^ n with temperature in helium at a heating rate of 5 ° C per minute;

Fig. 4 graphically illustrates the weight stability of polymers -fBI} -n and -fAI] -n with the temperature in helium at a heating rate of 5 ° C per minute;

Fig. 5 graphically illustrates the weight stability of polymers -fT] n and [vj-n with temperature in air at a heating rate of 5 ° C per minute;

Fig. 6 graphically illustrates the weight stability of polymers 4BI] n and [ΑΙ + η with the temperature in air at a heating rate of 5 ° C per minute;

Fig. 7 graphically illustrates the relationship of amount of useful PPA and P2O5 content required to reach f of 0.822 for selected polymer concentrations (graph of equation a *) showing an area of poor solubility of monomer 1a;

Fig. 8 graphically illustrates the relative P2O5 content profile for a 14.8 wt. % -fAIbn polymerization showing the limits of an attainable molecular weight assuming a high P2O5 content of pre-solvent;

Fig. 9 graphically illustrates the relative P2O5 content profile for 8.6 wt. % - (1¾ polymerization showing the limits of an attainable polymer concentration when a high P2O5 content of pre-solvent is assumed;

Fig. 10 graphically illustrates a typical relative P2O5 content profile for a 14.5 wt. % 4-Al4-n polymerization demonstrating the benefits of the invention when starting with a low P2O5 content prior solvent followed by an increase in P2O5 content at the start of polymerization;

Fig. 11 graphically illustrates a typical relative P2O5 content profile for a 13.0 wt. % -fBr] -n polymerization showing the advantages of the invention starting from a low P2O5 content of pre-solvent and stepwise addition of P2O5 followed by an increase of P2O5 content at the start of polymerization;

Fig. 12 graphically illustrates a typical relative P2O5 content profile for a 20.3 wt. % -fThn polymerization demonstrating the advantages of the invention when starting with a low P2O5 content of the preliminary solvent followed by an increase in P2O5 content at the start of the polymerization;

Fig. 13 graphically illustrates a typical relative P2O5 content profile for a 16.87 wt. % -EV -] - n polymerization demonstrating the advantages of the invention when starting with a low P2O5 content of the preliminary solvent followed by an increase of P2O5 content at the start of polymerization;

Fig. 14 is a percentage P2O5 profile diagram showing the profile ranges of percentage P2O5 to achieve the benefits of this invention.

3. Embodiment (s) of the Invention

The extended chain polymers of the compositions of the present invention are a class of polymers that can obtain a significant degree of shape anisotropy in the liquid state due to the limited rotations of bonds in the polymer backbone and / or suitable chain geometry of rigid backbone segments. The degree of shape anisotropy is generally defined by the axis ratio (P) / d where (p) is the chain's persistence length and d is the diameter of the chain. For extended chain polymers, (p) can be almost the same as or greater than the circumferential length 1 of the polymer. In the case of a rigid rod polymer, (p) is essentially infinite and the axis ratio is 1 / d.

By the method of the present invention, it is possible to prepare liquid crystalline compositions of extended chain copolymers, or block polymers containing 15% or more polymer. As will be seen, the invention is applicable to the preparation of liquid crystalline extended chain polymer compositions of lower polymer concentration, but there are special advantages to prepare high concentration compositions.

Prolonged chain polymer-polyphosphoric acid compositions of such higher polymer concentration are advantageous.

For example, if the polymer is one such as polybenzobisthiazole, polybenzobisoxazole, and polybenzimidazole, able to form liquid crystalline compositions at low concentration (e.g.

5-10%), that is, if the critical concentration necessary to form the anisotropic phase is low, compositions of even higher polymer concentration are spun to produce a fiber of better quality and strength. We believe this stems, at least in part, from a more complete anisotropic composition and improved composition integrity. These improvements permit greater air hole drawing, improve coagulation characteristics, leading to fewer fractures, and increase polymer throughput when a liquid crystalline composition is spun using a dry jet spinning technique to a polyphosphoric acid solvent / polymer non-solvent, such as methanol, water or dilute aqueous acid.

If the polymer is one such as poly (2,6-benzothiazole) which is less rod-shaped in structure than polybenzobisthiazole or polybenzobisoxazole and therefore has a critical concentration for anistrope phase formation greater than 10% and in the range of concentrations of this invention, extrude of these hitherto unattainable solutions, a tremendous increase in strength and modulus continues due to the arrangement of the polymer during manufacture.

These advantages lead to a more ordered fiber with a lower number of defects than results from spinning less concentrated polymer composition.

Another advantage of preparing these polymers in the anisotropic phase is a significant increase in the molecular weight of the polymer obtained. In advance it is useful to describe the chemistry of phosphoric acids and strong phosphuric acids or polyphosphoric acids as follows:

As the term "phosphoric acid (s)" is used, it means handheld phosphoric acid (s) containing 85-86% H3PO4.

The strong phosphoric acids, or polyphosphoric acids referred to as PPA (polyphosphoric acid), represent a continuous series of amorphous condensed phosphoric acid mixtures given by the formula: or

wherein the value of n depends on the molar ratio of water to phosphorus pentoxide present.

Characterization and methods for forming a variety of polyphosphoric acids and examples of such strong acids useful in accordance with the practice of the present invention can be found in the following publications: A.L. Huhti and P.A. Gartaganis "The Composition of the Strong Phosphoric Acids", Can. J. Chem., Vol. 34, 1956, biz. 785-797; and you. Such, "Linear Polyphosphoric Acids", Mellar's Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. VIII, Supplement III, Biz. 726-753, Wiley 1971. The subject matter of these articles is hereby incorporated herein.

In the most general definition, polyphosphoric acid composition can be in the range of distributions where the average value of n is less than one giving rise to a mobile liquid, to high values of n, the polyphosphoric acid being a glass at normal temperatures. Since the polyphosphoric acid types are in a mobile equilibrium, a given equilibrium composition can be achieved in many ways. For example, the same distribution of polyphosphoric acid composition could be prepared by either starting from concentrated orthophosphoric acid (Ηβ, ΡΟ, ^, n = 1) and expelling water or starting from phosphorus pentoxide (P2O5) and an appropriate amount of water.

All phosphoric acid compositions can be described as a ratio of P2O5 and water by reducing the variety of species present (on paper) to P2O5 and water. We will then adhere to the agreement that polyphosphoric acid composition will be expressed in terms of a P2O5 content (as a percentage) defined as P2O5 content

Therefore, the P2O5 content of pure orthophosphoric acid could be derived by reducing one mole of H3PO4 to 0.5 mole of P2O5 + 1/5 mole of H2O. Conversion to weights gives the P2 ° 5 content as

Similarly, the P2O5 content of commercially available phosphoric acid can be derived in the following manner. Polyphosphoric acid is commercially available in two grades, 105% and 115%. These percentages refer to H3PO4 content, which means that 100 g of the two grades contain 105 and 115 g of H3PO4. The P2O5 content of 115% polyphosphoric acid can then be calculated by knowing the P2O5 content of 100% H3PO4.

Freshly prepared polyphosphoric acid, as described by Wolfe and Loo - U.S. Pat. 4,225,700, used 1.52 grams of P2O5 to x grams of 85.6% H3PO4 so that the P2O5 content of the mixture is

Therefore, polyphosphoric acid compositions of this definition, equivalent to these three examples, could in principle be achieved starting from P2O5 and 27.6, 16.7 and 15.1 wt. add% water.

Copolymeric compositions and their preparation

In accordance with a further aspect of the invention, a liquid crystalline composition is provided useful in the preparation of fibers and films comprising a polycondensation product consisting essentially of a mixture of certain polyphosphoric acids and a high concentration of at least one high molecular weight extended chain copolymer selected from the group consisting of regularly recurring units of the general formula:

wherein Ar · ^ · represents an aromatic moiety and XXX is as defined below, X ^ and X2 are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and x ^ and X2 are bonded to aromatic carbon atoms of Ar ^, N and X ^ or X2 of any hetero ring placed ortho to each other, and Y2 is zero or represents a divalent organic radical and XXXI is defined below, a ^ bj represents the molar ratios of the respective different regularly recurring units present in said copolymer represents an average number of the respective different successive regularly recurring units present in said copolymer, where n is a positive integer;

X, wherein Ar · 1 · represents an aromatic portion and XXX is as defined below, X ^ and X2 are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and X ^ and X2 are bonded to aromatic carbon atoms of Ar1-1, N and Χχ or X2 of any hetero ring placed ortho to each other and Y2 represents a divalent organic radical and XXXI is defined below, ajbj / m + m ' represents the mole ratios of the respective different regularly recurring units present in said copolymer, an average number of the respective different successive regularly recurring units present in said copolymer, Ar3 represents a different aromatic portion and xxil is as defined below, while the nitrogen atom and X3 are bonded to aromatic carbon atoms of Ar3, c ^ m '/ m + m' the molar ratios of the respective different regularly recurring units present in said copolymer represent an average number of the respective different successive regularly recurring units present in said copolymer, wherein n is a positive integer;

XI, wherein Ar3 represents an aromatic moiety and XXII is as defined below, X3 is sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and X3 are bonded to aromatic carbon atoms of Ar3, N and X3 of each heterocycles are placed ortho to each other, represents the mole ratios of the respective different regularly recurring units present in said copolymer, y represents an average number of the respective different successive regularly recurring units present in said copolymer, wherein n is a positive integer;

XII, wherein Ar * * represents an aromatic portion and XXXII is defined below, Ar4 represents a different aromatic portion, and XXIII is defined below, while the nitrogen atoms are bonded to Ar * * and the carbon atoms are bonded to Ar4, a - ^ b represents the molar ratios of the respective different regularly recurring units present in said copolymer, y ^ j represents an average number of the respective different successive regularly recurring units present in said copolymer, n being a positive integer is;

XV wherein Ar4 represents a different aromatic portion and XXIII is defined below, Ar1 represents an aromatic portion and XXII is defined below, and Ar5 represents an aromatic portion different from Ar4 and Ar1 and XXIV is defined below, while the carbon atoms are bonded to Ar4 and Ar ^ and the nitrogen atoms are bonded to Ar1 and Ar ^, where n is a positive integer; c ^ m '/ m + m' represents the molar ratios of respective different regularly recurring units present in said copolymer, y ^ represents an average number of the respective different successive regularly recurring units present in said copolymer, a- j_bjm / m + m 'represents the molar ratios of the respective different regularly recurring units present in said copolymer, y ^ j represents an average number of the respective different successive regularly recurring units present in said copolymer, where n represents is a positive integer;

XVI, wherein Ar - * - represents an aromatic portion and XXX is as defined below, Ar ^ represents a different aromatic portion and XXV is as defined below, X ^ and X2 are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), while the NH groups and X4 and X ^ are bonded to aromatic carbon atoms of Ar ^ and Ar - * -, NH and X ^ and X2 of each hetero ring are placed ortho to each other, aj_bj the molar ratios of the respective different regularly recurring units are in said copolymer, y represents an average number of the respective different successive regularly recurring units present in said copolymer, where n is a positive integer;

XVII.

wherein Ar · * · represents an aromatic portion and XXX is defined as below. Ar6 represents a different aromatic portion and XXV is as defined below, X ^ and X2 are the same or different and are sulfur, oxygen or NR (where R is hydrogen or an organic group), while the NH groups are X ^ and X2 bonded to aromatic carbon atoms of Ar ^ and Ar · * ·, NH and Χχ and X2 of each heterocycle placed ortho to each other, ajbjm / m + m 'the molar ratios of the respective different regularly recurring units present in said copolymer, represents an average number of the respective different consecutive regularly recurring units present in said copolymer, Ar ^ represents an aromatic portion different from Ar ^ and Ar · * · and XXVI is as defined below, X4 sulfur, oxygen or NR (where R is hydrogen or an organic group), while the NH groups and X4 are bonded to aromatic carbon atoms of Ar 6 and Ar · * ·, c ^ m '/ rmk m1 represents the mole ratio of the respective different regularly recurring units present in said copolymer, y ^ represents an average number of the respective different consecutive regularly recurring units present in said copolymer, n being a positive integer is;

XVIII.

wherein Ar1 represents an aromatic portion and XXXII is defined below, Y7 represents an aromatic or heteroaromatic portion and XXVIII is defined below, while the nitrogen atoms are bonded to aromatic carbon atoms of Ar * * and bonded to neighboring carbon atoms of Y7, a ^ bj-, represents the mole ratios of the respective different regularly recurring units present in said copolymer, represents an average number of the respective different consecutive regularly recurring units present in said copolymer, where n is a positive integer is.

The aromatic portions Ar * *, Ar2, Ar ^, Ar ^, Ar ^, Ar ^ and Y2, Y7 and γ8 of the extended chain polymer formulas above are defined as follows: XX is.

XXI is

XXII is

. or

XXIII is

, or

XXIV is

XXV is

, or,

XXVI is

t is XXVII

or

XXVIII

XXIX is

XXX is

XXXI IS

XXXII

Any monomeric material or mixture of monomeric materials with the ability to react in phosphoric acid to form the extended chain polymers (i.e., the above formulas IX-XIX copolymers and block polymers defined herein) of the present invention can be used.

In general, suitable monomer materials have been selected for use in forming liquid crystalline elongated chain polymer compositions of the present invention of nine types as described below.

Type 1 monomers have the general formula

wherein Ar · * · is an aromatic portion; and X2 are the same or different atoms or groups selected from classes 0, S and NR; R is hydrogen or an organic group bound to N; the R's on the two nitrogen atoms where both Xg and X2 are NR may be the same or different; NH2, ΧχΗ and X2H are bonded to aromatic carbon atoms of Ar - * -; the groups on the left side of Ar1 are ortho to each other and the groups on the right side of Ar · * · are ortho to each other.

The two sets of NH2 and XH are located on Ar * * such that they both do not partially interact with the appropriate condensing portion of another monomer. Monomer 1 is typically isolated as a hydrohalide salt from the monomer.

Generally, Ar · * · may be any aromatic moiety (carbocyclic or heterocyclic) and may be a single ring such as is trivalent aromatic or heteroaromatic moiety, and X3, 0, S, or no (R = H or a organic group).

or h i j k a n ornv a 11 c n a number of ar e — a t i s c h rings connected by valence bonds or by b i nd i rig s a c oms or groups such as

ο ί

where β is a valence bond (as: ndifc ny I) or a divalent atom (-0- or -S-) or a group such as -NR-CR-H or an organic group), - (CH (n = 1 or a higher integer). Specific examples of Ar 'are as follows:

The aromatic ring or rings of Ar such as those described above and others may carry one or more substituents. These substituents, which may be organic or inorganic, may contain hydrogen atoms or contain any atom or group which is compatible with the reagent, the polycondensatic acid and the resulting oligomer or polymer. Substitutes which are chemically reactive with types 2 to 9 should be used (see below) with the solvent (PPA) or with the oligomer or polymer products.

Substituents which provide steric hindrance to poly condensation should also be avoided.

Of the allowable coolant substituents are alkyl (i.e. C (to C (q straight chain and branched chain alkyl, benzyl, etc) phenyl, chlorine substituted alkyl, phenyl and benzyl. Of the permissible hetero substituents are chlorine, bromine, nitro, alkovy, aryloxy, SO 4 H, SR, and -N'RjR (where R 1 and R 1 are organic groups).

Formula I monomer and useful in the preparation of extended chain polymers and novel liquid crystal compositions of the present invention can also be further classified in three groups: class I (1.1), class 2 (1.2) , and class 3 (1.3). The first number of the pairs of numbers indicate the monomer ype and the second number of the pairs indicate the monomer class.

Preferred (1,1) monomers are those where Ar is a six-atom atomic ring where the four atoms of the carbon atoms have a 1, 2, 4, 5 relationship to of each other, such as 1,2,4,3-benzene or 2,3,5,6-pyridine; R H is a monovalent aromatic radical, such as phenyl, or a univalent h c t c r o -ar omatic radical, such as 2-pyridyl, or a univalent if radical, such as methyl. Monomer and (1,1) which, when reacted with a diacid or one diacid derivative to give two substantially col linear bonds, are most preferred.

Specific examples of (1,1) preferred monomers for use in the invention include those monomeres (shown as hcir o ha I eyes) in Table I below.

Table I

2,5-diamino-1, 4-benzenedithiol dihydrochloride obtained in co-operation with Wo I, and others,

Ma c r omoIe c uIe s, Vol. 1 p. 915 (19 SI).

6,6-diamino-1,3-benzoic diol dihydrochloride obtained from </, 6-dinitro-1,3-benzenediol in accordance with Wolfe, et al.

I *. p. 909 (1981).

I-S-t-Traaminobenzobentetrahydrochlorid obtained from Aldrich Chemical Co. and purified by recrystallization and diluted from HCl by heating, adding charcoal, filtering and adding concentrated HCl.

2.5- diamino-l-benzene i o I d i hydroch! or ide prepared in accordance with Wolfe, and others, 3. Polyme-Sci., Part A-I, Vol. 6, p. 1503 (196S).

2,3,5,6-tetraaminopyridinctrinhydrochlorid prepared by the dinitration of 2,6-diaminopyridinc followed by hydrolysis and reduction using the method of A.H. Gerber, 3. Polymer Sci. , Po! yme r Ch cm i s t r Ed. , Full . II, p. 1703 (1973).

3.5-diamino-2,6-pyridine iodine hydrochloride prepared by dinitrating 2,6-dimethoxypyridine in accordance with C. D. Johnson et al., 3. Chem. Soc.

(D), 1967, p. 120, followed by reduction and removal.

3,6-diamino-2,5-pyridinedithiol dihydrochloride prepared from commercially available 2,5-diamino pyridine using methods analogous to the preparation of 1a.

N, N-diienyl-11-yl-tetraaminobenzene dihydrochloride prepared starting from m-dichlorobenzene in other reaction with H. Vogel and C. 5. Marvel, 3. Polymer. Sc i. , A, Vol.

I p. 1531 (1963) and purified from toluene before use.

The preferred (1,2) monomer and are those wherein Ar * consists of two six-membered aromatic rings bonded to a covalent carbon-carbon bond each with valences at the carbon atoms in 3 and 4 positions, such as 3,3 ', 4, 4 1 -bif eny I or 4, 4 1, 5, 5 '- (2, 2 1 -bipyridyl), or Ar' consists of two fused six atom rings with valence positions that are carbon atoms and have a 1,2,5,6 relationship to each other such as 1,2,5,6-naphthalene.

The four functional groups bonded to the valence positions of Ar * by covalent bonds include two aini rupons and the groups -X, H and '-XH so that one am i is still call ortho to -X (H and the other amino group ortho is relative to X2H and XH is bonded to either the 3 oi t; in the first case put oi the i oi 2 place in the second case and -X, H is bonded to either the 3 'oi 4' place in the first case and the 5 or 6 place ·. in the second case, X j and X? are as defined above.

Specific examples of (1,2) preferred ome rs for use in the invention include those that ome n (display w as h y d: o h a 1 c g e n i d e n) in Table 2 below.

Table 2

3,3'-dime reaptobenzine in d hydrochloride prepared by the Houben-Weyl method,

Methods of Organizing Chemistry, E. Miller, Ed. yo! IX, biz. 39 (1955).

3,3'-dihydroxybenzidine dihydrochloride prepared by the method of C.C. Vogt and F. Marschall, U.S. Patent No. 2,497 24 8 (1950) from o-dianisidinc and calci umc h 1 o r i d e.

3, 3 '- d i am i η o - ^ 1-dihydroxybif e n yId i h y d r o c hIo ri d e prepared using the method of Y. Ima i, I. Ta o k a, K. lino, and Y. i wa l <u r a, Makromol. Chem. S3, b I z.

167 (1963).

3,3'-diaminobenzidine tetrahydrochloride dihydrate prepared in accordance with measurement (same reference as for I h) and the tetrahydrochloride recrystallized from dilute HC! containing stanochloride with the addition of concentrated HCl.

3, 3 '- di ami no - 4, 4 1 - diani I inobi pheny Idihydrochioride prepared from dinitration of <i, ii, dichloro-phenyl, replacement of the chloro groups with aniline, and reduction.

1,5-diamino-2,6-nai talcendi tl ', diol dihydrochloride using methods analogous to monomers 1a and II.

1,5-diamine no-2,6-naphthalenediol dihydrochloride prepared from 2,6-dichloro-1,5-dinitronaphtha I a.

1,2,6,6-tetramine-phthalene tetrahydrochloride prepared by the amination of 2,6-dichloro-1,5-dinitro-naitalene followed by catalytic reduction in accordance with K. Imai. N. Kurihara, L. Mathias, J. Wittmann, W.B. Alston, and J. K. Stille, Ma c r omo I e c u I e s, 6, I, 5 S (1973)

The preferred (1,3) monomers are those in which Ar * is any aromatic moiety with two sets of ortho-valencies on carbon atoms, such as

4 in which i! is a divalent aromatic or its o - a i cma tic part, O, S, SO2, C = O, -CH2CH2-, etc.

The four functional groups attached to the I b va I and ti cp I ares of Ar are divided into nvec set ion (NH2 and X (H) c'n (NH2 cn X2H) with the dc functional groups within each set that form and the two sets placed on Ar 'such that they cannot react simultaneously with the same functional group of another monomer X 1 and X 2 are as defined above.

