CA1259736A - Liquid crystalline poly (2,6-benzothiazole) compositions, process, and products - Google Patents

Abstract

A B S T R A C T

Novel compositions comprising a high concentra-tion of poly(2,.beta.-benzothiazole) and certain polyphosphoric acids are prepared. Such composi-tions are optically anisotropic (liquid crystal-line), capable of exhibiting excellent cohesive strength, and are especially suited to the pro-duction of high molecular weight ordered polymer fibers by dry-jet wet spinning. These liquid crystalline compositions are capable of being drain through long air gap distances and spun at exceptionally high spin draw ratios. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

Description

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LIQUID C~YSTALLINE POLY(2,6-BENZOTHIAZOLE) C~MPOSITIONS, PROCESS, AND PRODUCTS

Technical Field of Invention .
The present invention relates broadly to novel anisotropic (liquid-crystalline) extended chain polymer-polyphosphric acid comPositions, to the production of high molecular weight extended chain polymers by polycondensation of selected monomers in certain polyphosphoric acids, and especially to the production of highly concentrated Poly(2,6-benzothiazole) compositions from which indus-trially useful polymeric articles such as fibers, fibrids, films and the like are readily produced. The instant invention also relates to the preparation of such polymers -and polymer-polyphosphoric acid compositions under con-di~ions to exercise control of molecular weight (characteri~ed by intrinsic viscosity).
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Among some of the most serious difficulties encountered in the production of thermally stable articles such as fibers and films from extended chain polymers are described in the Background Art below.

Back~round of Invention 1. Ori~in of Invention .

This invenkion was made with Government support under U.S. Department of Defense contract Nos. F33615-81-K-5070, F49620-81-K-0003, and/or F33615-82-C-5079 awarded by the Uni~ed States Air Force. The Government has certain rights in this invention.

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2. Reference to ~eLat~d A~lication~

Reference 18 made to other co-pending PCT International ~n~
corresponding United States patent applications all as-signed to SRI International and havlng as one of their inventors, James F. Wolfe. Said other PCT applicatlonsi are entitled:
"Liquid Crystalline Poly(2,6-benzothiaz~le) Compositions, Process, and Products", No. PCT/US82/01286, publication No.
W084/01161; "Liquid Crystalline Polymer Compositions, Process, and Products" 7 No. PCT/US82/01285, publi~ation No.
W084/01160; "Liquid Crystalline Polymèr Compositions, Process, and Products", No. PCT/US83/01437, publication No.
~084/01162; and "Liquid Crystalline Polymer Compositions, Process, and Products", No. PCT/US85/00258.

3 .~ ackground_Pur~
In general, the class of aromatic heterocyclic extended chain polymers are well known for their outstanding thermal, physical, and chemical pro-perties. Unfortunately, these polymers are essentially non-melting and have proven very di~-ficult to economically proc~ss into articles. In order to fashion such polymers into desired arti-cles of commerce, for ~xample ~ibers, films, fibrids, and the like, 1t is necessary that they be in solution or dope form. Although such poly-mers can be dissolved in various acidic sol~ents, -~
such as sulfuric acid, methanesulfonic acid, ~-chlorosulfonic acid, polyphosphoric acid, and the like, difficulty is often experienced in prepar-ing and using the polymer-acid compositions or dopes because of poor polymer-acid ~olubility.

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Normally, a precipitated or dried particulate form of the polymer is dissolved in a strong acidic solvent by mixing the (isolated) polymer particles at elevated tempera~ures and/or under high pressures for a period from several hours to several days. If the polymer is insoluble in the particular solvent, other s~lven~s or various solvent mixtures are employed. Usually heating and cooling cycles are applied and repeated to obtain a useful dope.
The resulting dopes often contain undissolved polymer and must be filtered before further pro-cessing into articles.

Although spinning dopes of poly([benzo(1,2-d:5,4-d')-bisoxazole-2,6-diyl~-1,4-phenylene)(PB0) and polyt[benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene)(PBT) in sulfuric acid and/or methanesulfonic acid and/or chlorosulfonic acid with polymer concentrations above about 10% are known in the art, the intrinsic viscosity of these polymers is for the most part below 5dL/g and oftentimes less than 3dL/g. Prior to the present invention, PB0 and PBT were not art-recognized equivalents from the standpoint of synthesis, attainable molecular weight, solution proc~ssing, fiber spinning, physicsl properties, etc. With respect to PB0 attempts by those skilled in the art to synthesize and form high molecular weight, high strength PB0 fibers (see Choe U.S. patent No. 4,423,202) resulted in failure. The cohesive strength of prior art PB0 dopes is inherently weak and economically less desirable for use in dry-jet wet spinning. In the case of PB0 numerous attempts of dry-jet wet spinnlng an approximately 10%
polymer/methane sulfonic acid-dope into fibers were not successful (E. W. Choe, et al., in Macromolecules 1981, 14, pp 920-924). It was recommended by those skilled in the art i,' ', ' ' . ' . ' ., ", . . ' ' '' ~.. , ' ' ' ' ' ', ~ . ' . . . .

~2~ 3~g that further effort on the formation of oriented, thermally stable polymers be directed toward PBT and away from PB0.
PB0 was acknowledged to have a "fatal flaw" (Wolfe et al., in Macromolecules 1981 Rigid-Rod Polymers 2', 14, pp 915-920).

Choe's recitation (in his patent U.S. No. 4,423,202) associating a molecular weight "of at least approximately 10,000, e.g, within the range of approximately 10,000 to 30,000 molecular weight" to PB0 is clearly erroneous. It is well known in the art (in Macromolecules 1981, 14, 930-934 by D. B. Cotts et al) that the intrinsic viscosity can be used to determine number average molecular weight. Since inherent viscosity is not dependent upon concentration for PB0 molecular weights below 10,000, inherent viscosity can be used to approximate the intrinsic viscosity. Choe's highest disclosed PB0 inherent viscosity corresponds to about 9,500 number average molecular weight while his lowest inherent viscosity is about 6,700 number average molecular weight. The highest PB0 viscosity disclosed in Choe's patent is 3.88 dL/g. This value is the highest mentioned in his Macromolecules article. Clearly, Choe is erroneous in stating that PB0 " ...having a number average molecular weight of at least approximately 10,000 which exhibits an inherent viscosity of at least approximately 2.0 dl/g... ".
All evidence points to Choe's having mistaken the molecular weight of PBT for that of PB0. Choe 202 patent does not disclose or suggest a liquid crystalline PB0/PPA dope. He clearly does not disclose high molecular weight PB0. Choe is not concerned with liquid crystalline PB0/PPA dope, but rather, he teaches preparation of PB0 dope by dissolving precipitated PB0 in MSA and CSA. Although Choe describes the synthesis of PB0 directly in PPA from diaminoresorcinol and terephthaloyl dlchloride, the resultant PB0/PPA product is isotropic and contains low molecular weight PB0.

` ~5~73~i In the case of polybenzimidazole, prior art dopes of this polymer lack adequate strength to main-tain filament integrity while dropping through the air-gap. In order to overcome this problem U. S. Patent No. 4,263,245 teaches dissolving a high concentration (up to 30%) of this polymer into suitable solvents such as concentrated sul-furic acid. At such high polymer concentrations lithium chloride is required to prevent the poly-benzimidazole from phasing out of solution.
In the case of polybenzobisthiazole, U. S. Patent No. 4,225,700 teaches the formation of a liquid crystalline composition of this polymer at con-centrations near 10% in methane sulfonic acid and chlorosulfonic acid and at about 6% in polyphos-phoric acid. Concentrations of polybenzobisthia-zole in polyphosphoric acid above about 10% by weight are difficult, if indeed possible to achieve. One difficulty encountlered is that the solution of the 2,5-diamino-1,4-benzenedithiol monomer in polyphosphoric acid with the P205 con-tent described in U. S. Patent INo . 4,225,700 is very viscous and dehydrohalogenation is diffi-cult. Also considerable foaming results.
Although solutions of precipitated polymer in sol~ents such as methané sulfonic acid and chlorosulfonic acid can be prepared, high concen-trations of polymer are difficult or impossible to achieve. S. R. Allen, et al., in Macromolecules 1981, 14, pp. 1135-1139 describes attempts at spinning polybenzobisthiazole directly from the polymerization medium (polyphosphoric acid) containing ~-6% polymer.

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3~i Insvfar as polybenzobisthiazole is concerned it is possible to obtain compositions near to 10% of the polymer in polyphosphoric acid with intrinsic viscosity equal to 26dL/g (J. F. Wolfe, et al., Macromolecules 1981, 14, pp. 915-920). High molecular weight, low concentration PBT dopes were known in the art.
Low molecular weight, high concentration PBT/PPA dopes were known in the art. Prior to Applicants' invention, high concentration and high molecular weight PBT/PPA spinning dopes were unknown in the art. High molecular weight PBT/PPA spinning dopes containing 10~ or greater solids were unknown in the art. High molecular weight PBT could only be synthesized at low solids level, i.e., at less than 10%.
Liquid crystalline compositions of PBT having intrinsic viscosities greater than 30.3dL/g in PPA are heretofore unknown in the art. Attempts by those skilled in the art to synthesize high solids concentration PBT/PPA dopes resulted in low molecular weight PBT.

The flexible coil-like polymer: poly-2,5(6)benzimidazole (ABPBI) is known in the art (see Wereta, et al., Society of Polymer Engineering 1975, Technical paper, 21, pp. 618-620;
~ereta, et al., Polymer Engineering and Science, February, 1978, Vol. 18, No. 3, pp. 204-209; Helminiak, et al., U.S.
Patent No. 4,207,407, June 10, 1980; Wellman, et al., Organic Coatings and Plastic6 Chemistry, August 1980, Vol 43, pp. 783-787; and Bulletin of the Americal Physical Society, 1981, Vol. 26, No. 3, page 430). As reported in the art, ABPBI (in solution) assumes a flexible coil conformation which provides an entangled, highly elastic (flexible coil) matrix for entrapping rigid rod molecules such as PBT. As described by Wereta, et al., ABPBI has a tendency to aggregate and is not chain-extended because the films have a prior history of dilute solution in which the chains became entangled. The "crystallites' described by 6 :

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Wereta, et al., are composed of stacked benze~e rings giving rise to a single meridional reflection rather than multiple reflections expected for a chain extended polymer. Unlike the flexible coil conformation or aggregate morphology of the prior art, the poly-2,5(6)benzimidazole of applicants' invention is an extended ~hain crystalline polymer, a polymer substantially ~ree of a~orphous regions. `~

In general, liquid crystalline exte~ded chain polymer compositions (with the exception of poly-benzobisthiazole as mentioned above) in polyphos-phoric acid are heretofore unknown in the art; ..
and moreover, liquid crystalline extended chain copolymer and block polymer compositions are heretofore unknown in the art. Furthermore, the preparation of anisotropic extended chain polymer-polyphosphoric acid compositions having :
high polymer content and under conditions to exercise control of molecular weight is hereto-fore unknown in the art.

In practical terms this means that prior art dopes are severely limited in their potential usefulness for the production of highly ordered high molecular waight polymeric articles. The prior art dopes may be less desirable for maXing articles of uniform quality and reproduciibility which must require polymers with the highest molecular weight a~tainable or a selected lower molecular weight for maintaining dope processa-bility or other difficult to control parame~ers.

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Disclosure of In~gn~iQn 1. Objec~s of Invention Accordingly, it is an object of the present invention to provide compositions substantially free of one or more of the disadvantages of prior art compositions.
Another object is to provide a process for preparing liquid crystalline extended chain poly-mer compositions.
A further object is to provide liquid crystalline extended chain polymer compositions having excel-lent cohesive strength.
Another object is to provide liquid crystalline extended chain polymer compositions having excel-lent spin stretchability.
Another object is to provids liquid crystalline extended chain polymer compositions capable of being drawn through long air gap distances.
Yet another object is to provide liquid crystal-line extended chain polymer compositions capable of being drawn at high spin draw ratios.
A further object of the invention is to prepare a liquid crystalline spinning composition having a high extended chain polymer content.
A still further object is to provide liquid cry-stalline extended chain homopolymer compositions.
Another ob~ect is to provlde liquid crystalline extended chain homopolymer compositions which homopolymers are substantially free of amorphous regions.

Another object is to provide liquid crystalline extended chain copolymer compositions.
Yet another object is to provide liquid crystal-line extended chain block polymer comp~sitions.
Another object of the invention is to provide a method of preparing a liquid crystalline polymer composition having a high polymer content of an extended chain homopolymer.
Another object of the invention is to provide a -method of preparing a liquid crystalline polymer composition having a high polymer content of an extended chain copolymer.
Another object of the invention is to provide a method of preparing a liquid crystalline polymer composition having a high polymer content of an extended chain block polymer.
Another object of the invention is to provide a method of preparing liquid crystalline extended chain polymer compositions from selected mono-mers.
Another object is to provide a process for preparing liquid crystalline high molecular weight extended chain polymer compositions.
A further object of the invention is to provide a method for synthesizing high molecular weight extended chain homopolymers.

Another ob~ect of the invention is to provide a method for synthesizing high molecular weight extended chain homopolymers which are substantially free of amorphous regions, .,~ . :

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A further object of the invention is to provide a method for synthesizing high molecular weight extended chain copolymers.
A further object of the invention is to provide a method for synthesizing high molecular weight extended chain block polymers.
A still further object to provide a method whereby the dehydrohalogenation of certain hydrohalide monomers may be carried out more easily and rapidly.
Yet another object is to provide a method whereby a substantially higher concentration of monomeric reactants can be employed which results in liquid crystalline extended chain polymer compositions of considerably higher polymer concentration than has been possible heretofore.
Another object is to alleviate the foaming prob-lem referred to above.
Another object is to provide articles prepared from liquid crystalline extended chain polymer compositions.

A further object of the invention is to prepare articles such as fibers and films from a liquid crystalline polymer composition comprising selected extended chain homopolymers.
Another object of the lnvention is to prepare articles such as fibers and films from a liquid crystalline polymer composition comprising selected extended chain homopolymers which are substantially free of amorphorus regions.

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A further o~ject o~ the invention is to prepare articles such as fibers and films from a liquid crystalline polymer composition comprising selected extended chain copolymers.
A further object of the invention is to prepare articles such as fibers and films from a liquid crystalline polymer composition comprising selected extended chain block polymers.
Yet another object is to provide a process for preparing liquid crystalline extended chain poly-mers compositions under conditions to exercise control of molecular weight (characterized by intrinsic viscosity) so as to obtain a molecular weight less than the maximum attainable.
Another object is to provide a process for preparing liquid crystalline extended chain homo-polymer, copolymer, or block polymer compositions under conditlons to excercise control of molecu-lar weight (characterized by intrinsic viscosity) so as to obtain a molecular weight less than the maximum attainable.

A still further object is to provide a process for preparing a liquid crystalline polymer compo-sition having a high polymer content of an extended chain homopolymer, copolymer, or blocX
polymer under conditions to exercise control of molecular weight (characterized by intrinsic viscosity) so as to obtain a molecular weight less than the maximum attainable.

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, Another object of the invention is to provide a process for the continuous production of extended chain homopolymer, copolymer, and block polymer articles such as fibers and films starting with selected monomers.
Anoth~r object ~f the lnvention is to provide a process for the c~ntinuous production of extended chain homopolymer, copolymer, ~nd block polymer articles ~uch aæ fibers and films starting with selected monomers.
The above and other objects of the invention will be apparent from the ensuing description and the appended claims.

. Statement of Invention In accordance with our discovery, thei present invention broadly encompasses novel polymer com-positions which are useful as dopes in the pro-duction of high strength shaped articles compris-ing blends of certain polyphosphoric acids, as described hereinafter, and a high concentration of one or more high molecular weight extended chain polymers having one or more mesogenic group or groups. The extended chain polymers can be homopolymers, copolymers, or block polymers, as exemplified hereinafter. The extended chain polymer is present in the blend at a sufficient concentration so as to be capable of exhibiting an anisotropic polymer phase alone or in combina- .
tion with one or more different polymers with or : 12 ~ ~ S ~ ~ 3 ~

without mesogenic group or groups. The blends according to the invention are polycondensation products obtained by reaction of selected mono-mers in an appropriate solution of phosphoric acid, as described hereinafter. Optionally, the reaction can be carried out under condition~ to exercise control of molecular weight (characterized by intrinsic viscosity).
Suitable control of ~olecular weight is accomplished by disco~tinuing the condensation at a desired degree of polymerization; the extended chain polymer molecular weight of such blends can be further adjusted on heating. Alternatively, molecular weight control or ~stabilization" can be accomplished by off balancing the stoichiometric proportion of monomers (i.e., adding a selected excess amount of one bifunctional reactant AA or BB) at a selected stage of condensation. Most preferably, molecular weight control (i.e., molecular weight ~stabili-zation" can be accomplished by the addition of one or more suitable monofunctional reactants in selected amounts and at a selected stage of con-densation. These methods of achieving molecular weight control are further described hereinafter.
The blends of the invention exhibit special pro-perties which make them very useful as dopes in the production of fibers, films, fibrids, and the like. In addition to being anisotropic (liquid-crystalline), the blends have a novel combination of properties including unexpectedly high spin-stretchability and excellent cohesive strength, as well as having the capability of being drawn through short, as well as extremely long, air-gap distances, and spun at lo~, as well as exception-- .

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ally high, draw ratios. It is believed ~hat these properties can be attributed to the combi-nation of high polymer c~ncentration, substan-tially high polymer m~lecular weight, and a high phosphorus pentoxide content comprising the bl6nds of the present in~ntio~.
The invention further pro~ides a process for prepari~g an extended chain polymer composition of workable viscosity which is usieful as a dope in the production of fibers :-and films, said composition comprising liquid crystalline poly(~,6-benzothlazole), said'proc~ss comprises the following steps~

(a) s~xing a selected monomer wlth or without oxidatlo~ :
prot2cting atom~ or groups ~ith 8 prellmlnary solvent of phosphoric ~cld havlng i~ relatively low pho6phorus pentoxide :~
content, (b) heatlng and optlonally placl~g the resultlng mixture under reduced pressure to remove any ~volatillzed protecslng atom~
or groups p~esent and provlde a solut:lon of the monomer ln the prellmlnary ~olvent, (c) then lncrea~lng the phosphorus peDtoxlde ~ontent of the mlxturé r~sultlng from 8tep (b) by addlng pho~phorus pentoxlde in two or more portionR to provlde A monomer reaction medlum of .
greater pho~phorus pentoxlde content ~ultsble for polymerlzatlon, (d) causl~g polymerlzatlon of ths monomer at ~ temperature ~ufflcient to effect reactlon at ~ rate to form a homo-ollgomerlc ~product havl~g a pre6eleceet lntrlnslc vi8c08ity or a homopolymer~c product.

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Our discovery further broadly encompasses a pro-cess for preparing noYel liquid crystalline extended chain polymer compositions which are useful as dopes in the production of fibers, ~ibrids, films, and the like. This process comprises:
(a) mixing at least one of a selected first monomer (as deæcribed hereinafter) with or ~ithou~ oxidatlon protecting atoms or groups with a preliminary solvent Or phosphoric acid having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a first mixture of the first monomer in the prelimlnary solvent, (c) adding at least one of a ~elected second monomer (as described hereinafter) in the result~
ing mixture of s~.ep tb) to provide a first mix-ture of the first and 6econd monomer in the prel-iminary solvent, (d) then increasing the phosphorus pentoxide content o~ the mixture resulting from step (b) or (c) to provide a first or a first and second monomer reactio~ medium of greater phosphorus pentoxide content 6uitable for polymerization, 14(a) . ~

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(e~ causing polymerization of the first or the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product or a first co-oligomeric product having a preselected intrinsicviscosity, or (f) causing polymerization of 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 copolym-eric product, (g) mixing a selected amount of the first homo-oligomeric product with a selected amount of at least one of a selected second homo-oligomeric product so as to form a first poly-oligomeric product, ~he second homo-oligomeric product being formed by like steps (a) and (b) follo~ed by:
(lg) adding at least one of a selected second monomer in the resulting mixture of step (b) to provide a mixture of a first and second monomer in the preliminary solvent, (2g~ then increasing the phosphorus pentox-ide content o~ the mixture resulting from step (b) or (lg) to provide a first or a first and : 15 59~

second monomer reaction medium of greater phos-phorus pentoxide content suitable for polymeriza-tion, (3g) causing polymerization of the first or first and second monomer at a temperature suffi-cient to effect reaction at a rate to form the second homo-oligomeric product having a preselected intrinsic viscosity, with the overall proviso that at least one of the selected monomers of step (a) or (lg) which forms the second homo-oligomeric product be different from at least one of the selected mono-mers of step (a) or (c) which forms the first homo-oligomeric product, 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 a selected first monomers or a first and second monomer in the preliminary solvent so as to form a monomer-oligomer mixture, and then increasing the phos-phorus pentoxide content of the monomer-oligomer mixture to provide a monomer-oligomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, the first monomer of the second mixture being formed by like steps (a) ~L25g ,f,3~i and (b) and the first and ~econd monomer of the second mixture being formed by like steps (a), (b) and (c), with the overall proviso that at least one of the selected monomers of step (a) or (c) which forms the first or first and second monomer of the second mixture, be different from at least one of the æelected monomers of step (a) or (c) which forms the first homo-oligomeric pro-duct, (i) causing polymerization of the poly-oligomeric product resulting from step (g) or the monomer-oligomer resulting from step (h) at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first block-polymeric product, (j) spinning, drawing, extruding, or casting an article from said first homo-oligomeric pro-duct, said first co-oligomeric product, said first homopolymeric product, said first copolym-eric product, said first poly-oligomeric product, said second homo-oligomeric product, said first block-oligomeric product, said first block-polymeric product, or mixtures thereof. In another embodiment o~ the invention, the molecu-lar weight (characterized by intrinsic viscosity) ~L259t~3~;

of 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, said first block-oligomeric product, and said firæt block-polymeric product is controlled by discontinuing steps (e), (f), (3g), and (i) (which forms said respective pro-ducts) at an early stage of reaction so as to achieve a preselected low intrinsic viscosity or said steps are continued at a temperature suffi-cient to effect further reaction to obtain a preselected higher intrinsic viscosity or further heating said products to achiev~ an intrinsic ~iscosity closer to the maximum attainable.
In yet a further embodiment of the invention, the molecular weight (characterized by intrinsic viscosity) of those said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolym-eric product, said first poly-oligomeric product, said second homo-oligomeric product, said first block-oligomeric product, and said first block-polymeric product whicb are formed by the respec-tive reaction steps (e), (f), (3g), and (i)involving ths reaction of a æelected first and ;.

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second monomer is controlled by adding a selected excess molar amount of said selected second mono-mer or more preferably a selected excess molar amount of said selected first monomer or allowing the loss of a small proportion of said selscted first or said selected second monomer during said polymerization steps thereby off-balancing the stoichiometry of the monomers to obtain a desired intrinsic viscosity value less than the maximum attainable.
In still another embodiment of the invention, the molecular weight (characterized by intrinsic viscosity~ of 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, said first block-oligomeric product, and said first block-polymeric product is controlled by adding one or more selected monofunctional reactants (as described hereinafter) having a single functional group in steps (a), (b), (c), and (lg) to achie~e an intrinsic viscosity value less than the max-imum attainable.
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2a. Figures The invention will be more fully explained with reference to the Figures wherin:
Figure 1. graphically illustrates the weight stability of ag spun polymer fibers of ~BI~n ~Example 13) and ~AI~n (Example 12) with time during isothermal aging in circulating air at 371C;
Figure 2. graphically illustrates the weight stability of precipitated polymers oE ~V3n (Exam-ple 120) and ~T~n (Example 27) with time during isothermal aging in circulating air at 371 C;
Figure 2a. graphically illustrates the weight stability by TGA of block copolymers AI-AN~
(Example 74) and AI-AGN (Example 73) with tem-perature in air at a heating rate oE 371C per minute;
Figure 3. graphically illustrates the weight stability by TGA of polymers ~T~n ~Example 27) and ~V~n (Example 120) with temperature in helium at a heating rate of 5C per minute;
Figure 4. graphically illustrates the weight stability by TGA of polymers ~BI~n (Example 13) ,, .:

and ~AI3dnu (Example 12) with temperature in helium at a heating rate of 5C per minute;
Figure i5. graphically illustrates the weight stability by TGA of polymers ~T~n (Example 27) and ~V~dnu (Example 120) with temperature in air at a heating rate of 5C per minute;
Figure 6. graphically illustrates the weight stability by TGA of polymeræ ~BI~n (Example 13) and ~AI~dnu (Example 12) with temperature in air at a heating rate of SC per minute;
Figure 7. graphically illustrates the relation-ship of amount of useable PPA and % P205 content required to achieve f of 0.822 for selected poly-mer concentrations Pc (plot of equation a*) show-ing a region (shaded dash area) of poor solubil-ity for monomer la;
Figure 8. graphically illustrates the % P205 content profile for a 14.8 wt% ~AI~n polymeriza-tion (Example 2) showing the limits of achievable molecular weight when starting with a high P205 content preliminary solvent, Figure 9. graphically illustrates the % P205 ~ .
content profile for a 8.~ wt% ~T~n polymerization showing the limits of achievable degree of . . ~1 ;

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polymerization when starting with a high P205 content preliminary solvent;
Figure 10. graphically illustrates a typical %
P205 content profile for a 14.5 wt% ~AI~n poly-merization (Example 12) showing the advantages ofthe invention when starting with a low P205 con-tent preliminary solvent followed by an increase of P205 content at the start o~ polymerization;
Eigure 11. graphically illustrates a typical %
P205 content profile for a 14.5 wt% ~AI~n poly-merization (Example 12) showing the advantages of the inven~ion when starting with a low P205 con-tent preliminary solvent followed by an increa~e of P205 content at the start of polymerization;
Figure 12. graphically illustrates a typical % :
P205 content profile for a 20.3 wt% ~T~n polymer-i~ation (Example 27) showing th~ advantages of ` .
the invention when starting with a low P205 con-tent preliminary solvent followed by an increase .
of P205 content at the start of polymerization;
Figure 13. graphically illustrates a typical % ~ :`
P205 content pro~ile for a 16.87 wt% ~V~n poly- ~ :
merization (Example 122) showing the advantages of the invention when starting with a low P205 .