Specific examples of (1,3) preferred monomers for use in the invention include those that are (shown as hydrohalides or as isomers) in Table 3 below.

Table 3

1, 3, 3 '- diocapto-ft.' '- di am inodi phenylethydrihydrochlorid prepared by the method of V. V. Korshak, E.S. Krongauz, Λ.Ρ. Travnikova, A.L. Ra sa now, cn A.D. Katsarava, Dok I, Akad. Na uk, SS SR, 196, 106 (197.1).

3. 3 1, ¾ 1 - tetraamine diodes f e n y I e t h c r t c t r a h y d r o c h I o - ride in hand obtained from Pialtz & Bauer.

3,3'-dihydroxy-4-diam inodiphenyl ether is prepared according to the procedure of 5. U.

Kantor and J. Sonnenberg, U.S. Patent 3,306.S7 6 (197 6).

3,3'-diamino-1, -'-dihydroxydi phenyl ether prepared in accordance with the method of Λ. Lindsey, $, E. Hunt, and G.K.L. Gibson, British Patent No.

I. I 8 I. I 53 I 1970.

3,3-tetraaminodiphenyl sulfone prepared from commercially available 4-aminode phenyl sulfone. su I f on by acctyl ring, dinitration, hydrolysis and reduction.

3,3'-dimercapoxy-1,1'-diam inodiienylsulion bromic from commercially available, 0''-diaminodiphenylamine using processes analogous to the preparation of 1a and 11.

3,3'-dihydroxy-i, V-di ami n o d i f e n y I s u I ion prepared in accordance with the method of G. I. B r a z, 1. Y.

Kar dash, and U.S. Yakubovich, Po Iym. Sc i. USSR, ji, p.

20 13 (1967).

3,3'-di am in 1,4,4-dihydroxydi phenyl sulf ion prepared from commercially available 4,4'-dihydroxydi phenyl is ion by acetylation, dinitration, hydrolysis and reduction.

3.3l, 11 '/' -tramaminobcn7.oinone commercially available from PolySciences, Inc.

3,6-diamino-1,2-benzenedithiol dihydrochloride prepared by isolating 2,7-diaminobenzene / 1,2-d; 6,5-d '7-bisthiazole from the scheme for preparing 1a followed by hydrolysis.

wherein is a divalent organic group and Zj and Σ2 are electron deficient carbon groups and the same or different groups may be selected from the following class:

(Rj = H or an organic group bound to N by a ko o Is t o f a t o om)

Hot only requirement of Z | and Z ^ is that they react with the XH and XH and react with the two hydrogen atoms of the primary type I amino groups to form suitable replaceable units, such as water, hydrogen sulfide, hydrogen halide, ammoniac, etc.

2

The divalent group Y may be an aromatic group, an acyclic aliphatic group, or a cycloaliphatic group, and such groups may be substituted. treated with carbon hydrogen groups (aliphatic or aromatic) and with hydrogen atoms and groups. Generally, any of the groups described above can be used as substituents of the aromatic ring or rings of Ar * subject to the same restrictions.

Formula 2 monomers useful in the preparation of extended molecule cycles and novel liquid crystal line compositions of the present invention can also be further assayed in three groups: class I (2.1), class 2 (2.2) , and class 3 (2.3). The first number of the pairs of numbers indicates the monomer type and the second number of the pairs indicates the monomer class.

Preferred (2,1) monomer and are those wherein 2 Y is zero, or includes at least two carbon atoms to which Z and Z are bonded such that the two exocyclic 2 1 2 bonds between Y and Z | and between Y and have a rigid and fixed relationship to each other and in 2 are essentially collateral, or Y may also be a cycloaliphatic group having at least two carbon ions which are bound to Z (and Z? such that the two bonds between Y and Zj and between Y have a highly preferred relationship to each other which is essentially collinear. Carboxylic acid derivatives of 2 J-2 q and 2 Z (as described below) such as CCOH which decarboxylate at Emperatures below those required for polycondensation with type I monomers are less preferred.

Specific examples of (2, I) monomer and preferred for use in the invention include that monomer and in Table b below.

Table U

tereital acid obtained from Amoco Chemicals Co. and micro-divided and dried before use.

obtained from Aldrich and sublimated immediately before use.

prepared from 2b nf commercially obtained from Pfaltz and Bauer.

obtained from Pfaltz and Bauer.

trans-1,4-cyclohexane dicarboxylic acid · supply a <d i r r i c h and recrystallize from water,

prepared from 2nd.

prepared from 21.

bcreiduit2g.

obtained from Aldrich Chemical Co.

prepared by diazoation of 2,6-diaminobenzobisthiazole (see reference for 1a) followed by treatment with copr o c y a n i d e.

prepared from the condensation of compound fb with urea followed by diazotization as for compound 2j.

prepared as for 2k using compound lc.

prepared as described for 2k using compound 1d.

prepared as for 2 k using compound le.

> prepared as for 2k using compound If.

prepared as for 2j, using 2,6-diaminopyrido-bisthiazole as prepared in the synthesis of Ig.

prepared as for 2k using compound Ih.

prepared by the condensation of compound la with p-10! uenic acid followed by oxidation.

prepared by the condensation of Ib with toluene acid followed by oxidation.

prepared using a method similar to 2s using Ic.

prepared using method similar to 2s using Id.

prepared using a method similar to 2s using Ie.

prepared using a method similar to 2s using I ί.

prepared using a method similar to 2s using Ig.

prepared using a method similar to 2 s using ih.

The preferred (2,2) monomer and are those wherein o Y comprise two six-membered rings attached via a covalent carbon-carbon bond each with plaats-position valencies or each with 3-position valencies, such as ft .V-biphenyl or 3, 3 - b ί i eny 1, or Y2 comprises two fused six-membered rings with valence sites that are on carbon atoms and have a 1.5 relationship to each other, such as 2 , 6-naphthalene or 2,6-quinoline, οί Y is a cycloal divalent portion with valences of carbon atoms and in a 1,2-transconi-2 guration, οί Y is a variety of condensed aromatic and hetero-aromatic ring systems only bonded via carbon-carbon bonds and having 2 valencies, Z ^ and the same are as defined above.

Specific examples of (2,2) preferred monomers for use in the invention include those monomer in Table 5 below.

Table 5

Phenyl dicarboxylic acid obtained from Aldrich Chemical Co.

obtained from 2 a a.

prepared in accordance with the method of B. Raecke and H. Schirp. Or g. Syn. Co II. Full. V, Page 8 13 (1973) from hand-available 1,8-naltalenedicarboxylic anhydride.

prepared from 2cc by treatment with thionyl chloride.

prepare owl commercially available (Aldrich) 2,6-dimethylamino Line by oxidation.

prepared from o-nitrobenzoic acid using the method of M. Kurihara and N. Yoda, 3. Macromol. Sci. Chcm Al (6) j p. 1069 (1967).

was obtained from Aldrich Chemical Co. and crystal crystallized from methanol before use.

prepared using the procedure of 3. Preston, W. DC Winter and W. L. Hofierbert, 3. Heterocyclic Chcm.

2, p. 269 (1 96S (d.

I, ii-bis (6-carbo: <ybcn2othiazole - 2 - y 1) benzene prepared using procedures analogous to 2 h i -.

prepared using procedures analogous to 2hi ".

The preferred (2,3) monomer and are those where ir.

2 Y may be any aromatics, hetero-ar orr.a: i s c h and alias divalent species not previously described.

Specific examples of (2,3) preferred monomers for use in the invention include those monomer in Table 6 below.

Table 6

prepared in accordance with the procedure of R. C. Evers, p. Arnold, cn T, C. Hclminiak Ma c r omoIc c u I e s, I ^, p.

925, 0 «1).

prepared in accordance with the method of T. Takekoshi, 3. G. Wirth, Dr. Heath, 3. E. Koeha newski, 3. S. Manel lo, and M, 3. Weber, Polym. Prepr. , 3. / Un. Chem. Soc, 20 (1), b I z. 17 9 (19 7 9).

prepared in accordance with the method of T. Takekoshi, 3. G. Wirth, Dr. Heath, 3. E. Kochanowski, 3. 5. Manel lo, and M, 3. We b e r, ^ Polym. Prepr. , 3. Am, Chcm. Soc. 2.0 (I), bz. 179 (1979).

ti i t 2nrm in accordance with the method of R. C.

Evers, F. E. Arnold, cn T. E. Hclminiak, Ma c r omo1c c u I c s, 11 bIz. 9 2 5 (I 9 S I).

- (m-phenylenedioxy) dibenzoni ir ί I.

prepared in accordance with the procedure of R. C. Evers, F. E. Arnold, cn T. E. Hclminiak Ma c r omo I c c u I c s, _l_4, biz.

92 5 (198 I).

in accordance with the method of R. C. Evers, F.

E. Arnold, and T. E. Helminiak Ma c r onto I e c u I e s, 19, biz.

925 (I 98 I).

t

prepared in accordance with the method of R. C. Evers, F. E. Arnold, and T. E. Hclminiak Ma c r omoI e c u 1 e s, 19, biz.

925 (I9SI).

prepared in accordance with the method of R. C. Evers, F. E. Arnold, cn T. E. Hclminiak Ma c r omoIc c u I e s, I 9. biz.

92 5 (198 I).

Obtained from Pfaltz and Bauer and recrystallized 1 L isated from 90% ethanol.

obtained from Polysciences, Inc.

prepared from a coupling of m-cresol and m-bromo oolene followed by oxidation using the method of M. T to t a, 3. Pharm. 5oc., Japan, 37 p. 391 (1937).

obtained from Aldrich Chemical Co.

obtained from Aldrich Chemical Co.

obtained from Aldrich Chemical Co.

obtained from Aldrich Chemical Co.

obtained from Aldrich Chemical Co.

Type 3 monomer and has the general formula

wherein Ar 4 is a trivalent aromatic or heteroaromatic moiety, and is O 5, or N-R (R = H or an organic group).

Formula 3 monomers useful in the preparation of extended chain polymers and novel liquid crystalline compositions of the present invention can also be further classified into two groups: class I (3.1) and class 2 (3.2). The first number of the pairs of numbers indicates the monomer type and the second pair of pairs indicates the monomer type.

The preferred (3,1) monomers are those in which 3 Z ^ is the same as defined for Σ j, * Ar is a trivalent aromatics or hetero-aromatics moiety with the three valence sites that are at the carbon a and have the relationship that the relationship between Z, and 3 i

Ar is almost collinear with the same variation band in monomers condensed immediately thereafter, and is defined as for Xj in Table I.

Xen NT-L are placed or to relative to each other 3 3 - to Ar.

Specific examples of (3,1) preferred monomers for use in the invention include the monomer in Table 7 below.

Table 7

prepared in accordance with R. F. Kovar and F. E.

Arnold, 3. Polym. Sci. Polym. Chem. Ed., 14, b) z. 2807 (1976).

The preferred (3,2) monomers are those wherein 3 Z-j, Ar and are as defined above. The bonds formed in homopolymerization vart (3,2) monomers are defined in their spatial relationship with an angle of chain formation of less than about 150 to about 180 °.

Specific examples of (3,2) preferred monomers for use in the invention include those monomers (shown as hydrohalides or as monomers) in Table 8 below.

Table 8

prepared in accordance with Wolfe, AF05R Final Technical.

Report, Dcc. 15, 1980.

prepared as described in example 5.

prepared as described by Y. Imai, K. Uno, and Y. Iwakura, Ma k r omoI. Chcm., 8 3, 17 9 (19 6 5).

prepared as described by K. Auwers and H. Rohrig, Chcm · Ber. , 30, 992 (1897).

obtained from Aldrich Chemical Co. and recrystallized from acid-released water before use.

prepared from p-aminobenzoic acid by chlorination, oxidation to 3-chloro-ear-b-nitrobenzoic acid, followed by clarification and reduction.

prepared by nitration of commercially available (Aldrich) p-chlorobenzoic acid, followed by annealing and reduction.

prepared by nitration of commercially available k-carboxybiphenyl (ICN / K and K) and reduction to 4-amino-ca-boxyb if eny 1, followed by placement of the β-mercapto group using analogous methods to those described for 3a.

4-carboxy-3 ', - amino-4'-hydroxybiphenyl prepared by the nitration of commercially available (IC.N / K and K) 4-carboxybiphenyl, conversion to 4-carboxy-p-phenol by reduction and diazotization, followed by acetylation, nitration, hydrolysis and reduction.

prepared by acetylation of 4-amino-4'-carboxylic acid (see 3h preparation) followed by nitration, hydrave, t and reduction.

------ _ - · «-.....

Type 4 monomer and have the general formula

4.

wherein Z 2, Σ y and Z -, are the same or different and are selected from the list of carboxylic acid derivatives given for Zj in Table 4. Z 2 and Zy or Z 2 and, or both sets may also be carboxylic anhydride groups. A r ** is an aromatic or aromatic heterocyclic moiety with four of 1 and 11 carbon atoms. Ar can be a six-membered ring with the valence sites with a 1,2,4,5 relationship, or Ar * can be two condensed six-membered rings, such as naphthalene.

Z ^ and Z ^ as one set and Z ^ and Z ^ as another set must either be placed within each set, or bear a 1,4,5,8 relationship to each other. An (imaginary) line perpendicular to the bond between the valence koo 1 material atoms bound to Z ^ and Z ^ must be collinear with the corresponding (imaginary) Jijn for Zg and Z-j.

Formulas monomers useful in the preparation of the extended chain polymers and new floc crystal crystalline compositions of the present invention have been classified as class I (4,1). It. first geta '; of the number pairs indicates the monomer type and the second number of the pairs indicates the monomer class.

Specific examples of (4,1) monomeric "preferred for use in the invention include those monomers in Table 9 below.

Table 9

obtained from Aldrich Chemical Co. and sublimed or recrystallized (acetic anhydride) before use.

obtained from Aldrich Chemical Co.

Type 5 monomers have the general formula

5 where Zg and Z 'are defined as for Z ^ and Z ^, in Table 9, Ar is defined as in Table 9, the two amino groups are ortho to each other, and Z g, Z ^, and the two amino groups are Placed such that two imaginary lines drawn perpendicular to the bonds between their valentine carbon atoms are col linear.

Formula monomer and useful in the preparation of the extended chain polymers and novel liquid crystal compositions of the present invention have been classified as Class I (5.1). The number pair (5.1) has the same meaning as above.

Specific examples of (5.1) monomer and preferred for use in the invention include the monomer in Table 10 below.

Table 10

^, 5-d i ami nonaphthalene-1, 8-d icarboxylic anhydride, which is derived from the d i n i t r ode r i by chemical reduction in accordance with I. Honda and M. Okazaki, J ^ Soc.

Or g. Synthet ic Chem. (Japan), 7_, biz. 2.5 (1950).

Type 6 monomccr hceit dc general formula

6 wherein Ar6 represents an aromatic portion and a tetrahydroxy fused ring system is Z ^, Zjj, ^ | 2 \ '^ \ (are the same HO atoms bound to carbon atoms of Ar6.

In general, Ar6 may comprise a single or a number of aromatic rings in the middle of a fully conjugated fused ring system. The central aromatic ring or rings of the fully conjugated fused ring system may be any of those described above and others.

FormuIe. 6 monomers useful in the preparation of the extended chain polymers and novel liquid crystal line compositions of the present invention can also be further classified into two groups: class I (6.1), and class 2 (6.2). Dc geta I pairs have the same meaning as above.

The preferred (6.1) monomers are those in which Ar6 comprises a single central aromatic ring in the center of the fused system.

The preferred (6.2) monomers are those in which Ar comprises at least two central aromatic rings at the center of the fused ring system.

Preferred specific examples of (6.1) and (6.2) for use in the invention include those which are included in Table II and 12, respectively.

Tabe! ! I

prepared from condensation of 11-tetraaminobenzene with oxalic acid in accordance with H. Tadamus, F. DeSchryver, W. DeWinter, and C. S. Marveil, 3. Po 1 µm. Sci-Fe, pp. 2831 (1966).

Table 12

prepared from condensation of 3,3'-diaminobenzidinc with oxalic acid in accordance with the method of H. Tadamus, et al., 3-ym-Sc i. Λ- I, b 1 z. 28 3 1 (1966).

Type 7 monomer has the general formula

7 where Y 1 represents an aromatic or hetero-aromatic portion and is a fused ring carbon group, the X? 's j' are double bound to k o o I $ t o i a t o om of Y.

Formula] monomers useful in the preparation of extended chain polymers and novel liquid crystal line compositions of the present invention are classified as class 1 (7.1). The number! En - pair (7.1) has the same meaning as above.

A specific example of (7.1) preferred for use in the present invention is 7a in Table 13 below.

Table 13

Type 8 monomer has the general formula

8

S

where Y is a single carbon cyclic portion, Xjq and X ,. HO and O are atoms, respectively, bonded to carbon atoms of Y.

Formula 1-8 monomer and useful in the preparation of the extended chain polymers and novel liquid crystalline compositions of the present invention can be classified as class I (8,1).

The number pair (8.1) has the same meaning as above.

A specific example of (8.1), which is preferred for use in the present invention is 8a in Table 11 below.

Table 14

Type 9 monomer has the general formula

9 in which Ar is an aromatic portion and a partial refinement is a s y s t e em, Z are at OH at ome n, Xj is selected from the classes O, S, and NR; R H to an organic group bound to N. S; NH 4, X 4, Z, and Z (5 are bonded to carbon initiators of Ar; NH 4 and X 4 H are placed ortho, Zf 2 and Z are placed.

Formulas 9 monomers useful in the preparation of the extended chain polymers and novel liquid crystal formulations of the present invention can be classified as class I (9,1). The number pair (9.1) has the same meaning as above.

A specific example of (9.1) preferred for use in the present invention is 9a in Table 15 below.

Table 15

prepared from diamino-dinitrobine by condensation with oxalic acid followed by reduction in accordance with R. F. Kovar and F. E. Arnold, 5k. Po 1 ymSc i. , Po I ym.

Chcm. Ed., U, biz. 2S07 (1976).

All patents and / or publications of Tables 1-6 cited above are specifically incorporated by reference herein.

All simplified polymer formula representations presented in the description are noted below and can be easily explained by reference to the appendix.

The most preferred extended chain homopolymers in accordance with the practice of the present invention include

Particularly preferred extended chain homopolymers in accordance with the practice of the present invention include

The preferred extended chain homopolymers in accordance with the practice of the present invention include

It is useful to define three P2O5 levels, acting at different stages of polymerization, that should be controlled to optimize the synthesis procedure of the present invention. We will define the initial P2O5 content m0 as the P2O5 content of the polyphosphoric acid active during the hydrohalogenation (in step b above and as will be explained more fully below). The initial P2O5 content in accordance with the practice of the present invention should be below about 83.3% and may range from about 83.3% to about 63%; preferably below about 82%, more preferably below about 80%, and most preferably below about 76%.

The intermediate P2O5 content is effective at the start of polycondensation and is calculated to give the third (or final) P2O5 content f responsible for polyphosphoric acid hydrolysis by 100% of the theoretical water of polycondensation. The final P2O5 content f must be above a minimum value if the solution is to maintain its effectiveness as a reaction medium in the late stages of polymerization. The final P2O5 content should be between about 82% to about 86%, preferably between about 82% to about 84%, and most preferably between about 82% to about 83%.

The various important general process steps for preparing liquid crystalline polymer compositions of the present invention may include one or more of the following stages which are considered to be within the process parameters described above. These stages are:

Stage one - One or more of a selected first monomer selected from the group consisting of (amino group-containing) monomer 1, 3, 5., or 9., is added to a specific initial weight in grams (given by a *) of a polyphosphoric acid with a P2O5 content mQ in accordance with the empirical equation a * = {[1 - f 3 ([Py / Pc] - Py) - [no (18.02) / Mw] Py} (1-nio) 1 where Py is the weight in grams of the theoretical yield of polymer, Pc is the weight fraction of polymer in the total weight of the final liquid crystalline polymer composition (and is chosen to be above the critical concentration of the polymer necessary for liquid -crystalline phase formation in the resulting polymer-polyphosphoric oxygen composition), nQ is an integer giving the number of moles of condensation byproduct per mole of polymer repeating unit. The number 18.02 is the molecular weight of the condensation by-product, Mw is the molecular weight of the polymer repeating unit, and f is the final P2O5 content to be above a minimum value to be defined by this invention.

Stage Two - Once the first monomer (s) are combined with polyphosphoric acid, and protecting groups, if present, are released (if desired, depending on the particular polymer and the reaction mechanism chosen), a stoichiometric amount of one or nut of a suitably selected second monomer from the group consisting of 2, 4, 6, 1_ or 8, then added, and the selected value of f is achieved by adding b * (an intermediate weight in grams of P2O5) to the mixture in accordance with the equation

Stage Three - The resulting mixture (containing the first monomer (s) and / or the second monomer (s) is then heated to a temperature suitable for polymerization. The reaction temperature may range from about 100 ° C to about 210 ° C, preferably about 110 ° C to about 200 ° C, more preferably about 160 ° C to about 190 ° C, and most preferably about 185 ° C.

The P2O5 content, m0 should be low enough to (1) achieve effective dehydrohalogenation and / or (2) achieve sufficient monomer charge to achieve desired Pete without foaming problem or unusually high mass viscosity. f should be high enough to: (2a) maintain a polyphosphoric acid composition, which is an effective reaction medium in late stages of polycondensation.

(2b) to provide an effective phosphorilization medium, as described in N. Yoda and Al. Kurihara, "New Polymers of Aromatic Heterocycles by Polyphosphoric Acid Solution Methods," J. Polymer Science, Macromolecular Reviews, Volume 5, (1971), 159, in the early stages of polymerization. The material of the publication of Yoda et al. Is specifically incorporated herein by reference.

(2c) to provide an effective solvent for the polymer at the end of polycondensation.

To illustrate, a graph of equation a * is presented in Fig. 7 showing regions (shaded streaked region) of poor monomer 1a solubility. In the case of polymer [AI] n, the fabrication of Pc curves can be exploited as follows: 1. Choose a [AI] n polymer concentration, Pc for example 0.16; 2. Choose a point of the curve Pc = 0.16 above the shaded streak area indicating poor monomer 1a solubility; 3. From that point, it is chosen, the gram weight of PPA (a *) of the corresponding P2O5 content (m0) to be added to 92.06 g of monomer 1a; 4. After dehydrochlorination is complete, the amount of monomer to be added is 62.38 g; and 5. If the final P2O5 content (f) is chosen to be 82.2, the amount of P2O5 to be added (b *) is the difference between the amount of PPA used in step 3 above and the weight of PPA to the end of the curve for Pc = 0.16.

The choice of the optimal m0 depends on the desired polymer concentration and the solubility limits of the first monomer. The poor solubility range of monomer 1a is shown in Figure 7. Other monomers exhibit different solubility limits. Solubility series of certain representative monomers are listed below.

Monomers with solubilities greater than 1a: 1f, 1g, 3a, 3b, 3c, and 3d.

Monomers with solubilities similar to la: ld and 3e.

Monomers with solubilities less than la: lb, lc, le, li, lk, 3f, 3g, 3h, 3i and 3j and monomers with solubilities much less than la: lh, 11, lm, In, lo, lp, 5a and 9a .

Accordingly, it is possible to dehydrohalogenate the selected dehydrohalide (monomers) more quickly; the foaming problem is reduced or eliminated; the PPA solution of less P2O5 content than that of U.S. Patent 4,225,700 is much less viscous and dehydrohalogenation can be performed much faster. Furthermore, a solution of selected monomers in PPA of considerably higher concentration is possible and a reaction product containing a much higher concentration of polymer is possible.

Reaction Mechanism Formation of Formula IX copolymer

Formation of Formula X copolymer

Formation of formula XI copolymer

Formation of formula XII copolymer

Formation of ion null XV copolymccr

Formation of formula XVI copolymccr

Formation of formula XVII copolymccr

Formation of formula XVIII copolymcer

The above formulas IX, X, XI, XV, XVI, XVII, XVIII copolymer composition 1 I can be prepared in accordance with the above process parameters by: (a) mixing at least two of the first monomer selected and (for example, two or more of a male selected from the group consisting of (1,1), (1,2), (1j3). (3,1), (3,2), (5, 1) or (9,1)) with or without oxidation-protecting atoms or groups with a preliminary solvent or phosphoric acid with a relatively low phosphorus p and oxide, heating (b) and, if desired, bringing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups present and to provide a solution of the first monomer in the preliminary solvent, (c) adding at least one of a selected second monomer and (for example one or more of a monomer selected from the group consisting of (2.1), (2.2), (2.3), (^, I), (6.1), (6.2), (7.1) or (8, 1)) in the resulting solution of step (b) to provide a mixture of the first and second monomers in the preceding solution, (d) thereafter increasing the phosphorus pentoxide content of the mixture resulting from step (c) ) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (e) polymerizing the first and second monomer at a temperature sufficient to react at a rate to form a first oligomeric product with a preselected intrinsic viscosity or a first copolymeric product.

Similar formulas IX, XII, XVI and XVI11 copolymer compositions can be prepared by: (a) mixing at least one of a selected first monomer (for example, one or more of a monomer selected from the group consisting of (1,1), ( 1,2), (1.3), (3,1), (3,2), (5,1) or (9,1)) with or without oxidation atoms or groups with a preliminary solvent of phosphoric acid with a relatively low phosphorus oxide content, (b) heating and optionally bringing the resulting mixture under reduced pressure to remove any volatilized protected atoms or groups present and to provide a solution of the first monomer in the preliminary solvent, (c ) adding at least two of a selected second monomers (for example, one or more of a monomer selected from the group consisting of (2,1), (2,2), (2,3), U, I), (8 , 1), (8.2), (7.1) or (8.1)) in the resulting solution from step (b) to provide a mixture of the first and second monomer in the preliminary solvent, (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer inheritance diameters of high phosphorus pentoxide content suitable for polymerization, ( e) polymerizing the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first oligomeric product of a preselected intrinsic viscosity or a first copolymeric product.

Preferred formulas IX, X, XI, XII, XV, XVI, XVII, XVIII copolymers which form liquid crystal I copolymer compositions of the present invention are those in which a. The mole fraction of the ith monomer selected from type 1, is, b. the mole fraction of the j-d c mo n ome selected from types 2, k, 6, 7 or 8 is, c,

K

the mo fraction of the k-th mon ome selected from types 3, 5 or 9, m and m 'is suitable molar amounts based on desired yield, is a µm / m + m' and ab the mo 1 ratios of the regularly recurring units arising from the condensation of the i-th monomer of type I and the j-th monomer of type 2, k, 6, 7 or 8, ck cn c ^ m '/ irum' are the mo The proportions of the regularly recurring unit arise from the condensation of the k-dc monomer of type 3, 5 or 9, y .. the average block length (i.e., the average number of consecutive regularly recurring units that do not are interrupted by a different regularly recurring unit) of the regularly recurring unit formed from the type I idomer of type I and the j-moment of type 2, ^, 6, 7 or 8, yk the mean block length of the regularly recurring unit formed by the condensation of the k-dc monomer of type 3, 5 or 9, and n is the mean t the total length of the copolymer (i.e. the average total number of regularly recurring units is independent of structure). The number of recurring units in the copolymer can be the product of the highest i and the highest j or the product of the highest i and the highest j plus the highest k. i, j and k may be as high as practical, but may have certain minimum values as copolymer and must be obtained rather than homopolymers.

Selected molar quantities (a, m, a ^ m, .....

f 1 L.

ajm) of type 1 monomers can be mixed with a phosphoric acid having a phosphorus pentoxide content of about 63% to about 78%, preferably greater than about 68%, most preferably about 78%, and the protecting groups such as hydrogen halide if present, can be substantially removed by heating, and by applying reduced pressure if desired. The amount of the phosphoric acid is most desirably determined in accordance with equation a above, making the necessary calculations for addition of monomers of optionally different mo I weights and different ratios. A stoichiometric amount (i.e., bm + bpm + .... bm = m) of monome selected from type 2, k, 6, 7 or 8 can then be added to the resulting solution. The phosphorus pentoxide content of the resultant mixture may then be increased in accordance with equation b * above, in order to increase the final phosphorus pentoxide content of the substantially copolymerized mixture to a value preferably within the range between about 81% to about 8% and most preferred between about 82% to about 83.3%. The resulting mixture can then be heated to a temperature, preferably about 100 ° C to about 210 ° C, most preferably to about 170 ° C to about 8.50 ° C within a practical period of time, of less than about 1 hour to more than about 5 hours, preferably within about 1 to about 3 hours. The temperature may be maintained for a sufficient time, which may range from less than about 1 hour to about 48 hours or more, most preferably between about 1 to about 23 hours, to achieve the desired n value. The practice of the present invention as it relates to the preparation of novel liquid crystalline compositions comprising polymers of the general formulas IX, XII, XVI, XV III is exemplified for those compositions including general formula IX wherein the selected monomer and of type 1 are further assayed crazy 1 as of types (1,1), (1,2) or (1,3) and the selected monomers of type 2 are of types (2,1), (2, 2) or (2, 3).

General formula IX copolymer and prepared from type (1.1) and type (2.1) monomers have the advantage that the critical concentration necessary for liquid crystal behavior is low. For the copolymer listed below, their critical concentration may even be as low as about 5% by weight in polyphosphoric acid at substantially moderate values, allowing a wide range of workable concentrations.

Since the regularly recurring units of copolymers are of substantially similar mesogenic properties, a wide range of copolymers can be achieved; for example, a j b ^ can be in the range from almost zero to nearly one while a j b ^ 0 ^ a2 ^ 1 ^ omda 1 equals 1 -a ^ b j) is in the range from nearly 1 to almost zero, respectively. The average block Icngtcn Yj | and y ^ or y ^ j are governed by the mono-tradition method described above and the mole ratios selected. For example, for monomer pairs of in. essentially equal reactivity y j ^, which is equal to I / I -a | b |, ranges from almost one to very high values. Likewise, y ^ or y ^ | are in the range of 7. very high values to almost one. Monomeric purity, control of st occh i ornc tric, and expression of nevcnrcactics caused by oxidizing impurities should be sufficient to obtain a total copolyester greater than approximately 50

In order to obtain the desired polymeric properties of useful mechanical strength, modulus, etc. The practice of the invention such as that related to copolymers derived from class I is being produced further illustrated in examples & 9-5 and 5 ^ -66 below.

General formula IX copolymers and can be prepared from type (1.1), (2.1) and (2.2) monomer and from type (1.1), (1.2) and (2.1) monomers. These monomer and are classified as class 2 due to either a moderately reduced mesogenic character of the regular recurring unit derived from them, or due to their tendency to reduce the solubility range of the resulting polymer, which in turn usually results from a total reduction in the hetero atom / carbon atom ratio of the resulting polymer. Both of these conditions are critical and that inclusion of class 2 monomers in copolymer and of the present invention should be carefully selected. The degree of this selectivity is illustrated by the following copolymer and prepared in accordance with the practice of the invention.

The immediately preceding list of copolymers is derived from monomer compositions containing monomer and which give reduced solubility of the copolymer. Oc for approval values of a | bj (i.e. dc mole fraction of dc nicer soluble regular return cc unit) are those which are greater than about 0.8, resulting in values of y ^ greater than about 5 and y (2 values of almost 1. Monomer purity, control of stoichiometry, exclusion of oxidizing impurities, and selection of the molar amount of the less soluble sample to maintain copolymer solubility should be sufficient to have an average value of more than about 50 Increased ratio of a less soluble mono necr can be achieved by selecting omnomers which give improved solubility to the copolymer In general, monomer and type I in which XS is, have greater solubilities than those wherein XO is O N. The practice of the invention as related to copolymers of partially reduced solubility is further illustrated in Examples 52, 53, 70, 71 and 72 below.

The following list of copolymer and is derived from inclusion of monomers of moderately reduced mc sogenicitcit in the practice of the invention is illustrated for them.

The predecessors of a | Nearly zero fate are nearly one for copolymers in this classification with the general understanding that the total copolymer concentration in the polyphosphoric acid is above a critical concentration determined by the least mesogenic regularly recurring unit. For example, above about 13%, the above copolymers a ^ b | values have between about one and zero, y j ^ values of nearly one and greater, and y ^ j values of nearly one and greater.

The preferred concentration with these ajb ^ and a ^ b (values may be between about 15 and about 22 gcw.%. If the molar ratio of the higher mesogenic regularly recurring unit (i.e. ajb}) is chosen to be values of greater than about 0.6, preferably greater than about 0.75, the range of workable concentrations is increased to include concentrations of the copolymer in greater than about 8 wt.%, preferably above about 10 wt. wt% Values of n greater than about 50 are preferred as set forth above.

General Formula IX Copolymer Compositions can be prepared from Class 3 monomer.

t

Moreover, because they belong to class 3, polymer polymer-return units have little or no mesogenic character. Their incorporation into copolymers prepared as above is within the scope of the present invention, but they are less preferred because the random incorporation of a significant mo (percentage of these non-mesogenic units results in insufficient block length of the mesogenic regularly recurring unit or units to impart liquid crystalline behavior Incorporation of less than about 3 mole percent of type 3 monomer and preferred Increased inclusion of class 3 polymers are highly preferred using a block polme There is a method described below A less preferred embodiment of the present invention is the preparation of general formulas X, XV and XVII by respectively adding addition of type 3, 5 and 9 monomers to the starting solution of the above copolymer process The only feature of the geometry of monomer and of type 3 (except for 3I <), 5, and 9 is that do bl ok lengths, y ^, is large, or if it is small, it is an even number. This condition dictates that the preferred compounds of formulas X, XV, and XV11 are prepared using the following methods: b 1 okpo 1 ym r r y w r y.

The general formula XI copolymer composition shown above is prepared according to the following procedure: (a) mixing at least two of a selected first monomer with or without oxidation-protecting atoms or groups with a preliminary solvent of phosphoric acid with a relatively low phosphorus pentoxide content, (b) heating and optionally bringing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups present and to provide a solution of the first monomer in the preliminary solvent, (c) then increasing of the phosphorus peroxide content of the mixture resulting from step (b) to provide a first monomer reactor of greater phosphorus pentoxide content suitable for polymerization, (d) causing polymerization of the first and second monomers at a temperature sufficiently of reaction at a rate to form a first oligomeric product kt with a preselected intrinsic viscosity or a first copolymeric product.

Selected molar amounts (Cjm, c-m, ..

..... c ^ m) of 3 monomer and can be mixed with a phosphoric acid having a phosphorus pentoxide content of about 63% to about 78%, preferably greater than about 6S%, most preferably about 78%, and the protective groups, if any, can be removed substantially by heating, and applying reduced pressure, if desired. The amount of phosphorus hour is determined in accordance with equation a * above, making the necessary calculations for the addition of monomer and of possibly different weight and different ratios.

The phosphorus pentoxide content of the resultant mixture may then be increased in accordance with equation b * above, so that the ci-phosphorus oxide of the major mixture is increased to a value greater than about 81%, with the most preferably between about 82% to about 8396 but less than about 8 096. The resulting mixture can then be heated to about 100 ° C to about 200 ° C, most preferably between about 150 ° C to about 185 ° C within a practical period of time. , preferably within a period of time from about 1 hour to about 5 hours or more, and most preferably within a period from about 1 hour to about 3 hours, and then maintained at the chosen empire for sufficient time 3 to achieve the desired n value.

The practice of the present invention as it relates to the preparation of novel liquid crystalline compositions comprising copolymer and of the general formula XI is further discussed for those compositions in which the selected monomer and type 3 are further classified as of type ( 3.2).

t

Dc po Iyme ren

are prepared in accordance with the above method wherein C | The mo r ratio of the more soluble regularly recurring unit is chosen so that it is above about 0.3, more preferably above about 0.7, ensuring the solubility of copolymcer formed to high concentrations required. his liquid behavior is behavior, the weight ratio of the copolymer above about 15 gcw.96, more preferably above about 17.5 gcw.96 may be selected.

Mo 1 ratios selected as indicated above and monomer activity ratios determine the mean block length and ydc block length does not depend on whether the crystalline crystalline behavior in polyphosphoric acid is obtained with these polymers. The important factor is the maintenance of solubility at high concentration and the preparation of these copolymers in phosphoric acid at high concentration from monomer and.

D I okopolymic compositions and their preparation.

In accordance with yet a further aspect of the invention, there is provided a liquid crystalline composition useful in the preparation of fibers and films comprising a polycondensatic product consisting essentially of a mixture of certain polyphosphoric acids and a high concentration of at least one length chain block polymer of high molecular weight selected from the group consisting of regularly recurring units of the general formulas:

IX, wherein Ar * ccn represents aromatic portion and XXX is as defined above, Xj and X ^ are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), while dc are nitrogen atoms

cn X. cn X- are bound to aromatic cage material ome n I

of Ar, N cn Xj or of each hctcroring are placed relative to each other, and is zero or represents a divalent organic radical cn XXXI is as defined above, a ^ bj the molar ratios of the respective different regularly recurring units present in represents said block polymer, represents an average number of the respective different successive regularly recurring units present in said block polymer, wherein n is a positive integer;

X.

wherein Ar1 represents an aromatic portion and XXX is as defined above, X ^ and X2 are the same or different and are sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and X ^ and X2 are bonded to aromatic carbon atoms of Ar ^, N and Xi and X2 of each hetero ring are ortho-relative to each other and Y2 is zero or represents a divalent organic radical and XXXI is as defined above, a ^ bin / m + m 'represents the molar ratios of the respective different regularly recurring units present in said block copolymer, y ^ represents an average number of the respective different successive regularly recurring units present in said block polymer, Ar3 represents an aromatic portion and XXII is as defined above, X3 sulfur, oxygen or NR (where R is hydrogen or an aromatic group), while the nitrogen atoms and X3 are attached to aromatics the carbon atoms of Ar1, N and X3 of each heterocycle are placed ortho to each other, c ^ m '/ itH-m' represents the molar ratios of the respective different regularly recurring units present in said block polymer, y ^ an average number of the respective different consecutive regularly recurring units that are represented in said biolpolymer, wherein n is a positive integer;

XI.

i wherein Ar ^ represents an aromatic portion and XII is as defined above, is sulfur, oxygen or bfR (where R is hydrogen or an organic group), while the nitrogen atoms and X, are bonded to aromatic carbons of Ar , N and X ^ of each hot poring orto are placed relative to each other, c ^ the mole ratios of the respective different regularly returning members present in said b 1 okpo I ymore, imagine !, y ^ an average number of the respective several consecutive regularly recurring units present in said block polymer, where n is a positive integer;

where Ar proposes an aromatic part and XXXI! is as defined above, Ar represents a different aromatic portion and XXII! As defined above, while the nitrogen atoms are bonded to Ar and the carbon atoms are bonded to Ar **, the mole ratios of the respective variables represent different recurring units present in said block polymer, y . . represents a gram number of the respective fresh bumping successive regularly recurring units present in said block polymer, where n represents a position! is an integer;

XIII

wherein Ar 'represents an aromatic portion and XXXI is I or XXX as defined above with the proviso that when Ar' is bonded to nitrogen atoms Ar is XXXII and when Ar 'is bonded to both nitrogen atoms and I. lf

Xj and X ^. Ar XXX is as defined above, Ar is a different aromatic portion and XXXIII is as defined above, where the carbon atoms are bound to Ar / m / m + m.1 the molar ratios of the various different regularly recurring units present - being in said block polymer, y represents an average number of the respective different consecutive regularly recurring units contained in the said bI okpo I yme er, represents, Xj and X ^ are the same or different in sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and X. and X. are bonded to aromatic carbon atoms of Ar, N and Xj or X ^ of any hetero-crest placed relative to each other 2 cn V is zero or a bivalent organic radical proposition! and XXXI is as defined above, m / num 'the mo I ratios of the respective different regularly recurring units present in said block polymer, y an average number of the respective different consecutive regularly recurring units present in said represents polymer, wherein n is a positive integer;

XIV,) where Λ r ^ represents an aromatic portion and XXX! ! is as defined above, X ^ is sulfur, oxygen or NR (where R is hydrogen or an organic group), while the nitrogen atoms and X * are bonded to aromatic 3 ^ carbon atoms of Ar , N and X ^ of each hetero ring are placed relative to each other, p the mole ratios of the respective level. Each of the several regularly recurring units present in said bio polymer represents 1/2 an average number of the respective several successive regularly recurring units present in said polymeric polymer, for example, Ar *. an aromatic portion and XXXII is as defined above, Ar represents a different aromatic portion and XXXIII is as defined above, while the nitrogen atoms are bonded to Ar * and the carbon atoms are bonded to Ar **, q the mole ratios of the respective different regularly recurring units present in said block represent y, r represents an average number of the respective different successive regularly recurring units present in said block polymer, n is a positive integer; xv,

l) where Ar represents a different aromatic part and XXII! is as defined above, Ar * represents an aromatic portion and XXXII is as defined above, and Λ r ^ is an aromatic portion different from A r ^ and Ar * and XXIV is as defined above, while the carbon if 5 atoms are attached to Ar and Ar and the nitrogen atoms are attached to Ar * and Ar \ where n is a positive t integer; c ^ m '/ m + m' the mole ratios of the respective different regularly recurring units present in said polymer polymer, for example 1 t, an average number of the respective different successive regularly recurring units present in said biopolymer, abm / m + m 'represents the mole ratios of the respective different regularly recurring units contained in said biopolymer, y represents an average number of the various successive regularly recurring units which are present in said b I okpo I ymeer, wherein n is a positive integer;

XVI, where Ar * represents an aromatic portion and XXX is as defined above, Ar ^ represents a different aromatic portion for Sic It and XXV as defined above, X | and let / be eleventh or different and are sulfur, oxygen or NU (where R Is hydrogen or an organic group), while the Nil groups and X and X- are bonded

6 ^ I

of aromatic carbon atoms of Ar and Ar, NH and X | or X2 of each heterocycle is placed relative to each other, after the mo ratio of the respective different regularly recurring units present in said block polymer, y, a 1 i average number of the reflective Each represents several consecutive regularly recurring units present in said block polymer, where> n is a positive integer; 1

XVII.

where Ar * represents an aromatic portion and XXX is as defined above, A r ^ represents a different aromatic portion and XXV is as defined above, Xj and are the same or different and sulfur, most acidic! or NR (where R is hydrogen or an organic group), while the NH groups and X, and X? are bound

b I

on aromatic carbon atoms of Ar and Ar, NH and Xj or Xj of each hetero ring are placed relative to each other, a.bjm / tTum 'represents the mo 1 ratios of the respective different regularly recurring units present in said block polymer Yj . represents an average number of the respective different successive regularly recurring units present ... 9 111 called block polymer, Ar represents an aromatic portion different from

Ar ^ cn Ar and XXVI is as defined above, X ^ is sulfur, oxygen or NR (where R is hydrogen or an organic group), while the NH groups and X ^ are bonded to aromatic carbon atoms of Ar6 and Ar ^, c. m '/ mim' k represents the mo 1 ratios of the respective various regular recurring units contained in said b I okpo I ymecr, y, an average number of the respective different consecutive regularly recurring units present in said ) represents polymer, wherein n is a positive integer;

XVIII,

wherein Ar * represents an aromatic portion and XXXII

7 is as defined above, Y represents an aromatic or heteroaromatic moiety, and XXVIII is as defined above, while the nitrogen atoms are bonded to aromatic carbon atoms of Ar * and bonded to adjacent carbon atoms of Y ^, at the mo I ver. positions of the respective different regularly recurring units present in said block polymer represents y, an average number of the respective different successive regularly recurring units present in said block polymer, where n is a positive integer.