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content preliminary solvent followed by an increase of P205 content at the start of polymer-ization;
Figure 14. is a % P205 profile diagram giving the profile area bounded by ABCDEFGHI- of % P205 for achieving the advantages of this invention.
Figure 15. graphically illustrates the intrinsic viscosity of the end-capped fA~ component of the reaction product as a function of polymerization time showing the advantage of the invention of obtaining a stabilized molecular weight after short polymerization time.

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~. Mode~s~ for Carrving Out the Invention The extended chain polymers of the compositions of the present invention are a class of polymers that can obtain a substantial degree of shape anisotropy in the liquid state due to restricted rotation of bonds in the polymer backbone and/or appropriate catenation geometry of rigid backbone segments. The degree of shape anisotropy is generally defined by the axial ratio>p/d, where pis the persistence length of the chain and d is the diameter of the chain. For extended chain polymers,p may be substantially the same as or greater than the contour length l of the polymer.
In the case of a rigid rod polymer,p is essentially infinite and the axial ratio is l/d.
By the method of the present in~ention, it is possible to prepare liquid crystalline compositions of extended chain homopolymers, copolymers, or block polymers containing 15 percent or more of polymer. As will appear, the invention is applicable to the preparation of liquid crystalline extended chain polymer compositionæ of lower polymer con~entration but there are special advantages to preparing compositions of high concentration.

i973~

Extended 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, capable of forming liquid crystalline compositions at low concentration (e.g., 5 - 10%), that is, if the critical concentration necessary for formation of the anisotropic phase is low, compositions of even higher polymer concentration can be spun to produce a better quality, higher strength fiber.
We believe this results, in part at least, from a more fully anisotropic composition and improved composition integrity. These improvements allow greater drawing in the air-gap, improve the coagulation characteristics, which leads to fewer flaws, and increase polymer throughput when a liquid crystalline composition i6 spun by a dry-jet-wet spinning technique into a polyphosphoric acid-solvent/polymer-nonsolvent such as methanol, water, or dilute aqueous acid(s).
If the polymer is one, such as poly (2,ô-benzothiazole) that is less rodlike in structure than polybenzobisthiazole or polybenzobisoxazole and thus possesses a critical concentration for t',.~ .
.~ ,;,1 .

: , ~ ~ . . ` ` `
~:: , ' ` ~ , ` ` , ~L2597~36 anisotropic phase formation greater than 10% and in the region of concentrations of this ~:
invention, extruding of these heretofore unattainable solutions produces a dramatic increase in strength and modulus because of the ordering of the polymer during this fabrication.
These advantages result in a more highly ordered, lower-defect fiber than results from spinning a less concentrated composition of polymers.
Another advantage of preparation of these polymers in the anisotropic phase is a considerable increase in the molecular weight of the polymer obtained.
In instances where extended chain polymers having a preselected low molecular weight, intermediate molecular weight, or ultra-high molecular weight (up to the maximum obtainable) a:re desired, the present invention is most advantageous. Extended chain polymers of essentially any desired moleculare weight (characterized by intrinsic ~iscosity) up to the maximum attainable my be prepared in the anisotropic phase without substantial difficulty in accordance with the practice of the invention.

1~:5~ 3~

In instances where the extended chain polymer molecular weight must be maintained at a level below the maximum ak~ainable, for example, if additional heating is necessary to effect storage and/or transfer of polymer dope from reactor to spinning lines or to carry out procedures such as filtering, degassing, and the like and that such heating will inducP further polymerization which may be undesirable, then preparation of such polymers in accordance with the practice of the invention is advantageous.
Preliminarily it is helpful to describe the chemistry of phosphoric acids and strong phosphoric acids or polyphosphoric acids as follows:
As used herein the term ~phosphoric acid(s)~
means commercial phosphoric acid(s) containing 85-86~ H3P04.
The strong phosphoric acids, or polyphosphoric acids referred to as PPA (polyphosphoric acid) are members of a continuous series of amorphous condensed phosphoric acid mixtures given by the :
formula Hn~2 Pn3n+1 . .~"~ .
., 27 ~25~

or H0 ~P03H~ H

where the value of n depends on the molar ratio ! of water to phosphorus pentoxide present.
Characterization and methods of forming various polyphosphoric acids and examples of such strong acids useful in accordance with the practice of :- .
the present invention can be found in the following papers: A. L. Hukti and P.A. Gartaganis ~The Composition of the Strong Phosphoric Acids,~
Can.J. Chem., Vol. 34, 195B pp. 785-797; and J.
E. Such, ~Linear Polyphosphoric Acids~, Mellar's Comprehensive Treatise on I~or~anic and Theoretical Chemistry, Vol VIII, Supplement III, pp. 726-753, Wiley 1971.
'.

In its most ge~eral definition, polyphosphoric acid composition can range ~rom distributions where the average value of n is less than unity, giving rise to a mobile liquid, to high values of n, ~here the polyphosphoric acid is a glass at normal temperatures. Because the species of polyphosphoric acid are in a mobile equilibrium, :.
.~ .

- 28 ~. ~
'''~'.-'`'"''`~"' . , .:

5~7~

a given equilibrium composition can be prepared in many ~ays. For instance, the same distribution or polyphosphoric acid composition could be prepared by either starting with concentrated orthophosphoric acid (H3P04, n = 1) and driving off water or by starting with phosphorus pentoxide (P205) and adding an appropriate amount of water.
All polyphosphoric acid compositions can be described as a ratio of P205 and water by reducing the various species present (on paper) to P205 and water. We will then use the con~ention that polyphosphoric acid composition lvill be expressed in terms of a P205 content (as a percentage) defined as P205 content weight ofP 0 2 5 x 100 weight fP205 + lveight ofH20 Thus, the P205 content o~ pure orthophosphoric acid could be derived by reducing one mole of H3P04 to 0.5 moles P205 ~ 1.5 ~oles H20 Converting to ~veights givles the P205 content as 0.5(142~
x 100 = 72.4%
0.5(142) ~ 1.5(18.01) , . . ~ .. . .... .. . . . . . ..

~25~3~

Similarly, the P205 content o commercial polyphosphoric acid can be derived in the following way. Polyphosphoric acid is available commercially in two grades, 105% and 115%. These percentages refer to H3P04 content, which means that lOOg of the two grades contain 105 and 115 grams of H3P04. The P205 content of 115%
polyphosphoric acid can then be calculated knowing the P205 content of 100% H3P04.
115(0.724) x 100 = 83.3%

Freshly prepared polyphosphoric acid as described by Wolfe and Loo U.S. Patent 4,225,700 employed 1.52 x g of P205 to x grams of 85.6% H3P04, thus the P205 content of that mixture is (1.52X) + (0.856) (0.724)X
:~ 100 = 84.9%
2.52X
Thus, polyphosphoric acid compositions, by our definition, equivalent to these three examples could be prepared in principle by starting with P205 and adding 27.~, 14.8, and 15.1% by weight of water.

~25~

Homopolymeric Compositions and their preparation In accordance with one aspect of the invention, there is provided a liquid-crystalline composition useful in the preparation of fibers and films comprising a polycondensation product consisting essentially of a blend of certain polyphosphoric acids and a high concentration of at least one extended chain homopolymer having a substantially stabilized molecular weight (characterized by intrinsic viscosity) said homopolymer having recurring units of the general formulas:

Xl ~ X ~ Y ~ I, ~herein Ar1 represen~s an aromatic ~oiety and is . , .. ... .. . . .. .. ...... . . . . ~ . . . . , , --~25~3~ :
XX as defined below, Xl and X2 are the same or different and are sulfur, oxygen, or NR ~R being hydrogen or an organic group), the nitrogen atoms and X1 and X2 being bonded to aromatic carbon atoms of Ar , N and X1 or X2 of each hetero ring are disposed ortho to one another and Y is nil or represents a bivalent organic radical and is XXI as defined below, n being a positive integer;

~ N ~ II, 10wherein Ar3 represents an aromatic moiety and is :.
XXII as defined below, X3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X3 being bonded to aromatic carbon atoms of Ar , N and X3 of each hetero ring :
15are disposed ortho to one another, n being a :

59~73~ --positive integer;
o \ ~ ~ 111 n wherein Ar1 represents an aromatic moiety and is XX as defined below, and Ar4 represents an aromatic moiety and i6 XXIII as defined below, the nitrogen atoms being bonded to aromatic carbon atoms of Ar1 and the carbon atoms being bonded to aromatic carbon atoms of Ar4, n being a positive integer;

~ ~/ ~ IV, ~herein Ar5 represents an aromatic moiety and is . ., i,. ,~, .

R --`

__ 59~
XXIV as defined below, the nitrogen atoms being bonded to Ar5, n being a positive integer;

~ X~X2~n wherein Ar6 represents an aromatic moiety and is XXV as defined below, Arl represents a different aromatic moiety and is XX as defined below, X1 and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X1 and X2 being bonded to aromatic carbon atoms of Ar and Ar , NH and X1 or X2 of each hetero ring are disposed ortho :. , , . . . . , . ~ .... . . . , :. ,, , . ., j, . .. .. . .. . . . . . . ... . .

r~

~2~

to one another, n being a positive integer;-.

_ ~ _ ` ~ ` X ~ ~n VI, wherein Ar9 represents an aromatic moiety and isXXVI as de$ined below, X4 is sul$ur, oxygen, or NR (R being hydrogen or an organic grouip), the NH
groups and X4 being bonded to aromatic carbon atoms of Ar9, ~ being a positive integer;
.

~N~

wherein Arl represents an aromatlc molety and i~
XXVII as defined belo~, Y7 represents an aromatic moiety and is XXVIII as defined .. . i . , ~ . . .. , .. ,.. ~ : ~

~59~

below, the nitrogen atoms being bonded to aromatic carbon atoms of Ar1 and bonded to adja-cent carbon atoms of Y7, n being a positiveinteger;

~Xl~X2~

wherein Ar1 represents an aromatic moiety and is XX as defined belo~, Y is XXIX as defined belo~, X1 and X2 are the same or different and are sul-fur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X1 and X2 being bonded to aromatic carbon atoms of Ar1 and adjacent carbon atoms of y8~ N and X1 or X2 of each hetero ring are disposed ortho to one another, n being a positive integer.
The aromatic moieties Ar1, Ar3, Ar4, Ar5, Ar6, Ar9, and y2> y7, and Y~ of the extended chain polymer formulas above are defined as follows:

.; 36 -~25~3~;

~ is ~ . ~. ' ~ , or XXI is ~. ~.

~~. ~

~ ' ~~ .

- ~ ;2 5~

~N~

~0~0~

~<y ~ ~ ~ :

H H

~\Sl~
. . ~ .
. . . ... .. " ,.. ~ . . . ~ " . . ,, ,, . .. . , . , . . ; ,. ,, , , ,, . ~ , . . . .

.. ' . .. . . : . . : ~ ' . ' ' . . ' ' ' . . ~: . . ' . ' ' ` ` , i ., -~5~3~3 Ei ~;~
C~HBS~HB

~N

I~ H H H

i~ s C~H6 C~H6 , ~ ~ , r ~CHa~ ,or ~LH

125~3~

~O(I I is ~ , or XXIII is $ ~ ~:

XXIV is ~ ;
' . 40 , ................................................................. :

: . ! ' . . .. ' , ' . ~ ' '; ' ' ;' ' . ' . i ' ' ' 9~3~i XXV i S
~ , or XN~N~

~VI is xN~

XXVI I is ~' '''.
~ .
or :

f97~3~;ff XXVIII is ~ .
~ ' .' ~ff XXIX is ~

. .. .
' .

5 XXX i s ~' ~' ~' ~, ~

~25~ ~r3~

~~ 52~

ll ,~C ,"
or ,~J ~;

X~(I is ~, ~, 5 ~, ~

~' ~~' ~

43 : :

'~ ?'~

~;25~

~ , .
~o~ o~

\

~~ ~

~</~

~--N>~ ~ , ~C~- ;, 44 .

. ~., .
., : .

:., , -, . , - ,, . : , . , . . .:: . . ~' .. ~ .- ' .. . ..

~2~ 3~
~rx~

~<N~
H H

~X~,X~

~<i~Nx~

~ ~_~

C~H6t:o~l5 :
~<N~S~

~N <0~ >

X~

. ~ . , .
.. ~ .

~25~3~;

i~Cs~ ' ;~ ' C~H~ C~H6 t CH2~ ~ CH2~ t CH2~

t: H~ ~ ~

~7L H ~7L
, or ~f H ` .

XXXII is ~' ~' '`'', ' -~ . ' ~,o~ ~S~2~, '':

Il .
~C~ ,. ~ .

~ .
r~

~2~:ii9~7~

Any monomeric material or ~ixture of monomeric materials having the ability to react in polyphosphoric acid to i'orm thP extended chain polymers (i.e., the above formulas I-VIII
homopolymers, and the various formulas IX-XIX
copolymers and block polymers herein defined in the specification) of this invention can be utilized.
In general, suitable monomeric materials selected for use in forming liquid-crystalllne extended chain polymer compositions of the present invention are of nine types as described below.
Type 1, 2, 4, ~, 7, and 8 are homo-bifunctional monomers. Type 3, 6, and 9 are hetero-bifunctional monomers.
Type 1 monomers has the general formula .
.
H2N ~ ,~ NH2 ( Ar1 ~
HXl X2H

wherein Ar1 is an aromatic moiety; X1 and X2 are the same or different atoms or groups æelectedfrom the class 0, S, and NR; R is hydrogen or an .

~ ':

....

973~

organic group attached to N; the R'B on the two nitrogen atoms where both X1 and X2 are NR may be the same or different; NH2, X~H and X~H ar~
bonded to aromatic carbon atoms of Ar : the groups on the left side of Ar1 iare ortho with respect to one another and the groups on the right side of Ar1 are ortho with respect to one another.
The t~o sets of NH2 and XH are each considered a functional group and are positioned on Ar1 such that they do not both interact partially with the appropriate condensing moiety of another monomer.
Monomer l i6 typically isolated as a hydrohalide -salt of the monomer. Type 1 monomers are homobifunctiional. by definition, whether or not X1 and X2 are the same of different.
In general, Ar1 may be any aromatic moiety (carbocyclic or heterocycllc~ and it may be a single rlng such as l ~ l ~ ~ XN~ ~

or lt may comprlse a plurallty of aromatlc rings connected by valence bonds or by llnking ato~s or ~:5~3~3~

group6 GUch a6 ~ r~

where ~ is a valence bond (as in diphenyl) or a divalent atom (-O- or -S-) or group such as 6 -NR-(R=H or an organic group), -(CH2)n (n=1 or a higher integer). Specific examples of Ar1 are as follo~s: :

~'~' .
~co~ s~[~ '`

~52~ ~CH2 ~L~5~3'73i~

~N H~

XNX ~ X X

or ,,~1' .

: . '. : ': ' : . `- ' ' .: :

:' . .. , ; .- .. ' '. ' '"

i9 ~3$~

The aromatic ring or rings of Arl, such as those described above and others, may bear one or more substituent. These substituents, which may be organic or inorganic may be or may contain hetero atoms, may be any atom or group which is compatible with the reactant, the solvent, the polycondensation reaction and the resulting oligomer or polymer. Substituents which are chemically reactive with Types 2 thru 9 monomers (see below), with the solvent (PPA) or with the oligomeric or polymeric products are to be avoided. Also, substituents which offer steric hindrance to the polycondensation are to be -avoided.
Among permissible hydrocarbon substituents are alkyl (e.g., C1 to C10 straight chain and branched chain alkyl, benzyl, etc.), phenyl, chloro substituted alkyl, phenyl and benzyl.
Among permissible hetero substituents are chloro, bromo, nitro, alkoxy, aryloxy, S03H, SR, and -NR1R2 (R1 and R2 being organic groups).
Formula 1 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention - ~2~ 3~

may also further be classified into three groups:
Class 1 (1,1), Class 2 (1,2), and Class 3 (1,3).
The first number of the number pairs denotes the monomer type and the second number of the pairs denotes the monomer class.
The preferred (1,1) monomers are those wherein Ar1 is a six-membered aromatic ring with the four ~alence positions being on carbon atoms having a 1, 2, 4, 5 relationship to each other, sucb as 1, 2, 4, 5-benzene or 2, 3, 5, 6-pyridine; R is H or a monovalent aromatic radical, such as phenyl, or a monovalent heteroaromatic radical, such as 2-pyridyl, or a monoYalent aliphatic radical, such as methyl. Uonomers (1,1) which when reacted with a diacid or a diacid deriYative give two substantiially collinear bonds are most preferred.
Specific examples o~ (1,1) monomers preferred for use in the invention include those monomers (shown as hydrohalides) in Table 1 below.

.~ ~ ., .

~259~3~

Ta~le 1 ~onomers of Type 1, Clas~ 1 .

HS ,~ NH2 ~ ~ 2HCI

la 2,5-diamino-1,4-benzenedithiol dihydrochloride obtalned according to Wolfe, et al., M~clomQlecules, Vol. 14, Page 915 (1981).

H2 N ~ N~2 . O ~ ~ 2HCi HO ~ ~ ~ OH
lb

4,6-diamino-1,3-benzenecliol dihydrochlorite obtained from 4,6-dinitro-1,3-benzenediol according to Wol~e, et al.~ ya5rg~Ql5~ a, Vol.
14, Page 909 (19Bl). .-.

~25~

H2 N ~ 4HCI

. lc 1,2,4,5-tetraaminobenzene tetrahydrochloride obtained from Aldrich Che~ical Co. and purified by recrystallization ~rom dilute HCl by heating, adding charcoal, fil~ering, and adding - concentrated HCl.

HO ~ NH2 ld 2,5-diamino-1,4-benzenediol dihydrochloride prepared according to Wolf, et al., 1- E~l~m Sci;, Part A-1, Vol. 6, page 1503 tl~68)~

H~N ~ 3HCI

H2N ~ NH2 le 2,3,5,6-tetraaminopyridine trihydrochloride prepared by the dinitration of 2,6-dia~ino pyridine, followed bg hydrolysis ant reduction by the method of A. H. Gerber, J. Polymer ~Si-, 1259~

Polymer Chemistry Ed., Vol. 11, page 1703(1973).

~1~0~¦~ ~ 3HCI
HO N OH
lf 3,5-diamino-2,6-pyridinediol trihydrochloride prepared by dinitration of 2,6-dimethoxy pyridine according to C. D. Johnson, et al., I. Çh~m. Soc.
(~), 1967, page 1204, followed by reduction and dealkylation.

HS W NH2 ' -~1~0~¦ ' 2HCI
H2N~ N ~SH
lg 3,6-diamino-2,5-pyridinedithiol dihydrochloride prepared from commercially available 2,5- :
diamino-pyridine by methods analogous to the : 55 ~2~ 73~;

preparation of la.

H2N ~ 2HCI

lh N1,N5-diphenyl-1,2,4,5-tetraaminobenzene dihydrochloride prepared starting from m -dichlorobenzene according to H. Vogel and C. S. Marvel, J.
~lym. Sci., ~, Vol. 1, page 1531 (1963) and purified from toluene before use.

The preferred (1,2) monomers are those wherein Ar1 is two six-membered aromatic rings attached by a covalent carbon-carbon bond each with valences on carbon atoms in the 3 and 4 positions, such as 3,3',4,4'-biphenyl or 4,4',

5,5'-(2,2'-bipyridyl), or Ar1 is two fused six-membered rings with valence positions being oncarbon atoms and having a 1,2,5,~ relationship to each other, such as 1,2,5,6-naphthalene.
The four functional groups attached to the valence positions of Ar1 by covalent bonds comprise two amino groups and the groups -X1H and .:. .

~2~ 73~;

-X2H such that one amino group is ortho to -X1H
and the other amino group is ortho to X2H and X1H
is attached to either the 3 or 4 position in the first case or the 1 or 2 position in the second case and -X2H is attached to either the 3' or 4' position in the first case and the 5 or 6 position in the second case. X1 and X2 are defined as above.
Specific examples of (1,2) monomers preferred for use in the invention include those monomers (shown as hydrohalides) in Table 2 below.

Table 2 Monomers of Type 1, Class 2 HS ~ SH ~ 2HCI

li 3,3'-dimercaptobenzidine dihydrochloride prepared by the method of Houben-Weyl, Methoden der Organisch~a Chemie, E. Miller, Ed., Vol IX, - . :, ,: : . : ~ , ~ , - ~ . , .: . - . . . : ::

. ~. , . . . ... . , . ... : . . . ,,:, . , . - . ::

~5~ ~'3~

page 39 (1955).

H~N ~ 2HCI

3,3'-dihydroxybenzidine dihydrochloride prepared by the method of C.G. Vogt and F.
Marschall, U. S. Patent 2,497,248 (1950) from o-dianisidine and aluminum chloride.

H2N~ 2HCI

lk 3,3'-diamino-4,4'-dihydroxybiphe~yl dihydrochloride prepared by the method of Y. Imai, I. Taoka, K.
Uno, and Y. Iwakura, Makromol. Ch~m~ ~3, page 167 .

~ S9~

(1965).

.

H2N ~ 4HCI 2H20 3,3'-diaminobenzidine tetrahydrochloride dihydrate prepared according to ~same ref. as for lh) and the tetrahydrochloride recrystallized from dilute HCl containing stannous chloride by adding concentrated HCl.

H2N ~ 2HCI
C6H6HN I\IHC6i'15 lm 3,3'-diamino-4,4'-dianilinobiphe:nyl dihydrochloride prepared from dinitration of 4,4'-dichlorobiphenyl, displacement of the chloro :~`

1~59 ~'3~

groups by aniline, and reduction.

HS ~ SH 2HCI
NH2 ln1,5-diamino-2,6-naphthalenedithiol dihydrochloride by methods analogous to Uonomers la and li.

~ 2HCI
HO ~
NH2 lo 1,5-diamino-2,6-naphthalenediol dihydrochloride prepared from 2,6-dichloro-1,5-dinitro-naphthalene.

,1~ 4HCI

NH2 lp 1,2,5,6-tetraminonaphthalene tetrahydrochloride prepared by the amination of 2,6-dichloro-1,5-dinitro-naphthalene followed by catalytic `
. .

"" ~ , , ! ~ . ' ~ ' ' i ~ . ` ' . . , '.', ; ,,, . ; .: ,; , ' ! .,, . i ~ , ~ ~, ;

, _~

reduction according to K. Imai, N. Kurihara, L.
Mathias, J. Wittmann, W. B. Alston, and J. K.
Stille, Maçromolecules, .6, 158 (1973).

The preferred (1,3) monomers are those wherein Ar1 is any aromatic moiety with two sets of ortho-valences at carbon atoms, such as ~ , or wherein ~ is a bivalent aromatic or heteroaromatic moiety, O, S, S02, C=O, -CH2CH2-, etc.
The four functional groups attached to the valence positions of Ar1 are divided into two sets (NH2 and X1H) and (NH2 and X2H) with the ' . . ' ' ,', ', ' " ' ' ' , ,, ' ' .;' . .. . ' " . ': ' . ' ' .' ': " ' . ' " ' ' i 7~

functional groups within each set being positioned ortho to each other and the two sets positioned on Ar1 such that they cannot simultaneously react ~ith the same functional group of another monomer. X1 and X2 are defined as above.
Specific examples of (1,3) monomers preferred for use in the invention include those monomers (shown as hydrohalides or as monomers) in Table 3 below.

Table 3 Monomers of Type 1, Class 3 H N ~ SNH 2 ' 2HCI
lq 3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride prepared according to the method of V. V.
Korshak, E. S. Krongauz, A. P. Travnikova, A. L.
Rasanov, and A. D. Katsarava, ~Qkl, Akad. Nauk.

~5~3~

, 106 (19713.

H;N ~ ~ ; 4HCI

3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride obtained commercially from Pfaltz ~ Bauer.

H \ ~ ~ NH2 lS
3,3'-dihydroxy-4,4'-diaminodiphenyl ether is prepared according to the method of S. U.
Kantor and J. Sonnenberg, U. S. Patent 3,306,876 (1967).

~ ~ OH
lt 3,3'-diamino-4,4'-dihydroxydiphenyl ether prepared according to the method of A. S.

: ,. ~., ~ - , .. . ,.:, : : ... . .. . . .. . .

~2~

Patent No. 1 181 53 nd C. }~- L. cibsOn ~J ~

H2 ~,So2~NHzH2 S ~ODe SH~,S02~NSH~2 10 ~ ~ ~V~ .e 4 q,_ 3'6 the preparation of la and li.

H,N S02~ H2 lw 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone prepared according to the method of G. I. Braz, I. Y. I~ardash, and V. S. Yakubovich, ~Qlym.
~ , page 2013 (1967).

H2N ,52~.~ NH2 lx 3,3'-diamino-4,4'-dihydroxydi.phenyl sulfone prepared from commercially available 4,4'-dihydroxydiphenyl sulfone by acetylation, . .

5~ 6 dinitration, hydrolysis and reduction.

~ Ntl 3,3',4,4'-tetraaminobenzophenone available commercially from Polysciences, Inc.

SH SH

H2N ~ NH2 2HCI
lz 3,6-diamino-1,2-benzenedithiol dihy~rochloride prepared by isolation of 2,7-diaminobenzol[1,2-d;6,5-d']bisthiazole from the scheme to prepare la followed by hydrolysis.

- '. ' ... : . ' ... ', . ' ' . ,'' ,, ' :; , . .. ,, . . ,: '' .

373~i Type 2 mc)nomers have the general formula Zl--y2--Z2 2 wherei~ y2 is a bivalent organic group and Zl and Z2 are electron- deficient carbon groups and may be the same or different groups selected from the following class.:

-COOH -CSSH -COBr -CSI
-CSOH -COCl -CSBr -CONHR
-COSH -CSCl -COI -CSNHR
-CN
(R1 = H or an organic group bonded to N by a carbon atom) The only requirement of Zl and Z2 is that they react with the X1H and X2H and with the t~o hydrogen atoms of the primary amino groups of Type 1 monomers to form suitable leaving entities, such as ~ater, hydrogen sulfide, hydrogen halide. ammonia, etc. Type two monomers are homobiunctional, by defin:ition, whether or not Zl and Z2 are the same or different. The bivalent group Y may be an aromatic group, an acyclic aliphatic group, or a cycloaliphatic ~ .
. j .

~5i97~3~
group, and such groups may be substituted by hydrocarbon groups (aliphatic or aromatic) and by hetero atoms and groups. In general any of groups described above as substituents of the aromatic ring or rings of Ar1 may be used subject to the same restrictions.
Formula 2 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant inYention may also further be classified into three groups:
Class 1 (2,1), Class 2 (2,2), and Class 3 (2,3).
The first number of the number pairs denotes the monomer type and the second number of the pairs denotes the monomer class.
The preferred (2,1) monomers are those wherein Y
is nil, or Y2 comprise at least two carbon atoms to which are attached Zl and Z2 such that the two exocyclic bonds between Y and Zl and between Y
and Z2 have a rigid and fixed relationship to each other and are substantiallg collinear, or Y
may also be a cycloaliphatic group that has at least two carbon atoms to which are attached Z
and Z2 such that the two bonds between Y and Z
and between Y and Z2 have a highly preferred relationship to each other that is substantially collinear. Carboxylic acid derivatives of 2j-2q .i ' ~5~

and 2z (as herein described below) such as COOH
that decarboxylate at temperatures below that required for polycondensation with Type 1 monomers are less preferred.
Specific examples of (2,1) monomers preferred for use in the invention include those monomers in Table 4 below.

Table 4 -Monomers of Type 2, Class 1 HOOC ~ COOH

2a terephthalic acid obtained from Amoco Chemicals Co. and micronized . .,~, .
:

c .... ,.... . . . , , ,, ~ . "

73~
and dried before use.

cloc ~ coc 2b terephthaloyl chloride obtained from Aldrich and sublimed immediately

6 before use.

H2NOC ~ CONH2 2c 1,4-benzenedicarboxamide prepared from 2b or obtained commercially from Pfaltz and Bauer.

NC ~ CN
2d terephthalonitrile : 70 :

~S9~3~;

obtained from Pfaltz and Bauer.

HOOC ~ COOH

2e trans-1,4-cyclohexanedicarboxylic acid obtained from Aldrich and recrystallized from water.

CIOC ~ COCI

2f trans-1,4-cyclohexanedicarboxylic acid chloride prepared from 2e.

H2NOC ~ I:ONH2 2g trans-1.4-cyclohexanedicarboxamide ~;: 71 ~2~9~73~

prepared from 2f.

NC ~CN

2h trans-1,4-dicyanocyclohexane .
prepared from 2g.

HOOC ~ COOH

2i :.
2,5-pyridinedicarboxylic acid obtained from Aldrich Chemical Co.

NC--</ ~N~>--2j 2,B-benzo[1,2~d:4,5-d']bisthiazoledinitrile prepared by diazotization of 2,ô-diaminobenzobisthiazole (see reference for la) . 72 ~25~

followed by treatment with cuprous cyanide.

NC (~ CN

2k 2,6-benzo[1,2-d:5,4-d']bisoxazoledinitrile prepared from the condensation of compound lb with urea followed by diazotization as for compound 2j.

NC--</ ~ \>--CN

2,6-benzobisimidazoledinitrile prepared as for 2k using compound lc.

~ CN

2m 2,6-benzo[1,2-d:4~5-d']bisoxazoledinitrile , ," . . , . : ', : :

~2~ 3~i prepared as described for 2k using compound ld.

NC----(/ ~ \>--CN
N N N
2n 2,6-pyridobisimidazoledinitrile prepared as for 2k using compound le.

~N~ CN
N

2,6-pyrido[2,3-d:6,5-d']bisoxazoledinitrile prepared as for 2k using compound lf.

S~,_ N~
~\ ~l N N S
2p 2,6-pyrido[2,3-d:5,6-d']bisthiazoledinitrile prepared as for 2j`, using 2,6-diaminopyridobisthiazole as prepared in the : ,, .

.. 74 .'h : :'` -' 3 ~ ' ' ~2~

synthesis of lg.

NC--</ ~ \>--CN

C6 H5 C6 H!i ~q .
1,7-diphenyl-2,6-benzobisimidazoledinitrile prepared as for 2k using compound lh.

HOOC ~<N~[SX~ COOH

2r 2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bistbiazole prepared by the condensation of compound la with ~-toluic acid followed by oxidation.

~ o ~ o HOOC ~<N~ COOH

2,6-bis(4-carboxyphenyl)benzo~1,2-d:5.4-d']bisoxazole prepared by the condensation of lb with ~-toluic . . ~
.

. , ~59~

acid followed by oxidation.

HOOC~<N~ \>~ COOH
H H
2t 2,6-bis(4-carboxyphenyl)benzobisimidazole prepared by a method similar to 2s using lc.

HOOC ~<~ ~ \>~ COOH

5 . 2u 2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisoxazole prepared by method similar to 2s using ld.

H H
HOOC ~<\ $~ ~ COOH

2,6-bis(4-carboxyphenyl)pyridobisimidazole 37~

prepared by a method similar to 2s using le.

HOOC ~</ ~[ \>~ COOH

2w 2,6-bis(4-carboxyphenyl)pyrido[2,3-d:6,5-d']bisoxazole prepared by a method similar to 2s using lf.

HOOC ~(N~ \>~ COOH

~x 2,6-bis(4-carboxyphenyl)pyrido[2,3-d:5,6-d']bisthiazole prepared by a method similar to 2s using lg.

HOOC ~C~ COOH

2y 1,7-diphenyl-2,6-bis~4-carboxyphenyl)benzobisimidazole , ~Z~9~73~

prepared by a method similar to 2s using lh.

o ~
Il 11 .

oxamide obtained from Aldrich Chemical Co.

The preferred (2,2) monomers are those wherein y2 comprise two six-membered rings attached by a covalent carbon-carbon bond each with valences on the 4-position or each with valences on the 3-position, such as 4,4'-biphe~yl or 3,3'-biphenyl, or y2 comprise t~o fused six-membered rings with valence positions being on carbon atoms and having a 1,5 relationship to each other, such as 2,6-naphthalene or 2,6-quinoline, or y2 is a cycloaliphatic divalent moiety ~ith valences on carbon atoms and in a 1,2-trans configuration, or Y is a variety of condensed aromatic and heteroaromatic ring systems attached only by carbon-carbon bonds and having 2 valences, Zl a~d Z2 are the same as defined above.

~25~7'~

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

Table 5 Monomers of Type 2, Class 2 HOOC ~ COOH

2aa 4,4'-biphenyldicarboxylic acid obtained from Aldrich Chemical Co.

CIOC ~- COCI

2bb 4,4'-biphenyldicarboxylic acid chloride .: . .. :, :' ' i, ,,;, i:, :.. :: '' :;,' .. ,'~' ~5~

prepared from 2aa.

HOOC ~ COOH

2,6-naphthalenedicarboxylic acid .
prepared according to the method of B. Raecke and H. Schirp, Qr~. ~yn- Coll. Vol. V, page 813 (1973) from commercially available 1,8-naphthalenedicarboxylic a~hydride.

CIOCJ~ COCI
2dd 2,6-naphthalenedicarboxylic acid chloride prepared from 2cc by treatment with thionyl ::',' .

~2~ 73~

chloride.

~ COOH

HOOC
2ee 2,6-quinolinedicarboxylic acid prepared from commercially available (Aldrich) 2,6-dimethyl quinoline by oxidation.

HOOC ~ OOH

2ff 3,3'-biphenyldicarboxylic acid prepared from o-nitrobenzoic acid by the method of M~ Kurihara and N. Yoda, 1. ~acromol. Sci.
ÇhQ~ Al(6), page 1069 (1967).

HOOC
H
COOH
2gg trans-1,2-cyclohexanedicarboxylic acid ~253~

was obtained from Aldrich Chemical Co. and recrystallized from methanol before use.

HOOC ~N~I~ COOH

2hh 1,4-bis(5-carboxybenzoxazole-2-yl)benzene prepared by the method of J. Preston, W. De Winter and W. L. Hofferbert, I. Heterocyclic Che~m. 5, page 269 (1968).

HOOC ~<N~ COOH

2ii 1,4-bis(6-carboxybenzothi~zole-2-yl)benzene ..

~L~5~

prepared by methods analogous to 2hh.

I-IOOC~N>~N (N~ COOH

2jj 2,5-bis(6-carboxybenzothiazole-2-yl)pyridine.
prepared by methods analogous to 2hh.

The preferred (2,3) monomers are those wherein y2 may be any aromatic, heteroaromatic and aliphatic divalent species not pre~iously described.
Specific examples of (2,3) monomers preferred for use in the invention include those monomers in Table 6 below.

Table 6 -Monomers of Type 2, Class 3 ~ .

; , . ., ~, ,, : :, ,, .... ,. , . ~ , ~ . ..... . . .

~5~

t:iOC~O~O~ COCI

2kk 4,4'-(p-phenylenedioxy)dibenzoyl chloride prepared according to the method of R. C. Evers, F. E. Arnold, and T. E. Helminiak Macromolecules, 51~ , page 925 (1981).

NC ~O~O~ CN

4,4'-(p-phenylenedioxy)dibenzonitrile prepared according to method of T. Takekoshi, J.
G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.
Manello, and M. J. Weber, ~Ql~m~ ~L~L., 1- ~m-Ch Q . Soc., 20(1), page 179 (1979).

HOOC ~O~ (~ COOH

2mm 4,4'-(m-phenylenedioxy)dibenzoic acid prepared according to method of T. Takekoshi, J.
G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.
Manello, and M. J. Weber, _Qlym- Pl~r.. J. ~m.

. ~

~5~3~3i~

Chem. ~ (1), page 179(1979).

cloc ~ o~ co~l 2nn 4,4'-(m-phenylenedioxy)dibenzoyl chloride from 2mm according to method of R. C. Evers, F.
E. Arnold, and T. E. Helminiak, Macromolçcules, 14, page 925(1981).

NC ~0~0~ CN

4,4'-(m-phenylenedioxy)dibenzonitrile prepared according to the method of R. C. Evers, F. E. Arnold, and T. E. Helminiak Macromolecules, ,; ~ . , .

~5~

1~. page 925(1981).

cloc ~~ cocl 2pp 3,3'-(m-phenylendioxy)dibenzoyl chloride according to the method of R. C. Evers, F. E.
Arnold, and T. E. Helminiak MacrQmolecules, 14, page 925(19B1).

NC ~/ ~)\[~ CN

2qq 3,3'-(p-phenylenedioxy)dibenzonitrile prepared according to the method of R. C. Evers.
F. E. Arnold, and T. E. Helminiak Macromolecules, .. ; , .

~ t~3 1~, page 925(1981).

NC ~O~_~,~ CN
<~
2rr 4,4'-(o-phenylenedioxy)dibenzonitrile prepared according to the method of R. C. Evers, F. E. Arnold, and T. E. Helminiak ~3~romoleçules, 1~, page 925(1981).

HOOC ~ COOH

2 S 6 .
isophthalic acid obtained from Pfaltz and Bauer and recrystallized from 90% ethanol.

HOOC ~ COOH

2tt 4,4'-dicarboxydiphenyl ether -' ~:

~7 i259~3~ : .

obtained from Polysciences, Inc.

HOOC ~O~ COOH .;

3,3'-dicarboxydiphenyl ether prepared from a coupling of m-cresol and m-bromotoluene followed by oxidation by the methodof M. Tomita, 1. Pharm. Soc., l~n. 57, page 391(1937).

HOOC ~ CH2 ~ COOH

succinic acid obtained from Aldrich Chemical Co.

HOOC ~ CH2 ~ COOH

21~.'W
glutaric acid ~8 `_J

~:~S~3~73iE;

obtained from Aldrich Chemical Co.

HOOC ~ CH2 ~ COOH

adipic acid obtained from Aldrich Chemical Co.

HOOC ~ CH2 ~ COOH

2yy : -pimelic acid obtained from Aldrich Chemical Co.

HOOC ~ CH ~ ~ COOH

sebacic acid obtained from Aldrich Chemical Co. ; .

'':.--... 89 :-.
.

~9~3~;

Type 3 monomers have the general formula ~ NH2 Z3t A~ ~ 3 wherein Ar3 is a trivalent aromatic or heteroaromatic moiety, and X3 is O, S, or N-R (R
= H or an organic group). Type 3 monomers are heterobifunctional, by definition.

Formula _ monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention may also further be classified into t~o groups:
Class 1 (3,1) and Class 2 (3,2). The first number of the number pairs denotes the monomer type and the ~econd number of tbe pairs denotes the monomer class.
The preferred (3,1) monomers are those wherein Z3 is the same as defined for Zl' Ar3 is a trivalent aromatic or heteroaromatic moiety with the three valence positions being on carbon atoms and having the relationship that the valence bond between Z3 and Ar3 is nearly collinear with the same valence bond in subsequently condensed :

.. ~, 90 S~73~

monomers, and X3 is defined as for X1 in Table 1.
X3 and NH2 are positioned ortho to each other on Ar3 Specific examples of (3,1) monomers preferred for use in the invention include the monomer in Table

7 below.

Table 7 Monomers of Type 3, Class 1 2HCI ~ ~ COOH

3k 2-(4-carboxyphenyl)-5,6-diami~obenzimidazole : ~
dihydrochloride ..
prepared according to R. F. Kovar and F. E.
Arnold, 1. Pol~m. ~i. Eçlym. Çh~m. ~ . pa~e 2807 (1976). ;
:

: 91 ~2~i9~3~

The preferred (3,2) monomers are those ~herein Z3, Ar3, and X3 are defined as above. The bonds that are formed in homopolymerization of (3,2) monomers are defined in their spatial relationship having an angle of catenation of less than about 150 to about 180.
Specific examples of (3,2) monomers preferred for use in the invention include those monomers (shown as hydrohalides or as monomers) in Table 8 below.

Table 8 Monomers of Type 3, Class 2 HOOC ~ SH
~ lCI ' ~'.

3a 3-mercapto-4-aminobenzoic acid hydrochloride :` 92 .

,, ,. , j .; : ! : . ' ` i , ' '. .' . , . : ', ;

~;~5~73~i prepared according to Wolfe, AFOSR Final Technical Report, Dec. 15, 19~0.

HOOC ~ SH

N H2 .
3b : :
3-mercapto-4-aminobenzoic acid ; `
prepared as described in Example 5 .
.

HOOC ~ OH ~.
HCI ~:
NH2 .
3C ~:
3-hydroxy-4-aminobenzoic acid hydrochloride .
prepared as described by Y. Imai, K. Uno, and Y. :
Iwakura, ~akromol. ÇhQm-. 83, 179(1~65).

HOOC~ HCI

3d 103-amino-4-hydroxybenzoic acid hydrochloride prepared as described by K. Auwers and H. Rohrig, `: 93 ~:~59~73~;

Chem. ~., 30, 992(1897).

HOOC~ NH2 3e 3,4-diaminobenzoic acid obtained from Aldrich Chemical Co. and recrystallized from deoxygenated water before use.

HOOC ~ NHC6H6 3f N3-phenyl-3,4-diaminobenzoic acid prepared from p-aminobenzoic acid by chlorination, oxidation to 3-chloro-4-nitrobenzoic acid, follo~ed by aLnilation and .~. 94 r ~iL25 reduction. ~

HOOC ~,~ N H2 3g N4-phenyl-3,4-diaminobenzoic acid prepared by nitration of commercially a~ailable (Aldrich) p-chlorobenzoic acid, followed by anilation and reduction.

HOOC ~ N H2 SH
3h 4-carboxy-3'-mercapto-4'-aminobiphenyl prepared by nitration of commerc:ially available 4-carboxybiphenyl (ICN/K and K) and reduction to 4-amino-4'-carboxybiphenyl, followed by placement :
of the Q-mercapto group by methods analogous to ::: 95 .

~25~73~

those described for 3a.

HOOC ~ OH

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

HOOC ~ N H2 NH2 . .
3j 4-carboxy-3',4'-diaminobiphenyl prepared by acetylation of 4-amino-4'-carboxylbiphenyl (see preparation of 3h) followed by nitration, hydrolysis, and reduction.

~-.. ; 96 ;:

Type 4 monomers have the general formula Z4 ~ Z6 ~ Ar4 J
Z5 ~'~ r~ Z7 ;~

Z4' Z5' Z6' and Z7 are the same or different and are chosen from the list of carboxylic acid derivati~es gi~en for Zl in Table 4. Z4 and Z5, or Z6 and Z7, or both sets can also be carboxylic acid anhydride groups- Z4 and Z5 are defined as one functional group (as are Z6 and Z7) and thus Type 4 monomers are homobifunctional by definition, whether or no~ Z4. Z5~ Z6 and Z7 are the same or different. Ar is an aromatic or aromatic heterocyclic moiety having four valence positions at carbon atoms. Ar4 can be a six-member ring with the valence positions having 1, 2, 4, 5 relationship, or Ar4 can be two condensed six-member rings, such as naphthalene. Z4 and Z5 as one set -and Z6 and Z7 as another set must either be ortho-positioned within each set or bear a 1, 4, 5, 8 relationahip to each other. An (imaginary) line perpendicular to the bond between the valence carbons ~ -~
attached to Z4 and Z5 must be collinear with the corresponding (imaginary) line for Z6 and Z7.
Formula 4 monomers useful in preparing the extended chain polymers and nov~l liquid-~;~Si9~3~

crystalline compositions of the instant invention are classified as Class 1 (4,1). The first number of the number pairs denotes the monomer type and the second number of the pairs denotes the monomer class.
Specific examples of (4,1) monomers preferred for use in the in~ention include those monomers in Table 9 below.

Table 9 ~onomers of Type 4, Class 1 o o o\'~ ~o o o 4a pyromellitic dianhydride obtained from Aldrich Chemical Co. and sublimed ,~ .

~J' 98 ~5g~73~i -or recrystallized (acetic anhydride) before use.
O rrrrrc~ ~C~
~
,.

O'~c~O~c~O
4b 1,4,5,8-naphthalenetetracarboxylic dianhydride obtained from Aldrich Chemical Co.

Type 5 monomers have the general formula ZB ~~~ NH2 ~ A~ J 5 Zg ~ NH2 ~ , .
wherein Z8 and Zg are defined as for Z4 and Z5 in Table 9, Ar5 is defined as in Table 9, the two amino groups are ortho to each other, and Z8' Zg' and the two amino groups are positioned æuch that two imaginary lines drawn perpendicular to the bonds between their ~alence carbons are collinear. Type S monomers are heterobi-functional, by definircion.

~ . :
:
~::

iL~59~

Formula 5 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention are classified as Class 1 (5,1). The number pair (5,1) has the same significance as above.
Specific examples of (5,1) monomers preferred for use in the invention include the monomer in Table 10 below.

Table 10 Monomers of Type 5, Class 1 O~C~O~C~O
5a 4,5-diaminonaphthalene-1,8-dicarboxylic anhydride prepared from the diDitroderivati~e by chemical reduction according to I. Honda ,and M. Okazaki, 1- ~Q~- Q~g. Synthetic Çh~m. (l~n). ~, page 25(1950).

~J

~LZ5~'~36 Type 6 monomers have th~ general formula Zlo ~ ~12 Z ~ 6 .
11 Z13 .`

wherein Ar6 represents an aromatic moiety and is a tetrahydroxy fused ring system, ZlO' Zll' Z12' -~16 are the same HO atoms bonded to carbon atoms ';
of Ar . Type S monomers are defined as homobifunctional monomers.

In gener.al, Ar6 may comprise a single or a plurality of aromatic rings in the center of a completely conjugated fused ring system. The center aromatic ring or rings of the completely conjugated fused ring system can be any of those described above, and others.
Formula 6 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention ..
may also be further classified into two groups:
Class 1 (6,1), and Class 2 (6,2). The number pairs have the same significance as above. `

'`,,`~ 101 ,~

`
~L~59736 The preferred (6,1) monomers are those ~herein Ar6 comprise a single center aromatic ring in the center of the fused ring system.
The preferred (6,2) monomers are those wherein Ar6 comprise at least two center aromatic rings in the center of the fused ring system.
Specific examples of (6,1) and (6,2) preferred for use in the invention include those monomers in Tables 11 and 12 respectively.

10Table 11 Monomers of Type 6, Class 1 -~N~

6a 162,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene prepared from condensation of 1,2,4,5-tetraaminobenzene ~ith oxalic acid according to .... - .. .......... .... - .. -- - - . - . - . . , ., .- . . . . . - . .

~2S9~36 H. Tadamus, F. DeSchryver, W. DeWinter, and C.
S. Marvel, 1. ~lym. ~Çi. ~ , page 2831(1966).

Table 12 Monomers of Type 6, Class 2 X' ~ NX ~
6b 2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline prepared from condensation of 3,3'-diaminobenzidine with oxalic acid according to method of H. Tadamus, et al., J. ~Qlym. ~i.
4, page 2831 (1966).

.... .

~25973~i Type 7 monomer has the general formula X7 ~ X7 ~ y7 J 7 X7 ~ X7 wherein Y7 represents an aromatic or heteroaromatic moiety and is a fused ring carbon group, the X7's are double bonded to carbon atoms of Y7.
Type 7 monomers are homobifunctional, by definition.
Formula 7 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention can be classified as Class 1 (7,1). The number pair ~7,1) has the same significance as above..
A specific example of (7,1) preflerred for use in the present invention is 7a in Table 13 belo~.

12~9~if36 Table 13 ..

Monomers of Type 7, Class 1 ~
.
~
D~O -:

7a 1,2,6,7-tetraketopyrene M. Corell, and H. Streck, ~nn. 5~1. page 6(1937).
~ :

~;973~

Type 8 monomer has the general formula Xlo~7~ Xll k y8 ~ 8 Xll X10 wherein Y is a single carbon cyclic moiety, X10 and X11 are H0 and 0 atoms respectively, bonded to carbon atoms of y8~ Type 8 monomers are homobifunctional, by definition.

Formula 8 monomers useful in preparing the extended chain polymers and novel liquid-crystalline compositions of the instant invention can be classified as Class 1 (8,1). The number pair (8,1) has the same significance as above.
A specific example of (8,1) preferred for use in the present invention is 8a in Table 14 below.

^`'J ~:

59~3~;

Table 14 :
Monomers of Type 8, Class 1 HO ~o oO~ OH
8a 2,5-dihydroxy-1,4-benzoquinone obtained from Aldrich Chemical Co. -Type 9 monomer has the general formula Zl4 ~ NH2 ~ J
Z ~ r~ X4H

wherein Ar9 represents an aromatic moiety and is a partially fused ring system, Z14 and Z15 are OH
atoms, X4 are selected from the class 0, S, and NR; R is H or an organic group attached to N;

' 107 -125~73 Ei NH2, X4H, Z14' a~d Z15 ~re bonded to carbon atoms of Ar , NH2 and X4H are positioned ortho; Z14 and Z15 are positioned ortho. Type 9 monomers are heterofunctional, by definition.
Formula 9 monomers useful in preparing the extended cbain polymers and novel liquid-crystalline compositions of the present invention can be classified as Class 1 (9,1). The number pair (9,1) has the same significance as above.
A specific example of (9,1) preferred for use in the present invention is 9a in Table 15 below.

Table 15 Monomers of Type 9, Class 1 H ~N~ 011 9a 2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride prepared from 1,2-diamino-4,5-dinitrobenzene by ~ -condensation with oxalic acid followed by ~
reduction according to R. F. Kovar and F. E. -Arnold, I. ~Qlym~ Qlym Çhçm. E~.... 1~.
page 2807(1976).
:
'' '. '''-. 108 ::
... ' ' '' ~L2Sg73~

.' '-::

In accordance with the practice of the present ~
in~ention, the synthesis of the aforementioned . .
formulas I-VIII homopolymers may be illustrated by the following general reaction ~ystem: ..