In accordance with the practice of the present invention, the synthesis of the foregoing formulas IX-XIX bicycles can be exemplified by the following general reaction system:

Reac (i cmcchan i smc

Formation of formula JX b 1 okpo) ymccr

Form / ng of formula X block polymer cc

Formation of formula XI block polymer

Formation of formula XI I block polymer

Formation of formula XMl biopolymer

Formation of formula XIV bIokpoiymecr

Formation of formula XV biopolymer

Formation of Formula XVI Bio-polymer

Formation of formula XVII b I οί <ρο! ynicc r

Formation of formula XV1 I 1 block polymer

Formation of formula XIX block polymer

The above formulas IX, XII, XVI, XVIII, and XIX polymer polymers can be prepared in accordance with the above process parameters by: (a) mixing at least one of a selected first monomer with or without oxidation-protecting atoms or groups with (b) heating a preliminary solvent of phosphoric acid with a relatively low phosphorus pentoxide content, and optionally placing the resulting mixture under reduced C-U to remove any volatilized inhibiting atoms or groups present and to provide: dissolving the first monomer in the preceding solvent, (c) adding at least one of a selected second monomer into the resulting solution of step (b) to provide a mixture of the first and second monomers in the preceding on losmi part, (d) do eme n then ·. The phosphorus pentoxide content of the mixture obtained from step (c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content is suitable for polymeric risk, (e) polymerization of the first and second monomer to satisfy a temperature · :: · triggers reaction at a rate to produce a first homogeneous product with a preselected intrinsic viscosity, (f) mixing a selected amount of the first homogeneous product is a selected amount of at least one of a selected second homogeneous product to form a first poly-isomeric product, said second homogeneous product being formed by generate the same step (a), (b), (c), (d), and (e) with, on the whole, it is understood that at least one of the selected samples from step (a) or (c) the second homo - o i gome risk product forms, is different v at least one of the selected monomer of step (a) or (c) which forms the first hom: -o I igomeric product, (g) do po I yme riser and of -et po I yo I i gomc- ri This product at a temperature is sufficient to effect a reaction at a rate to reduce a first bioligomeric product of a predetermined intrinsic viscosity or a first biolomeric product.

Alternatively, formulas IX, XII, XVI, XVIII and XIX block polymeric compositions can be prepared by: (a) mixing at least cc of a selected first monomer with or without oxidation-protecting atoms or groups with a preliminary solvent of phosphoric acid with a relatively low phosphorus. toxydc content, (b) heating if desired bringing the resulting mixture under vacuum pressure to remove all volatilized protective atoms present in groups and to provide a solution of the first monomer in the preliminary solvent, (c) adding at least one of a selected second monomer in the resulting solution of step (b) to provide a first mixture of the first and second monomer in the preliminary solvent.

(d) thereafter increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (e) polymerizing the first and second monomers at a temperature sufficient, triggering reaction at a rate to form a first homo-oligomeric product with a preselected intrinsic viscosity, (f) mixing a selected amount of the first homeric product with a selected amount of a second mixture egg of a different first and second monomer in the preceding solvent, the second mixture consisting of equal steps (a), (b) and (c) with, on the whole, provided that at least one of the selected monomer of step (a) or (c) forming the second mixture is different from the one of the selected monomer of step (a) or (c) that it the first homo goric product, (g) then increasing the phosphorus pentoxide content of the mixture resulting from step (f) to provide a first oligomer monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (h) polymerizing the mixture resulting from step (g) at an empirically sufficient reaction reaction at a rate to produce a first bulk product with a prior selected intrinsic viscosity or a first bulk polymer product.

The above 1X-XIX block polymers constituting the liquid crystal block polymers of the present invention may be characterized in that they have more than one regularly recurring unit, the distribution of which may be different in sequence. obtained by the random condensation of monomer and as in the copolymer and described above, and is further characterized in that they have adjacent blocks of the same regularly recurring unit as obtained by the random condensation of oligomer and.

The preferred formulas IX, XII, XVI, XVI1I and XIX bloc polymers are those polymers in which ab is the mo fraction of the regularly recurring unit formed by the condensation of a homogeneous reaction product (defined below) derived from the i-th monomer of type I with a stoichiometric amount of j-th monomer of resp. 7 th I th type 2, 4, 6, 7, or 8 and incorporated by a b 1 polymeric process described below , and y .. and π have the same meaning as described above for copoliner.

The preferred XI polymer polymers have those in which C is the mole fraction of the regularly recurring unit formed by the condensation of a homo-oligomeric reaction product (defined below) derived from the type 3 polymer and surrounded by a block polymical method described below, and y

K

and n are as defined for copolymer and.

The preferred X, XV, and XVII biopolymers are those in which a ^ b ^ m / m + m1 is the mole fraction of the regularly recurring unit formed by the condensation of m mole of regularly recurring units derived from a homogeneous reaction product. of the i-type monomer of type 1 and the j-monomer of type 2, 4 or 6 and combined with a mill of regularly recurring units of a homogeneous reaction product derived from condensation of the k-dc monomer of type 3, 5 or 9, and y .., y, respectively. and n are as defined for copolymers.

The preferred XIII blocking polymers are those in which m 'and m are suitable molar amounts of the monomer and are those which form the reaction products and are selected to provide desired yields and proportions of the respective recurring units, y1 and y block lengths. as defined above, n is the total number of regularly recurring units, and x is a molar amount significantly less than m1 selected to provide an appropriate block length of the first homoigomer having end groups having o- diamine functional groups,

The preferred XIV b 1 okopolymers are those in which m1, m, x, n, y, y1 are as defined above, q is m '/ m + m' and p is m / 2 (m + m ' ).

Selected molar amount m, of a type 1 monomer can be mixed with a phosphoric acid having a phosphorus pentoxide content of from about 63% to about 78%, preferably greater than about 68%, most preferably about 78%, and the protecting groups, if they are present, can be removed as described above. The amount of the phosphoric acid is most desirably determined in accordance with equation a * as described above. A stoichiometric amount (i.e. m) of a type 2, 4, 6, 7 or 8 monomer can then be added to the resulting solution. The phosphorus pentoxide content of the resulting mixture can then be increased in accordance with equation b * given above, in order to increase the final phosphorus pentoxide content of the substantially polymerized mixture to a value greater than about 81%, most preferably between about 82% to about 83.5%, but less than about 84%.

The resulting mixture can then be heated to about 100 ° C to about 185 ° C, most preferably to about 170 ° C to about 185 ° C, within a practical period of time, preferably within a period of less than about 1 to about 5 hours, most preferably from about 1 to about 3 hours. This temperature is maintained for a sufficiently long time to reach a selected n value, which will hereinafter be referred to as the homo-igomeric. n value, that is above a minimum value to be described for specific cases below, is characterized in that it is equal to h (lp), where p is the degree of reaction, defined as the mole fraction of any type of functional group present which has undergone condensation and stability, and which is preferably below a selected maximum value characteristic of full polymerization. A chosen molar how much It eid, m.. of the thus obtained omeric reaction product is transferred to a second vessel containing a selected molar amount of m. contains of a similarly obtained but qualitatively different homo-o 1 i g outer i sch r cac t i e prod t and continues heating at elevated temperatures. The average block lengths, y. ., of the blocking polymers of the compositions of the present invention can be determined in the following manner:

The mean b I o k I e n g t ^ e n, y. of o 'c b I o l <polymers can be determined in the following manner. Hexalomeric reaction product is obtained by adding j mill of a first monomecr to an equimolar amount b. of the Second monomccr. The sum of a lie or b. is I. The mixture is polymerized to a selected intermediate reaction progression, p ... The o i gome ric sc value of the iron oiomeric reaction product, n. , is given by fc (I -p). The molar ratios of the regularly recurring units included in the polymer block are given by

The block ling ten y .. can be calculated by the equation

assuming that the homoelomers condense with equal reactivity. The above equation for y ... shows that if each of two homo-ogomercric reaction products are polymerized to high conversion (ie, a high n. Value is allowed to be achieved for mixing) then both block lengths in the resulting block polymer are high.

The practice of the present invention as it relates to the preparation of novel liquid crystalline compositions that include bocolymers of general formulas IX, XII, XVI, XVII and XIXl is explained for those compositions which include general formula IX homo-oligomer can be prepared from monomer and type 1 and type 2, further classified as belonging to class I and the chosen second homoigome further characterized by belonging to either class I, class 2 or class 3.

General Formula IX Bio-Polymers can be prepared from homogeneous gomers. u i t s I u i t end all class I monomer and. The biopolymer,

t.

have the same advantage of a wide range of workable concentrations as described for copolymer and which are formed exclusively from class I monomer and. The advantage for the polymerization process described above for these polymers is the ability to yield yj j and yj 21 or 21 'Y 22' independently of the mo I ratio a | b |, or a £ b 2> 0 * a2 ^ l 'P * al ^ 2 drill to select appropriate reaction sizes for the corresponding homo o i gomer. For example, y j j can be 20 or greater for a wide range of a ^ b ^ values by increasing the reaction magnitude p while decreasing the a | b j value. Y \ 2 'Y 2 \' 0 ^ Y2 2 of the above formulas can be obtained with values from about I to about 75, meter. most preferred from about 25 to about 50, by choosing suitable pjj and p ^ i P 21 »P? 2 values. In practice, since all regularly recurring units have a high degree of mesogeneity, the representatives of this chosen class of bio-polymers are liquid crystalline when an n value of greater than about 40 is obtained at a concentration greater than about 6 wt% regardless of the block lengths obtained. The practice of the invention as it pertains to class I block polymers is further illustrated in Examples 7-5-84 below.

General Formula IX Block Polymers can be prepared from a first class I homomer of class I and a second homo oligomer derived from monomer pairs containing class 2 monomers. The b 1 okpo I ymer,

are derived from homo g i gomers of different me o genicity. The choice of a j b ^ (the moire ratio of the first and the higher mesogenic regularly recurring unit) and the preference (the average block length of the first and the higher mesogenic regularly recurring unit) are governed by the following consideration.

The block polymer reaction product in the first case may exhibit liquid crystallinity behavior due to the sole presence of the first regularly recurring unit when γ is greater than about 30, more preferably greater than about 0, with concentrations of the first regularly recurring unit separately ( i.e., the weight of the first added oligomer / weight of the final polymer reaction product (greater than about 7%), or the bulk polymer reaction product in the second case may derive liquid crystalline behavior due to the combined presence of both regularly diffracting units, independent of Yjji at concentrations above which the moderately mesogenic regularly recurring unit derived from the second homo-i. gome er liquid-crystal! I am alone. The preferred values of ajbj are from about 0.4 to about I, with the range being from about 80 to about 20, respectively, while ajb (ranges from 0.4 to 1. The most preferred concentrations of these block polymers is above about 15 gw% but may be lower because either the ajbj value or the value or both values are increased The preferred n value for these compositions is from about 50 to 150, with the most preferably greater than 100. Obtaining sufficient n values can be facilitated by the addition of the second hydrogen reaction product before the phosphorus pentoxide content is increased to the value necessary for polymerization (i.e. say when ° f p21 is zero and n ^ ° f π 2 ^ = &) and then adding the appropriate amount of phosphorus pentoxide to increase the mixture to sufficient phosphorus pentoxide content This process aids in mixing and is most preferred r when the homo-oligomeric n value of the first homo-oligomer is n, j. The practice of the invention as it relates to the preparation of class 2 block polymers is further illustrated in Examples 85-88 below.

General Formula ΓΧ Block Polymers can be prepared from a first Class I homo-igomer and a second homo-O 1 igomer derived from monomer par and containing class 3 monomer. The b 1 oPolymers

their liquid crystal line behavior derives entirely from the presence of the first regularly recurring unit, its mean block length> ||> and its concentration only in the total weight of the end block polymer reaction product. Dc values of α j b | , and concentration must meet the conditions of the first case described for the class 2 monomer containing polymers. The process of the invention allows for the preparation of such highly concentrated mixtures of mesogenic units, that is to say reactants significantly higher in polymer concentration than that required for liquid crystalline behavior, and that incorporation of significant amounts of non-mesogenic units is possible if the above conditions are met.

The preferred values of a ^ b ^ are from about 0.6 to about 1. The preferred values of y ^ are from at least about 30 to about 100, more preferably between about 30 to 100. The preferred values of y ^ or y j j are from about 1 to about 5050. The preferred values are from about 50 to 200 with the most preferred values being between about 100 to 150. The preferred concentrations of the b 1 okpo 1 ymer are above about 15 wt .96, especially while increasing the percentage of the non-mesogenic regularly recurring unit The practice of the invention as it relates to the preparation of class 1 monomer containing 3 monomer and further illustrated in Example 73, 74, 89-94 below.

The practice of the invention as it relates to the preparation of novel liquid crystalline compositions which include polymer polymers with the general formulations: X, XV, XVII are exemplified for polymer polymers of formula X wherein the first Igomer is prepared from type (1.1) or (1.2) and type (2.1) monomer and the selected second homoigome is prepared from monomer and type (3.2).

The general formulas X, XV, and XVII liquid crystal line block po! yrne c r s arne n s t c I 1 i n g n es shown above are prepared in accordance with the following method: (a) mixing at least one of one. selected first monomer with or without oxidation protecting atoms or groups with a prior solvent of ionic acid having a relatively low phosphorus pentoxide content, (b) heating and optionally bringing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups and to provide a solution of the first monomer in the preliminary solvent, (c) then increasing the phosphorus pentoxide content of the mixture generated from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (d) polymerizing of the first monomer at a temperature sufficient to effect the reaction at a rate to form a first homogeneous product having a preselected intrinsic viscosity, (e) mixing a selected amount of the first homogeneous product with a selected amount id of at least one of a selected second homogeneous product to form a first polyomeric product, the second homogeneous product being formed by equal steps (a) and (b) followed by: (le) adding of at least one of a selected second monomer in the resulting solution of step (b) to provide a mixture of a first and second monomer in the preliminary solvent, (2e) increasing thereafter the phosphorus pentoxide content of the mixture. from step (le) to provide a first and second monomeric reaction mediurr. of greater phosphorus oxide content suitable for polymerization, (3c) polymerizing the first and second monomer at a temperature sufficient to effect reaction at a rate to produce said second homogeneous product of a preselected intrinsic viscosity form, with, on the whole, with the understanding that, in at least one of the selected modes of step (a) or (Ie) that the second homogeneous product forms, is different from By setting the selected motor of step (a) which forms the first homogeneous omeric product, (f) causing polymerization of the polyolomeric product at a temperature sufficient to reaction at a rate to form a first bulk polymer with a preselected intrinsic viscosity or a first bulk polymeric product.

Another possibility is that the general formulas X, XV, and XV11 liquid crystal block polymer compositions shown above can be prepared by: (a) mixing at least one of a selected first monomer with or without oxidation-protecting atoms or groups with a relatively low phosphorus pentoxide content pre-solvent phosphoric acid, (b) heating and optionally bringing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups present and to provide a solution of the first monomer in the pre-solvent, (c) mixing a selected amount of the solution of step (b) with a selected amount of at least one of a selected first ergonomic product such that a first olig omic-first mon because reaction medium is formed, said first homo-oligomeric product being formed by equal step pen (a) and (b) followed by: (Ic) adding at least one of a selected second monomer into the resulting solution of step i (b) to provide a mixture of a first and second monomer in the preceding solvent, (2c) then adding the phosphorus pentoxide content of the mixture resulting from step (e) to provide a first and second monomer reaction medium of larger phosphorus pentoxide suitable for polymerization, (3c) polymerizing the first and second monomers at a temperature sufficient to effect reaction at a rate to form said first homogeneous product having a preselected intrinsic viscosity, with, over. Overall, with the exception that at least one of the selected monomer from step (a) or (Ic) constituting the first monomer solution is different from at least one of the selected monomer from step (a) that it first homoigomeric product, (d) thereafter increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a compound of larger phosphorus pentoxide content suitable for polymerization, ( e) polymerizing the first oligomer monomer at a temperature sufficient to effect reaction at a rate to form a first b-olomeric product of a preselected intrinsic viscosity or a first b-ol polymeric product.

General Formula X Bio-Polymers can be derived from a first Class I homo-oligomer and a second homo-oligomer of type (3,2). The type X bio-polymers are prepared by a process analogous to that described for type IX bio-polymers, except that the second homoigomer is prepared from a single monomer.

The polymers

have preferred mo ratio of the first regularly recurring unit, a | b | m / mim 'from about zero to about 0.5 when the concentration is selected such that 7. i is above about 15%. When aj / um / rrnm 'is chosen to be above about 0.5 but less than 1, the workable concentration range is stretched to include concentrations of 7%, more preferably 10% by weight. At concentrations above 3, about 15 wt% all selected values of y j j give values of greater than 5 liquid crystalline products, but n should be greater than about 50, preferably greater than about 100, to provide desirable mechanical properties.

The practice of the invention as it relates to the block polymers of this class is further illustrated in Examples 102-112 below.

General formula X b I olpolyme can be derived from a first class 2 homo-igomer and a second homo-oligomer of type (3,2). Block the blocks

are prepared from two class 2 homo-igomers which dictates the choice of concentrations greater than about 15% by weight. The proportions of the various regular return units are selected based on desired mechanical properties or the maintenance of solubility in two regularly recurring units of different solubility characteristics. The preference values of y | are those of about 5-50, more preferably greater than 30. The practice of the invention as it relates to block polymers of this class is further illustrated in Examples I13-115 below.

The practice of the invention is illustrated for general formula XI for biopolymers prepared from a single monomer of type (3,2).

The general formula XI liquid crystal linear b okopolymer compositions shown above are prepared in accordance with the following method: (a) mixing at least one of a selected first monomer with or without oxidizing agent, or groups with a preliminary solvent of phosphoric acid with a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protective atoms or groups present and to provide a solution of the first monomer in the preliminary solvent, (c) increasing thereafter from the phosphorus pentox compound of the mixture formed from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (d) polymerizing the first monomer at a temperature sufficient to effect reaction at a mold speed ing a first homogeneous product with a desired intrinsic viscosity, mixing a selected amount of the homogeneous product with a selected amount of at least one of a selected second homogeneous product in order to form a first polyigomeric product, said second homogeneous product being formed by equal steps (a), (b), (c) and (d) with, and generally speaking, provided that at least one of the selected monomer (a) constituting the second homogeneous product, different from at least one of the selected monomer of step (a) da: forming the first homogeneous product, (f) polymerizing the oligomic product at a temperature sufficient to effect reaction at a rate to form a first polymeric product of a preselected intrinsic viscosity or a first block polymeric product. The biopolymers

have preference values of Cj between 0.5 and I, due to the greater solubility and viscosity of the first regularly recurring units, and preferable values greater than about 25 but less than about 100, due to the higher mesogenicity . Concentrations greater than about 15%, more preferably greater than about IS%, and most preferably 20% are selected. Examples 9S-101 below further illustrate the method of the present invention.

The process of the invention also relates to the preparation of polymeric polymers by the condensation of co-oligomeric reaction products, rather than the homo-olomeric reaction products described in the above processes, but these will not be described for the sake of simplicity.

Intrinsic viscosity

Intrinsic viscosity is determined by extrapolation from - 1 / c and ln Π ^ / c to zero concentration in methanesulfonic acid at 30 ° C.