Reaction Mechani~m Formation of formula I homopolymer H2N NH2 - .., 10HX 1 3~ + Zl--y2--Z2 -- I, Formation of formula II homopo:lymer _~ NH2 -: ., Z3~ A~ ~ ~~~~ II, ~~ X3H ;~

Formation of formula III homopolymer Zl~ Z6 H2N ~ NH2 Ar4 J ~ ~ Arl ~
Z~~ Z7 H2N~ NH2 -:

~5 Formation of formula IY homopolymer .
Z~l ~ NH2 , .. ..
~ ~ ~ IV, 2~ Nl'(2 ;

'':~ `"' ' ', ' ' ~2S~3~73t~

. Formation of formula V homopolymer H2N ~ NH2 Zlo ~ Z12 C Arl J + C Ar6~3 ~V, HXl X2H Zll Zl3 Formation of formula VI homopolymer ~ VI, Formation of formula VII homopolymer H2N ~ NH2 X7~ X, YII, Formation of formula VIII homopolymer HXl ~ NH2 X10 ~ Xll VIII, H2N X2H Xl l X10 .:

,~ " ' ~, 110 ~ ':' : . ' .' . ' .' . . : . . ; . . ~

~ 25973~

Representative examples of suitable homopolymers :
forming liquid crystalline homopolymer composi-tions in accordance with the practice of the present invention (provided they fall within the above-defined general formulas I-VIII) include the following polymers. For the sake of conveni-ence, polymer formulas are hereinbelow shown in simplified representation. As an example, ~AI~n E' ~ >~ ;

The structures representing ~AI~ are defined iD
the Appendix. ~A~ has the structure ~ ~ /~

and ~I~ has the structure ~ ' ''' ~9~3~

Their sequential combination is therefore ~A~ + ~ AI~ or N

E' ~ >~

All simplified polymer formula representations appearing in the specification ~lay be readily .
interpreted by reference to the Appendix. . ;

~AI3n, ~AIBI~n. ~BI~n, and ~T~n~ :
~AIDI~n, fAIEI~n, ~AIFI~n, ~AILI~n, ~AIMI~n, ~AINI3n, ~ATIT'~n. ~ATKT ~n' ~BIDI~n' ~B~EI~n' ~BIFI~n' ..
~BILI3n, ~BIMI~n, ~BINI~n, ~BTIT'3n, ~BTKT'3n, .' ~EILI~n. ~FILI~n. ~LI~ TI~n, ~U~n, and ~V3n, ~A~n~ ~AB~n, ~AC~n, ~AE~n, ~AF~n, ~AICI~n, ~AIOI~n, n' ~ ~n' ~AL~n~ ~AM~n~ ~AN3n. ~AQ~n, -EAVIV~3 1~ ~B~n~ -EBC~n, ~BD~n, ~BE~ BF~n, ~BICI~n, ~BIOI~n, . ;
n' ~ 3n' ~BL3n, ~B~n, ~BN~n, ~BQ~ , ~BVIV'3 ::
~B'A'B'~n, -EB'A'F'Z~n, ~B'H'~n*(~ denotes ~ oxygens always meta on B') ~B'I'~n, ~B'P'~n, n ~ .~C~n, ~ OE~n~ -ECF~n~ ~CI~n, ~CIEI~

1;~5~373fi ~CIFI3n, ~CILI3n, ~CIMI3n, ~CINI~n, ~CIOI~n, ~CJ3n, ~CL~n, ~CM~n, ~CN~n, ~CTIT'~n, ~CTKT'~n, ~C'A'B'Z~n, ~C ' A ' F ' Z3n ~ ~D ' A ' B ' Z3n ~ ~D ' A ' F ' Z~n, ~E~n ~ ~EF~n ' ~EI~n, ~EIFI~n, ~EIMI~n, ~EINI3n, ~EIOI~n, ~EIQI3n, ~EJ~n, ~EL~n. ~EM~n. ~EN~ ETIT ~n~ ~ETKT ~n~
~E'A'B'Z3n, ~E'A'F'Z~n, ~F~n~ ~FI~n, ~FIMI~n, ~FINI~, ~FIOI~n, ~FJ~n~ ~FL~n, ~FM~n, ~ ~n n ~L3n ~ ~LJ~n ~ ~LTIT ' ~n ~ ~LTKT 3n ~ ~M~n ~ ~MI3n ~ ~MTIT ~n ~n, ~N~n~ ~NI~n, ~NTIT ~n, ~NTKT'~, ~QI~
~QJ~n~ ~RI3n, ~RJ3n, and ~UI3n, ~AD~n, ~AG~n, ~AH3n, ~AIGI~n, ~AIHI3n, ~AIPI~n, . ' ~AIRI~ . ~AISI~n, ~AK~n, ~AO~n, ~AP~n, ~ ~n n n ~BIGI~n, ~BH~n, ~BIHI~n, ~BIPI~n, ~BIRI~n, ~BISI3n, ~8K~ , ~B03n, ~BP3n, ~BR~n, ~BS~n, ~ n ~B'H'~n** (** denotes oxygens always para on B'), ~B'J'~n, ~B'K'~n* (* denotes oxygens always meta on B'), ~B~K~ **. ~B'L'~n. ~B M 3n~ ~B N ~n~ ~B n n ~ S ~n ~ ~B U ~n' ~CD3n, ~CC~n, ~CH3 ~CIDI3 , ~CIGI~n, ~CIHI~n, ~CIP:I~n, ~ Q n n ~CISI3n. ~CK~n. ~C0~n. ~CP~n~ Q~n~ ~ ~n n ~CVIV'~ , ~C'G'~n, ~C H ~n' ~C I ~n' ~ n n ~C ' L ' ~n ~ ~C ' ' ~n ~ ~C Q ~n ~ ~C R ~n ~ n ~D~ , ~DE~n. ~DF3n. ~DG~n~ ~DH~n' ~DI~n' ~ n ~DIFI3n, ~DIGI3n, ~DIHI~n, ~DILI~n, ~DIMI~n. ~DINI~n, ~DIOI3n. ~DIPI~n. ~DIQI~n. ~DIRI~n. ~DISI~n.
~DJ~ , ~DK~n. ~DL~n~ ~DM~n~ ~DN~n' ~ ~n n ~DQ3n~ ~DR~n, ~DS~n, ~DTIT'3n~ ~DTKT'~n, ~DVIV'~n, , .,, .. . . . .. . ~ .,: .. . .. . . . ~ , ~

~2597;~

~D'C'~n, ~D'H'~n~ (* denotes oxygen al~ays in 3,3'-positions on D'). ~D'H'~n** (** denotes oxygen al~ays in 4,4'-positions on D'), ~D'I'~n, ~D'J'~n, ~D'K'~D$,~D'K~n**, . n ~n~ ~D N 3n~ ~D '~n~ ~D'~'3 , ~D'R'~
n ~n ~ ~D U ~n' ~EG~n ~EH3n, ~EIGI~
~EIHI~n, ~EIPI~n, ~EIRI~n, ~EISI~ EK~n, ~EO~n, n~ ~ Q~n ~ER~n~ ~ES~n~ ~EYIV~ E~C~
~E'H'~ , ~E'I'~n, ~E J ~n' ~E K ~n' ~ n n ~E'Q'3n, ~E'R'3n, ~E'S ~n' ~FG3n, ~FH~n, ~FIGI~n, ~FIHI~n,,~FIPI3n, ~FIQI~n, ~FIRI~n, ~FISI~n, , , ~FK~n, ~FO~n, ~FP~n~ ~FQ3n~ ~FR3n, ~FS~n. ~FTIT ~n~ :
~FTKT'~n, ~FVIV'~n, ~C~n, ~GH~n, ~GI~n, ~GIHI~n, :
tGILI3~n, ~GIMI3n. ~GINI~n~ tGIOI3n tGIPI3-n ~GIQI3-n n' ~ SI~n~ ~GJ3n~ ~GK~n, ~GL3'n, ~GM3- , ~GN3' n~ ~ P3n~ tG~3n~ tGR3~n. tGS~n. t~GTIT~3- , tCTKT'3-n, ~CVIV'3'n, ~H3'n, tHI~n, ~HILI3~n, ~HIMI3n, tHINI3-n, tHIOI3'n, ~HIPI3-n, tHIQI3'n. tHIRI~n.
t ISI3n, tHJ~n~ ~HK3n, tHL3'n, tHM3-~, tHN3 , tH03' tHP3n, tHQ3-n~ ~HR3n, ~HS3~n, tHTIT~3-n.
~HTKT'3'n, tHVIV'3~n. tLK3'n. tLVIV'3rrl.
tMJ3Ln ~ tMK3Ln r ~MVIV'3~n, tNJ3-n~ tNK3-n.
~NVIV'3~n~ ~OI3n ~0J3n tOK3n, tOTIT 3n~
tOTKT'3'n, ~OVIV 3'n~ ~PI3n, ~P 3n n tPTIT'3n. tPI'KT'3-n. ~PVIV'3n, tQ3n t'QK3'n.
~QTIT'3~n, ~QTKT'3n, ~QVIV ~n~ ~R~, tRK3n.
tRTIT'3'n, tRTKT'~n, ~RVIV'~n, ~SI3n, ~SJ3 , tSK3'n. tSTIT'3-n. ~STKT'3rn, ~SVIV'3'n, tW3'n, ~.

... ..

1~5g73~ ~

~X~n, and ~Y3n.

The most preferred extended chain homopolymers in ~
accordance with the practice of the present ~ .
invention include ~AI3n, ~AIBI3n, ~BI~n, and ~T3n.

The especially preferred extended chain homopolymers in accordance with the practice of the present invention include ~ AIDI3n, ~AIEI~n, ~AIFI~n, ~AILI3n, ~AIMI~n, ~AINI~n, ~ATIT'3~, ~ATKT'~n, ~BIDI~n, ~BIEI~n, ~BIFI~n, ~BILI3n, ~BIMI3n, ~BINI3n, ~BTIT'3n, ~BTKT'~n,'':' ~EILI3n, ~FILI~n, ~LI3n, ~TI~n, ~U~n, an ~ n The preferred extended chain homopolymers in accordance ~ith the practice of the present .
invention include ~A3n, ~AB~n, ~AC~n, ~AE3n, ~AF3n, ~AICI~n, ~AIOI3n, ..~,.

~2~3736 ~AIQI~n, ~AJ~n~ EAL~n, ~AM~n, ~AN~n, ~AQ~n, ~AVIV'3n, ~B3n, ~BC~n, ~BD3n, ~BE~n, ~BF~n, ~BICI3n, ~BIOI~n, ~BIQI3 , ~BJ~n, ~3L~n~ ~BM~n, ~BN~n, ~BQ3n, EB n EB'A'B'Z~n. ~B'A'F'Z~n. ~B'H'~n*, (* denotes oxygens always meta on B') ~B'I'~n, -EB'P'3n, ~B'Q'~n, ~B'S'~* EC~n. ~CE~n, ~CF~n, ~CI3n, ~CIEI~n, ~CIFI~n. ~CILI~n. ~CIMI~n ~CINI~n~ ~CIOI~n~ ~CJ~n~
~CL~n, ~Cbl~n, ~CN3n, ~CTIT'3n, ~CTKT'~n, ~C'A'B'Z~n, ~C'A'F'Z~n. ~D'A'B'Z~n. ~D'A'F'Z~n, -EE~n. ~EF~n, EEI~n. -EEIFI~n, EEIMI~n, -EEINI~n, EEIOI~n, ~EIQI~n, ~EJ3n, ~EL~n, ~EM~n, EEN~n, -EETIT ~n' EETKT 3n' :
`EE'A'B'Z3n, ~E'A'F'Z~n, ~F3n, ~FI3n, ~FIMI~n, :
~FINI~ , ~FIOI3n, ~FJ~n, ~FL~n, ~FM3n. E n n ~L3n, ~LJ~n, ~LTIT'3n. ~LTKT ~n~ ~M3n ~MI~n, ~MTIT ~n~
~MTKT'3n, ~N3n, ~NI~n, ~NTIT'~n, ~NTKT'~n, ~QI3n, ~QJ3n ~RI~n, ~RJ3n, and ~UI~n.

It is helpful to define three P205 contents, operative at different stages of polymerization, that must be controlled in order to optimize the synthesis procedure of the present invention. We will define the initial P205 content mO as the P205 content of the polyphosphoric acid operative during dehydrohalgenation (in step b above and as explained more fully hereinafter~. The initial P205 content in accordance with the practice of ~ , ~ ..... ~ j~ r~it~ ''~ ~

59~36 the instant invention should be below about 83.3%, and may range from between about 83.3% to about 63%; preferrably below about 82%, more preferrably below about 80~, and most preferrably below about 76~.
The intermediate P205 content is operative at the initiation of polycondensation and is calculated so as to gi~e the third (or final) P205 content f that accounts for polyphosphoric acid hydrolysis by 100% of the theoretical water of polycondensation. The final P205 content, f, must be above some minimum value if the solution is to maintain its effectiveness as a reaction ; .
medium at the la~e stages of polymerization. The final P205 content should be between about 82% to -.about 88~, preferrably between about 82% to about 84%, and most preferrably between about 82% to about 83%.
The various important general process steps for preparing liquid crystalline po].ymer 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:

., , : '.'' ';. ': ^ . ~ :: ' ::' . :. .: ' .: : . , ' . - ' ' ' ' ' ~ ' ' ', ', ' .' ', . ' ' ' . ': : . : ' ' :'. : ' ' ', ' :` ' ' :, '` ' '' ' :' . ' ; . "'` . . :' . " ' ., ' . ~ : "' lZ51~736 Stage One--One or more of a selected first monomers selected from the group consisting of (amino-group-containing) monome~ , 5 , or 9 is added to a specified initial weight in grams (given by a ) of a polyphosphoric acid with a P205 content mO according to the empirical equation a = {[1-f]([Py/Pc] -Py) - [nO(18.02)/~w] Py} (1-mO) 1 where Py is the weight in grams of the theoretical yield of polymer, Pc is the weight fraction of polymer in the total ~eight 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 acid composition), nO is an integer giving the number of mo:Les of condensation by-product per mole of polymer repeating unit, The number 18.02 is the molecular weight of the condensation by-p:roduct, M~ is molecular weight of the polymer repeating unit, and f is the final P205 content that must be above a minimum value as defined by th~s invention.

;' ' , ,. ", " ,I " ~," , " . ;",, '" " , ~;~` .,, . ~' ::,, .,,..~,,, , ;,,~ ~; `, ,,. , ,~, .,; , "., ~5973~

Stage Two--Once the first monomer(s) are combined with polyphosphoric acid, and protecting groups, if present, released, (optionally, depending on the particular polymer and reaction mechanism chosen) a stoichiometric amount of one or more of a selected second monomer selected from the group consisting of 2 , 4 , 6 , 7 or 8 is next added and the chosen ~alue of f is achieved by adding b (an intermediate weight in grams of P205) to the mixture according to the equation.
[Py/Pc] Py ~ [{nO(18.02)/Mw}] P - a*
Stage Three--The resulting mixture (containing the first monomer(s) and/or the second monomer(s)) is then heated to a temperature suitable for polycondensation. The reaction temperature may range from about 100C to about 210C, preferrably about 110C ko about 200C, more preferrably about 160C to about 190C, and mo6t preferrably about 185C.
The P205 content, mO, should be low enough to:
(1) achieve efficient dehydrohalogenation and/or (2) achieve sufficient monomer loading to achieve desired Pc without foaming problem or unusually high bulk viscosity. f should be high enough to:

:. "

.

~25~73~;

(2a) mai~tai~ a polyphosphoric acid composition that is an effective reaction medium at late -~
stages of pol~condensation.
(2b) provide an sffective phosphorylating medium as described in N. Yoda and ~. Kurihara, ~New Polymers of Aromatic Heterocycles by Polyphosphoric Acid Solution ~ethods~, J. Polymer Science, Macromolecular Reviews, Volume 5, (1971), p. 159 at initial stage of polymerization.
' ' , (2c) provide an effective solvent for the polymer at the end of polyco~densation.

For purpose of illustration, a plot of equation a is presented in Figure 7 showlng regioDs (shaded dash area) of poor monomer la solubility,, In the case of polymer ~AI~n, the family of Pc cur~es can be utilized as follows:

l. choose a ~AI~n polymer concentratlon, Pc, as an example 0.l6; . .

2. ~elect a point on the curve Pc ~ 0.16 above the ..
shaded dash area lndicating poor monomer la Qolubillty;

'~

.

; ' ~ ,,": .

.

12S~

3. ~rom that point selected, the weight in grams of PPA (a ) of the corresponding P205 content (mO) that should be added to 92.06g of monomer la can be determined;

4. after dehydrochlorlnation is complete, the amount of monomer 2a to be added is 62.38 g; and 5. if the final P205 content (f) has been chosen to be 82.2%, then the amount of P205 to be added (b ) is the difference between the amount of PPA used in step 3 above and the weight of PPA at the end of the curve for Pc = 0.16.

The choice of the optimal mO iB dependent on the desired polymer concentration and the solubility limits of the first monomer. The region of poor solubility for monomer la is shown in Figure 7. Other monomers lS exhibit different solubility limits. Solubility rankings of some representive monomers are llsted below~

monomers with solubilities greater than la;
lf, lg, 3a, 3b, 3c, and 3d;

~onomers with solubilities comparable to la:

ld, and 3e;

:. ' ~5~'7~6 monomer~ with solubilitles 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, ln, lo, lp, 5a, and 9a.

Accordingly, it is possible to dehydrohalogenate the selected hydrohalide (monomers) more rapidly;
the foaming problem is alleviated or eliminated;
the solution in PPA of lesser P205 content than that of U.S. Patent 4,225,700 is much less viscous and dehydrohalogenation can be carried out much more readily. Further, 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.

5i973~

The above-mentloned formulas I, III, V, VII, and VIII
homopolymer compositions may be prepared in accordance with the above process parameters by:

(a) mixing a selected first monomer (for example, a selected first monomer selected from the gr~up consisting of (1,1), ~1,2), or (1,3) with or wlthout oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a solution of the first monomer in the preliminary solvent, (c) adding a selected second monomer (for example, a second monomer selected from the group consisting of (~,1), (2,2), (2,3), (4,1), (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 monomer in the preliminary solvent, (d) then increasing the phosphorus pentoxide conten~ 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) causing polymerization of the first ~nd second monomer at a temperature sufficient to .-effect reaction at a rate to form a first homo-- 30 oligomeric product having a preselected intrinsic viscosity or a first homopolymeric product.

.
~2~;97~

Formulas II, IV, and VI homopolymer compositions ~ay be prepared by:
(a) mixing a selected first monomer (for example, a selected first monomer selected from the group consisting of .
(3,1), (3,2), (5,1), or (9,1)) with or without -oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content, i .
(b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a solution of the first monomer in the preliminary solvent, (c) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, . `
(d) causing polymerization of the first monomer at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsic viscosity or a first homopolymeric product.

..

. ...

7~

Copoly~eric Compositions and their preparation In accordance with a ~till further aspect of the invention, there i6 provided a liquid-crystalline composition useful in the preparation of fibers and films comprising a polycondensation product consisting e~sentially of a blend of certain polyphosphoric acids and a high concentration of at least one high molecular welght extended chain block polymer having the general formulas:

~<x~ ~
~herein ~r represents an a,romatic moiety and i6 XXX as defined above, Xl snd X2 are the same or different and are sulfur, cxygen, or NR ~R being hydrogen or an organic group), ths nitrogen atoms and X1 and X2 being bonded to aromatic carbon ato~s of Ar , N and X1 or X2 of each hetero ring are disposed ortho to one another, and y2 i~ nil or represents a bivalent organic radical and is XXXI as defined above, aibj represents the molar propsrtions of the respective different recurring units present in said copoly~er, Yi; represents an average number of the respective different sequential reeurring units present in said ~2~i9736 copolymer, n being a positive integer;

~[y2</ ~ \~ >~ X, ajbjm X~ X2 Yi; ckm' X3 y m+m' m~m' n wherein Ar1 represents an aromatic moiety and is XXX as defined above, Xl and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X1 and X2 being bonded to aromatic carbon atoms of Ar , N and X1 or X2 of each hetero ring are disposed ortho to one another and y2 10 represents a bivalent organic radical and is XXXI
as defined above, aibjm/m+m' represents the molar ~:
proportions of the respective different recurring units present in said copolymer, Yij represents an average number of the respecti~e different 15 sequential recurring units present in said copo-lymer, Ar3 represents a different aromatic moiety and is XXII as defined above, the nitrogen atom and X~ being bonded to aromatic carbon atoms of Ar3, ckm'/mtm' represents the molar proportions 20 of the respective different recurring units present in said copolymer, Yk represents an aver-age number of the respectiva different sequential recurring units present in said copolymer, n being a positive integer;

~5973~

, ~ XI, wherein Ar3 represents an aromatic moiety and is XXII as defined above, X3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X3 being bonded to aromatic carbon atoms of Ar , N and X3 of each hetero ring are disposed ortho to one another, ck represents the molar proportions of the respective different recurring units present in said copolymer, y~
represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer;

~n wherein Ar1 represents an aromatic moiety and is XXXII as defined above, Ar4 represents a dif-fere~t aromatic moiety and is XXIII as defined above, the nitrogen atoms bei~g bonded to Ar1 and the carbon atoms being bonded to Ar4, aibj represents the molar proportions of the respec-tive different recurring units present in saidcopolymer, Yij represents an a~erage number of the respective different sequential recurring units present in said copolymer, n being a posi-~ tive integer; . 127 -- ~LZ.~g733~

o o -~herein Ar4 represents a different aromatic .
moiety and is XXIII as defined above, Arl represents an aromatic moiety and is XXXII as defined above, and Ar5 represents an aromaticmoiety different from Ar4 and Ar1 and is XXIV as defined above, the carbon atoms being bonded to Ar4 and ArS and the nitrogen atoms being bonded to Ar1 and Ar5, n being a positive integer;
ckm'/mlm' represents the molar proportions of the ~.
respective different recurring units present in said copolymer, Yk represents an average number of the respective different sequential recurring units present in said copolymer, aibjm/m+m' represents the molar proportions of the respec-tive different recurring units present in said copolymer, Yij represents an average number of the respective different sequential recurring units present in said copolymer, n being a posi-tive integer;

~ XVI, wherein Ar1 represents an aromatic moiety and i~
XXX as defined above, Ar~ represents a different ~.
aromatic ~oiety and is XXV as defined above, X~ ;
, 128 ' ~;~5!~736 and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group~, the NH groups and X4 and X1 being bonded to aromatic carbon atoms of Ar and Ar1, NH and X1 or X2 of each hetero ring are disposed ortho to one another, aibj represents the molar propor-tions of the respective different recurring units present in said copolymer, Yi~ represents an average number of the respective different sequential recurring units present in said copo-lymer, n being a positive integer;

~N L

m~m' n wherein Ar1 represents an aromatic moiety and is XXX as defined above, Ar6 represents a different aromatic moiety and is XXV as defined above, Xl and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and Xl and X2 being bonded to aromatic carbon atoms of Ar and Ar , NH and X1 or X2 of each hetero ring are disposed ortho to one another, aibjm/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, Yi; represents an average number of the respective different sequential recurring units present in said -- :

i2~9~3~

copolymer, Ar9 represents an aromatic moiety dif-ferent fro~ Ar6 and Arl and is XXVI as defined above, X4 is sulfur, oxygen, or NR (R being hydrogen or an organic group), khe NH groups and -X4 being bonded to aromatic carbon atoms of Ar6 and Ar9, ckm'/m+m' represents the molar propor- ~ .
tions of tbe respective different recurring units - .
present in said copolymer, Yk represents an aver-age number of the respective different sequential recurring units present in said copolymer, n bein~ a positive integer;

~ jbl n ~herein Arl represents an aromatic moiety and is XXXII as defined above, Y7 represents an aromatic 1~ or heteroaromatic moiety and is '~XVIII as defined above, the nitrogen atoms being bonded to aromatic carbon atoms of Arl and bonded to adja-cent carbon atoms of Y , aibj represents the molar proportions of the respective different recurring units present in said copolymer, Yij represents an average number of the respectiYe different sequential recurriDg units present in - said copolymer, n being a positive integer.

~59736 In accordance with the practice of the present invention, the synthesi6 of the aforementioned formulas IX - XVIII copolymerfi may be illustrated by the follo~ing general reaction system:

Reackion Mcchanism Formation of formula IX copolymer /H2N NH2\
ajm ¦ ~ + bjm (Zl--Y--Z2) IX, \HX1~--~X2H

Formation of formula X copolymer 3jm ~ + blm (Zl--Y Z2) HXl X2H

+ C m~(z ~X3H) X~

, 1 3 1 `

-~2~i97~36 Formation of formula XI copolymer XI, Formation of formula XII copolymer :

1H2N NH2\ / 4 26\
m ~ 1 ~ bjm ~

XII, Formation of formula XV copolymer ;~ H ) (Z43~z~) / ZD NH2 \
c~m' ~ ~ ) Xv, .. .
.~ .

~;~59736 Formatio~ of formula XVI copolymer ¦ H2N ~ NH2 \ ~10 712~
~ HXl ) bj ~ ~Z13) XVI .

Formation of formula XVII copolymer ~H2N~ NH2\ /Zlo Z12\

~H 1 ) + bj ~ 3~Zl3) / ~14 ~ NH2\
+ ckm'~ ~ J - XVII .

Formation of formula XVIII copolymer /H2N NH2~ / X~ X~ \
Djm ~ + blm ~ ~ XVI I I .
H2N '--'f NH2 xl7 x~

The above-mentioned formulas IX, X, XII, XV, XVI, XVII,~and XVIII copolymer composit~ons c~n be prepared in accordance with the above process parameters by:
(a) mixing at least two of a fielected first monomers (for example, two or more of a monomer -~
selected from the group consisting of (l,l~
133 :
~, ...... .

~ i9736 (1,2), (1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a solution of the first monomer in the preliminary solvent, (c) adding at least one 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), (4,1), (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 monomer in the preliminary solvent, (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and secoDd monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, ~e) causing polymerization of the first and , second monomer at a temperature sufficient to effect reaction at a rate to form a first co--~59736 oligomeric product ha~ing a preselected intrinsic vi6cosity, or a first copolymer~c product, (f) optionally adding a preselected excess -~
molar amount of 6aid selected first monomer in step (a) thereby off-balancing the stoichiometry proportion of said selected first and second monomers in said ~irst and second monomer reac-tion medium so as to provide a said first co- :
oligomeric product or a said first copolymeric .
product following polymerization step (e) having a predetermined intrinsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both said selected fir~t and ~econd monomers, :
(g) optionally adding a preselected excess molar amount of ~aid selected 6econd monomer in step (c) thereby off-balancing the stoichiometry :
proportion of said ~elected first and second monomers in said first and ~.econd monomer reac-tion medium 60 as to provide~ a said first co~
oligomeric product or a 6aidl fir~t copolymeric product following polymerization step (e) having .
a predetermined intrinsic viscosity less than the maximum attainable for a 6toichiometric equivalent amount of both said selected first and ~econd monomer8, :
~ ' ~L:25973~

(h) optionally adding one or more of a selected monofunctional reactants in step (a) so as to provide a said first co-oligomeric product ~ or a said first copolymeric product following ; 5 polymerization ~tep (e) having a predetermined intrinsic viscosity less than the maximum attain-able in the absence of said selected monofunc-tional reactants.
Similarly formulas IX, XII, XVI, and XVIII copo-lymer compositions can be prepared by:
(a) mixing at least one of a selected first selected from the group consisting of (1,1) or ..
' (1,2) with or without oxidation protecting atoms or groups with a preliminary sol~ent of phos-phoric acid having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the I resulting mixture under reduced pressure to ,Z remove any volatilized protecting atoms or groups ', 20 present and provide a mixture of the fir6t mono- :
mer in the preliminary 601vent, (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), .

.

. . 136 ~.,.
.
:' .

~;~5973~i (2,2), (2,3), (4,1), (~,1), (6,2), or (7,1) in the resulting mixture of ~tep (b) to provide a mixture of the first and 6econd 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 reaction medium of greater phosphorus pentoxide content -~
suitable for polymerization, (e) causing polymerization of the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first co~
oligomeric product having a preselected intrinsic .
vi6cosity or a first copolymeric product, :
(f) optionally adding a preselected excess molar amount of said selected first monomer in step (a) thereby off-balancing the 6toichiometry . .
proportion of ~aid selected first and second monomer6 in 6aid first and 6econd monomer reac- ;~
tion medium 60 as to provide a 6aid first co-oligomeric product or a said fir6t copolymerlc ~ .
product following polymerization 6tep (e) ha~ing .
a predetermined intr~nsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both 6aid 6elected fir6t and :~ 137 1~59731Ei second monomers, (g) optionally adding one or more of a selected monofunctional reactants (a) ~o as to provide a said flrst co-oligomeric product or a said first copolymeric product following polymer-ization step (e) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reac-tants.

Preferred formulas IX, X, XI, XII, XV, XVI, XVII, and XVIII copolymer~ forming liquid crystalline copolymer compositions of the tnstant invention are those ~herein ai is the mola fraction of the ~-:
ith monomer selected from Type 1, b; is the mole fraction of the ~th monomer selected from Types 2, 4, B, 7, or 8, ck is the mole fraction of the kth monomer selected from Types 3, 5, or ~, m and m' are appropriate molar quantities based on desired yield, aib~ and aib~m/m+m' are the molar proportion~ of the recurring units resulting from the condensation of the ith monomer of Type 1 and the jth monomer of Type 2, 4, ~, 7, ore 8, ck and ckm'/m~m' are the moalr proportions of the recur- . .
ring unit resulting from thc condensation of the kth .:

:
~ 138 .

125973~;

monomer of Type 3, 5, or 9, Yi; is the average block length (i.e., the average number of sequential recurring units unbroken by a .-different recurring unit) of the recurring unit formed from the ith monomer of Type 1 and the jth monomer of Type 2, 4, 6, 7, or 8, Yk is the average block lengtb of the recurring unit formed by self-condensation of the kth monomer of Type 3, 5, or 9, and n is the average overall length :
of the copolymer (i.e., the average total number .
of recurring units independent of structure).
The number of recurring units in the copolymer may be the product of the highest i and the highest j or may be the product of the highest i :~
and the highest ~ plus the highest k. i, j and k can be as high as is practical, but may have certain minimal values if copolymers, rather than :
homopolymers, are to be obtained.
Selected molar quantities (a1m, a2m, ... aim) of monomers of Type 1 may 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, such as hydrogen halide, if present, may be substantially remo~ed by heating, and applying reduced pressure if desired. The quantity of the phosphoric acid is ~2S973~, most desirably determined in accordance with equation a* above, making the necessary calculations for addition of monomers of possibly different molecular weights and different proportions. A stoichiometric quantity (i.e., b1m ~ b2m + ... bjm = m) of monomer selected from Type 2, 4, 6, 7, or 8 may then be added to the resulting solution. The phosphorus pentoxide content of the resulting mixture may then be raised in accordance with equation b* above, so :
as to raise the final phosphorus pentoxide content of the substantially copolymeri~ed mixture to a value preferably within the range between about 81% to about 84% and most preferably between about 82% to about 83.5%. The resulting mixture may then be heated to a temperature preferably about 100C to about 210C, most preferably to about 170C to about 185C within a practical time period, from less ~0 than about one hour to greater 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 betueen from about 1 to about 23 hours, to achieve the desired n value. The practice of the present invention as it relates , 140 '`~

~2597~S

to the production of novel liquid-crystalline compositions comprising copolymers with the general formulas IX, XII, XVI, and XVIII ls illustrated for those compositions including general formula IX ~herein the selected monomers of Type l are further classified as being of Types (l,l), (1,2) or (l,3) and the selected monomers of Type 2 are of Types (2,l), (2,2), or (2,3).
General formula IX copolymers prepared from type (l,l) and type (2,l) monomers have the advantage that the critical concentration necessary for liquid-crystalline behavior is low. For the copolymers listed below, their critical concentration may be as low as about 5 weight percent in polyphosphoric acid at substantially moderate n values, thus allowing a broad range of :
operable concentrations.

~973~

~b~ V~ o~b~ n ., ~ '.' ~b~ Ib2 N ~1 yl~

' +~ ~ 2~'=~s 'bl ¦
yl~ ~Ib~ , Yl~ n _ _ _ _ `:':
_ ~ _ - ;
Ibl ~ Yn Since the recurring units of the copolymers are of essentially comparable mesogenicity, a broad range of copolymer compositions may be achieved;
for instance, a1b1 can range from nearly zero to nearly one while a1b2 or a2b1 (because it is equal to 1-a1bi) ranges from nearly one to nearly ~2S~7~

zero, respectively. The average block lengths Yl1 and Y12 or Y21 are governed by the method of monomer addition described above and the molar quantities selected. Thus, for monomer pairs of S essentially equal reactivity, Yll- which equals 1/1-albl, may range from nearly one to very high values. In a like manner, Y12 or Y21 can range from very high values to nearly one. ~onomer purity, control of stoichiometry, and exclusion of side reactions caused by oxidizing impurities must be sufficient to obtain an overall copolymer length, n, greater than about 50 in order to obtain the desired polymeric properties of useful mechanical strength, modulus, etc. The practice of the invention as it relates to copolymers derived from Class 1 monomers is further illustrated in Examples 49-51 and 54-66 below.
Ceneral formula IX copolymers ma,y be prepared from type (1,1), (2,1) and (2,2) monomers and from type (1,1), ~1,2) and (2,1) monomers. These monomers are classified as Class 2 o~ing either to a moderately reduced mesogenic character of the recurring unit derived from them or to their tendency to reduce the solubility range of the resulting polymer, which in turn is usually owing to an overall reduction of the heteroatom/hydrocarbon ratio of the resul~ing ~259736 polymer. Both of these conditions dictate that incorporation of Class 2 monomers into copolymers of the present invention should be carefully selected. The degree of this selectivity is illustrated by the following copolymers prepared in accordance with the practice of the invention.

s~

Yl2 n ' ':
~31 ~1.
15 ~
~,~{
n .~ . . . . . . . .. . . . ... . . .

'"' , ~L2S9736 The immediately preceding list of copolymers is derived from monomer compositions containing monomers imparting reduced solubility to the copolymer. The preferred values of aib1 (i.e., the mole fraction of the more soluble recurring unit) are those greater than about 0.8, leading to values of Y11 greater than about 5 and Y12 values of nearly one. Monomer purity, control of stoichiometry, exclusion of oxidizing impurities, and selection of the molar quantity of the less soluble monom.er to maintain copolymer solubility must be sufficient to achieve an average n value of greater than about 50. Increased proportion of a less soluble monomer may be achieved by -selecting comonomers that impart improved ' `
solubility to the copolymer. In general, monomers of Type 1 wherein X is S impart greater solubility than those in which X is 0 or N. The practice of the invention as it relates to copolymers of partially reduced solubility is further illustrated in Examples F)2, 53, 70, 71, and 72 below.
The following list of copolymers is derived from incorporation of monomers of moderately reduced mesogenicity and the practice of the invention is illustrated for them.

~, ~ 145 ~.

:,-, ~2S~736 :

q b~ b~
r~

~ ~ ~ , or The preferred ranges of a1b1 are from nearly zero to nearly one for copolymers in this classification with the overall proviso that the overall copolymer concentration in the polyphosphoric acid be above a critical concentration determined by the least mesogenic recurring unit. Thus, above about 13% the above copolymers may have a1b1 values between about one and zero, Y11 values of nearly one and greater, and Y21 values of nearly one and greater. The preferred concentration with these a1b2 and a2b values may be between about 15 and about 22 weight percent. If the molar proportion of the more highly mesogenic recurring unit (i.e., a1b1) is selected to have values of greater than about 0.6, preferably greater than about 0.75, then the range of operable concentrations is increased to "' ' ~ ' ' ' ' ' ' ` ','. ` ! ~ ;, ; , ~S9736 include concentrations of the copolymer in greater than about 8 ~eight percent, preferably -above about 10 weight percent. Values of n greater than about 50 are preferable as stated above.
General formula IX copolymer compositions may be ::-~
prepared from Class 3 monomers.
Monomers characterized as belonging to Class 3 lead to polymer recurring units that have little or no mesogenic character. Their incorporation into copolymers prepared as above are ~ithin the scope of the present invention but are less preferred because the random incorporation of a significant molar proportion of these non-mesogenic units leads to insufficient blocklength of the mesogenic recurring unit or units to impart liquid-crystalline behavior.
Ir.~orporation of less than about 3 molar percent of Class 3 monomers is preferred. Increased incorporation of Class 3 polymers are highly preferred by use of a block polymer procedure described below. A less preferred embodiment of the present invention is the preparation of General formulas X, XV, and XVII by the addition of monomers of Types 3, 5, and 9, respectively, to the initial solution of the above copolymer ........ .... . . . ... .. . . .

~59~3~i procedure. The unique feature of the geometry of monomers of Types 3 (except for 3k), 5, and 9 is the requirement that the block lengths, Yk, be large or, if small, be an even number. This condition dictates that preferred compositions of formulas X, XV, and XVII are prepared by a block polymer procedure described below.
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 having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protectin,g atoms or groups present and provide a solution of the first monomer in the preliminary solvent, (c) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for ~L~5~ 36 ,.

polymerization, (d) causing polymerization of the said t~o of a selected first monomer at a temperature suf-ficient to effect reaction at a rate to form a first co-oligomeric product having a preselected intrinsic viscosity or a first copolymeric pro-duct, (e) optionally adding one or more o~ a selected monofunctional reactants in step (a) 60 as to provide a said first co-oligomeric product or a said first copolymeric product following polymerization step (d) having a predetermined intrinsic viscosity les~ than the maximum attain-able in the absence of said selected monofunc-tional reactants.

Selected molar quantities (c1m, c2m, ... ckm) ofType 3 monomers may be mixed witb a phosphoric acid having a phosphorus pentoxide content of from about 63% to about 78%, preferably greater tha~ about 68%, most preferably about 78%, and the protecting groups, i~ present, may ~e substantially removed by heating, and applyi~g reduc~d pressura, lr desired. The quantity o~ ;

~ .

125973~

phosphoric acid is determined in accordance ~ith equation a* above, making the nec~ssary . .
calculations for the addi~ion of monomers of possibly different molecular weights and S different proportions. The phosphorus pentoxide content of the resulting mixture may then be raised in accordance with equation b* above, so as to raise the final phosphorus pentoxide of the substantially copolymerized mixture to a value greater than about 81%, most pre~erably between about 82% to about 83% but less than about B4%.
The resulting mixture may then be heated to about 100C to about 200C, most preferably between about 150C to about 185C within a practical 15 period of time, preferably within a time period of less than about 1 hour to about S hours or more, and most preferably within a period of about 1 hour to about 3 hours, and then main~ained at the selected temperature for sufficient time to achiave the desired n value.
The practice of the present invention as it relates to the production of novel liquid-crystalline compositions that include copolymers with the general formula XI is further illustrated for those compositions ~herein the selected monomers of Type 3 are further classified as being of Typ~ (3,2).

. ~,. . .

3L~S9~73~

The polymers ~ ` ' ~ ; ~ ~ , or are prepared according to the above procedure wherein cl is the molar proportion of the more soluble recurring unit and selected to be above about 0.5, more preferably above about 0.7, to ensure the solubility of the resulting copolymer to the high concentrations required for liquid-crystalline behavior. A ~eight percent of the copolymer above about lS ~eight percent, more ~;~5973~ `

preferably above about 17.5 weight percent, may be selected. ~olar proportions selected above and monomer reartivity ratios determine the average blocX lengths Y1 and Y2. The block length does not bear on whether liquid-crystalline behavior in polyphosphoric acid is obtained with these polymers. The important factor iæ the maintenance o~ solubility at high concentration and the preparation of these copolymers in polyphosphoric acid at high concentration from monomers.

~_J . '., 1~:597~6 Blockpolymeric Compositions and their preparation In accordance with a still further aspect of the invention, there is provided a liquid-crystalline composition useful in the preparation of fibers and films comprising a polycondensation product consisting essentially of a blend of certain polyphosphoric acids and a high concentration of at least one high molecular weight extended chain `~ :
block polymer havin~ the general formulas:

{ ~ IX, wherein Ar1 represents an aromat;ic moiety and is XXX as defined above, Xl and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), l;he nitrogen atoms and X1 and X2 being bonded to aromatic carbon :~
atoms of Ar , N and X1 or X2 of each hetero rin~
are disposed ortho to one another and Y is nil or represents a bivalent organic radical and is : 20 XXXI as defined above, aibj represents the molar : proportions of the respective different recurring units present in said block polymer, Yi;
represents an average number of the respective ~2~;9~36 different sequential recurring units present in said block polymer, n being a positive integer;

--E N~3<N>~N\>~ X, ajbjm X~ X2 `/ii ckm' X3 y m+m' m+m' n ~herein Ar1 represents an aromatic moiety and is XXX as defined above, Xl and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X1 and X2 being bonded to aromatic carbon atoms of Ar , N and X1 or X2 of each hetero ring are disposed ortho to one another and Y is nil or represents a bivalent organic radical and is XXXI as defined above, aibjm/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, Yi; represents an average number of the respec-tive different sequential recurring units present in said block polymer, Ar3 represents an aromatic moiety anA is XXII as defined abo~e, X3 is ~ul-fur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X3 being bonded to aromatic carbon atoms of Ar1, N and X3 `
of each hetero ring are disposed ortho to one another, ckm'/m~m' represents the molar propor- :`
tions of the respecti~e different recurring units present in said block polymer, Yk represents an ; :

154 : :

.' '` .

~`
_, ;~ .. ,.,, ,. , ,... , ,.,,~ "" ",,~ " , ~ "".;,, , "," "

59~736 average number of the respec~ive differ~nt sequential recurring units present in said block polymer, n being a positive integer;

~ XI, wherein Ar3 represents an aromatic moiety and is XXII as defined above, X3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X3 being bonded to aromatic . .
carbon atoms of Ar , N and X3 of each hetero ring are disposed ortho to one another, ck represents the molar proportions of the respective different recurring units present in said block polymer, Yk represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer;

_ _ 11 ajbi C yjj n ~herein Ar1 repreæents an aromatic moiety and is XXXII as defined above, Ar4 represents a dif-feren~ aromatic moiety and is XXIII as defined above, the nitrogen atoms being bonded to Ar1 and the carbon atoms being bonded to Ar4, aib~
represents the molar proportions of the respec-tive different recurring units present in said . -- ~
: ~S973~i block polymer, Yij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer;

8 1l ~ ~ ~ ~x ~ ~ Y~ XIII, wherein Ar1 represents an aromatic molety and is XXXII or XXX as defined above with the proviso that when Ar1 is bonded to nitrogen atoms Ar1 is XXXII and when Arl is bonded to both nitrogen atoms and Xl and X2, Arl is XXX as defined above, Ar4 represents a different aromatic moiety and is : -XXIII as defined above, the carbon atoms being ~;
bonded to Ar4, m'/m+m' represents the molar pro-portions of the respective different recurring ~ :
units present in said block polymer, y~
represents an average number of the respective different sequential recurring units present in ~:
said block polymer, X1 and X2 are the same or - .
different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X1 and X2 being bonded to aromatic carbon atoms of Ar , N and X1 or X2 of each hetero ring are disposed ortho to one another and Y is nil or represents a bivalent organic radical and is XXXI as defined above, m/m+m' represents the ~ . .
:~., : .

73~i molar proportions of the respective different - recurring units present in said block polymer, y represents an average number of the respective different sequential recurring units present in 5 said block polymer, n being a positive integer;
e 1l ~ .~, ~"~ Xl~, wherein Ar3 represents an aromatic moiety and is XXII as defined above, X3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X3 being bonded to aromatic carbon atoms of Ar , N and X3 of each hetero ring are disposed ortho to one another, p represents the molar proportions of the respective differen~
recurring units present in said block polymer, y'/2 represents an average number of the respec-tive different sequential recurring units present in said block polymer, Ar1 represents an aromatic moiety and is XXXII as defined above, Ar4 represents a different aromatic moiety and is XXIII as defined above, the nitrogen atoms being bonded to Ar1 and the carbon atoms being bonded to Ar4, q represents the molar proportions of the respective different recurring units present in said block polymer, y represents an average number of the respective different sequential 157 .

1259~3~;
recurring units present in said block polymer, n being a positive integer;

~ ~n wherein Ar4 represents a different aromatic S moiety and is XXIII as defined above, Ar represents an aromatic moiety and is XXXII as .
defined above, and Ar5 represents an aromatic moiety different from Ar4 and Arl and is XXIV as defined above, the carbon atoms being bonded to :
Ar4 and Ar5 and the nitrogen atoms being bonded - -to Ar1 and Ar5, n being a positive integer; ~- ;
ckm'/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, Yk represents an average number of the respective different sequential recurring units present in said block polymer, ::~
aibjm/m+m' represents the molar proportions of -~
the respective different recurring units present in said block polymer, Yi; represents an average number of the respective differ~nt sequential recurring units present in said block polymer, n .
being a positive integer;
~.

~ o .".,. ~ .

~2597~6 wherein Ar1 represents an aromatic moiety and is XXX as defined abo~e, ArB represents a different aromatic moiety and is XXV as defined above, X
and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X1 and X2 being bonded to aromatic carbon atoms of Ar6 and Ar1, NH and X1 or X2 of each hetero ring are disposed ortho to one another, aibj represents the molar propor-tions of the respective different recurring unitspresent in said block polymer, Yi; represents ian average number of the respective different sequential recurring units present in said block polymer, n being a positive integer;

~5 ~ x, ~ ~ ~N XVII, ~Iblm m t m' m~m' n wherein Ar1 represents an aromatic moiety and is XXX as defined above, Ar6 represents a different aromatic moiety and is XXV as defined above, Xl and X2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X1 and X2 being bonded to aromatic carbon atoms of Ar and Ar , NH and X1 or X2 of each hetero ring are disposed ortho .
to one another, aibjm/m+m' represents the molar proportions of the respective different recurring ',, ' .

:
.c................................................................... ..

' : ' ' ' ~ i , ;, ; ~ , i ! ~

1~.,59~3~

units present in said block polymer, Yij represents an average number of the respective different sequential recurring units present in said block polymer, Ar9 represents an aromatic S moiety different from Ar6 and Arl and is XXVI as defined above, X4 is sulfur, oxygen, or NR (R
being hydrogen or an organic group), the NH
groups and X4 being bonded to aromatic carbon atoms of Ar6 and Ar9, ckm' /m+m' represents the molar proportions of the respective different recurring units present in said block polymer, Yk represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; :~-wherein Arl represents an aromatic moiety and is XXXII as defined above, Y represents an aromatic or heteroaromatic moiety and is XXVIII as defined above, the nitrogen atoms being bonded to aromatic carbon atoms of Arl and bonded to adja-cent carbon atoms of Y7, aibj represents the molar proportions of the respective different recurring units present in said block polymer, Yi; represents an average number of the respec-tive different sequential recurring units presentin said block polymer, n being a positive integer.
: 160 ~2~i973~

In accordance ~ith the practice of the pres~nt invention, the synthe~is of the aforemsntione,d for~,ul~s IX -XIX block poly~,ers can be lllustrated by the following general reaction system:

Reaction Mechanism Formation of formula IX block polymer /H2N NH2~
9jm ~ bjm (Zl--y2--Z2)--_ IX, \HXI X2H/

Formation of formula X block polymer ) ~ bjm ( Zl--y2--Z2 ) , ' N H2 \
tckm' Z3~ 3 ~ X.

61 ~

~L~5973Çi Formation of formula XI block polymer :
` .

~ NH2\
~m(Z3 ~ X3H) XI, Formation of formula XII block polymer /H2N NH ~\ l 24 Z6\
m ~ ~ bjm H2N NH2 Z5 Z7 . ..

--~~ XII, :

Formation of formula XIII block polymer .

/ 4 Z~\ / H2N NH2\
~Z6 ~ Z7 ) ~ H2 N ~ N H2) and /H2N NH2\ ' ' ~HX ~ 3~ ) + m + x ( Z1--y2--Z2 ) XIII

. ~
., ,:

t~ r~ ,6~

iL259736 Formation of formula XIV block polymer Z4 Z.6 H2N NH l ~~~r~ NH2 .' m ~ I m ~ ~ ~ ~nd m Z3~ XIV, Formation of formula XV block polymer ( H~N3~ 7) 5 7 ) NH~ \
2~o NHI ) Formation of formula XVI block polymer / H~N~ NH~\ /Z10 17\
~HX~ ) ~ b~m ~ ~ ~ ~ XVI .

Formation of formula XVII block polymer /H~N NH~\ ¦Zlo~,~yZl~\
~HX13~ X~H) ~ 11 13J

~ c m ( ~ ) ~ XVII
Zl~ X~ H

;

.~: . . . .. , .. i. .. i. ...

~L259~3~i :

Formation of formula XVIII block polymer :

~H2N ~ ~H2\ / X7~ X~ \ .
~ 2 ) t bjm ~ ~ J ~ XVIII .

Formation of formula XIX block polymer /HX~ NH2 / X10~ X11\
a~m ~, Arl ) ~ bjm L Y I XIX .
~H2N X2H X11 ~X10 The above-mentioned formulas IX, XII, XYI, XVIII, and XIX block polymer compositions may be prepared in accordance with the above process parameters by:
(a) mixlng at leaet one of a selected first monomer chosen from (1,1), tl,2~, or (1,3) wlth or wlkhouk oxldatlon protecting atoms or groups with a prellmlnary solvent o~ phosphorlc acld having a relatively low phosphorus pentoxlde con-tent, ~ (b) heating and optionally placing the resulting mixture under reduced pressure to ~;.
- remove any volatilized protecting atoms or groups ~2S~37~

present and provide a mixture of the first mono-mer in the preliminary solvent, (c) adding at least one of a selected second monomer in the resulting mixture of step (b? to provide a mixture of the first and second monomer :
chosen from (2,1), (2,2), (2,3), (4,1), (~,1), (7,1), or (8,1) 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 reaction medium of greater phosphorus pentoxide content suitable for polymerization, (e) causing polymerization of the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsic viscosity, (f) mixing a selected amount of the first homo-oligomeric product ~ith a selected amou~t of at le~st one of a selected l~econd homo-oligomeric product so as to form a fir~t poly-oligomeric product, said second homo-oligomeric product being formed by like step~ ~a), (b), (c), (d), and ~e) with the overall proviso that at least ;

;i9 ~3~

one of the 6elected monomer of step (a) or (c) :
which forms the second homo-oligomeric product be different from at least one of the selected mono-mer of step (a) or (c) which forms the first homo oligomeric product, (g) causing polymerization of the poly-oligomeric product at a temperature sufficient to :
effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first block-polymeric product, (h) optionally adding one or more of a selected monofunctional reactants prior to end of polymerization ln step ~g) 60 as to provide a said first block-oligomeric product or a said first block-polymeric product having a predeter-mined intrinsic visc06ity less than the maximum attain3ble in the absence of 6aid selected mono-functional reactants. `.
Altern3tively, formula6 IX, XII, XVI, XVIII, and XIX block polymer compositiolls may be prepared by: :
(a) mixing at least one of a selected firstmonomer with or without oxidation protecting atoms or groups with a preliminary solvent of 59~73&~

phosphoric acid having a relatively lo~ phos-phorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups . present and proYide a mixture of the first mono-mer in the preliminary solvent, (c) adding at least one of 3 selected 6econd monomer in the resulting mixture of step (b) to provide a first mixture of tha first and second monomer in the preliminary sol~ent, (d) then increasing the phosphorus pentoxide content of the mixture resulting from step (c) to provide a first and second monomer reaction medium of greater phosphoru6 pentoxide content suitable for polymerization, ~ e) causing polymerization of the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product having a preselected intrinsicviscosity, (f) mixing a selected amount of the first homo-oligomeric product with a selected amount of a second mixture of a diffsrent first and ~econd ~ . :

~L2S~7~

monomer in the preliminary 601vent, caid second mixture being formed by like steps (a~, (b) and :
(c) with the overall provi~o that at least one of the selected monomer of 6tep (a) or (c) ~hich forms the 6econd mixture be different from at least one of the selected monomer of Etep (a) or (c) which forms the first homo-oligomeric pro-duct, (g) then increasing the phosphorus pentoxide content of the mixture resulting ~rom ~tep (f) to provide a first oligomer-monomer reaction medium of greater pho6phorus pentoxide content ~uitable for polymerization, (h) causing polymerization of the mixture resulting from step (g) at a temperature ~uffi-cient to effect reaction at a rate to form a fir6t block-oligomeric product having a pre6elected intrinsic Vi6CoE:ity or a fir6t block-polymeric product, (i) optionally adding one or more of a selected monofunctlonal reactant6 prlor to end of polymerizatlon in step (h) E,'O a6 to provide a æaid first bloc~-ollgomeric product or a ~ald ~irst block-polymeric product baving a predeter-~,ined intrinEic vi6cosity les6 than ths maximum .

.. . .

~ i;9~73 attainable in the absence of sald selected mono-! functional reactants.

The above IX-XIX block polymers forming the liquid crystalline block polymer compo~itions of ths instant lnvention can be characterized as having more than one recurring unit, the distri-bution or sequencing of which may be different from that obtained by the random condensation of monomers as in the copolymers described abo~e and is further charaeterized as having eontlguous blocks ol the same recurring unit as obtained by the random condensation Or oligomers.
The preferred formulas IX, XII, XVI, XVIII, and XIX block polymers ar~ those polymers wheretn .I
aibj is the mole fraction of the recurring unit formed by the conden~ation o~ a homo-oligomeric reaction product (defined below) derived from the ith monOmQr Or Type 1 with a stoichiometric quan-tity of ~th monomer of Typls 2, 4, e, 7, or 8, respectlvely, and lncorpor~ated by a block-polymeric procedure descrlbed below, and Yi,~ and n have the same mesning as described above for copolym~rs.

The preferred XI block polymer~ are those :
~.

.

~L259736 wherein ck is the mole fraction of the recurring unit formed by the condensation of a homo-oligomeric reaction product (defined below) ~--derived from the kth monomer of Type 3 and incor-porated by a block polymeric procedure described below, and Yk and n are as defined for copoly-mers.

The preferred X, XV, and XYI~ block polymers are those wherein aibjm/m~m' is the mole fraction of the recurring unit formed by the condensation of m moles of recurring units of a homo-oligomeric reaction product derived from the ith monomer of Type 1 and the jth monomer of Type 2, 4, or 6 and combined with m' moles of recurring units of a homo-oligomeric reaction product derived from condensation of the kth monomer of Type 3, 5, or ~, respectively, and Yij. Yk. and n are as defined for copolymers.