Anisotropic character of the compositions

The extended chain polymer compositions of this invention are optically anistropic, i.e., microscopic regions of a given extended chain composition are birefringent; a mass of extended chain composition samples depolarizes in one plane of polarized light because the light transmission properties of the microscopic regions of the extended chain composition vary with direction. This feature is linked to the existence of at least part of the extended chain polymer compositions in the liquid crystalline or mesomorphic state.

The extended chain polymer compositions of this invention, which exhibit optical anisotropy, do so when the extended chain polymer compositions are in the relaxation state. This is in contrast to conventional polymer solutions which can depolarize polarized light in one plane when subjected to significant shearing.

The extended chain polymer concentration of the compositions of the present invention is above the "critical concentration point". The "critical concentration point" is routinely determined using conventional concentration and viscosity measurement techniques (see Kwolek - U.S. Patent No. 3,671,542).

Another qualitative determination of the liquid crystalline character of these extended chain polymer compositions can be made with the naked eye.

These extended chain polymer compositions can prove to be cloudy or hazy and yet contain little or no dissolved solid. When the extended chain polymer compositions, viewed under reflected ordinary light, are disturbed by shaking or rolling the vessel containing the extended chain polymer compositions, or by only slow stirring, a characteristic, easily perceived, satiny appearance or glow is observed even after the disturbance ceases, and then decreases in intensity. This can be described to be a pearly or opalescent quality of the extended chain polymer compositions of this invention. Compositions distorted as described above often appear to have streaks and / or graininess in the surface. These visual effects are observed in the liquid crystalline extended chain polymer compositions of the invention. This can usually be referred to as "rudder opalescence". Further details on qualitative and quantitative determinations of optical anisotropy are shown in Kwolek U.S. Patent No. 3,671,542.

Fiber preparation

The liquid crystalline compositions can be formed into high quality fibers by spinning them in suitable baths such as by wet and "air hole" spinning techniques, using spinnerets and other equipment constructed from materials resistant to the materials used. strong acids. In the "air hole" spinning, the spinneret is usually placed in air or in an inert gaseous medium a short distance (e.g. 1 to 24 cm) above the surface of a coagulating bath.

However, air holes suitable for use in the present invention may range from less than about 1 cm to about 150 cm or longer, preferably from about 2 cm to about 300 cm, more preferably from about 10 cm to about 200 cm, and most preferably from about 10 cm to about 100 cm.

In the present invention, the initial draw ratio is approximately from about 1: 1 to about 50: 1 and above. Preferably, the initial draw ratio is from about 20: 1 to about 80: 1, especially preferably from about 60: 1 to about 200: 1, and most preferably from about 100: 1 to about 150: 1.

The term "draw ratio" as is known is a measure of the degree of stretch during the orientation of the fibrous material. In the present invention, the initial draw ratio is a measure of the degree of stretching of the filaments that occurs between the extruder nozzles and the effluent from the coagulation bath. The initial draw ratio is defined as discharge speed divided by beam speed.

The blasting speed is the speed at which the extruded polymer exits an extruder opening. It is usually determined by dividing the total polymer extrusion rate by the total area of the extruders.

The discharge rate is the rate at which the filaments leave the coagulation bath. Although any measuring device can be used, the discharge speed is usually determined by the surface speed of the rollers that the filaments take up after they have been removed from the bath. Thus, the speed of the wash rolls is preferably measured for this purpose.

Spinning of polybenzimidazole fibers using one operation of this general technique is described, for example, in Tan - U.S. Patent No. 4,263,245. A variety of the baths can be used to coagulate the extruded dope into fibers. The baths can be, for example, from water or methanol or the like, or a dilute solution of an inorganic acid (e.g. phosphoric or sulfuric acid or the like). Preferably, the temperature of a coagulation bath is room temperature or less.

It is desirable to completely remove the spinning solvent from fiber samples prepared from the liquid crystalline compositions of this invention. Water alone or aqueous alkaline solutions can be used to remove the residual acid. A suitable method is to spray the wireline when it leaves the coagulation bath with an aqueous alkaline solution (e.g. saturated sodium bicarbonate), remove the surface liquid from the wireline with a sweeper (e.g. a sponge) or jet, wash with water and / or aqueous alkaline solutions to reduce the acidity, and to wind the fibers on spools. The fibers can be soaked in water for a period of time sufficient to remove the acid. The thoroughly washed fibers can be dried on the spool in the range of temperatures up to about 110 ° C. They can also be suitably dried on heated rolls.

The liquid crystalline compositions are particularly suitable for extrusion. These and other object manufacturing methods are fully described in J.S. Robinson, "Spinning, Extruding, and Processing of Fibers"; Chemical Technology Review No. 159, Noyes Data Corp., 1980. The above-cited patents and / or publications are incorporated herein by reference.

The fibers made from the polymers of this invention exhibit high values of tensile strength properties, and especially in the state as extruded, i.e. without subsequent heat drawing or annealing. The tensile strength properties of these fibers as extruded can be increased by subjecting the non-drawn fibers to a heat treatment.

Fiber tensile strength properties

Filament properties are measured on fibers conditioned at 21 ° C and 65% relative humidity (R.H.) for at least 16 hours unless otherwise specified. Yarn properties are measured on yarns which are conditioned at 24 ° C and 55% R.H. for at least 16 hours. All measurements were made in the fiber conditioning environment.

Toughness (fracture toughness) (T), elongation (fracture elongation) (E), and initial modulus (Mi) are obtained by breaking a single filament of a multifilament yarn on an Instron tester (Instron Engineering Corn., Canton, Mass.).

Single filaments are broken with a gauge length (distance between claws) of 1.0 inch (2.54 cm). The results on three filaments are averaged. Yarns are given 3 turns per inch (2.54 cm) twist (under 0.1 g.p.d. tension) and yarns are broken with a 10 inch (25.4 cm) meter length. All samples are stretched at a constant elongation rate (10% elongation per minute for fibers with an E of less than 896, and 60% elongation per minute for fibers with an E of 8 to 100%) until the sample breaks.

The single filament denier (d.p.f.) is calculated from its functional resonant frequency, determined by fibrating a 7 to 9 cm fiber under tension with changing frequency (ASTM D1577-1973). This filament is then used for one break.

The denier of yarn is determined by weighing a known length (at 0.1 g.p.d. tension); 90 cm length is suitable.

Toughness (grams / denier), elongation (percent) and initial modulus (grams / denier) as defined in ASTM 3379-75e are obtained from the load-elongation curve and the measured denier. In actual practice, the measured sample denier, test conditions and sample identification can be fed to a computer before the start of a test; the computer records the load-elongation curve of the fiber if it is broken, and then calculates the fiber properties.

It should be noted that different values can be obtained from single filaments (filament properties) and multi-filament strands (yarn properties) of the same sample. Unless otherwise noted, all properties shown herein are filament properties.

Additives

It will be understood that the usual additives such as dyes, fillers, antioxidants, and the like can be included in the compositions of the present invention for the intended purposes for the preparation of the molded article.

Inorganic acids which are solvents for the extended chain polymers of the present compositions such as polyphosphoric acid, methanesulfonic acid, 100% sulfuric acid, chlorosulfonic acid, and the like, can be added to the compositions of the invention in minor amounts (without departing from the scope of the invention) with for the purpose of modifying conditions for processing into molded articles. The strong acid additives may contain one or more of the acid soluble polymers described in Helmimiak et al. No. 4,207,407 and P.D. Sybert, "Rigid-Rod Polyquinolines: Synthesis, Structure-Property Relationships and High-Strength Fibers" Colorado State University, Ph.D. Thesis, 1980. The above-cited patent and thesis are incorporated herein by reference.

4. Industrial applicability

The liquid crystalline extended chain polymer compositions are excellent for spinning into highly ordered fibers of high strength. Such fibers are useful as reinforcement substitutes for other inorganic or organic products. Various examples include glass fibers, asbestos, boron fibers, carbon and graphite fibers, mustaches, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers. A reinforcing material can simply be defined as the material added to a resinous matrix to improve the strength and other physical and chemical properties of the material.

Furthermore, the polymers of the present compositions can be used in any application typically performed by thermoplastic materials common in the art, such as metal substitute materials and those areas where high performance is required.

Elongated chain polymer compositions can be used for use in forming high strength films that are useful in the preparation of composites, belts, belts, i.e. as tire cords, and the like. The films are suitable as construction materials for rocket nose cones and various other parts of aerospace equipment.

Depending on the extended chain polymer fibers or films selected (i.e., homopolymer, copolymer, block polymer, or mixtures thereof), the properties of the article can be controlled to make it suitable for the desired use. The control of polymer properties is an advantage because, in the diverse fields of application for such polymers, for example as laminates, building materials, adhesives and deposition materials, needs vary considerably.

- EXAMPLES -

Example 8 122.7 G var, a PPA solution with an effective P2 ^ 5 content of 77.2% (prepared by mixing 30 wt% H ^ PO ^ and 70 wt% 113% PPA) was added to a 500 ml resin kettle containing 52.62853 g (0.21460 mol) of 1a. (Large crystal size monome er 1a was prepared by a final recrystallization in accordance with the method of Wolfe, Loo, and Arnold, Macromole-1, 14, 915 (1981) using the final isolation process comprising a transfer the di-k a 1 umz out of monom er la as solid s..t or in 6 N hydrochloric acid). After stirring to incorporate the solid monomer into the PPA, the mixture was substantially dehydrochlorinated by heating the mixture at 55-70 ° C under reduced pressure for approximately 31 hours. Monomer 2 a (35.6520 g, 0.1460 mol) was added to the resin chain and taken up as described in the previous example. Powdered (123.35g) was then added to increase the effective content to approximately 86.4% and the resulting mixture was stirred at 100 ° C for 17 hours under an argon flow. The polymerization mixture was then heated with stirring as follows: 100-170 ° C in 1 hour, 170 ° C for 23 hours, and 200 ° C for 24 hours. The intrinsic viscosities (in di / g) were determined for the polymer from samples drawn at the indicated times: 17.2 (7 hours), 22.8 (24 hours), and 35.4 (48 hours). Heating without stirring for an additional 24 hours did not increase the intrinsic viscosity of the fAlJ1 polymer. The vegetable reactant product exhibited stirring grandfathering and was characterized in that it had a final effective P 2 O 2 content of 82.2% with polymer content that was approximately 15.1% by weight.

Example 12 S6, 17 G of a PPA solution with an effective Seha 1 l of 74.996 (prepared by mixing 40 wt% g 5% H 2 PO 4 and 60 wt% 115% PPA) was added to a 500 ml resin kettle containing 27.62485 g (0.112605 mol) of 1a. The monomer was incorporated into the solution by stirring and the resulting mixture was then substantially dehydrochlorinated by heating the mixture at 55-80 ° C under reduced pressure for approximately 2! hour. The percentage profile profile for this example is explained in FIG. 10. Concentrate 2a (18.720 g, 0.112686 mol) was then added to the resin.

Powdered P2 ^ (83.17 g) was then added to increase the effective P2O5 content to approximately 87.2%. The resulting yellow slurry was stirred at 100 ° C for 15 hours under an argon cream. This slurry, which had not appreciably increased in mass viscosity, was then stirred vigorously and heated by increasing the oi bath temperature from 100 ° C to 178 ° C within ¢ 0 min., And to IS5 ° C within 1 hour. Po I polymerization times shown below started with times above • 100 ° C. The DC85 ° C temperature was then maintained for 76.5 hours. Intrinsic viscosities in MSA at 30 ° C (in dl / g) were determined for the ifAlj1 polymer from samples drawn at the indicated polymerization times: 16.6 (1.5 hours), 21.7 (2.25 hours) , 2.4, 2 (3.25 hours), 35.7 (7.7 hours), and 42.1 (76.5 hours). The intrinsic viscosity of 42.1 corresponds to an average n value of polymerization of about 140. The polymerization product was crystalline after a polymerization time of 0.75 hours and was found to be highly tensile after 1.25 hours. Fibers, prepared by drawing this product directly and depositing the strands in water, were yellowish brown, translucent, double-breaking (crossed polar) exhibited transmitted light absorbance when a single polar sheet was placed perpendicular to the fiber direction, and. could be fibrillated into microfibres. Fibers prepared after 1.5 hours using the same procedure became noticeably stronger than the sample at 1.25 hours. The mass viscosity of the product and the relaxation time of opalescence increased noticeably after 2.25 hours. The P2 ^ 3 content of the PPA component of the product was approximately 83.2% and the concentration of the {ΛΙ} polymer was 14.5% by weight based on the total weight of the reaction product formed.

Example 13

A mixture of 17.7 g of concentrated orthosulfic acid (S 5J 7% H 3 PO 4) and 26.6 g of 1596 PPA was stirred under reduced pressure at 100 ° C for 2 hours. f-fet percentage PO ^ gdtalte profile for this example is tcegelicnt Ir. Fig. II, The resulting solution was then poured at approximately 100 ° C under a stream of argon into a 200 ml resin kettle containing 11.41145 g (0.054028 mol) of 4, 6-diamino-1,3- benzene dioidhydrochloride (Ib) was prepared in accordance with the method of Wolie and Arnold, Macromolecules, Vol. 14, 909 (1981), recrystallized from aqueous hydrochloric acid containing 3% w / w stannol chloride, and dried for 20 hours at 63 ° C under reduced pressure immediately before use.

The mixture was stirred at 53 ° C for 15 hours and 62 ° for 4 hours under reduced pressure. When heated to 70 ^ 0, the monomer precipitated. Addition of 16.6 g resulted in redissolving of the monomer. The solution was then heated at 100 ° C for 3 hours under reduced pressure to complete the dehydrochlorination. Monomer 2a (8.9761 g, 0.05403 mol) was then added under an argon flow. Additional P2C> 5 (19.0 g) was then added. The solution was then heated as follows: 100 ° C for 48 hours, 150 ° C for 2.5 hours; 160 ° C for 10 hours (the dark green solution became stir-opalescent during this period); and 180 ° C for 25 hours. The resulting reactic product was deep purple with a metallic luster, exhibited rudder-grandfathering, polarized plane-polarized light as evidenced by strong birefringence when observed between crossed poles, and was characterized in that it had an end. had an active content of S2%, the / BI concentration being 13.3 wt% ws. The intrinsic viscosity of the polymer isolated from the reaction product was 23.9 d I / g MSA at 30 ° C, which corresponded to an average number of regularly recurring units, n, of approximately 110.

Example 16

The procedure of Example 8 was essentially repeated. Instead of monuments 1a and 2a, 6i '; 7 0 g (0.26 2 8 4 mo I) of monomer era dehydrochlorinated in a "starting" solution of 3d I, 97 g PPA with a P 2 O 2 content of 77.2% (prepared by 102.6 g of 8 5.4% H..PO, to be mixed with 239, dg of 115% PPA). When dehydrochlorination was nearly complete, 63.6826 g (0.26284 mol) of monomer was added 2 y followed by the gradual addition of 137.3 g of P2 ^ 3 · 1 mixture then stirred and heated essentially in over a test with example S. The amount of ^ 2 ^ 3 was preselected (as determined in formula with the above formulas a * and b *) to provide the reaction reaction with an effective P2 ^ 5 content of approximately 83.7% prior to commencement of polymerization and an effective P2 3 content of approximately 82.2% following substantially complete polymerization. The resulting reaction product showed stir opalescence and was further characterized as having a polymer concentration of 17% ha'd; Fibers were easily formed by direct spinning or drawing from the reaction product. The polymer obtained had the following structure:

characterized by an intrinsic viscosity of 15 dl / g in MSA at 30 ° C which corresponded to an n value of average polymerization of about 100.

Example 17 f

The procedure of Example 8 was essentially repeated. Instead of monomers 1a and 2a, we rd 6 1.16 19 g (0.28706 mol) of monomer 1 dehydrochlorinated ir. A "starting" solution of 338.4 g PPA with a P 2 content of 77.2% (prepared by mixing 101.5 g of 85.4% PO4 with 236.8 g of 115% PPA). When the dehydrochlorination was nearly complete, 69.5488 g (0.2S706 mo I) of monomer 2j 'was added followed by the gradual addition of 140.1 g 1 mixture then stirred and heated essentially according to Example 8. The amount of P 2 O 4 was primarily selected (as determined in accordance with formulas a * and b * above) to provide the reaction mixture with an effective P 2 O 3. content of approximately 83,896 prior to the start of polymerization and an effective P2 O2 content of approximately S2.2% immediately following substantially complete polymerization. The reaction product obtained exhibited stir-opalescent and was further characterized that it had a polymer concentration of 1796; fibers were easily formed by direct spinning or drawing from the reaction product. the polymer obtained had the following structure:

due to an intrinsic viscosity of 1 6 d I / g in MS Λ at 30 ° C, which corresponded to an n value of average polymerization of about 60.

Example 18

The procedure of Example 8 was essentially repeated. Instead of monomer and 2a, 81.99 g (0.28869 mol) of monomer Ic was dehydrochlorinated in an "initial" solution of 366.8 g of PPA with a PjCI content of 77.2 % (prepared by mixing 110g of 85.9SOH ^ PO with 256.8g of 115% PPA). When dehydrochlorination was almost complete, 69.9999 g (0.28869 mol of mome 2 y was added followed by the addition of 198.9 g of P 2 O 3. The mixture was then stirred and heated essentially in accordance with Example S. The amount of P2O4 was preselected (as determined in accordance with the above formulas a * b *) to provide the reaction mixture with an effective P2O4 content. of approximately 83.8% prior to the start of polymerization and an effective P 2 O 2 content of approximately 82.2% following almost complete polymerization The reaction product obtained showed stirring opacity and was furthermore Note that it had a polymer concentration of 16%, fibers were easily formed by direct spinning or drawing from the reaction product The polymer obtained had the full structure:

characterized by an intrinsic viscosity of 16 d in Μ5Λ at 30 ° C which corresponded to an n value of average polymerization of about 60.

For bee Id I 9

The procedure of Example S was essentially repeated. Instead of monomer and 1a and 2a, 93.52 32 g (0.29202 mol) of monomer li was dehydrated in an "initial" solution of 263.5 g ΡΡΛ with a P 2 O 2 content of 77.2 % (prepared by mixing 79 g of Sb H 2 PO 3 with 184.4 g of 1 L 5% ΡΡΛ). When dehydration was almost complete, 48.5129 g (0.29202 mol) of monomer 2a was added followed by the gradual addition of 171 g of P 2 O 2. The mixture was then stirred there, heating essentially in accordance with Example S.

The amount of preselected (as determined in accordance with the aforementioned formulas a * and b *) to provide the reaction mixture 1 with an effective Pj content of approximately 85.3% prior to the start of polymer polymer and an effective P 2 O 3 content of approximately 86.2% following almost complete polymerization. The resulting reaction product exhibited rudder opalescence and was furthermore characterized as having a polymer concentration of IS%; fibers were easily formed by direct spinning or drawing from the reaction product. The resulting polymer had the following structure:

characterized by an intrinsic viscosity of 15 dl / g i η Μ5Λ at 3 00 C.

Example 22

The procedure of Example 8 was essentially repeated. Instead of monomers 1a and 2a, 128.4748 g (0.32431 mol) of monomer 11 was dehydrochlorinated in a "starting" solution of 2 2 3.5 g PPA not having a Ρ20 ^ content of 79.4% (prepared by 44.7 1 1 g of 85.4% L PO PO 2 te mix with 17 S, S gg of 115% ΡΡΛ). When dehydrochlorination was nearly complete, 53.8778 g (0.324 31 mol) of monomer 2a was added followed by gradual addition of 197.0 g of P2 O5. Inorganic salts such as I-thiuric salts (e.g., LiCI, LiF, I-Li-phosphate, and the like) are applied to this syringe, if required, to promote polymeric solution. mixture was then stirred and heated essentially in accordance with Example 8. The amount of P 2 O 4.

was preselected (as determined in accordance with the above formulas aA and bA) to provide the reaction mixture with an effective Ρ90 <content of approximately 89.1% prior to the start of polymerization in an effective P2 O9e ial (e) of approximately 82.2% following substantially complete polymerization. The reaction product obtained showed agitation opalescence and was further characterized as having a polymer concentration of 18%; fibers were easily formed by direct spinning, or drawing from the reaction product The resulting polymer had the following structure:

characterized by an intrinsic viscosity of 12 dl / g in MSA at 30 ° C.

Example 23

The procedure of Example 8 was essentially repeated.

Instead of monomers 1a and 2a, 70.3707 g (0.21902 mol) of monomer li was dehydrochlorinated in a "starting" solution of 323 µg PPA with a content of 77.2% (prepared by 96 9 g of 85.4% H 2 PO 3 to be mixed with 226.2 g of 115% PPA). When dehydrochlorination was nearly complete, 53.0654 g (0.21902 mol) of monomer 2j was added, followed by the gradual addition of 125.0 g of P2O5. The mixture was then stirred and heated essentially in accordance with Example 8. The amount of PjO. was preselected (as defined in

accordance with the aforementioned A

formulas a and b) to provide the reaction mixture with an effective P2O5 content of approximately 8 3.6% prior to the onset of. » polymerization and an effective ^ 2 ^ 5 content of approximately 82.2% immediately following substantially complete polymerization. The resulting reaction product showed stir opalescence and was further characterized as having a polymer concentration of 18%; fibers were easily formed by direct spinning or drawing from the reaction product.