The preferred XIII block polymers are those wherein m' and m are appropriate molar quantities of the monomers that form the reaction products and are selected to give desired yields and molar 1259~73~;
proportions of the respective recurring units, y' and y are block lengths as defined above, n is the total number of recurring units, and x is a molar quantity substantially less than m' that is selected to give an appropriate block length of the first homo-oligomer end-capped with o-d.lamine functional groups, The preferred XIV block polymers are those wherein m', m, x, n, y, y' are as defined above, q is equal to m'/mtm' and p is equal to m/2(m+m').
Selected molar quantity, m, of a monomer of Type l may 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 tbe protecting groups, if present, may be removed as described previously. The quantity of ~he phosphoric acid is most desirably determined in accordance with equation a* as described above. A stoichiometic quantity (i.e, m) of a monomer of Type 2, 4, 6, '7, or 8 may then be added to the resulting solu-tion. The phosphorus pentoxide content of the resulting mixture may then be raised in i2S97~G
accordance with equation b* given above, so as to raise 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 may then be heated to about 100C to about 185C, most preferably to about 170C to about 185C, within a practical period of time, preferably wi~thin a period of from less than about one to about 5 hours, most preferably from about one to about 3 hours. This temperature is maintained for sufficient time to achieve a selected n value, hereinafter referred to as the homo-oligomeric n value, that is above a selected minimum value to be described for specific cases below, is characterized as being equal to 1/2(1-p), where p is the extent of reac-tion, defined as the mole fraction of either type .
of functional group present that has undergone ~-.
condensation, and being preferrably below a selected maximum value characteristic of complete polymerization. A selected molar quantity, mij, of the homo-oligomeric reaction product thus obtained is diverted into a second vessel con-taining a selected molar quantity, mij, of a similarly obtained but structurally different :
homo-oligomeric reaction product and the heating , 172 ~

:

~L2S9736 at elevated temperatures continued.

The average block lengths, Yij, of the block polymers may be determined the following way. The ijth oligomeric reaction product is prepared by adding ai moles of a first monomer to an equlmolar amount b; of the second monomer. The sum of 811 ai or bj is 1.
The mixture is polymerized to a sèlected intermediate extent of reaction, Pi;. The oligomeric n value of the ijth oligomeric reaction product, ni~, is given by 1/2(1-pi~). The molar proportions of the recurring units incorporated into the block polymer are given by ~.

The block lengths Yi~ can be calculated by the equation nii Yi~ ~ (1 ~ Pij) ~ ~j (1 - Pij) iJ

which assumes that the homo-oligomers condense with equal reactivity. The above equation for Yi; sho~s that if either of two homo-oligomeric reaction products are polymerized to high conver-sion, (i.e., allowed to achieve a high nij value -~' :
~2~9~7~36 before mixing) then both block lengths in the resulting block polymer will be high.
The practice of the present invention as it relates to the production of novel liquid-crystalline compositions that include block poly-mers with the general formulas IX, XII, XVI, XVIII, and XIX is illustrated ~or those composi-tions including general formula IX ~herein the ~elected first homo-oligomer may be prepared from monomers of Type 1 and Type 2 that are further classified as belonging to class 1 and the selected second homo-oligomer is further charac-terized as belonging to either class 1, class 2, or class 3.
General formula IX block polymers may be prepared from homo-oligomers derived exclusively from class 1 monomers. The block polymers, .

r~

~12~i;9736 ~3~

~ ~ ~ ~ ~ ~ ~ ~ , or 5 Jl~ y~

have the same advantage of a broad range of oper-able concentrations as described for copolymers formed exclusively from Class 1 monomers. The advantage to the block polymer procedure described above for these polymers is the ability ry Y11 and Y12, or Y21, or Y22 essentially independent of the molar proportion a1b1, or a2b2, or a2b1, or a1b2 by selecting appropriate extents of reaction lor the corresponding homo-. 175 :
... - '' ~25~73~

oligomer. For example, Y11 may be 20 or greater for a broad range of a1b1 values by increasing the exkent of reaction, P11~ as the a1b1 value is Y12- Y21. or Y22 of the above formu-S las may be obtained with values from about one toabout 75, most pre~erably from about 25 to about 50, by selecting appropriate P11 and P12~ P21~ or P22 values. In practice, the members of this selected class of block polymers, because all the recurring units have a h~gh degree of mesogeni-city, are liquid-crystalline when an n value of greater than about 40 is obtained at a concentra-tion of greater than about 6 weight percent independent of the block lengths achieved. The practice of the invention as it relates to block polymers of Class 1 is further illustrated in Examples 75-84 below.
General formula IX .block polymers may be prepared from a first homo-oligomer of Class 1 and a second homo-oligomer derived from monomer pairs containing Class 2 monomers. The block polymers, } ~

. . . ! , ! .~ ; , ,., . , , .. . ~ .. ; ' : . , ~' , . . .

1259'?'36 { 3 ~ ~}~

are derived from homo-oligomers of different mesogenicity. The selection of a1b1 (the molar proportion of the first and more highly mesogenic recurring unit) and the preferred Y11 (the aver-age block length of the first and more highly mesogenic recurring unit~ are governed by the following considerations. The block polymer reaction product in the first case may derive liquid-crystalline behavior by virtue of the sole presence of the first recurring unit when Y11 is greater than about 30, more preferably greater than about 40, at concentrations of the first - recurring unit alone (i.e., the weight of the Sirst oligomer added / weight of the final block .- ' " ".

~ 177 ~2~97~6 polymer reaction product) greater than about 7 percent, or the block polymer reaction product in the second case may derive liquid-crystalline behavior by virtue of the combined presence of both recurring units, independent of Y11. at con- -centrations above which the moderately mesogenic recurring unit derived from the second homo-oligomer is liquid-crystalline alone. The pre-ferred values of a1b1 are from about 0.4 to about one, with Y11 ranging from about 80 to about 20, respectively, as a1b1 is varied from 0.4 to one.
The most preferred concentrations of these block polymers is above about 15 weight percent but may be lower as either the a1b1 value or the Y11 value or both values are increased. The pre-ferred n value for these compositions is ~rom about 50 to 150, most preferably greater than 100. Obtaining sufficient n values may be aided by the addition of the second homo-oligomeric reaction product before the phosphorus pentoxide content is raised to the value necessary for polymerization (i.e., when P12 or P21 is zero and n12 or n21 = 1/2) and then adding the appropriate amount of phosphorus pentoxide to raise the mi~-ture to sufficient phospborus pentoxide content.
1'his procedure aids in mixing and is most pre-ferred ~hen the homo-oligomeric n value of the ~.~,................................................................ .
~,y :

.

~L~Si973~

flrst homo-oligomer, n11, is large. The practice of the invention as it relates to the ?reparation of block polymers of Class 2 is further illus-trated in Examples 85-88 below.
General formula IX block polymers may be prepared from a first homo-oligomer of Class 1 and a second homo-oligomer derived from monomer pairs containing Class 3 monomers. The block polymers --E ~<N~]

~C~ ~</~ CH2~ ~. ~

~<N~3~

~/5~~' ~ ~n ~ ~

', , .

~. ..

~Z~i~37~

':

~ ~-~N~'~C \>t CH2 ~ r --,bl Yll ~lb2 Y12 n derive their liquid-crystalline behavior entirely from the presence of the first recurring unit, its average block length Y11~ and its concentra-5tion alone in the total weight of the final block polymer reaction product. Thus, the values of a1b1, Y11~ and concentration must meet the condi-tions of ths first case described for the block polymers containing Class 2 monomers. The method .. `
10of the invention allo~s the preparation of such h~ghly concentrated mixtures of mesogenic units, i.e., reaction products substantially higher in polymer concentration than that required for liquid-crystalline behavior, that incorporation 15of significant amounts of non-mesogenic units is possible if the above conditions are met.
The preferred values of a1b1 are from about O.ô
to about one. The preferred values of Y11 are from at least about 30 to about 100, more prefer-ably bet~een about 50 to 100. The preferred values Of Y12 or Y21 are from about one to about 50. The preferred values of n are from about 50 ~.

, .

373~

to 200 with the most preferred values being about 100 to 150. The preferred selected concentra-tions of the block polymer are above about 15 ;
weight percent. especially as the proportion of the non-mesogenic recurring unit is increased.
The practice of the invention as it relates to production of block polymers containing Class 3 monomers i6 further illustrated in Examples 73, 74, 89-94 below.
The practice of the invention as it relates to the production of novel liquid-crystalline compo-sitions that include block polymers with the gen-eral formulas X, XV, XVII are illustrated for block polymers of formula X wherein the selected lS first homo-oligomer is prepared from Type (1.1) `-or (1,2) and Type (2,1) monomers and the selected second bomo-oligomer is prepared from monomers of ;`
Type (3.2).
The general ~ormulas X, XV, and XVII liquid cry-stalline block polymer compositions shown above are prepared according to the following pro-cedure:
(a) mixing at least one of a selected first monomer with or without oxidation protecting atoms or groups with a preliminary solvent of . ' . -~-' ' .:

~L~59736 phosphoric acit having a relatively low phos-phorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a mixture of the first mono- .
mer in the preliminary solvent, (c) then incrPasing the phosphorus pentoxide content of the mixture resulting from step (b) to proYide a first monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (d) causing polymerization of the flrst monomer at a temperature sufficient to effect reaction at a rate to form a first homo- ;
oligomeric product having a preselected intrinsic viscosity, (e) mixing a 6elected amount of the first homo-oligomeric product with a selected amount of at least one of a 6elected second homo-oligomeric product 60 as to form a first poly-oligomeric product, said second homo-oligomeric product being formed by like steps (a) and (b) follo~ed by:

~;~5973~

(1e~ adding at least one of a selected second monomer in the resulting mixture of step (b) to provide a mixture of a first and second monomer in the preliminary solvent, (2e) then increasing the phosphorus pentox- .
ide content of the mixture resulting from step (le) to provide a first and second monomer reac-tion medium of greater phosphorus pentoxide con-tent suitable for polymerization, (3e) causing polymeri~ation of the first and second monomer at a temperature sufficient to ~: :
effect reaction at a rate to form said second `~:
homo-oligomeric product having a preselected intrinsic viscosity, with the overall proviso that at least one of the selected monomer of step (a) or. (le) ~hich forms the second homo-oligomeric product be dif-ferent from at least one of the selected monomer :
of step (a) which forms the first homo-oligomeric product, (f~ causing polymeri~ation of the poly-oligomeric product at 3 temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first block-polymeric produc~, . 183 i~X ~ , , , Si ' ?,, ~ ?~;' 'J~d ~

973~i (g) optionally adding one or more of a selected monofunctional reactant6 prior to end of polymerization in step (f) so as to provide a said first block-oligomeric product or a said first block-polymeric product having a predeter-mined intrinsic viscosity less than the maximumattainable in the absence of said selected mono-functional reactants.

Alternatively, the general formulas X, XV, and XVII liquid crystalline block polymer composi- , tions shown above may be also prepared by:
(a) mixing at least one of a selected first monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phos-phorus pentoxide content, (b) heatin`g and optionally placing the resulting mixture under reduced pressure to remove any volatilized prot~cting atoms or groups present and provide a mixture of the ~irst mono-mer in the preliminary solv~nt, (c) mixing a selected amount of the solution of step (b) with a selected amount of at least one of a ~elected first homo-oligomeric product so as to form a firæt oligomeric-first monomer :.~,.;

~2~i~73S

reaction medium, said first homo-oligomeric pro-duct being formed by like ~teps (a) and (b) fol-lowed by: .
(lc) adding at least one of a selected second monomer in the resulting 601ution of step : ~:
(b) to provide a mixture of a first and second .:
monomer in the preliminary solvent, (2c) then increasing the phosphorus pentox-ide content of the mixture resulting from step (lc) to provide a first and 6econd monomer reac- . .
tion medium of greater phosphoru6 pentoxide con~
tent suitable for polymerization, (3c) causing polymerization of the first and second monomer at a temperature sufficient to - :
effect reaction at a rate to form said first homo-oligomeric product havillg a preselected intrinsic viscosity, with the overall provis0 that at least one of the selected monomer of step (a) or (lc) ~hich forms the first monomer mixkure, be different from at least one of ~he 6elected monomer of 6tep (a) which forms the first homo-oligomeric pro-duct, (d) then i~creasing the phosphorus pent~xide 185 .
i;. ~ .

~f~59736 The polymers ~ ' ' ~
_['-: t9C~Q ~

. .~'.' 5. ~3,~, ~[~ ' {~3.~ , or ~.

~ZS9~36 have preferred molar proportion of the first recurring u~it, a1b1m/m+m' of from about zero to about 0.5 when the concentration selected to be above about 15 weigh~ percent. When a1b1~/m~m' ~-5 is selected to be above about O.S but less than one then the operable co~centration range iE ; -~`
extended to include concentrations of 7%, more pre~erably 10 weight percent. At concentrations above about 15 ~eight percent all selected values of Y11 and values of Y1 greater than about 5 give liquid-crystalline products, but n must be greater than about 50~ preferably above about 100 to give desirable mechanical properties.
The practice of the invention as it ralates to the blocX polymers of thi~ Class is further illustrated in Examples 102-112 below Ceneral formula X block polymer may be derived from a first homo-oligomer of Clas6 2 and a second homo-oligomer of Type (3,2). The block polymer6 .. ~,~ ' " .

~ f~ "~

~L25973 >~m m ~t . or N~

H H Vl 1 ~, Yl n , . :

~2S~736 are prepared from ~wo homo-oligomers of Cla~s 2 which dic~ates the selection of concentrations grea~er than about 15 weight parcent. The molar proportions of the various recurring units are selected based on desired mechanical properties or the maintenance of solubility in two recurring units of different solubility characteristics.
The preferred values f Yl are those from about 5-50, more preferably greater than 30. The prac-tice of the invention as it relates to block polymers of this class is further illustrated in .Examples 113-115 below.
The practice of the inventicn is illustrated for general formula XI for block polymers prepared from a single monomer of Type (3,2).
The general formula XI liquid crystalline block polymer compositions shoun above are prepared according to the following procedure:
(a) mixing at least one of a selected first monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phos-phorus pentoxide content, ~, :~ , ~2S973~

(b) heating and optionally placing the resulting mixture under reduced pressure to remove any ~olatilized protecting atoms or groups present and provide a mixture of the fir~t mono-mer in the preliminary ~olvent, (c) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) to provide a first monomer reaction medium of greater phosphorus pentoxide content suitable for ~ 10 polymerization, (d) causing polymeriza~ion of the first monomer.at a temperature sufficient to effect reaction at a rate to form a firs~ homo-oligomeric product having a preselec~ed intrinsic viscosity, (e) mixing a selected amount of the first homo-oligomeric product with a selected amount Or at least one of a selected second homo-oligomeric product so as to form a first poly-oligomeric product, said second homo-oligomeric product being formed by like steps (a), (b), (c), and (d) with the o~erall proviso that at least one of the s~lected monomer of step (a) which forms the second homo-oligomeric product be different from at least one of the selected monomer of step (a) - `

whlch forms the first homo-oligomeric product, (f) causing polymerization of the poly-oligomeric product at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic ~ -.
viscosity or a first blocX-polymeric product.
(g) optionally adding one or more of a selected monofunctional reactants prior to end of polymerization in 6tep (f) so as to provide a said first block-oligomeric product or a said first block-polymeric product having a predeter-mined intrinsic viscosity less than the maximum attainable in the absence of said selected mono-functional reac~ants.
The block polymers _ _ . ' .

_ ~ _ n ~~

_ _ . ', ~.

.. 191 .~ .

~25973~

have preferred values of c1 between 0.5 and one, owing to the greater solubility and mesogenicity of the first recurring unit and preferred values ~ Y1 greater than about 25 but less than about 100, owing to the higher mesogenicity. Concen-trations greater than about 15%, more preferably greater than about 18%, and most preferably 20%, are selected. Examples 98-101 below further illustrate the method of the present invention.
The method of the invention also relates to the preparation of block polymers by the condensation of co-oligomeric reaction products, instead of the homo-oligomeric reaction products described in the above procedures.

Intrinsic Viscosity Intrinsic viscositiy is determined by extrapola-tion f~rel ~ 1/c and ln~rel~c to zero concen-tration in methane ~ulfonic acid at 30C.

~L~5973~i Anisotropic Character of the Compositions The extended chain polymer compositions of ~his invention are optically anisotropic, i.e., microscopic regions of a given extended chain composition are birefringent; a bulk extended chain composition sample depolarizes plane-polarized light because the light transmission properties of the microscopic areas of the extended chain composition vary with direction. This characteristic is associated with 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 that exhibit optical anisotropy do .
so while the extended chain polymer compositions are in the relaxed state. This is in contrast to conventional polymer solutions which may be caused to depolarize plane-polarized light ~hen subjected to appreciable shear.
The extended chain polymer concentration of the compositions of the instant invention is : 193 :,, .

~L2~9~36 above tbe acritical concentration point.~ The ~critical concentration point" is routinely determined using conventional concentration and viscosity measuring techniques (see Kwolek U.S.
3,671,542).
Another qualitative determination of the liquid crystalline character of these extended chain polymer compositions may be made with the naked eye. These extended chain polymer compositions may appear turbid or hazy and yet contain no, or practically no undissolved solid.
When the extended chain polymer compositions, seen under reflected ordinary light, is disturbed by shaking or rolling ths vessel containing the extended chain polymer compositions or by only slow stirring, there is produced a characteristic, readily observed, satin-like sheen or glow which is observed even after the disturbance ceases, and which decreases in intensity thereafter. Thls may be described as being a pearly or opalescent quality of the extended chain polymer composi1;ions of this invention. Compositions which are disturbed as described above often give the appearance of having striations and or graininess in the surface. These visual effects are obs~r~ed in the liquid crystalline extended chain polymer -, .. ; 194 125973~

compositions of this invention. This may commonly be referred to as ~tir opalescence. R
Further details on qualitative and quantitative determinations of optical anisotropy are presented in Kwolek U.S. 3,671,542.

Fiber Preparation The liquid crystalline compositions may bs formed into fibers of high quality by spinning them into suitable baths such as by ~et and ~air gap~ spinning techniques, using spinnerets and other apparatus constructed of materials resistant to the strong acids used. In ~air-gap~ -spinning the spinneret is usually located 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-gaps 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.

., ~2S9~36 In the present invention, the initial draw ratio is approximately from about 1:1 to about 50:1 and higher. 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 ~dra~ ration, as is æell known, is a measure of the degree of stretching 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 ~hich occurs bet~een the extrusion orifices and the exit from the coagulation bath.
The initial draw ratio is defined as exit velocity divided by jet speed.
The jet speed is the speed at ~hich the extruded polymer exits an extrusion orifice. It is conveniently determined by dividing the total polymer extrusion velocity by the total surface area of the extrusion orifices.
The exit velocity is the speed at ~hich the filaments leave the coagulation bath. Although any means of measurement may be used, the exit velocity is conveniently determined by the 2~ surface speed of the rolls ~hich take up the . .

~L2S97~;

filaments after their exit from the bath. Thus, the speed of the wash rolls is preferably measured for this purpose.
Spinning of polybenzimidazole fibers by one working of this general technique is described in, e.g., Tan U.S. 4,~63,245. A variety of baths may be used to coagulate the extruded dope into fibers. The baths may be, e.g., water or methanol and the like, or a dilute solution of a mineral acid (for example, phosphoric acid or sulfuric acid and the like). Preferably, the temperature of a coagulation bath is room temperature or below.
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 may be usied for removal of the residual acid. A convenient method is to spray the threadline as it leaves the coagulating bath with an aqueous alkaline solution (e.g., saturæted sodium bicarbonate), remove th~ surface liquid from the threadline with a ~iping device (e.g., a sponge) or a jet, wash with water and~or aqueous alkaline solutions to reduce the acid content, ;
and wind up the fibers on bobbins. The fibers `:~ 197 ~2~9736 may be soaked in water for a period sufficient to remove the acid. The thoroughly washed fibers may be dried on the bobbin in the area of temperatures of up to about 110C. They can also be conveniently dried on heated rolls.
The liquid crystalline compositions are especially suitable for extruding. This and other me~hods of article frabication are fully described in J. S. Robinson, ~Spinning, Extruding, and Processing of Fibers~; Chemical Technology Review No. 159, Noyes Data Corp., 1980.

The fibers prepared from the polymers of this invention exhiblt high values of tensile ! properties, especially in the as-extruded state, i.e., without subsequent hot drawing or annealing. The tensile properties of these as-extruded fibers can be enhanced by subjecting the -undrawn fibers to a heat treatment.

~ ";; ' "
:'' .

'"'~.

. ... ' '' ~ :' ...... ..
.::: :.

1~i'9~73S :.

Fiber tensile properties Filament properties are measured on fibers that are conditioned at 21 degrees C. and 65% relative humidity (R.H.) for at least 16 hours unless otherwise specified. Yarn properties are measured on yarn that are conditioned at 24 degrees C and 55% R.H. for at least 16 hours.
All measurements are made in the fiber conditioning e~vironment.
Tenacity (breaking tenacity) (T), elongation (breaking elongation) (E), and initial modulus (Mi) are obtained from breaking a single filament or a multifilament yarn on an Instron tester (Instron Engineering Corp., Canton, Mass.).
Single filaments are broken with a gage length (distance between jaws) of 1.0 inch (2.54 cm.).
The results on 3 filaments are a,veraged. Yarns are given 3 turns per inch (2.54 cm.) t~ist (under 0.1 g.p.d. tension) and broken with a 10 inch (25.4 cm.) gage length. All samples are elongated at a constant rate of exte~sion (10%
elongation/ minute for fibers having an E of under 8~, and 60% elongation/minute for fibers with E of 8 to 100%) until the sample breaks.
The denier of a single filament (d.p.f.) is calculated from its functional resonant .:.

~ ~i97~6 frequency, determined by vibrating a 7 to 9 cm.
length of fiber under tension with changing frequency ~ASTM D1577-1973). This filament is then used for 1 break.
The denier of yarn is determined by weighing a kno~n length (at 0.1 g.p.d. tension); 90 cm.
length is convenient.
The tenacity (grams/denier), elongation (percent) and initial modulus (gram/denier) as defined in ASTM 3379-75e are obtained from the load-elongation curve and the measured denier. In actual practice, the measured denier of the sample, test conditions and sample identification maybe fed to a computer before the start of a test; the computer record the load-elongation curve of the fiber as it is broken and then calculates the fiber properties.
It should be noted that different values maybe obtained from single filaments (filament properties) and from multifilament strands ~yarn properties) of the same sample. Unless specified otherwise all properties given herein are filament properties.

: :.
: ~ -.
~L2S9736 ~dditives It will be understood that the usual additiYes ~uch as dyes, ~illers, antioxidants, and the like ~-can be incorporated into the compositions of the present invention for the purpose intended, before preparation of the shaped article.
Mineral acids that are solvents ror the extended chain polymers of the instant compositions such as polyphosphoric acid, methane sulfonic acid, 100~ sulfuric acid, chlorosulfonic acid, and the like, may be added to the compositions of the invention in minor amounts (without departing from the scope of the invention) for purposes of modifying conditions for processing into shaped articles. The strong acid additives may contain one or more of the acid-solubls polymers describeà in Helmimiak, et al., U.S. 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.

.:: .

.
.. ' ':'''"

1259~73~, 4. Industrial Ap~licabili~y The liquid crystalline extended chain poly~er compositions are extremely suitable for 6ipinning into highly ordered and high 6trength fibers.
Such fibers are usef~l as reinforcement ~ubstitutes for other inorganic or organic products. Various examples include glass fibers, asbestos, boron fibers, carbon and graphite fibers, whiskers, quartz and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers. A reinforcement may be defined simply as ~-the material that is added to a resinous matrix to improve the strength and other physical and chemical properties of the material. -Furthermore, the polymers of the instant composi-tions can be employed in any use typically per-formed by engineering thermoplaE:tic materials, such as metal replacements and those areas ~here high performance is ~ecessary. Extended chain polymer compositions may be emp].oyed for use in forming high strength films ~uit,able in the pro-duction of composites, beltæ, tires, i.e., as tire cords, and the like. The films are suitable as construction materials for rocket nose cones and various other parts of space craft.
Depending on the extended chain polymer fiber or films selected (i.e., homopolymer, copolymer, ~5~73~i block polymer, or mixture thereof) the properties of the article formed may be controlled to suit the desired use. The control of polymer proper-ties is an advantage, since~ in the various areas of utility for such polymers, e.g. as laminates, structural materials, adhesives and ablative materials, the needs vary considerably.

By way of comparison, Examples 1-5 below are illustrative of low molecular weight (i.e., lo.~
intrinsic viscosity) and/or lo~ polymer concen-tratlon compositions.

.. ;, . .:

EXA~PLE 1 In a B-L resin flask were placed 388.7Bg ~1.5774 mol) of 2,5-diamino-1,4-benzenedithiol dihydro-chloride ~la) and 2.98kg of freshly prepared PPA.
The PPA was prepared as described in Wolfe and Arnold, Macromolecules, Vol 14, ~Og (1981). The mixture was stirred at room temperature under a flow of argon for 24h and heated at 60-70C for 34h. The resulting 601ution was clear ~ith no evidence of bubbles. Terephthalic acid (26~.35g, 1.5792 mol) was tben added and incorporated into the solution by rapid stirring at 110C. Addi-tional PPA (4.lkg) was then added. The yellow mixture was heated as follows: 110-1~5C in 5h, 165C for 12h, 180C for 12h, and 195C for 12h.
The mixture became stir-opalescent after Bh at polymerization temperatures. Reduced pressure .
was applied during the first ~h of reaction but was alternated with an argon strea~ such that the mixture did not foam abo~e a predetermined flasX
wall level. The hazy green product exhibiting yellow-green opalescence was removed from the flask and precipitated into a large volume of water. T~e copper-colored polymer was washed until the water was no longer acidic and then dried at 80-100C under reduced pressure for 48h.
A portion of the reaction product was bottled for ., .
.~ ~04 ~973~

use in fiber-spinning studies: intrinsic viscos-ity [~] = 30.3 dL/g (USA). Anal.Calcd for C14H6N2S2; C,63.l3; H,2.27; N,lO.51; S,24.08.
Found: C,62.75; H, 2.346; N, 10.24; S, 23.22.
The foregoing procedure provided a 5.6wt% of .
polymer ~AI~n in PPA. Polymerization mixtures of -higher polymer concentration (up to 10%) were prepared. Thesa runs required higher monomer la concentration during dehydrochlorination. Inter-mittent cooling was cycled ~ith argon pressure as required to control foaming at the desired level in the reaction vessel. Similarly, polymer EAI~n in PPA of lower concentration were prepared and these required less time for complete dehydro-chlorinat.ion than that described.

In a 6-L resin flask were placed 919.94g ~3.7519 mol) of la and approximately 2.7k~ of 115% PPA ; the X
P205 content profile for thi~ Example ls lllustrated in Figure 8.
The 115% PPA was obtained fro~ FUC Corporation a~d heated to 150C under an argon ~tmospbere, heated a~ 150C under reduced pressure for 18h, and cooled to room temperature immediately before use. The viscous mi~ture ~as ~tirred and an ice bath was applied for 24h to prevent vigorous foaming. Five additional days of stirring at .,

9~73~

room temperature were required to remove enough hydrogen chloride to allow heating ~bove room temperature. A clear, viscous solution was obtained after heating for 18h at 80C. Finely po~dered 2a (622.90g, 3.7454 mol) and an addi-tional 2,773g of the above 115% PPA were ~hen added. The mixture was then stirred and heated to 140C for 3h and then heated at 150-160C for 16h. The mixture gradually darkened, became opt-ically isotropic, and never became noticeably more viscous. Samples that were removed and pre-cipitated in water gave a dark green non-fibrous material. Additional heating failed to increas~
the viscosity to an extent to yield a fibrous material. The theoretical polymer concentration ~AI~ for this experiment was 14.8~ in a PPA with `
an intermediate P206 content of 83.8% and a fi~al of 79.8%.

EXA~PLE 3 To a 100 mL flask containiDg 15.8g of concentrated orthophosphoric acid (85.4% H3P04) that had been cooled in an ice bath was added 24.2g of phosphorus pentoxide and the mixture heated at 150C for 6h under an argon atmosphere.
The ~ P205 rontent profile for th~s Example is illustrated in Figure 9.
After cooling the PPA (84.9~ P205) to room ;

..

~ ' 1;25~73~;

temperature, 6.0g (0.029 ~ol) of 4-amino-3-mercap~obenzoic acid hydrochloride t3a) (prepared by the method of ~olfe, AFOSR Final Techsical Report, Dec. 1~ 80) was added and the ~iscous mixture stirred at 40C for 24h. The ~ixture ~as theu placed under reduced pressure and the temperature slo~ly raised ko 70C. The oraage-yellow mixture ~as then heated to 150C o~er a 2h period. The resulting dar~ red solution was optically isotropic. The ~olution ~as then stirred at 150C for an additional 24h. The poly~er was isolated from t~e resulting optisally isotropic ~olution containing 8.6% of the polymer by precipitation with water to give brittle films. The intrinsic viscosity of the isolated polymer ~T~n ~as 3.0 dL~g in methanesulfonic acid at 30C.

EXA~PLE 4 To a 50 mL round bottom flask containing 48.15g of PPA that ~as prepar~d as described in Wolfe and Arnold, ~2gs~Ql~s~l~a. Vol. 14, 909 (lg81) was added 7.436g ~0.0361~ mol) o~ 4-amino-3-mercaptobenzoic acid hydrochloride (3a~ that ~as prepared as described in Wol~e. AFOSR Final Technical Report. Dec. 15, 1980. The mixkure w s 207 ;

~, .

12~;9~

stirred at room temperature under an argon flow for 18h. After stirring for 2h under reduced pressure between 50 and 80C the solution ~as a clear orange color. The solution ~as then heated under reduced pressure as follows: 90C for 0.5h; 100C for 0.5h; 110C for 0.5h; 130C for 0.5h; 140C for 0.5h; 180C for 8h; 150C for 5h;
190C for 16h; 160C for 16h; 160C for 16h;
200C for 200h and 170C for 7h. The resulting isotropic solution having a concentration of polymer ~T~n f 9-4% by weight gave only brittle amorphous films when precipitated in water. The intrinsic viscosity of the isolated polymer ~as 3.80 dL/g in methanesulfonic acid at 30.0C.

To 38g of PPA that was prepared as described in Wolfe and Arnold, M~romolecule~, Vol. 14, 909 (1981) was added 1.421g (~.41 mmol) of 4-amino-3-mercaptobenzoic acid (3b) tha1; waæ prepared by neutrali~ation of an aqueous ~uspension of 4-amino-3-mercaptobenzoic acid hydrochloride (3a) (prepared according to Wolfe, ~OSR FiDal Technical Report, Dec. 15, l9BO~ followed by extraction with ethyl acetate, evaporation of the ethyl acetate, and recrystallization of the pale 20~ -~ ~i97~6 yellow residue from methylene chloride. The viscous mixture was heated to 140C under an argon flow in a 0.5h period. The temperature was raised to 160C over a 0.5h period and then maintained at 160C for 18h under reduced pressure. The optically isotropic, red solution was then heated under reduced pressure for 8h at 200C. The isolated polymer ~T3n had an intrinsic viscosity of 4.57 dL/g in ~SA at 30.0C.
The compositions of this invention, their production and their advantages and uses are further illustrated in the following examples.
These are intended only to demo~strate the invention and are not to be construed as limiti~g its scope, which scope is instead defined by the appended claims.
All polyphosphoric acid (PPA) hereinafter referred to as 115% was obtained from F~C
Corporation and used as received. Terephthalic acid (2a) was obtained from Amoco Chemicals Company, reduced to an average particle size of 95% ~10 um by an air-impact method, and dried before use. All monomers and P205 that were added to PPA were deaerated by placing them in a desiccator, applying reduced pressure, filling ,A ., .. .. , , ' ` . , ' i .: ,;

~;~S~ 36 with an inert gas, and repeating the procedure at least once.

EXAMPLE B
A mixture of 88.2g of concentrated orthophosphoric acid (85.4% H3P04) and 20S.2g of 115% PPA was stirred at 100C for 2h under reduced pressure. After allowing the PPA
solution to cool to approximately 50C a portion of this solution (282.lg) was added to a 500 mL
resin kettle containing 53.01013g (0.21620 mol) of la. After stirring to incorporate the solid monomer into the PPA, the mixture was stirred at room temperature for 2h under argon and then under reduced pressure at: 25-30C for 24h; 50C
for 3h; and 70~C for 16h. ~onomer 2a (35.91734g, 0.216196 mol) was then added to the resulting clear light green solution in four portions.
After the addition of each portion, the reaction kettle was placed under reduced pressure before u the 2a was incorporated by stirring. The mixture was allowed to cool to approximately 50C before 118.3g of P205 was added to increase the effective P205 content to 83.9%. The viscous slurry was then heated as follo~s: 100-170C in 3h: 170C for i7h; 185C for 5h; and 200C for -.
l9h. The intrinsic viscosities (in dL/g) of the ~2~;97~

polymer ~AI3D were determined from samples of the polymer solution withdrawn at the polymerization times indicated: 9.2 (8.5h), 12.6 (25.5h), 15.8 (44.Oh). Heating this reaction solution at 200C
for an additional 76h only increased the intrinsic viscosity of the ~AI~n component to 16.4 dL/g. The reaction product is characterized as having a final P2~5 content of approximately 80.8% with the ~AI~n polymer concentration being approximately 12.6wt%.

A mixture of 57 . 3g of concentrated orthophosphoric acid (85.4~ H3P04) and 133.7g of 115% PPA was stirred at 100C for 4h under reduced pressure. After allowing the PPA ~'~
solution to cool to room temperature, a portion of this solution (185.0g) was atlded to a SOO mL
resin kettle containing 53~6142'2g (0.21866 mol) of la. (Monomer la of small crystal size was prepared without a final recrys1;allization according to the method of Wolfei, Loo, and Arnold, Macromolecules Vol. 14, 915 (1981) using the final isolation procedure involving the transfer of the dipotassium salt of la as an aqueous solution into 6N hydrochloric acid.) ... .

~25973~ ~:
;
After stirring to incorporate the monomer into the PPA, the mixture was stirred at 55-65C for 5.5h under reduced pressure, at 25C for 15.5h under an argon flo~, and at ô5-72C for 4h under reduced pressure. ~onomer 2a t3B.32~8g. 0.21866 mol) was added to the resin kettle containing the dehydrochlorinated solution of monomer la in PPA.
After the addition of each of the six por~ions, the incorporation of the solid into the ~olution was aided by placing the kettle under reduced pressure before stirrlng was initiated. Powdered phosphoru~ pentoxide (114.4g) was then added to increase the effective P205 content to 8~.4% and the mixture was stirred at 100 C for 27h. The `
polymerization mixture was then heated as ` -follo~s: 100-170C in lh; 170C for 21.5h; and 200C for 71.5h. The intrinsic viscosities (in dL/g) of the polymer ~AI~n were determined from samples withdrawn at the polymerization times indicated: 23.1 (22.5h~, 24.8 t29.0h), 27.0 (94h). The reaction product i~ characterized as having a ~inal effective P205 content of approximately 82.2% and a polymar ~AI~n concentration being approximately 15.2 ~t~.

:,:
~
,, : :

':
~p~ ;,'"'';
'`'~" .
.: ' ~L259736 EXP~lPLE 8 182.7g of a PPA solution with an effective P205 content of 77.2% (prepared by mixing 30 ~t~ of H3P04 and 70 wt~ of 115% PPA) was added to a 500 mL resin kettle containing 52.B2853g (0.21460 mol) of la. (Monomer la of large crystal size was prepared with a final recrystallization according to the ~ethod of Wolfe, Loo, and Arnold, MacromoleclLL~, 14, 915 (1981) using the final isolation procedure involving a transfer of the dipotassium salt of moDomer la as solid into 6N hydrochloric acid.) After stirring to incorporate the solid monomer i~to the PPA, the mixture was substantially dehydrochlorinated by heating the mixture at 55-70C under reduced pressure for approximately 31h. ~onomer 2a (35.6522g, 0.21460 mol) was added to the resin kettle and incorporated as described in the previous Example. Powdered P205 (123.35g) was then added t~ increase the effective P205 content to approximately 8B.4% and resulting mixture was stirred at 100C for 17h under an argon flow.
The polymerization mixture was then heated with stirring as follows: 100-170C in lh, 170C for 23h, and 200C for 24h. The i~trinsic viscosities (in dL/g) were determined for the ~AI~n polymer from samples withdrawn at the indicated times: 17.2 (7b), 22.8 (24h), and 35.4 r~J

5~36 (48h). Heating without stirring for an additional 24h did not increase the intrinsic viscosity of the ~AI~n polymer. The green reaction product exhibits stir-opalescence and is characterized as having a final effective P205 content of 82.2~ with ~AI~n polymer concentration -being approximately 15.1wt%.

EXA~PLE 9 A mixture of 4,925g of concentrated orthophosphoric acid (85.4% H3P04) and 11,4~1g of 115% PPA was stirred in a 22 L flask for 5h at 100C under reduced pressure. After allowin~ the PPA solution to cool to 50C under a flo~ of argon, a portion of this solution (11,321g) was added to a 40-L glass resin kettle (equipped with a mechanical stirrer consisting of a 3/4hp variaDle speed drive and stirrir~g blades made of Hastelloy C-276) containing 2,380.55g (~.7088 mol~ of la prepared as describecl in Example 7.
The mixture was then stirred at: 65C for 17h und~r a flow of argon; 65C for 2h at 700-400 mm Hg; and 65C for 2n at 40 mm Hg. An additional 2,552.77g (10.4112 mol) of monomer la that had been prepared and deaerated as described in Example 8 was then added under a flow of arpon~

... . . .

~5~7'36 An additional 4,874g of the above-mentioned PPA
was added and the mixture stirred at: 65C for lh -~
at 700-300 mm Hg; 65-70C for 3.25h at 40 mm Hg;
70C for 2.5h at less than 5 mm Hg; 700C for 7.5h under a flow of argon; and 80C for 26h at less than 5 mm Hg. ~onomer 2a (3,342.62g, 20.1205 mol) was then added. The resulting slurry was then cooled to 40C and 6,512.lg of powdered P205 was added over a 4.5 period. The resulting viscous mixture was stirred at 80C for 17h under an argon flow. The mixture was then heated to 100C and an additional 4,655.4g of P205 ~as added to increase the effectiYe P205 content to 86.5%. After stirring for an additional 48h at 100-108C, the polymerization mixture was heated as follows: 100-170C in 3h;
170C for 20h; and 200C for 1.5h. The intrinsic viscosities (in dL/g) were determined from samples withdrawn at the indicated reaction times: 17.9 (14h), 18.5 (16.5h), 19.0 (23h), 24.34 (24.5h). Additional heating at 200C only increased the intrinsic viscosity to 24.6 dL/g.
The reaction product exhibited stir-opalescence and is characterized as havin~ a final effective P205 content of 82.2æ with the ~AI3n polymer concentration being approximately 15.6% by weight.

,:, ~S97~36 To a 500 mL resin kettle containiDg a deaerated mixture of 12.06155g (0.0594092 mol) of terephthaloyl chloride (2b) and 14.5665g (0.0594081 mol) of la was added approximately 140g of 115% PPA that had been ætirred at 100C
under reduced pressure for 1-2h, and had cooled to room temperature. The mixture wæs then stirred under an argon flow at: 40C for 23h;
50C for 3h; 60C for 2h; 70C for 19h; and 80C
for 3h. The solution was then stirred at 80C
under reduced pressure for lh. An additional 140g of deaerated 115% PPA was then incorporated into the solution. The polymerization was stirred under argon at: 100C for 30 min; 110C
for 30 min; 120C for 30 min; 130C for 30 min;
140C for 30 min; 150C for 30 ~in; 160C for 45 min; 170C for llh; 185C for 5h; and 200C for -.
46.5h. Precipitation in water of a small amount of the anisotropic product provided polymer ~AI~n which possessed an intrinsic viscosity of 17.7 (dL/g) in MSA at 30C.

EXA~PLE 11 : .

.~,; ~,, .

~v ,,, ., . ~ .. , .. ;,, . ~ . . .. . .... . .. . .

,.' ,.' . ! '; ', ' . :' ' ' ' ~ ' '' : ' ' '; : "

:~2597~

A mixture of 74.52g of 85.7% orthophosphoric acid and 173.88g of 115% PPA (83.8~ P205 content) is stirred under reduced pressure for 2h at 100C.
After cooling to room temperature, 55.23561g ~0.225273 mol) of la (prepared as described in Example 8) and 45.73607g (0.225273 mol) of 2b ~freshly sublimed) are added in eight portions.
After the addition of each portion of monomer stirring is initiated to incorporate the monomer.
The mixture is.then stirred while the temperature is slo~ly increased and the pressure is slo~ly decreased until dehydrochlorination is complete.
Deaerated phosphorus pentoxide (87.54g) is then added to the dehydrochlorination mixture at 50C.
The mixture is then stirred at 100C for several hours. The polymerization is then stirred under an argon atmosphere at 170C for approxi~ately 20h, at 180C for approximately 8h, and at 200C
for 3h. The resulting product contains 15 wt% of ~AI~n in PPA (82.2% P205).

86.17g of a PPA solution with an effective P205 content of 74.9% (prepared by mixing 40 ~t% of 85% H3P04 and 60 wt% of 115% PPA) was added to a 500 mL resin kettle containing 27.62485g ..~

" .

~L259~736 (0.112665 mol) of la. The monomer was incorporated into the PPA solution by stirring and the resulting mixture was then substantially dehydrochlorinated by heating the mixture at 55-80C under reduced pressure for approximately 2I hours. The % P205 content profile for this Example ls illustrated i~ Figure 10. Mono~er 2a (18.7208g, 0.112686 mol) was ~:.
then added to the resin kettle. Powdered P205 (83.17g) was then added to increase the effective P205 content to approximately 87.2%. The resulting yello~ slurry was stirred at 100C for 15h under an argon flow. This slurry, which had not noticeably increased in bulk viscosity, was then stirred vigorously and heated by increasing the oil bath temperature from 100C to 17SC : .
within 40 minutes, and to 185C within lh.
Polymerization times indicated below be~in with time above 100C. The 185C temperature Y~as then maintained for 76.5h. IDtrinsic viscosities in MSA at 30C (in dL/g) ~ere determined for the AI~n polymer from samples ~ithdra~n at the indicated polymerization times: 16.6 (1.5h), 21.7 (2.25h), 24.2 (3.25h), 35.7 (7.7h), and 42.1 ~76.5h). The intrinsic viscosity of 42.1 corresponds to an average n value of polymerization of about 140. The polymerization product ~as stir-opalescent after a polymerization time of 0.75h and was found to be .

; . j . , ' ; ' .. , , , ' . , . , . ,; ! . .. . . .

~S973~

highly drawable after 1.25h. Fibers prepared by directly dra~ing this product and precipitating the strands into water were amber, translucent, birefringent (crossed polars), sho~ed extinction of transmitted light when a single polaroid sheet was placed perpendicular to the fiber direction, and could be fibrillated into microfibrils.
Fibers prepared after 1.5h by the same method were noticeably stronger than the sample ~t 1.25h. The bulk viscosity of the product and the relaxation time of opalescence had noticeably increased after 2.25h. The P205 content of the PPA co3ponent of the product ~as approx.mately 83.2% and th~ concentration of the ~AI~n polymer ~as 14.5~ by u~eigh~ based on the total ~eight of the resulting reaction product.

A mixture of 17.7g of concentra-ted orthophosphoric acid (~5.7% H3P04) and 26.6g of 115% PPA ~as stirred under reduced pressure at lOO~C for 2 hours. The X P205 content profile for this Example i8 illufierated in Figure ll. The resulting solution was then poured at approximately 100C under a stream of argoD into a 200 mL resin kettle containing 11.41145g (0.054028 mol~ of 4,6-diamino-1,3-benzenediol dihydrochloride (lb~ tbat was .. .

~25973~

prepared according to the method of Wolfe and Arnold, Macromolecules, Vol. 14, 909 (1981), recrystallized from aqueous hydrochloric acid containing 3 wt% stannous chloride, and dried for 20h at ô3C under reduced pressure immediately before use. The mixture was stirred at 53C for 15h and 62C for 4h under reduced pressure. Upon heating to 70C, the monomer precipitated.
Addition of 16.6g of P205 resulted in redissolution of the monomer. The solution was then heated at 100C for 3h under reduced pressure to complete the dehydrochlorination.
Monomer 2a (8.9761g, 0.05403 mol) was then added under an argon flow. Additional P205 (l~.Og) was then added. The solutior. was then heated as follows: 100C for 48h; 150C for 2.5h; 160C for lOh (the dark green solution became stir-opalescent during this period); and 180C for `
25h. The resulting reaction product was deep purple with a metallic luster, lexhibited stir-opalescence, depolarized plane-polarized light as evidenced by strong birefringence when viewed between crossed polars, and is further characterized as having a final effective P205 content of 82% with the ~BI~n polymer concentration being 13.3% by weight. The intrinsic viscosity of the polymer ~BI3n isolated ~L259~3~i from the reaction product was 23.9 dLJg in MSA at 30C, which corresponds to an average number of recurring units, n, of approximately 110.

The reaction product from Example 13 ~as drawn many times its length to give highly fibrillar fibers. A portion of the solution *as removed from the reaction flask and placed in a KBr press equipped ~ith a die with a circular orifice of 0.13 mm in diameter. The solution was extruded into the air and stretched by pulling manually and then the fiber ~as dipped in water. The fiber thus produced was ~ashed ~ith water and then dried under tension in an ~,ir oven overnight at 110C. The fiber produced was measured to be between 0.0093 mm and 0.012 mm in diameter. High orientation *as evident from fibrils which split ~rom the surface of the fiber and by the complete extinction of light transmitted through the fiber hen a single polaroid ~às placed in a perpendicular direction only bet~7een the source and the fiber. ~

,'` ' : ,.

r~t ' :
,~ 221 : ... .
'.~
,~ .
: ::

73~i The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 48.9831g (0.19978 mol) of monomer la is dehydrochlorinated in an ~initial~ solution of 269.68g PPA having a P205 content of 77.2%
(prepared by mixing 80.9g of 85.4% H3P04 with 188.8g of 115% PPA). When dehydrochlorination is substantially complete, 79.9805g (0.19978 mol) of monomer 2s is added followed by the gradual addition of 142.23g of P205. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P20~ content of approximately 85.07% prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerlzation. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 19%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:

.~ ;

, 9~

characterized by an intrinsic viscosity of 20 dL/g in ~SA at 30C which corresponds to an n value of average polymerization of about 50.
EXAMPLE lB
The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 64.4470g (0.26284 mol) of monomer la is dehydrochlorinated in an ~initial~ solution of 341.97g PPA having a P205 content of 77.2%
~prep~red by mixing 102.66 of 85.4% H3P04 with 239.4g of 115~ PPA). When dehydrochlorination is substantially complete, ~3.6826g (0.26284 mol) of monomer 2j is added follo~ed by the gradual addition of 137.3g of P205. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 is preselected (as determined in accord ~ith the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 83.7% prior to the start of .
polymerization and an effective P205 content of approximately 82.2~ subse~uent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 17%; fibers are readily formed by direct :-` . :' ~L~5i973~i spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
~A~n characterized by an intri~sic viscosity of 15 dL/g in MSA at 30C which corresponds to an n value of average polymerization of about 100.

The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, ;
61.16i9g (0.28706 mol) of monomer lb is dehydrochlorinated in an ~initial~ solution of 338.4g PPA having a P205 content of 77.2%
(prepared by mixing 101.5g of 85.4% H3P04 with 236.8g of 115% PPA). When dehydrochlorination is substantially complete, 69.5488g (0.28706 mol) of monomer 2j is added followed by the gradual addition of 140.lg of P205. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 :is preselected (as ;
determined in accord with the a:torementioned formulae a* and b*) to provide tbe reaction mixture with an effective P205 content of approximately 83.8% prior to the start of . ~ !
: .,;~

~ 25~ 36 p~lymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction prGduct obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 17%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
IAB~n characteri~ed by an intrinsic viscosity of 16 dL/g in MSA at 30C which corresponds to an n value of average polymerization of about 60.

The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 81.9923g (0.28869 mol) of monomer lc is dehydrochlorinated in an "initia.l~ solution of 366.8g PPA having a P205 content of 77.2%
~prepared by mixing 110g of 85.4% H3P04 with 256.8g of 115% PPA). When dehydrochlorination is substantially complets, 69.9438g (0.28869 mol) of monomer 2~ is added follo~ed by tbe gradual addition of 148.4g of P205. The mixture is then :

/ - -~25973~

stirred and heated essentially according to Example 8. The amount of P205 is preselected (as determined in accord with the aforementioned formulae a* and b*) to pro~ide the reaction mixture with an effective P205 content of approximately 83.8% prior to the start of polymerization and an effecti~e P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 16%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
~AC~n characterized by an intrinsic viscosity of 16 dL/g in ~SA at 30C which corresponds to an n value of a~erage polymerization of about 60.

' . . !
._,i ;~' ', ' ' ' . ' ' "" '' ' . , ' . ' ' j: '. ' , . ~ ' . ' . . ' .

~2~i9~3~

The procedure of Example 8 is essentially repeated.
Instead of monomers la and 2a, 93.8232g (0.29202 mol) of monomer 1i is dehydrochlorinated in an "initial"
solution of 263.5g PPA having a P205 content of 77.2~
(prepared by mixing 79.1g of 85.4% H3P04 with 184.4g of 115~ PPA). When dehydrochlorination is substantially complete, 48.5129g (0.29202 mol) of monomer 2a is added -~
followed by the gradual addition of 171g of P205. The mixture is then stirred and heated essentially accord-ing to Example 8. The amount of P205 is preselected (as determined in accord with the aforementioned formu- -lae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 86.2X prior to the start of polymerization and an e~fective P205 con-tent of approximately 82.2~ subsequent to substantially complete polymerlzation. The reaction product obtained exhibits stir-opalescence and ls furl:her characterlzed as having a polymer concentratlon of 18%; flbers are resdily formed by dlrect spinnlng, or drawlng from the reaction product. The polymer obtained is of the fol-lowing structure:

n characterized by an intrinslc viscosity of 15 dL/g in MSA at 30C.

,, ~.

~L~59~7~6 ~XAMPLE 20 The procedure of Example 8 16 essentislly repeated.
Instead of monomers la and 2a, 93.1836g (0.32225 mol) of monomer 1~ is dehydrochlorinated in an "initial"
solutlon of 254.0g PPA having a P205 content of 77.2%
(prepared by mixing 76.2g of 85.4% H3P04 with 177.8g of 115% PPA). When dehydrochlorination is substantially complete, 53.5357g (0.32225 mol) of monomer 2a is added, followed by the gradual addition of 178.4g of P205. The mixture is then stirred and heated essen-tially according to Example 8. The amount of P205 is preselected (as determined in accord with the aforemen-tioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 86.6~ prior to the start of polymerization and an effective P205 content of approximately 82.2% subse-quent to substantially complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concen~ra-tion of 18~; fibers are readily formed by direct spinning, or drawing from the reaction product. Thepolymer obtained is of the following structure:

~MI~n ' . .

characterized by an intrinsic viscosity of 14 dL/g in MSA at 30C.

~ ~ J

:: - . . . : , ~; . ~ : . . , : - ,~ :: ::. : .

i: . , : i : .

: ~259~3~

~ EXAMPLE 21 ,. .
,. .
The procedure of Example 8 ls essentially repeated.
Instead of monomers la and 2a, 93.1836g (0.32225 mol) `
of monomer lk is dehydrochlorinated in an "initial"
solution of 254.0g PPA having a P205 content of 77.2%
(prepared by mixing 76.2g of 85.4% H3P04 with 177.8g of 115~ PPA). When dehydrochlorination is substantially complete, 53.5357g'(0.32225 mol) of monomer 2a is added, followed by the gradual addition of 178.4g of P205. The mixture iæ then stirred and heated essen-eially according to Example 8. The amount of P205 is preselected (as determined in accord with the aforemen-tioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 86.6X prior to the start of polymerization and an effective P~05 content of approximately 82.2X subse-quen~ to substantially complete polymerization. The I reaction product obtained exhibits stlr-opalescence and '~ ls further characterized as having a polymer concentra-tion of 18~; fibers are readlly formed by dlrect spinning, or drawing from the reaction product. The ' polymer obtained i8 of the following structure:
~NI~n characterized by an intrinsic viscosity of 14 dL/g in MSA at 30C.
~ .