The polymer obtained had the following structure:

characterized by an intrinsic viscosity of 17 dl / g in MSA at 30 ° C.

Example 26

A solution consisting of 63.34 g of concentrated phosphoric acid and 147.49 g of 115% PPA was stirred at 100 ° C under reduced pressure in a 300 ml three-necked flask for 3 hours. To a 500 ml resin kettle was added 63.49 g (0.3087 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a) (prepared using the Wolfe method, AFOSR Final Technical Report,

Dec. 15, 1980). A portion of the above prepared PPA with a P2O of 77.3% (207.57 g) was poured into the resin kettle containing the monomer while under argon flow. After the monomer was taken up, a second portion of monomer (30.71 g, 0.1493 mol) was added. The mixture was heated to 55 ° C and the pressure was gradually reduced over 1.5 hours. An additional 5.35 g of monomer was added to the kettle under argon flow to bring the total of added monomer to 99.65 g (0.4845 mol). The mixture was then stirred under reduced pressure at 50 ° C overnight ". The temperature was then raised to 70 ° C for 8 hours. Phosphorus pentoxide (138.62 g) was then added to increase the effective PjO9 content to 86.4%. After heating to 100 ° C with stirring overnight, the reaction product was stirring opalescent. After placing the mixture, which still contained undissolved monomer, under reduced pressure for 3 hours, a sample was removed and placed between a microscope slide and a cover slip. The non-precipitated product depolarized in one plane of polarized light. The reaction mixture was then heated under argon as follows: An additional 2.5 hours at 100 ° C; 2 hours at 120 ° C7 16 hours at 130 ° C; 31 hours at 170 ° C; 43.5 hours at 200 ° C. A sample of the green, opalescent polymer reaction product yielded golden-orange fibers upon precipitation in water. The sample was extracted in water for 24 hours and dried under vacuum at 140 ° C for 24 hours. The intrinsic viscosity was determined to be 8.2 dl / g in MSA at 30.1 ° C.

The reaction product was characterized as being a final effective PO. It had a content of 82.2% with the polymer zfTy having a concentration of 15.1% by weight.

Example 27

A mixture of 125.8 g of 115% ΡΡΛ and 63.9 g of concentrated phosphoric acid (S5.7% H ^ PO ^) was heated to 100 ° C for 4 hours under reduced pressure in a 500 ml three-necked co 1 . the percentage P ^^ content profile for this example is shown in Figure 12. 91.85 g (0.4466 mol) of 3a was added to a 500 ml resin kettle. The kettle containing the monomer was vented. 108.17 G of the above-prepared PPA (with a °2 ° 5 content of 77.2%) was then added. The kettle was then heated with an oil bath at 50 ° C under a thin stream of argon overnight. The kettle was then again pressurized and heated to 70 ° C for 23 hours. P2 ° 5 (108.32 g) was then added in three portions to increase the effective level to 88.5%. Reduced pressure was applied to degas and froth the P2 O5, which assisted mixing. After stirring for 3 hours, the temperature was raised to 100 ° C and held at that temperature under reduced pressure for 21 hours. The mixture was stir-opalizing and depolarized in one plane polarized light. The mixture was then heated as follows: 115 ° C under argon for 3 hours; 130 ° C under reduced pressure for 2 hours; 170 ° C for 0.5 hours; 190 ° C for 17 hours. A mixture of the green, opalescent reaction product was removed to give a fibrillar, gold-colored fiber on drawing followed by precipitation in water. After extracting with water in a Soxhlet apparatus for 24 hours, the sample was dried for 24 hours at 110 ° C under reduced pressure. The intrinsic viscosity of the sample was 15.8 dl / g in MSA at 30.0 ° C. An additional 7.5 hours of heating gave a sample with an intrinsic viscosity of 16.7 dl / g. The reaction product thus obtained was 20.3% by weight of polymer / T / in PPA with a final P2 O2 content of 82.4%.

Example 28

The procedure of Example 27 was essentially repeated. Instead of monomer 3a, 146.9123 g (0.4305753 mol) of monomer 3k was dehydrochlorinated in a "starting" solution of 256.9 g of PPA with a P2 ° 5 content of 77.3% (prepared by 78, 6 g of 85.4% H ^ PO ^ to mix with 187.4 g of 115% PPA). When dehydrochlorination was nearly complete, an additional 144.85 g of P 2 O 3 was gradually added to the mixture and dissolved by stirring and heating essentially in accordance with the scheme given in Example 27. The amount of P 3 O 3 added was preselected (as determined in accordance with ae in the above formulas a and b) to provide the reaction mixture with an effective P20 content of approximately 85.3 L prior to the start of polymerization and an effective P20 content of approximately 82.2% immediately following virtually complete polymerization.

The resulting reaction product showed stir opalization and was further characterized as having a polymer concentration of 19%; fibers were easily formed by direct spinning or drawing from the reaction product. The polymer obtained had the following structure:

characterized by an intrinsic viscosity of 15 dl / g in MSA at 30 ° C corresponding to an average n value of polymerization of about 70.

Example 29

The procedure of Example 27 was essentially repeated. Instead of monomer 3a, 161.90 g (0.85391 mol) of monomer 3c were dehydrochlorinated in a "starting" solution of 198.8 g of PPA with a P 2 O 3 content of 77.3% (prepared by 58. Mix 7 g of 58.4% H3PO4 with 140.0 g of 115% PPA). When dehydrochlorination was nearly complete, an additional 196.8 g of P902 was gradually added to the mixture and dissolved by stirring and heating in fibers in accordance with Example 27. The amount of P2 O 3 added <3 preselected (as determined in accordance with of the aforementioned formulas a and b) to provide the reaction mixture with an effective P2 O2 content of approximately 88.6% prior to commencement of polymerization and an effective content of approximately 82.2% immediately following substantially full polymerization. The resulting reaction product showed stirring opalization and was further characterized as having a polymer concentration of 19%; fibers were easily formed by direct spinning or drawing from the reaction product. The polymer obtained had the following structure:

characterized by an intrinsic viscosity of 12 dl / g in MSA at 30 ° C.

Example 30

The procedure of Example 27 was essentially repeated.

Instead of monomer 3a, 161.90 g (0.85391 mol) of monomer 3d was dehydrochlorinated in a "starting" solution of 221.7 g PPA with a P20 content of 77.3% (prepared by 65.50 g of 85.4% H 2 po 2 to mix with 156.2 g of 115% PPA). When dehydrochlorination was nearly complete, an additional 203.1 g of P 2 O 2 was gradually added to the mixture and dissolved by stirring and heating in essentially accordance with example. 27. The amount of P2 ° 5 added was preselected (as determined in accordance with formulas a 'and b' above) to provide the reaction mixture with an effective P20 content of approximately 88.2% prior to the beginning of polymerization and an effective Ρ-, Ο ^. content of approximately 82.2% immediately following substantially complete polymerization.

The reaction product obtained: exhibited stirring opalization and was further characterized as having a polymer concentration of 18%; fibers were easily formed by direct spinning or drawing from the reaction product. The resulting polymer had the following structure. ture:

characterized by an intrinsic viscosity of 12 dl / g in MSA at 30 ° C.

Example 49

A mixture of 123.38 g of 113% PPA and 32.63 g of concentrated orthosorphic acid (83.7% HjPO2) was stirred at 100 ° C for 2 hours under reduced pressure. After the solution was allowed to cool / cool to 30 ° C under a stream of argon, a portion (168.18 g) of the ΡΡΛ (77.3% p2 ^^) was added under a stream of argon to a resin kettle containing 37.6108 2 g (0.2346 mol.

a = 0.93) of 1a prepared as described in Example 8 and 2.638 g (0.0 12371 mo I, a ^ = 0.05) of Ib prepared using the method of Wolfc and Arnold , Ma cr οιηο I ecu I es, Vol. 14, 909 (1981) and crystallized from hydrochloric acid containing 3% by weight of stannous chloride. The mixture was then stirred at 50 ° C for 33 hours under reduced pressure and 90 ° C for 4 hours under reduced pressure. Monomer 2a (41.0899 g, 0.24733 mo I = m, b = 1) was then added. The mixture was a / cooled to approximately 40 ° C and 139.18 g was added to increase the effective polymerization content to 87.6%. The mixture was then stirred at the specified temperatures for the specified times under a stream of argon: 100®C for 2 hours; 150 ° C for 1 hour; 160 ° C for 1 hour; 170 ° C for 3.3 hours; and 200 ° C for 64 hours. The final concentration of the resulting "random" copolymer was 16.8% in a PPA with an approximate P 2 O 3 content of 82.3%. Fibers of the copolymer were isolated by drawing the resulting green opalescent product and precipitating it in water. The intrinsic viscosity of the isolated copolymer after heating at 200 ° C for 1½ hours was found to be 23.4 dl / g and actually increased from 1 to 24.4 dl / g after completion of the above heating schedule. The resulting co-op apparently had the following structure:

where it was assumed that the mole fractic of Λ! units (a ^ j) was 0.93, and the moirirphy of D1 units (a ^ bj) was assumed to be 0.05, assuming the mean block lengths y | | and y were 20 cn 2, respectively, and it was assumed that the average total number of regular cross unit units of both types (n) was approximately 100.

Example 50

To a deaerated mixture of 16.09147 g (0.0656 27 5 mol, 8 ^ = 0.7 5) of 1a and 4.66149 g (0r02 18778 mol, a ^ = 0.2 5) of Ib was added 220 g freshly prepared and deaerated PPA (the PPA was prepared from 173.81 g of 86.8% orthophosoric acid and 267.64 g of phosphorus pentoxide, equilibrated and deaerated). The mixture was stirred under an argona flow at: room temperature overnight; 50 ° C for 3.3 hours; and 72 ° C for 21 hours. The mixture was stirred under reduced pressure at 72 ° C overnight to dehydrochlorinate almost completely / Terephthalic acid (2a) (14.33762 g, 0.0873039 mol) was added to the solution and the mixture was vented before stirring started. The PPA prepared above was then added to the mixture to give a total of 394.5 g of PPA. The slurry was then stirred under reduced pressure at 110 ° C for 0.5 hour and under an argon atmosphere at: 120 ° C for 1 hour; 130 ° C for 0.5 duration, 140 ° C for 0.5 hour; 150 ° C for 0.5 hours; 6 0 0 C for 1.0 hour; 70 ° C for 15.5 hours; 185 ° C for 6.5 hours; and 200 ° C for 19 hours. The optically anisotropic product contained 5.3 wt.% Polymer in PPA (84.0% P 2 O content). Precipitation of a small amount of the polymeric product gave the "random" copolymer, and was believed to have the following structure:

where fig j- 0.7 5, Υ || = ^> a 7 b ^ = 0.25 and y = 1.33, with an intrinsic viscosity of 26.59 di / g in MS A at 30 ° C, which agreed mot ar. value of approximation 110.

Example 5!

To a deaerated mixture of 22.36319 g (0.05 i 2061 mol, a | = 0.9) of 1a and 2.15918 g (0.0101300 mol, a 2 = C ', I 0) of lb added approximately 230 g of freshly prepared vented PPA (the PPA was prepared by stirring a mixture of 135.97 g of 25.4% ertoiosioric acid and 207.56 g of phosphorus pentoxy at 15 ° C overnight under an argon tmos f ee r, followed by defl.

by stirring under reduced pressure at 150 ° C

for 5.5 hours. The solution was allowed to cool to> room temperature under argon before use). The mixture was stirred under an argon flow at: room temperature overnight; 50 ° C for 3 hours; and at 70 ° C overnight. The solution was then stirred under reduced pressure at 70 ° C for 2.5 hours. Tereitic acid (2a) (16.83595 g, 0.101340 mol); was added to the solution and, after placing the kettle under reduced pressure, stirring was started. The remaining above-mentioned PPA was then added to the mixture (total PPA added = 317.6 g) under an argon atmosphere. The polymerization mixture was then stirred under an argon atmosphere at 100 ° C for 30 min .; 120 ° C for 30 min .; 130 ° C for 30 min .; 40 ° C for 30 min .; 150 ° C for 30 min .; 160 ° C for 30 min .; and 170 ° C for 14.5 hours.

The polymerization mixture 1 was heated under an argon atmosphere without stirring at 185 ° C for 5 hours and at 93-200 ° C for 28 hours. The final polymer concentrations were 7.6 wt% in PPA (3.0% PjO). Precipitation of a small amount of an anisotropic polymer product gave the random type IX, class I copolymer having the structure:

where a j b j = 0.9, a ^ b j = Ό '0> and it is assumed that the average block lengths y j j and y ^ j were 10 and 1.11, respectively. The isolated copolymer had an intrinsic viscosity of 26.36 dl / g in MSA at 30 ° C, which corresponded to an n value of approximately 1.

>

Example 32

Their solution of 133.31 g of 113% PPA and 39.10 g of 83.7% H 2 PO 2 was stirred at 100 ° C for 2 hours under reduced pressure. The solution was allowed to cool to room temperature under reduced pressure, and 180.16 g of the mixture was added to 30.20054 g of 1a under an argon atmosphere. After a homogeneous mixture was obtained, 28.29941 g (38.49993 g total, 0.23839 mol total r a j-f) of vented la was added. The mixture was stirred under reduced pressure at: 30 ° C for 18.5 hours; 70 ° C for 10 min .; 80 ° C for 10 min .; and 90 ° C for 5.5 hours. Deaerated 2a (35.6892g, 0.21482mol, b (= 0.9) and 5.79905g (0.02394 mol, b2 = 0.10) of deaerated 4.4 'biphenyl-carboxylic acid (2aa) added under an inert atmosphere After the monomer and were incorporated into the mixture, the reaction mixture was cooled to 40 ° C and 136.11 g of vented P2 ^ 5 was added to give an effective polymerization content of 87.01 %.

After stirring at 100 ° C for 63 hours, the polymerization was stirred at: 60 ° C for 2.5 hours; 170 ° C for 5.5 hours, and 200 ° C for 64 hours. The concentration of the resulting copolymer was 15.9% in PPA with a Pq content of approximately 8 2.5%. The reaction product; was r ocr - grandpa I i r, e r e nd and was drawn to oriented vein. The company had an i n t r i n s i c! <C v i s c i; e i t var, 7.9 d / g in MSA at 30 ° C. The structure of the resulting polymer was believed to be:

where a j b j is 0.9, a | b 2 is 0.1, y j (is 10, is!,: and n is approximately 9 0.

Example 53

A mixture of 20.10 g concentrated ortodos formic acid (85.7% H 2 PO 3) and 9 6.79 g of 1 5% PPA wg r d stirred at 100 ° C for 2 hours under reduced pressure in a 100 ml three-necked colony. After this PPA solution was allowed to cool to 50 ° C at a reduced pressure with a content of 77.3, a portion (62.4 g) was added under a stream of argon to a 200 ml resin kettle containing 20 ml. 2783 g (0.082702 mo I = m, aj = 1) of la prepared as in Example 49 and vented.

The mixture was then stirred at the specific temperatures for the specific times under either reduced pressure (vac) or argon flow (Ar): 50 ° C, 9 hours, vac; 50 ° C, 15 hours, Ar; 60 ° C, 3 hours, vac; S0 ° C, 1 hour, vac; 90 ° C, 3 hours, vac; 60 ° C, 15 hours,

Ar; 80nC, 7 hours, vac. Trans-1,2-cyclohexanedicarboxylic acid (2 µg) (0.6781 g, 0.009132 mol, b = 0.05) which was purchased from Aldrich Chemical Company and recrystallized from methanol before use was added to the kettle and then terephthalic acid (2a) (13.05955 g, 0.078579 mol, B1 = 0.9 5) was added. [P 1, 2, 00 g)

then added to the mixture that had cooled to 50 ° G to increase the effective P10 content for polymerization to 86.8%. The mixture was then stirred at 100 ° C for 17 hours under an argon flow. The yellow mixture was then heated with stirring under argon as follows: 120 ° C for 1 hour; I30-I40 ° C

for 1 hour; 50 ° C for 2 hours; 166 ° C for 0.5 hour; 170 ° C for 4 hours (rudder opalization was evident during this time); 185 ° C for 15.5 hours; and 200 ° C for 75 hours. The final concentration of the resulting "random" copolymer was 16.4% in PPA, with a P1. content of approximately 82.2%. The polymer obtained apparently had the following structure:

characterized by having an intrinsic viscosity in methanesulfonic acid at 30eC of 10.0 dl / g, which corresponded to an average n value of about 50, a mole fraction of fA ^ units (ajb ^) of 0.95, and a mole fraction of units (ajb ^) of 0.05. It was assumed that the mean bioklengths y 1 'i and yj2 r e spek t i ve i i k k 20 and I.

YoorbecId 5¾

The procedure of Example 49 was essentially repeated. Instead of using 95 mole% of monomer 1a, 5 mole% of monomer 1b, and 100 mole% of monomer 2a, a mixture of 50 mole% of monomer 1a and 50 mole% of monomer 1c was practically dehydrochlorinated in a similar percentage by weight of PPA with essentially similar content. After the addition of a test o ome r ric how much of mo n ome er 2 a and an appropriate amount of P? 0 ,. (so that the final ^ 2 ^ 5 content was increased to considerably above about 22%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The aerosol formed product was anisotropic liquid crystalline (exhibited stir-opalization) and could be used directly to form into articles by spinning, o (pulling. The resulting copolymer had the following structure: /

Example 5 5 * * »

The procedure of Example 49 was essentially repeated. Instead of applying 95 mo I.% of mo ome er la, 5 mo 1. % of mon om er Ib, and l0 0 me I. % of mo normer 2a, a mixture of 50 mo 1% of mo normer 1b and 50 mol% of mo normer 1c was substantially dehydrochlorinated in a comparable weight percentage of PPA with essentially similar P 2 O 2 content. After the addition of a stoichiometric amount of monomer 2a and an appropriate amount of P 2 O 3. (so that the end was increased significantly above about 82%), the resulting mixture was then heated in essentially the same manner in accordance with Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited agitation opalization) and could be used directly to form objects by spinning or drawing. The obtained copolymccr had the following report:

Example .5 6

The procedure of Example 51 was essentially repeated. Instead of using 100 mole% of monome er 1a, 95 mole% of monome er 2a. and 5 mole% of monomer 2 g g, 100 mole% of monome er 1a was dehydrochlorinated in a substantial proportion in a comparable weight percent of PPA with essentially similar P 2 O 3. degree. After the addition of 50 mol% of monomer 2a and 50 mol% of monomer 2j and an appropriate amount (so that the final P2 content was increased to substantially above about 82%), the resulting mixture was then heated to substantially the same manner in accordance with Example 12 to provide a copolymerization product 11 kt. The product thus formed was anisotropically liquid crystalline (exhibited stir opalization) and could be used directly to form into articles by spinning, or to pull. The resulting copolymer had the following structure:

Example 5 7

The procedure of Example 53 was essentially repeated. Instead of using 100 mol% mo n-more, 95 mol% of monomer 2a 'and 5 mo! Of monomer 2 µg, 100 mole% of monomer 1a was dehydrohydrated in a similar manner in a comparable percentage by weight of PPA with essentially similar P 2 0 content. After the addition of 50 mol% of monomer 2a and 50 mol% of monomer, 2k is added to an appropriate amount of P 2 O 3. (so that the final P105 content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stirring opalization) and could be used directly for particulate spinning, or drawing.

The resulting copolymer had the following structure:

Example 58

The procedure of Example 53 was essentially repeated. Instead of using 100 mol% of monomer 1a, 95 mol% of monomic 2a and 5 mol% of monomer 2 µg, 100 mol% of monomer 1a was essentially dehydrochlorinated in a similar percentage by weight of PPA with essentially similar P2-5 content. After the addition of 50 mole% of monomer 2a and 50 mole% of monomer 21 and an appropriate amount of P2 ^ 5 (so that the end P0.0 content was increased to significantly above about 82%), the resulting mixture was added there -n a heats in essentially the same way in corresponding cmr. Incorporated with Example 12 to provide a ropoly-crimatic product. The product thus formed was anisotropic liquid crystalline (exhibited rocr-opa ic ring) and could be used directly for shaping into articles by spinning or pulling. The resulting copolymer had the following structure:

l

Example 39

The procedure of Example 33 was essentially repeated. Instead of using 100 mole% of monomer cc, 93 mole% of monomer 2a, and 5 mole% of monomer 2 µg, 100 mole% of monomer Ib was substantially dehydrochlorinated in a comparable weight percent var, PPAmct in fibers. similar P ^ O ^ content. After the addition of 30 mol% of monomer 2a and 30 mol% of monomer 2j and an appropriate amount of P 2 O 3 (so that the final P 2 O content was increased to significantly above about S2%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stir-opalization ring) and could be used directly for shaping into objects by spinning or drawing. The resulting copolymer had the following structure:

Example 60

The procedure of Example 5 3 was repeated. Instead of using 100 mo I .¾ menomer la, 95 mo I. % of mom n er er 2a, and 5 mo I. % of monomer 2 g g, 100 mol. 96 by mo normal Ib practically dehydrochlorinated in a variety of weight per age with similar p., 0, g e h a I te. After the addition of 50 mol% of monomer 2a and 50 mol% of monorec 2k and an appropriate amount of (so that the final content was increased to significantly above about 82%), the resulting mixture was then heated to essentially the same way in accordance with Example 12 to provide a copolymerization. The product thus formed was anisotropic-smearable crystal in (cured stir-opalization) and could be used to mold into articles by spinning or drawing.

The resulting copolymer had the following structure;

Vocr bee I d 6 1

The procedure of Example 53 was essentially repeated. Instead of applying 100 mo I. 6 of monomer, 1, 5 mole% of monomer 2a, and 5 mole% of monomer 2gg, 100 mole% of monomer 1b in main 7.And was dehydrochlorinated in a similar process percentage of ΡΡΛ with essentially similar ^ 2 ^ 5 §e ^ a I te. After the addition of 50 mol% of monomer 2a and 50 mol% of monomer 21 and an appropriate amount of P 2 O 4. (so that the end of P106e3-3e1e was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner in Example 12 screen to provide a copolymer risk product. The product thus formed was anisotropic liquid crystalline (exhibited stirring opacity) and could be used directly to form objects by spinning, or pulling. The copolyme obtained had the following structure:

Example 62

The procedure of Example 53 was essentially repeated. Instead of applying 100 mo I. % of monomer 1, 95 mole% of monomer 2a, and 5 mole% of monomer 2 µg, 100 mole% of monomer 1a was substantially dehydrochlorinated in a comparable weight percentage of ΡΡΛ with essentially similar 1 "^^ content After adding 75 mol% of monomer 2a and 5 mol% of monomer 2i and an appropriate amount of (so that the final P 2 O 2 content was increased to significantly above about 82%), the The resulting mixture is then heated in substantially the same manner in accordance with Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited crystallization) and could be used directly to form articles by spinning, o-drawing The resulting copolymer had the following structure:

Example 63

The procedure of Example 53 was essentially repeated. Instead of using 100 mol% of monomccr 1a, $ 5 mol% of monomer 2a, and 5 mol% of monomccr 2 µg, 100 mol% var. monomer Ib substantially dehydrochlorinated in a comparable weight percentage of PPA with essentially similar? 2®5 content. After the addition of 75 mol% of monomer 2a and 25 mol% of monomer 2i and an appropriate amount of P2 * ^ 3 (so that the final P ^ O ^ content was increased to significantly above about 82%), the resulting mixture is then heated in essentially the same manner in accordance with g with Example 12 to provide a copolymerization product. The product thus formed was anisotropic-vlocibar crystalline (exhibited stirring opalization) and could be used for molding into articles by spinning or drawing. The resulting copolymer had the following structure:

Example

The procedure of Example 53 was essentially repeated. Instead of using 100 mole% of monomer cc, 95 mole% of monomcer 2a, and 5 mole% of monomer 2 µg, 100 mole% of monomer ic was virtually dehydrochlorinated in a similar weight percentage of PPA with essentially similar degree. After the addition of 75 mol of monomcer 2a and 2.5 mol% of monomer 2i and an appropriate amount (so that the final P 2 O 2 content was increased to significantly above about 2 2%), the resulting mixture was then heated in essentially the same manner in accordance with Example 12 to provide a copolymerization product. The product thus obtained was anisotropic liquid crystalline (exhibited stir opalization) and could be used directly to form objects by spinning, or drawing. The resulting copolymer had the following structure:

For bee Id 65

The procedure of Example 53 was essentially repeated. Instead of using 100 mole% of monomer 1a, 95 mole% of monomer 2a, and 5 mole% of monomer 2 µg, 100 mole% of monomer 1a was substantially dehydrochlorinated in a comparable weight percent of ΡΡΛ with essentially similar P2O3 content. After addition of 75 mol% of monomer 2a and 25 mol% of monomer 2e and an appropriate amount of P 2 O 3 (so that the final P 2 O 3 content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The product thus formed was anisotro-liquid crystalline (exhibited stir-opalization) and could be used directly for shaping by spinning or drawing. The resulting copolymer had the following structure:

• Example 66

The procedure of Example 53 was essentially repeated. Rather than using 100 mole% of monomer 1a, 95 mole% of monomer 2a, and 5 mole% of monomer 2 µg, 100 mole% of monomer tb was substantially gchydrochlorinated in a similar weight percentage of ΡΡΛ with similar al in.

After the addition of 75 mole% of monomer 2a and 25 mole% of monomer 2e and an appropriate amount of (so that the final P 2 O 2 content was increased to significantly above about 82%), again The mixture is then heated in essentially the same manner in accordance with Example 12 to provide a copolymer risatic product. The product thus formed was anisotropic liquid crystalline (exhibited stir opalization) and could be directly used to shape into objects by spinning, or drawing. The resulting copolymer had the following structure:

f

Example 67

The procedure of Example 69 was essentially repeated. Instead of using 93 mol% of monomer 1a, 3 mol% of monomer Ib, and 100 mol% of monomer 2a, a mixture of 60 mol% of monomer 1a and 60 mol% of monomer 1 1 was used. substantially dehydrochlorinated in a comparable weight percentage of PPA with essentially similar ^ 2 ^ 5 content. After the addition of a stoichiometric amount of monomer 2 a and an appropriate amount of it (so that the final P10 content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited crystallization) and could be used directly to form toll objects by spinning or drawing. The resulting copolymer had the following structure:

For bee Id 6 8

The procedure of Example 9 was essentially repeated. Instead of using 93 mol.% Of rr.o η o -me er I a, 3 mo I. % of mo ne e r lb, and 100 mo I. % of monomer 2a, a mixture of 80 mol. 96 of monomer Ie and 20 mol.% of monomer II was substantially dehydrochlorinated in a comparable weight percentage of PPA with essentially similar P2 ^ 5 content. After the addition of a 5tc hometric amount of monomer 2 a and an appropriate amount of P10, (so that the final P ^ C content was increased to significantly above about 8296), the resulting mixture is then heated in essentially the same manner in accordance with Example 12 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (showed stir opalization) and was formed into ordered fibers by simple drawing. The copolymer was believed to have the following structure:

P? 0 ^ (so that the egg - P ^ O ^ hai te increased by tctaa η - 2 'eniijkbove η about S 2%), we rd the resulting me η gsei then heated cp 1 n essentially the same way: ncverecnsi cm -My example 12 to provide a copolymerization risk product. The product thus formed was anisotropic liquid crystalline (exhibited stirring opalization ring) and could be used directly to form articles by spinning, drawing. The resulting copolymer had the following structure:

Example 71

The procedure of Example 53 was essentially repeated. Instead of applying 100 mo I. % of monomer 1, 95 mo I% of monomer 2a, and 5 mo I% of monomer 2 µg, 100 mo 1% of monomer 1 essentially gcdchydrochorated in a similar weight percentage of PPA with being similar Ρ2 ^ ge ha '{e ·

After the addition of 95% of% of monomer 2a and 5% by volume of monomer 2µg and an appropriate amount of P 2 O 2.

(so that the final polypropylene was increased to substantially above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 12 to provide a copolymerization product. The product thus formed was anisotropically-flocatable crystalline (exhibited stir-opalization) and could be used directly for shaping into articles by spinning, or drawing. The polymer obtained had the following structure:

Example 7 2

The procedure of Example 33 was essentially repeated. Instead of applying '00 mo I.% of mo ne e r la, 93 mo I. % of mom n er er 2a, and 3 rno I. % of monomcer 2 g g, 100 mo I. % of monomer la · η essentially dehydrochlorinated at a similar weight percentage of ΡΡΛ with essentially similar P ^ O ^ content. After the addition of 93 mol% of monomer 2 a and 3 mol% of monomcer 2 f / and an appropriate amount of ^ 2 ^ 5 (so that the cind-P ^ O ^ content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner in accordance with Example 12 to provide a copolymerized product. The product thus formed was anisotropically liquid crystalline (exhibited rudder opalization) and could be used to shape into objects by spinning or drawing. The copolymer obtained had the following structure:

Example 73

Two po! ymc r sations (step Λ and step B) were simultaneously run in separate resin chains and combined at a later stage (step C) to give a product of a block copolymer, which was of the following structure. :

where a.b, is 0.7 9 3 and fig. 117 11 I 2 is 0.207 enyis greater than about 30.

Stop Λ: preparation of

A mixture of 92.06 g of 113% PPA and 39.5 g of concentrated ortho-1 for 7 hours (33.7% H 2 PO 4) was stirred at 100 ° C for 2 hours under reduced pressure. A portion (123.63 g) of the hot PPA (77.3% P 2 O 3) was added under a stream of argon to a resin kettle containing 1 1, 2 682 g (0.16896 mol) of 1a. The mixture was stirred at 30 ° C under argon flow for 13 hours, then under reduced pressure at 60 ° C for 23.5 hours, 70 ° C for 6 hours, and 80 ° C for 8.5 hours to induce dehydrochlorcrine . Tere i acidic acid (2a) (28.0688 p 0.16895 mol) was then added in four portions.

The mixture was cooled to approximately b0 ° C and 92.22 g ^ 2 ^ 5 wer <^ added. The mixture was rowed at the following temperatures for the specified times under argon flow: 100 ° C for 2.5 hours; I 2 0 ° C to I60 ° C in increments of 10 ° C per 0.5 hour: I70 ° C for 2.5 hours. At this time, the mixture was rocopalizing, and a sample of the dope showed birefringence under a plane polarized light. After an additional 3 hours at 70 ° C, the polymer from step B was added (see step C) · Intrinsic polymer viscosity

isolated from the reaction mixture I

immediately for step C was 2.3 dl / g, which corresponded to an n value (average number of regularly recurring units) of 30 and a p value (degree of progress of reaction) of 0.983.

Step B: preparation of

A mixture of 30.72 g of 15% ΡΡΛ and 13.13 g of concentrated ortho-phosphoric acid (S5.7% H 2 PO 2) was stirred at 100 ° C for 2 hours under reduced pressure. The PPA (41.66 g; 77.3% P 2 O 4) was added without cooling under argon flow to a resin kettle containing 1 3 S 0 S 7 7 g (0.05632 mol) of 1a. The mixture was stirred at 15 ° C under argon pattern for 15 hours, then under reduced pressure at 60 ° C for 23.5 hours, 70 ° C for 6 hours, and 80 ° C for 35.5 hours. Isophthalic acid (2 ss} (9.3569 g, 0.05632 mol) purchased from Aldrich Chemical Company in 99696 purity wcir d gc-recrystallized twice from 9096 aqueous ethanol and dried at 100PC for 24 hours and then added int Two portions of the solid were taken up after each addition The mixture was cooled to approximately 40 ° C and then 31.59 g P 2 O 3 was added The mixture was then heated simultaneously and according to the same heating scheme as the solution in step A.

Step C: Bio-copolymerization. After 5.5 hours at 170 ° C, 72 g of the viscous, red, optically isotropic proriuk; from step B added to the boiler from step A under an ar rorta tmos f e r at the time indicated in step Λ. Both boilers were heated under an argon flow as follows: 170 ° C for 12.8 hours; 190 ° C for 2 hours, 200 * 0 for 26 hours. The resulting mixture remained rocr-grandfathering and continued to polymerize as indicated by intrinsic viscosities of samples removed at various times. When precipitated in -HO, the sample of the resulting copolymcer had an intrinsic viscosity of 17.5 dl / g in MSA at 30 ° C. The stored sample of the portion of the product from stopper B dot was not added to the product of step Λ but was heated according to the same scheme as the mixture had an intrinsic viscosity of 1.1 di / g <n M5A at 3 0 '' C. The weight *

,, "" ^ Percentage before p o! ymc er from step Λ vgj i 6 -

j -, h c * weight barrier (age of polymer in the; P r o The 1.1 of step 5 was 16.3. The weight percentage, ..

b v c n b! o · <_ co po 1ymee r

it was calculated to be 16.2; the weight * -. . The proportions of the individual and segments x the biocopo polymer in the final product were rs.

μ e K 11 e v e i jji 12,9 and 3,4, so a Is calculated from the weights of c * 0e added constituent polymers and the total weight:,.,

of the resulting product. The miper percentage of m <> r-

Those and flexible units were resoektic · -j.

79.3 and 20.7, as calculated from the weights of C 'added constituent polymers.

Before I d 7 4

Two polymerizations were simultaneously carried out in separate resin boilers (steps A and b 'and combined in an stage (step C) to give a polymer polymer which was believed to have the following structure:

v / aaroij a j b j is 0.587 and a j b ^ IS 0.413 and Y ^ is greater than about 40.

Step Λ: Preparation A mixture of 36.73 g of 115% ΡΡΛ on 24.43 g of concentrated phosphoric acid (85.0% MjPO 4) is stirred at 100 ° C for 4.5 hours under reduced pressure. A portion (58.69%) of the hot PPA (74.9% ^ 2 ^ 5 ^ werc *) was added under a stream of argon to a resin kettle containing 20.71434 g (0.08448 mol) of 1a. The mixture was stirred under reduced pressure at 50 ° C for 1 hour, 706C for 1.3 hours and 80 ° C for 23 hours In order to dissolve the monomer, 6.02 g was added, and the kettle was heated to SO 0 ° C for an additional 26 hours Treitric acid (2a) (14.0351 g, 0.08448 mol) was then added in three portions The acid monomer was taken up by stirring after each addition The kettle was cooled to 50 ° C and an additional 46 24 g of vented was added.

The mixture was stirred under argon flow at the following temperatures for the specified times: 100 ° C for 18 hours; 150 ° C for 2 hours; 170 ° C for 5 hours. (After 1 hour at 170 ° C, the mixture showed crystallization). At this time, the polymer was added from step B (see step C).

Step B: preparation of

A mixture of 63.88 g of 115% ΡΡΛ and 42.51 g of concentrated orthophosphoric acid (S5.0% H 2 PO 3) was stirred at 100 ° C for 4.5 hours under reduced pressure. A portion (104.4 g) of the PPA (74.9% P2O5) was added without cooling under argon flow to a resin kettle containing 20.26865 g (0.08266 mol) of 1a. The mixture was stirred under reduced pressure at 50 ° C for 0.8 hours, 60 ° C for 7.5 hours, and SO ° C for 9.5 hours. Sebacic acid (nonomer 2 / .7., Purified by crystallization of the disodium salt, then recovery of the free acid in H 2 O and dried in vacuo at 80 ° C for 24 hours) (16.7190 g, 0.08266 mol), was then added in three portions to the haze ce I, taking up after each addition. The mixture was cooled to 50 ° C and 70.91 g of P 2 O 3 was added slowly. The polymerization proceeded quickly, and the gel-like solid was heated without stirring at 100 ° C for 16.5 hours and at 30 ° C for 7.8 hours. At this time, the polymer was removed in an inert atmosphere, with a portion of the k c t e! was left which was reconstituted egg, heated in accordance with the same scheme as the block copolymer.

Step C: Bio-copolymerization. A portion of the hei polymer from step B (153.13 g) was added to the kettle from step onder under an argon atmosphere.

The mixture was then stirred under arc flow at 170 ° C for 16 hours and at 200 ° C for 28 hours.

The mixture remained stir-opal and continued to polymerize as evidenced by an increase in the mashavis viscosity. The weight: polymer polymer backing

in the product from step A was 16.1; the weight percentage of polymer

in the product from step B was 12.1. The weight percentage of block copolymer was calculated to be 12.1; the weight percentages of

and

Sections of the block copolymer in solution were 6.8 and 5.6, respectively. The mole percentage of mesogenic

and

units were 58.7 and 1.3, respectively, as calculated from the weights of the added constituent polymers. The resulting isolated polymer was not completely soluble in methanesulfonic acid, so that intrinsic viscosity measurements were excluded.

example 75

The procedure of Example 73 was essentially repeated. Immediately after the initiation of polymerization and a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homomers) of Examples 8 and 13 were in an ordinary stirred reaction vessel in quantities to obtain a ratio of 3: 1. The polymerization of the resulting mixture was allowed to continue to produce a substantially polymerized polymerization polymerization product.

The product thus formed was also capable of being numerous (exhibited rudder opacization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

[

Example 76 t

The procedure of Example 73 was essentially repeated. Immediately after the onset of polymerization and at a pre-selected range of intrinsic viscosities or after a pre-determined emp eratuer and reaction rate, the (partially completed) individual Polymer products (i.e., the omers) of Examples 8 and 13 were transferred to a regular stirred reaction vessel in amounts to give a ratio of 1: 1. The polymerization of the resulting mixture was allowed to proceed to form a polymerized mainstream polymer product. The product thus formed was anisotropic liquid crystalline (showed stirring opalization) and could be used directly for molding articles by spinning or pulling or the like. The block pcly lake obtained had the following structure:

Example 7 7

The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homo-oligomers) of Examples S and 13 transferred into an ordinary stirred reaction vessel in amounts to obtain a ratio of 1: 3. The polymer of the resulting mixture was allowed to proceed to form a substantially polymerized bloc polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stirring solution) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 78

The procedure of Example 73 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e. homogeneously inverted) of Examples S and 13, transferred into a regular stirred reaction vessel in amounts to obtain an I: Q ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized bulk polymerization product.

The product thus formed was anisotropic liquid crystalline (exhibited stir opalization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 79

The procedure of Example 73 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosities or after predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e. homogeneous polymer) of Example were 8 and 28 are transferred in a regular stirred reaction vessel in amounts to obtain a ratio of 2: 1. The polymer of the resulting mixture was allowed to proceed to form a substantially polymerized bulk polymerization product. The product thus formed was anisotropically liquid crystalline (exhibited rudder opalization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

f

Example 80 t

The procedure of Example 73 was essentially repeated. Immediately following the onset of polymer risk and at a preselected range of intrinsic viscosities -or after a predetermined temperature and reaction rate selected, the (partially completed) individual polymerization products (i.e., homo-oi I (ome) of Examples 13 and 28 transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 1: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization polymerization product. The product thus formed was anisotropic-liquid crystalline (exhibited stir-opalization) and could be used directly for shaping by spinning or drawing or the like. The resulting block polymer had the following structure:

For bee Id 8!

The method of example 73 werH; .. “i M α ir, essentially repeated. Immediately following the start of p0 | ymcrisa. At a preselected range of intrinsic viscosities or after a predetermined temperature and reaction rate, the (partially completed) individual polymerization products (oat wj | z ° ggen homo-oligomer) of Examples 8 and 16 were transferred to a ordinary stirred reaction vessel in amounts to obtain a 1: 1 ratio. The polymerization var. the resulting mixture was allowed to proceed to form a substantially polymerized bulk polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stirring grandfathering) and could be used directly to form objects by spinning or pulling or the like. The resulting buffer had the following structure:

Example 82

The procedure of Example 73 was essentially repeated. Immediately after the start of pol / me r i s a; At a preselected range of intrinsic viscosities or after a predetermined selected temperature reaction rate, the (partially completed) individual polymerization products (i.e. homo-oligomers) of Examples 8 and 17 were transferred into an ordinary stirred reaction vessel in amounts to obtain a 1: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polydisated bI okpo polymerization product. The product thus formed was anisotropic liquid crystalline (showed stir opalization / and could be used directly to form to objects by spinning or pulling Qt such.

The resulting block polymer had the following structure:

Before bee Id 8 3

The procedure of Example 73 was essentially repeated. Immediately following hot initiation of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homogeneous polymers) of Examples 8 and 28 were transferred in an ordinary stirred reaction vessel in amounts to obtain a ratio of 1: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization product.

It thus formed an anisotropic liquid crystalline (exhibited agitation opalization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 84 t

The procedure of Example 73 was essentially repeated. Immediately following at the beginning of the polymerization and at a predetermined range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual pelymerization products (i.e. - ** gene homomers) of Examples 13 and 17 were transferred to a regular stirred reaction vessel in amounts to obtain a 1: 1 ratio. Polymerization of the resulting mixture is continued to form a substantially polymerized block polymerization product. The product thus formed was anisotropically-flocatable crystalline (exhibited stir-opalization) and could be directly used to mold into articles by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 83

The procedure of Example 73 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected empire time and reaction rate, the (partially completed) individual polymerization products (i.e., homo-o Ligomers) of Examples 8 and 19 transferred to an ordinary stirred reaction vessel in amounts to obtain a ratio of 1: 1. The polymerization of the primer mixture was allowed to proceed to form a substantially polymerized polymerization polymer. The product thus formed was anisotropic liquid crystalline (exhibited agitation opalization) and could be used to form articles by spinning. or pulling and the like. The resulting block polymcer had the following structure:

Example 86

The procedure of Example 7 3 was essentially repeated. Immediately after the onset of pelyme ric and at a preselected range of intrinsic viscosities or after a pre-determined temperature and reaction rate, the (partially completed individual polymerization products (i.e. homo-oligomers} of Examples 8 and 22 were transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 1.5: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized bump polymerization product. was anisotropic-liquid crystalline (exhibited rudder-grandfathering) and could be directly used to mold into articles by spinning or pulling and the like.

The resulting buffer had the following structure: «

Example 87 • The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a predetermined range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., converted) of Examples 28 and 22 transferred into a regular stirred reaction vessel in amounts to obtain a 1.5: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a highly polymerized biopolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited crystallization) and could be used directly to form objects by spinning or pulling or the like.

The polymer block obtained had the following structure:

f

For bee Id 8S

The procedure of Example 7 3 was essentially repeated. Instead of using monomer and 1a and 2ss in step D, equimolar amounts of monomer and 1a and 2 ƒ ƒ were polymerized at a similar concentration and at a similar degree of reaction. The (partially completed) individual polymerization products (i.e., homo-oligomers) of steps Λ and B were transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 1.3: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized block of polymerization product.

The product thus formed was anisotropically fluid crystalline (exhibited stir opalization) and could be used directly to form objects by spinning or pulling and the like. The resulting BPOPO I yme er had the following structure:

Example S9

Dc wc r kw i j z e of example? 3 was in we?. and repeated. Rather than using monomers 1a and 2ss in step B, equal amounts of monomer cn 1a and 2xx were polymerized at a similar concentration and to a similar degree of reaction progress. The (partially completed) individual polycrisatic products (i.e., homo-igomers) of steps Λ and B were transferred to an ordinary stirred reaction vessel in how many people to obtain a 1.5: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymer-crimped polymerization product. The product thus formed was anisotropic-liquid crystalline (exhibited stirring opaque) and could be directly used to form into articles by spinning. or "pulling or the like. The resulting block polymer had the following structure:

Example 90

The procedure of Example 7 3 was essentially repeated. Rather than using monomers 1 and 2s in step B, equimolar amounts of monomer and 1a and 2 hours were polymerized at a comparable concentration and to a similar degree of reaction progress. The (partially completed) individual polymerization products (i.e. homo-oligomers I of steps A and B were transferred into a normal stirred reaction vessel in quantities to obtain a 1.5: 1 ratio. Dc polymerization of the resulting mixture Proceed to form a substantially polymerized polymeric chromatic product The product thus formed was anisotropic liquid crystalline (exhibited stir opalization) and could be directly used to form into articles by spinning or drawing etc. The resulting block polymer had the following structure:

Example 9I

The procedure of Example 73 was essentially repeated. Instead of using monomers 1a and 2ss in step B, equimolar amounts of monomers 1q and 2a were polymerized at a similar concentration and to a similar degree of reaction progression. The (partially completed) individual polymerization products (i.e., homo-oligomers) of steps Λ and B were transferred to a conventional stirred reaction vessel in amounts of 1.5: 1. The polymerization of the resulting mixture was allowed to proceed to form a highly polymerized risk polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited crystallization) and could become direct. used for shaping into objects by spinning. or pulling and the like. The resulting block polymer had the following structure:

Example 92

The procedure of Example 73 was essentially repeated. Instead of using monomer er 1a in step Λ, an equimolar amount of Ib was used.

Instead of using monomers 1a and 2ss in step B, equimolar amounts of monomer and 1b and 2ss were polymerized at a similar concentration and to a similar degree of reaction progression. The partially completed individual polymerization products (i.e. homo-oligomers) from steps Λ and 0 were transferred to an ordinary stirred reaction vessel in amounts to obtain a ratio of 1.5: 1. The polymeric risk of the resulting mixture was allowed to proceed to form a substantially polymerized bocopolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited agitator ring) and could be directly used to shape into objects by spinning or pulling or the like. The obtained b l-okpo I ymce r had the following structure:

Example 9 3

The procedure of Example 73 was essentially repeated. Instead of applying var, monomer er in step Λ, an equimolar amount of! B was used. Instead of using monomer 1a and 2s s in sta o B, equimolar amounts of monomer and 1b and 2 x x g c p o l yme were rised at a similar concentration and to a similar degree of reaction progression.

The (partially completed) individual polymerization products (i.e. homo-oligomers) from steps Λ and B were charged in a regular stirred reaction vessel in amounts to obtain a ratio of 2: 1. The polymerization of the resulting mixture allowed me to proceed to form a substantially polymerized vine. The product thus formed was anisotropic liquid crystalline (exhibited stir opalization) and could used directly for shaping into objects by spinning or pulling and the like. The resulting block polymer had the following structure:

Example

The procedure of Example 73 was essentially repeated. Instead of using monomer ia in step Λ, an equimolar amount of lb was used.

Instead of using monomer and 1a and 2ss in step B, equimolar amounts of monomers 1b and 2zz were polymerized at a similar concentration and to a similar degree of reaction progression.

The (partially completed) individual polymeric products (i.e., h omo i g ome rers) from steps A and B were transferred to an ordinary stirred reaction vessel in aliquots to give a 2: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized block polymerization product. The product thus formed was anisotropically smooth crystalline (C rudder opalization shown) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 93

The procedure of Example 27 was essentially repeated. Instead of using monomer 3a, a mixture of 80 mol% of monomer 3a and 20 mol% of monomer 3c was substantially dehydrochlorinated at a comparable weight percentage of ΡΡΛ with essentially similar content. After the addition of appropriate amount of P 2 O 2 (2 ° that the final content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 27 to provide a copolymer. sation product. The product thus formed was anisotropic liquid crystalline (exhibited stir-opalization) and could be directly used to form into articles by spinning, or drawing. The resulting copolymer had the following structure:

t

Example 97

The procedure of Example 27 was essentially repeated. Instead of using monomer 3a, a mixture of 80 mo.% Of monomer 3a and 20 mol.% Of monomer 3d was dehydrochlorinated in essentially a similar weight percent PPA with essentially similar P 2 O 2 content. After the addition of appropriate amount of P 2 O 3 (so that the final P 2 O 3 content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 27 to provide a copolymer -sation product. The product thus formed was anisotropic liquid crystalline (exhibited rudder opalization) and could be directly used to shape into articles by spinning, or drawing. The resulting copolymer had the following structure:

Example 97

The procedure of Example 27 was essentially repeated. Instead of using monomer 3a, a mixture of 80 mole% of monomer 3a and 20 mole% of monomer 3e was essentially dehydrated in a similar weight percent PPA content of essentially similar P 2 O 2 content. After the addition of appropriate amount of P 2 O 2 (so that the final P 2 content was increased to significantly above about 82%), the resulting mixture was then heated in essentially the same manner as in Example 27 to provide a copolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stirring opaque), highly pourable, and could be used directly to form objects by spinning, or pulling. The resulting copolymer was believed to have the following structure:

Example 98

The procedure of Example 7 3 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymeric risk products (i.e., homogeneous gums) of Examples 27 and 29 were transferred to a regular stirred reaction vessel in amounts to obtain a 2: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized block polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stir opalization) and could be used directly to form objects by spinning or pulling and the like. The resulting block polymer had the following structure:

Example 99

The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homo-oligomers) of Examples 27 and 30 in an ordinary stirred reaction vessel in amounts to obtain a ratio of 2: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization product. The product thus formed was anisotropically smooth crystalline (exhibited rudder opalization) and could be used directly to form objects by spinning or pulling or the like.

The resulting block polymer had the following structure:

EXAMPLE 100 ^ 3,4-Diaminobenzoic acid (3e) (Aldrich, 97%) was crystallized from hot water with 3- <fg charcoal and 0.5 g sodium ithionite added per every 30 g 3rd. The recovered light orange crystals were dried at room temperature under reduced pressure for 2 hours. An acidic mixture prepared from 183.5 g of 1.5% cn 78.6 g of 85.7% H 2 PO 3 (3.T. Baker analyzed reagent) was vented by heating in a three-necked flask at 100 ° C C for 2 hours under reduced pressure and then at 50 ° C under reduced pressure for 17 hours. 20.2 µg of 3c was added to a 500 ml resin kettle. The kettle was then vented by applying reduced pressure and then nitrogen fill three times. 51.11 g of the above-mentioned PPA was added to the kettle and the contents were stirred until good mixing was achieved. 38.77 g of Ρ2 ^ T. Baker analyzed reagent, 99.1%) was added. The temperature of the kettle was raised to 100 ° C and the P2 * 5 added to the mixture. The following heating scheme was applied with color changes as noted: 100 ° C for 20 min .; 110 ° C for 20 min .; I 2 0 0 C for 20 min .; 130 ° C for 20 min .; changed from yellow brown to green; I 4 0 ° C for 2 0 min .; the green color darkened. Reduced pressure was exerted briefly, causing considerable foaming on the stroll; I 50 ° L for 20 min .; 160 ° C for 20 min. · A sample was removed and precipitated in water to give a red polygry substance with an intrinsic viscosity in Μ5Λ at 30.0 ° C of 4.25 dl / g · Heating at 160 ° C was continued for an additional 30 hours. The intrinsic viscosity in Μ5Λ at 30 ° C of po! The cream component of a sample removed at this time was 4.3 dl / g according to measurement. The reaction was heated at 175 ° C for an additional 33 hours. The resulting reddish brown polymeric material isolated from this solution had an intrinsic viscosity of 4.5 dl / g in methane sulfonic acid at 30.0 ^ 0. The final reaction product contained 16.8% of polymer / \ v7 in ΡΡΛ. Initial P2 ^ 5 content was 77.3%, final content was S2.2%.

Example 10 1

The procedure of Example 73 was essentially repeated. Following the initiation of polymerization and at a preselected range of intrinsic viscosity and at after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e. homomers) of Examples 27 and 100 were transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 2.5: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization polymerization product. The product thus formed was an anhydrous, flocculant crystalline (exhibited stirring grandpa ring) and could be used directly for shaping into articles by spinning or pulling or the like. The resulting polymer polymer had the following structure:

Example 102

The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction time, the (partially completed) individual polymerization products (i.e. homo-oligomer) of Examples 8 and 27 were transferred to an ordinary stirred reaction vessel in quantities to obtain a ratio of 1: 3. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stirring opalization) and could be used directly to form objects by spinning or pulling and the like. The resulting block polymer had the following structure:

Example 103

The worl <we? .C of example 73 was repeated in we z and. Omni cldc II i) k following the onset of polymer sage and at a predominantly selected range of intrinsic viscosity compounds after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization r that is, homogeneous omers of Examples 8 and 26 are transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 2: 1. The polymerization of the resultant mixture was allowed to proceed to form a substantially potted polymer in an okay polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited agitation opalization) and could be used directly for shaping into articles by spinning or drawing or the like. The resulting block polymer had the following structure:

Example 10 '4

The procedure of Example 73 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined emp empirical reaction rate, the (partially completed) individual polymerization products (ie homogeneous creams) were of Examples 13 and 27 were transferred to a conventional stirred reaction vessel in quantities to obtain a ratio of 1: 1. The polymerization of the resulting mixture was continued to produce a substantially polymeric acid product. molding, the product thus formed was anisotropic, liquid crystalline (exhibited stir-opalization) and could be used directly for molding into articles by spinning or pulling or the like. The resulting polymer had the following structure:

example 105

The procedure of Example 7 3 was essentially repeated. Following the initiation of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (ie (homo-igomers) of Examples 13 and 26 were transferred to a conventional stirred reaction vessel in amounts to obtain a ratio of 2: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization product. Anisotropic liquid crystalline (exhibited stirring opalization) and could be directly used to form into articles by spinning or pulling or the like. The resulting polymer was of the following structure:

Example 106

The procedure of Example 7 3 was essentially repeated. Following the initiation of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homomers) were exemplified. δ and 30 are transferred in a regular stirred reaction vessel in amounts to obtain a ratio of 1: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized bio-polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited agitation opalization) and could be used directly to form objects by spinning or pulling or the like. The resulting polymer was of the following structure:

For bee! D I 07

The procedure of Example 73 was repeated in wc7.cn. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected emp and reaction rate, the (partially completed) individual polymeric products (i.e., homomers) were of Examples 8 and 30 were transferred to an ordinary stirred reaction vessel in amounts to obtain a ratio of 3: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized bulk polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited agitation opalization) and could be used directly for casting into articles by spinning or pulling or the like. The resulting copolymer had the following structure:

For image I OS

The procedure of Example 73 was essentially repeated. Immediately after the start of polymerization and at a preselected range of intrinsic viscosity or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., oligomer and examples 13 and 30) were transferred to an ordinary stirred reaction vessel in quantities to obtain a ratio of Γ: 3. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized copolymerized product. product was anisotropic liquid crystalline (exhibited stirring opalization) and could be directly used to form into articles by spinning or pulling or the like. The resulting block polymer had the following structure:

i

Example 109

The procedure of Example 73 was essentially repeated. Following the initiation of polymerization at a preselected range of intrinsic viscosities oi after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homolymers} of Examples 13 and 30 were transferred in a conventional stirred reaction vessel in volume units to obtain a ratio of 1.3: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization product The product thus obtained was anisotropic liquid crystalline (exhibited stirring opalization) and could be directly used for molding into articles by spinning or pulling or the like The resulting block polymer had the following structure:

Example 110

The procedure of Example 73 was essentially repeated. Following initiation of polymerization at a preselected range of intrinsic viscosities oi after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homo-igomers) of Examples 8 and 100 were transferred to an ordinary stirred reaction vessel in quantities to obtain a ratio of 1.2: 1. The polymerization of the resulting mixture was allowed to proceed to form a highly polymerized pelletization polymerization product. The product thus formed was anotropically crystalline (exhibited crystallization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following structure:

Example 111

The procedure of Example 7 3 was essentially repeated. Following the initiation of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymeric risk products (i.e., homogeneous polymers) of Examples 13 and 100 transferred into a regular stirred reaction vessel in quantities to obtain a ratio of 1.3: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization polymerization product. The product thus formed was anisotropic liquid crystalline (exhibited crystallization) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymer had the following effect. structure:

Example 112

The procedure of Example 73 was essentially repeated. Following the initiation of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., homomers) of Examples 28 and 100 transferred into a regular stirred reaction vessel in amounts to obtain a 2: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized bulk polymerization product. The product thus formed was anisotropically-flocatable crystalline (exhibited rudder opalization) and could be directly used to form into articles by spinning or drawing (etc.) The resulting block polymer had the following structure:

Example! DM3 *

The procedure of Example 73 was essentially repeated. Immediately following the onset of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e., h-oligomer and) of Examples 19 and 27 were transferred to a regular stirred reaction vessel in amounts to obtain a 1: 1 ratio. The polymerization of the resulting mixture was allowed to proceed to produce a substantially polymerized biopolymerization product. The product thus formed was anisotropic liquid crystalline (exhibited stir-opalization) and could be used directly to form objects by spinning or pulling or the like. The polymer block obtained had the following structure:

Example 114

The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (partially completed) individual polymerization products (i.e. homomigomers) of Examples 23 and 27 were transferred in an ordinary stirred reaction vessel in amounts to obtain a ratio of 1: 1. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized blocpolymerization product. The product thus formed was anisotropic, liquid crystalline (exhibited stirring opacity) and could be used directly to form objects by spinning or pulling or the like. The resulting block polymeci had the following structure:

Example 115

The procedure of Example 73 was essentially repeated. Immediately following the start of polymerization and at a preselected range of intrinsic viscosities or after a predetermined selected temperature and reaction rate, the (fully completed) individual polymerization products (i.e., homomers) ) of Examples 22 and 27 transferred to a regular stirred reaction vessel in amounts to obtain a ratio of 1: 2. The polymerization of the resulting mixture was allowed to proceed to form a substantially polymerized polymerization polymerization product. The product thus formed was amsotropic liquid crystalline (showed stir opalization) there. could be directly used to form into vocyr throw by spinning or pulling or the like. The resulting block polymer had the following structure:

As indicated in the above examples, the compositions of the invention are here batchwise but more continuous methods can be used.

Certain process and product advantages due to better control of certain process parameters such as shear and temperature in a continuous process are: (1) a more homogeneous reaction product of a much higher order of mix size; (2) higher throughput; (3) and improved economic operations.

Another advantage of continuous processing is that the resulting reaction products can be mixed in essentially all portions with other reaction products of different polymers and / or r a c t i e p r o d u k t e · b i; different stages of reaction.

In a continuous process, the aforementioned dehydration solution's tap of "stage i" and monomer - addition of "stage two" is run at a temperature not to exceed about 100 ° C in an I preferred is reactor var. the type described in example 116. "Stage three" of the invention can be performed in a motionless (static) mixer. Such mixers for pasta e-sea: viscous materials are described in "Chemical Engineers' Handbook", R.H. Perry et al., McGraw-Hill Kogakusha, LTD., International Student Edition, pp. 19-24 (197 3); "Fluid Mixing Technology", from James Y, Oldshue, McC'aw-Hill Publishing Company, pp. 43I-43S, (I9S3); and Cr: ut et al., U.S. Patent No. 3S00.9S5. These publications and patent are incorporated herein by reference. The reaction stage I of "stage two" is fed from an outlet of the charge pointer reactor by a constant displacement pump "to a static mixer (tubular reactor), preferably of the type described in U.S. Pat. No. 3S00.9S5 where the first mixture Element is heated at a temperature between about 140 ° C and about IS5 ° C. The second and subsequent intermixing elements are heated at temperatures between about 160 ° C and about 200 ° C.

The latter mixtures are heated at temperatures between about 50 ° C and about 200 ° C depending on the desired temperature chosen for spinning of just used particular extended chain polymer.

In order to avoid interruptions in the continuous process, two or more charge-type reactors (carrying out "stage one" and "stage two") are connected to the static mixer (tubular reactor) in parallel to provide said tubular reactor in time sequence to feed. Preferably, stage one and stage two can be run in an empty batch reactor without the need for cleaning. The primary requirement of the tubular reactor is a function of the size and number of the batch reactor series, the desired (mixing elements) residence time, and the desired flow rate.

Such a continuous process is particularly suitable for the preparation of the polymers of the present invention. Block copolymers can be made by mixing a second reaction mixture after the first reaction mixture has been passed through an intermediate number of mixing elements.

A very important aspect of the continuous process and further for the batch process to be emphasized is that "stage one", "stage two", and "stage three" of the invention must be performed within the shaded phosphorus pentoxide content. teprofie lopperv lacquer limited by ABCDEFC.Hi of fig. 1. This has not been brought about by the state of the art.

Appendix

GENERAL STRUCTURE REFERENCE 1E

Claims (10)

Copolymer or block copolymer, containing repeating units, represented by one of the formulas:

wherein Ar * -, Ar ^, Ar ^, Ar ^, Ar ^ and Ar are aromatic organic groups, respectively, and X2 are the same or different and sulfur, oxygen or NR (where R is hydrogen or an organic group), Y ^ is a bivalent organic radical, is an octavalent organic group, (ajbj m / m + m '), (¾ m' / m + m '), and a-j_bj represent the molar ratios of the respective different repeating units, present in their respective copolymers, and greater than 0 and less than 1, Y ^ and Y ^ represents an average number of the successive repeating units present in their respective copolymers, and n is a positive integer, characterized in that Ar1 is represented by one of the formulas:

Ar ^ is represented by one of the formulas

Ar4 is represented by one of the formulas

Ar5 is represented by the formula:

Ar ^ is represented by one of the formulas

Ar5 is represented by the formula

Y2 is represented by one of the formulas:

η Υ is represented by the formula

and that the average total number of repeating units in the copolymer is at least 50. Baptismal solution comprising a solution of polyphosphoric acid (acids) and at least one polymer or randomly distributed sequential or block copolymer according to claim 1, characterized in that the polymer or copolymer has a molecular weight and concentration such that the doping solution has a liquid crystal region and if the polymer consists of repeating units represented by the formula

then the concentration of polymer solution is at least 12 wt. % and the intrinsic viscosity of the polymer is at least 12 dl / g in methanesulfonic acid at 30 ° C. Baptismal solution according to claim 2, characterized in that the baptismal solution contains a polymer according to claim 1, wherein Ar 1 is one of

Y2 is represented by one of

which polymer has a molecular weight and concentration such that the doping solution has a liquid crystal region and, if the copolymer consists of repeating units, represented by the formula

7 then the concentration of polymer in solution is at least 12 wt. % and the intrinsic viscosity of the polymer is at least 12 dl / g in methanesulfonic acid at 30 °. Baptismal solution according to claim 2 or 3, characterized in that the concentration of polymer or copolymer in baptismal solution is at least 10%. Baptismal solution according to any one of claims 2 to 4, characterized in that each of X 1 and X 2 are oxygen. Baptismal solution according to any one of claims 2 to 4, characterized in that each of X 1 and X 2 are sulfur. Fiber containing a polymer according to claim 1, characterized in that Ar · * · is one of

has been suggested by one of

and that the fiber has a breaking strength of at least 3.12 GPa. Fiber according to claim 7, characterized in that it has an elongation modulus of at least 303 GPa. A method comprising the step of making polymer is there and of at least one first monomer represented by one of the following formulas:

and at least a second monomer represented by one of the following formulas:

in a solution of polyphosphoric acids, characterized in that the phosphoric acids have on average at least 82 wt. % P2O5, and that the concentration of monomers is such that the doping solution, resulting from the polymerization, is at least 10 wt. % polymer or copolymer with an average of at least 50 repeating units. 10. Process according to claim 9, characterized in that the polymerization is carried out at a temperature between 100 ° C and 210 ° C.