:`-.~' ` , .: :

~ , l~S9~3~

The procedure of Example 8 ls essentially repeated.
Instead of monomers la and 2a, 128.474g (0.32431 mol) of monomer ll is dehydrochlorinated in an "initial"
solution of 223.5g PPA having a P205 content of 79.4%
(prepared by mixing 44.7g of 85.4% H3P04 with 178.8g of 115% PPA). When dehydrochlorination is substantially complete, 53.8778g (0.32431 mol) of monomer 2a is added, followed by the gradual addition of 197.0g of P205. Inorganlc salts, such as lithium salts (e.g.
LiCl, LiF, Llthium phosphate, and the like) can be added at this point, if required, to promote polymer solubility. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 ls preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 89.1~ prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantlally complete polymerization. The reaction product obtained exhibit~ 8tlr-0pale6cence and ls further characterized as havlng a polymer concentratlon of 1OZ; flbers are readlly formed by direct spinning, or drawlng from the reaction product. The polymer obtained is of the following structure:

~OI~n I
characterized by an intrinsic viscosity of 12 dL/g in MSA at 30C.
.. .
~30 ~25g73~

The procedure of Example 8 is essentially repeated.
Instead of monomers la and 2a, 70.3707g (0.21902 mol) of monomer 1i is dehydrochlorinated in an "initial"
solution of 323.lg PPA having a P205 content of 77.2%
(prepared by mixing 96.9g of 85.4% H3P04 with 226.2g of 115X PPA). When dehydrochlorlnation is substantially complete, 53.0654g (0.21902 mol) of monomer 2~ is added followed by the gradual addition of 125.0g of P205.
The mixture is then stirred and heated essentially according to Example 8. The amount of P205 is pre-selected (as determined in accord with the aforemen-tioned formulae a* and b*) to provide the reactlon mixture with an effective P2O5 content of approximately 83.6% prior to the 8tart of polymerization and an effective P205 content of approximately 82.2X subse-quent to substantially complete polymerization. The reaction product obtained exhibits stlr-opalescence and is further characterized as having a polymer concentration of 18~; fibers are readily formed by direct splnning, or drawing from the reaction product.
The polymer obtained is of the following 8tructure:

~AL~n ~-characterized by an lntrinsic viscosity of 17 dL/g in MSA at 30C.

~25~73S

The procedure of Example 8 is essentially repeated.
In6tead of monomers la and 2a, 68.1280g (0.23560 mol~
of monomer l; is dehydrochlorinated in an "initial"
solution of 320.7g PPA having a P205 content of 77.2%
(prepared by ~ixing 96.2g of 85.4% H3P04 with 224.5g of 115Z PPA). When dehydrochlorination is substantially complete, 57.824g (0.23560 mol) of monomer 2j is added followed by the gradual addition of 126.9g of P205.
The mixture is then stirred and heated essentially according to Example 8. The amount of P205 is pre-selected (as determined in accord with the aforemen-tioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 83.7% prior to the start of polymerization and an effective P205 content of approximately 82.2% subse-quent to substantially complete polymerization. The reaction product obtained exhibits stir-opalescence and i8 further characterized as having a polymer concentra-tion of 18%; fibers are readily formed by direct spin-ning, or drawing from tha reaction product. The polymer obtained is of the following structurc:

~AM~n characterized by an intrinsic vi~cosity of 15 dL/g in MSA at 30C.

:-.

~`- 232 ~:~59'7~S :

The procedure of Example 8 is essentially repeated.
Instead of ~onomers la and 2a, 68.1280g (0.23560 mol) of mono~er lk is dehydrochlorinated in an "initial"
solution of 320.64g PPA having a P205 content of 77.2%
(prepared by mixing 96.19g of 85.4% H3P04 with 184.4g of 115% PPA3. When dehydrochiorination is substanti-ally complete, 57.0824g (0.23560 mol) of monomer 2j is added followed by the graduaI addition of 126.88g of P205. The mixture is then stirred and heated essen-tially according to Example 8. The amount of P205 is preselected (as determined in accord with the aforemen-tioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 83.7% prior to the start of polymerization and an effective P205 content of approximately 82.2~ subse-quent to substantially complete polymerization. The reaction product obtained exhiblts s~:ir-opalescence and is further characterized as having a polymer concentra-tion of 18~; fibers are readily formed by direct spin-ning, or drawlng from the reactlon product. The polymer obtained is of the following 8tructure:

n characteri7ed by an intrlnsic viscosity of 14 dL/g in MSA at 30C.

; 233 ~L2~36 Analogous to the foregoing Examples 6-25, other Type I extended chain polymers may be synthesized to yield liquid-crystalline compositions having varying proportions of polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present invention. .
The synthesis is illustrated by the reaction systems in Tables 16a, 16b, 17a, 17b, and 17c.
The m------>, e------>, and p------> denote most preferred, especially preferred, and preferred selected monomer reactions respectively.

TABLE 16a :
Polymers of Type I, Class 1 Polymerization Reactions:

H2N~ ~ ,~ z~_y~--Z~ X~

~onomer (1,1) t Monomer (2,1) ------> Polymer I(1) la + 2e e------> ~AJ~n la ~ 2f e~ AJ~n 5~73~; -la + 2i e------> ~AK3n la + 2k e------> ~AB~n la + 21 e------> ~AC3n la ~ 2m e------> ~AD~n la + 2n e------> ~AE3n .
la + 20 e------> ~AF~n la + 2p e------~ ~AC~n la + 2q e------> ~AH3n la + 2t e------> ~AICI~n la + 2u e------> ~AIDI~n :~
la + 2~ e------~ ~AIEI~n la + 2w e------> ~AIFI3n la + 2x e--~ AIGI3n la + 2y e--~ AIHI~n lb + 2e e------> ~BJ~n lb + 2i e------> ~BK3n lb + 2k e------~ ~B~n lb + 21 ~------> ~BC~n lb + 2m e------> ~BD~n lb + 2n e------> ~ E3n .
lb + 20 e-~ -> ~ 3n 235 . :
. .

~L259'73~; :

lb + 2p e~ -> ~BG3n lb + 2q e------> ~BH~n lb ~ 2t e------> ~BICI~n lb + 2u e------> ~BIDI~n lb + 2v e------> ~BIEI3n lb + 2w e------> ~BIFI3n lb + 2x e------> ~BIGI3n lb + 2y e------> ~BIHI~n lc + 22 e------> ~CI3 lc + 2e e------> ~CJ~
lc + 2i e------~ ~CK~n lc + 2k e------> ~BC~n lc + 21 e------> ~C~n lc + 2m e------> ~CD3n lc + 2n e------> ~CE3n lc + 20 e------> ~CF~n lc + 2p e------> ~CG~n lc + 2q e------> ~CH3n lc + 2u e------~ ~CIDI~n lc + 2v e------> ~CIEI~n lc + 2~ e------> ~CIFI~n ~;9~3~

lc + 2x e~ -> ~CIGI~n lc + 2y e------> ~CIHI3n ld + 2a e------> ~DI~n ld + 2e e------> ~DJ~n ld + 2i e------> ~DKln :-ld + 2m e------> ~D3n ld + 2n e------> ~DE3n ld + 20 e------> ~DF~n ld + 2p e------> ~DG~n ld + 2q e------> ~DH~n ld + 2v e------> ~DIEI~n ld ~ 2w e------> ~DIFI3n ld + 2x e------> ~DICI~n ld + 2y e------> ~DIHI3n le + 2a e------> ~EI~n le + 2e e~ E~n le + 2i e-~ EK3n :.
le + 2n e- ----~ ~E3n le + 20 e------> ~EF3n ~ .
: ~ 20 le + 2p e------> ~EC~n le + 2q e------> ~EH~n :

' ' .

~2597;36 le t 2w e------> ~EIFI~n le + 2x e------> ~EIGI3n le + 2y e------~ ~EIHI~n lf + 2a e------> ~FI~n lf + 2e e------> ~FJ~n lf + 2i e------> ~FK~n lf + 20 e------> ~F~n lf + 2p e------> ~FC3n lf + 2q e------> ~FH~n .
lf + 2x e------> ~FIGI~n lf + 2y e------> ~FIHI~n lg + 2g e------> ~GI~n lg + 2e e------> ~GJ~n lg + 2i e------> ~GK~n lg + 2p e------> ~G3n lg + 2q e------> ~GH3n lg + 2y e------~ ~GIHI~n lh + 2a e------> ~HI3n lh t 2e e------> ~HJ3n .

.

;~ -~5~ 6 lh + 2i e~ -> ~HK~
lh + 2q e------> ~H3n ' TABLE l~b Polymers of Type I, Class 1 ;

Polymerization Reactions:
H2N ~ NH2 r ,~ N~
HXl t Zl--Y2--Z2 ~' t~

Monomer (l,l)+Monomer (2,1) ------> Polymer I~
.

la + 2c p-~ -> ~AI~n la t 2d p~~~~~~> ~AI~n la + 2g p------> ~AJ~n la ~ 2h p------> ~AJ~n :;

~;~59736 la + 2r p------> ~AI3n 1 a + 2z p------> ~A3n 1 b + 2b p------> ~BI~n lb + 2c p------> ~BI3n lb + 2d p------~ ~BI~n 1 b + 2f p------> ~BJ3n 1 b + 2g p------> ~BJ~n 1 b ~ 2h p------> ~BJ3n lb + 2r p------> ~AIBI~n lb ~ 2s p------> ~BI~n 1 b + 2z p------> ~B3n 1 c + 2b p------> ~CI~n 1 c + 2c p------> ~CI~n lc + 2d p------> ~CI~n 1 5 1 c + 2f p--- ---> ~CJ~
1 c + 2g P~~~~~~> ~CJ~n 1 c + 2h P~~~ ~~~~ ~CJ~n lc ~ 2r p------> ~AICI~
lc ~ 2s p------> ~BICI~
1 c ~ 2t p------> ~CI~n ld + 2b p------> ~DI3n i2:S~73~i 1 d + 2c p~ DI3n ld + 2d p------> ~DI3n 1 d + 2f p------> ~DJ3n 1 d + 2g p------> ~DJ3n 1 d + 2h p------> ~DJ3n 1 d + 2 j p------> ~AD3n 1 d ~ 2k p------> ~BD3n 1 d + 21 p------> ~CD3n ld + 2r p------~ ~AIDI~n .
ld + 2s p------> ~BIDI3n ld + 2t p------> ~CIDI~n :
ld + 2u p------> ~DI3n le + 2b p------> ~EI3n le + 2c p------~ ~EI3n le + 2d p------> ~EI3n :
1 e + 2f p------> ~EJ3n 1 e + 2g P------~ ~EJ3n 1 e + 2h p------> ~EJ~n le + 2j p------> ~AE3n 1 e + 2k p------> ~BE3n 1 e + 21 p------> ~CE3n : .

~S~3~

1 e + 2m p------> ~DE~n le + 2r p------> ~AIEI~n le + 2s p------> ~BIEI3n 1 e + 2t p------> ~CIEI~n le + 2u p------~ ~DIEI3n le + 2v p------> ~EI~n 1 f + 2b p------> ~FI~n 1 f + 2c p------> ~FI~n lf + 2d p------> ~FI3"
1 f + 2f p~-----> ~FJ3n 1 f t- 2g P------' ~FJ~n 1 f + 2h p------> ~FJ~n lf + 2j p------> ~AF3n 1 f + 2k p---~~~> ~BF3n lf + 21 p------> ~CF~n 1 f + 2m p-- ----> ~DF3n 1 f + 2n p-- ----> ~EF3n lf + 2r p------~ ~AIFI~n lf + 2s p------> ~BIFI~n ~: : 20 lf + 2t p------> ~CIFI~n :~
lf + 2u p------> ~I)IFI~n ~59~

lf ~ 2v p------> ~EIFI~n lf ~ 2w p------> ~FI~n lg + 2b p------> ~GI~n lg ~ 2c p____~ GI3n lg + 2d p------> ~GI~n 1 g + 2f p------> ~ 3n .
1 g + 2g P------' ~GJ3n l g ~ 2h p------> ~GJ3n 1 g + 2 j p------> ~AG~n 1 g ~ 2k p------> ~BG~n lg + 21 p------> ~CG~n lg + 2m p------> ~DG~n 1 g + 2n p------> ~EG~n lg + 20 p------> ~FG~n lg + 2r p------> ~AICI~n lg + 2s p------> ~BIGI~n lg + 2t p------> ~CIGI~n ig + 2u p------> ~DICI~n lg + 2v p_ ___-~~EICI3n lg + 2w p______>~FIGI3n lg + 2x p------> ~GI3n -~

:.. .

259~73~i lh ~ 2b p~ HI~n lh + 2c p------> ~HI~n lh + 2d p--____>~HI3n 1 h + 2f p------> ~HJ~n lh + 2g p------> ~HJ3n lh + 2h p------> ~HJ~n lh + 2j p------> ~AH~n lh + 2k p------>. ~BH~n 1 h + 21 p------> ~CH3n 1 h + 2m p------> ~DH~n lh + 2n p-_____~~EH3n .
1 h + 20 p-_____~~FH3n 1 h + 2p p------> ~CH~n lh + 2r p------~ ~AIHI~n lh + 2s p--~ BIHI3n lh + 2t p__-___>~CIHI3n lh + 2u p-------> ~DIHI~n lh + 2~r p--~ EIHI~n lh + 2w p------> ~FIHI~n ' ` ' ` '':

244 :.
'.

'''': ' ~,P3~ ~ r3 3~

,_ 1~597~6 lh ~ 2x p------> ~CIHI~n lh + 2y p------> ~HI~n TABLE 17a Polymers of Type I, Class 2 Polymerization Reactions: :

H:2 N ~ N H2 N ~ N ~
0 HXl X2H 1 Y Z2 ~~ --~</ ~X~y2_ n Monomer (1,2)+Monomer (2,1) ------~ Polymer I(2) li + 2b e------> ~LI~n li + 2c p------~ ~LI~n li + 2d p------> ~LI3n li + 2e e------> ~LJ~n :, '3 1259~36 li + 2f p~ -> ~LJ~n li + 2g p--~ LJ3n li + 2h p------> ~LJ~n li + 2i e------> ~LK~n li + 2k e------> ~BL~n li + 21 e------> ~CL3n li + 2m e------~ ~DL~n li + 2n e------> ~EL~n li + 20 e------> ~FL~n li + 2p e------> ~GL~n li + 2q p------> ~HL~n li + 2r m------> ~AILI~n 2s m------> ~BILI~n li +~ 2t e------> ~CILI3n li + 2u e------~ ~DILI~n li + 2v e------> ~EILI~n li + 2w e------> ~FILI~n li + 2x e--~ GILI~n li + 2y p------> ~HILI~n . .
li + 2z e------> ~L~n ; ~
lj + 2b e------> ~MI~n . ;; .

. ' .:
: 246 ;` :

~ .

`~

2c p~ EMI~n lj + 2d p------> EMI3n lj + 2e e------> ~J~n , lj + 2f p------~ EMJ3n lj + 2g P------' -EMJ~n ~ 2h p------~ -EMJ~n i lj + 2i e------> ~MK~n 1 j t 2k e------> -EBM~n 1; + 21 e------> ~CM~n lj + 2m e---- -> ~DM3n lj + 2n e------> ~EM~n lj + 20 e------> -EFM~n lj + 2p e------> ~GM~n lj + 2q e------> ~HM~n 1; + 2r e------> -EAIMI~n lj + 2s e------> -EBIMI3n lj + 2t e------> -ECIMI~n lj + 2u e------~ -EDIMI~n 1; ~ 2Y e------> ~EIMI~n lj * 2~ e------> EFIMI3n :~ lj + 2x e------> ~GIMI~n 2~7 59~6 lj + 2y p------> ~HIMI~n lj + 2z e~ -> ~M3n lk + 2b e---~--> ~NI~n lk + 2c p------~ ~NI~n lk + 2d p------> ~NI3n lk + 2e e------> ~NJ~n lk + 2f p------> ~NJ3n lk + 2g p------> ~NJ~n lk + 2h p------> ~NJ3n lk + 2i e------> ~NK3n lk ~ 2k e------> ~BN~n lk + 21 e------> ~CN3 lk + 2m e-------> ~DN~n lk + 2n e-------> ~EN~n lk ~ 20 e-------> ~FN~n lk + 2p e------> ~GN~ ~
lk + 2q p-------> ~HN~n .
lk + 2r e------> ~AINI3n lk + 2s e------> ~BINI3n lk + 2t e------> ~CINI~n lk + 2u e------> ~DINI3n ':

.. 24~

97;~6 lk + 2v e------> ~EINI3n lk + 2w e------> ~FINI~n lk + 2x e------> ~GINI~n lk + 2y p------> ~HINI~n lk + 2z e------> ~N~n 11 + 2b e------> ~OI~n 11 + 2c P-~~~~~>~OI3n 11 ~ 2d p------> ~OI~n 11 + 2e e------> ~J3n 11 + 2f P~~~~~~>~J~n 11 + 2g P~~~~~~>~J~n 11 + 2h P-~~~ J~n 11 + 2i e------> ~OK~n 11 + 2j e~ --> ~Ao3n 11 + 2k e------> ~BO~n .
11 + 21 e------> ~C~n 11 + 2m e------> ~DO~
11 ~ 2n e------> ~EO~n il + 20 e------> ~FO~n 11 + 2p e------> ~C~n 11 + 2q p------> ~H03n ~.

.

rc~ ,4~ f`-~ s ~ ` q -``

~2~73~ ` ~

11 + 2r e------> EAIOI~
11 + 2s e------> ~BIOI3 11 + 2t e-~ > -ECIOI~
11 + 2u e------> -EDIOI~
11 + 2~ e------> EEIOI3 11 + 2w e------> -EFIOI3 11 + 2x e------> ~GIOI3 11 + 2y p------> -EHIOI~
lm + 2a p------> ~PI~n lm + 2b p------> ~PI3n lm + 2c p------> ~PI~n lm + 2d p------> ~PI~n lm + 2e p--~ > -EPJ3n lm + 2f p-------> ~PJ~n lm + 2g p__.___> ~PJ3n lm + 2h p------> EPJ3n lm + 2i p~ --> EPK3n lm + 2j p------> EAP3n lm + 2k p------> EBP~n lm + 21 p------> ~CP~n lm + 2m p------> ~DP~n ~- 250 ~ ~ ¢~

12597~36 lm + 2n P------' ~EP3n lm + 20 p------> ~FP~n lm + 2p p------> ~GP~n lm + 2q P------' ~HP3n lm + 2r p------> ~AIPI3 lm + 2s p~ BIPI~
lm + 2t p------~ ~CIPI~
lm + 2u p------~ ~DIPI~
lm + 2v p------> ~EIPI3 lm + 2w p------> ~FIPI~
lm + 2x p~ GIPI~
lm ~ 2y p------> ~HIPI3 ln + 2a e-~ QI~n ln + 2b p--~ QI~n ln + 2c p-------> ~QI3n ln + 2d p-------> ~QI~n 1 n ~ 2~ QJ3n ln + 2f P~~~~~~> ~QJ~n ln + 2g P~~~~~~> ~QJ~n ln + 2h P~~~~~~~ ~QJ~n ln + 2i e------~ ~QK3n ~, 251 ~2S9736 ln + 2j e------> ~AQ~n ln ~ 2k e------> ~BQ~n ln + 21 e------~ ~CQ~n ` .
ln + 2m e------> ~DQ3n S ln + 2n e------> ~EQ~n -:
ln + 20 e------> ~FQ3n ln + 2~ e------> ~GQ~n ~`
ln + 2q p------> ~HQ~n ln + 2r e------> ~AIQI3n ln ~ 2s e------> ~BIQI~n ln + 2t e------> ~CIQI~
ln + 2u e------> ~DIQI~n ln + 2v e------> ~EIQI~n ln +. 2w e------> ~FIQI3~
1~ ln + 2x e------> ~GIQI~n ln + 2y p------> ~HIQI~n ln + 2z e- ~~~~>~Q~n lo + ~a e------> ~RI~n lo + 2b p------> ~RI~n lo + 2c p------> 3n lo + 2d p-_____>~RI3n i97~6 lo + 2e e~ ~-> ~RJ~n lo + 2f p------> ~RJ~n lo + 2g p--~ RJ3n lo + 2h p------> ~RJ~n lo + 2i e------> ~RK3n lo + 2j e------> ~AR3n lo + 2k e------> ~BR~n lo + 21 e------> ~CR~n lo + 2m e------> ~DR3n lo + 2n e------> ~ER3n lo + 20 e-- ---> ~FR~n lo + 2p e------> ~GR3n :
lo + 2q p------> ~HR~n lo + 2r e------> ~AIRI~n lS lo + 2s e------> ~BIRI3n lo + 2t e------> ~CIRI3n ..
lo + 2u e------~ ~DIRI~n lo + 2v e------> ~EIRI~n lo + 2w e-~ EFIRI~n lo + 2x e------> ~&IRI~n lo ~ 2y p___---> ~HIRI3n .

, ,.. .

~2597~36 lo + 2z e------> ~R~n lp + 2a e------> ~SI3n lp + 2b p------> ~SI~n lp + 2c p------> ~SI~n lp + 2d p------> ~SI~n lp + 2e e------> ~SJ~n lp + 2f P~~~~~~> ~SJ~n lp + 2g P~~~~~~~ ~SJ+n lp + 2h P~~~~~~~ ~SJ~n lp + 2i e------> ~SK~n lp + 2j e------> ~AS3n lp + 2k e------> ~BS1n lp + 21 e------> ~CS~n lp + 2m e------> ~DS~n lp + 2n e------> ~ES~n lp + 20 e-------> ~FS3n lp + 2p e------> ~GS~n lp + 2q p------> ~HS3n lp + 2r p------> ~AISI~
lp + 2s p------> ~BISI3 ; lp + 2t p------> ~CISI~

.- '`''''';''' .. - 254 .

~:5~73~i lp + 2u p~ DISI3n lp + 2v p------> ~EISI3n lp + 2w p__~ FISI3n : .
lp + 2x p------> ~GISI3n lp + 2y p------> ~HISI~n `
' ' :: :
~25~37~i TABLE 17b ':
Polymers of Type I, Class 2 Polymerization Reactions: --HX,~ + Z1--y2 Z2 ~<X~

Monomer (1,1)+Monomer (2,2) ------> Polymer I(2) la t 2hh e------> ~AVIV'~n la + 2ii e------> ~ATIT'~n la + 2jj e------> ~ATKT'3n lb + 2hh e--~ BVIV'~n lb + 2ii e-------> ~BTIT'3 lb + 2jj e-------> ~BTKT'3n lc ~ 2hh e------> ~CVIV'~n .
lc + 2ii e------> ~CTIT'~n lc ~ 2jj e----~~> ~CTKT'3n ~.

; - -~LXS9~3~

ld + 2hh e------> ~DVIV'~n ld ~ 2ii e------> ~DTIT'3n ld + 2jj e------> ~DTKT'~n le + 2hh e------> ~EVIV'~n -le + 2ii e------> ~ETIT'~n le + 2jj e------> ~ETKT'~n lf + 2hh e------> ~FVIV'~n lf + 2ii e------> ~FTIT'~n lf t 2jj e------> ~FTKT'~n lg + 2hh e------> ~CVIV'~n lg + 2ii e------> ~GTIT'~n lg ~ 2jj e------> ~GTKT'~n j,:
lh + 2hh e------> ~HVIV'~n lh + 2ii e-~ > ~HTIT'~n `
' ' . 257 / -1~5~73~

lh + 2jj e~ --> ~HTKT'~n TABLE 17c Polymers of Type I, Class 2 Polymerization Reactions: .

0 H2N~ ~ Z _y2--Z2 ~~ ~/ ~ ~y2 HX1 X2H Xl X2 n Monomer (1,2)+Monomer (2,2) ~ --> Polymer I(2) li + 2hh e------> ~LVIV'~n li + 2ii e------> ~LTIT'3n li + 2jj e------> ~LTKT'~n :. .

. , ~, .:

~259736 ,:
lj + 2hh e------> ~MVIV'~n lj + 2ii e------> ~MTIT'~n lj + 2jj e------> ~TKT'~n lk + 2hh e------> ~NVIV'~n lk + 2ii e------> ~NTIT'~n lk + 2jj e------> ~NTKT'~n 11 ~ 2hh e------> ~OVIV'~n 11 + 2ii e------> ~OTIT'3n 11 + 2jj e------> ~OTKT'3n lm + 2hh e------> ~PVIV'3n lm + 2ii e--~ -> ~PTIT'~n lm + 2jj e-------> ~PTKT'3n ln + 2hh e-------> ~QVIV'~n ln ~ 2ii e------> ~QTlT'~n ln + 2jj e------> ~QTKT'~n lo + 2hh e------> ~RVIV'~n ,.- . .,... :... .... : :;.. :, "; ,, ~;~59~3~
.. :
t 2ii e------> ~RTIT'~n lo + 2jj e------> ~RTKT'3n ,' lp + 2hh e------> ~SVIV'~n lp + 2ii e------> ~STIT'~n lp ~ 2jj e------> ~STKT'3n :; .. ,;.

' 10 A solution consisting of 63.34g concentrated phosphoric acid and 147.59g of 115% PPA was stirred at 100C under reduced pressure for 3h in a 300 ml 3-necked flask. To a 500 mL resin kettle was added 63.49g (0.3087 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a) (prepared by the method of Wolfe, AFOSR Final Technical Report, Dec. 15, 1980). A portion of the above-prepared PPA having a P205 of 77.3%
~207.57g) was po~red into the resin kettle coDtaining the monomer while under argon flow.
After th~ monomer had been incorporated, a second ' ~'.' '::

59~

portion of monomer (30.71g, 0.1493 mol) was added. The mixture was heated to 55C and the pressure was gradually decreased over 1.5h. An additional 5.35g of monomer was added to the kettle under argon flow bringing ~he total monomer added to 99.65g (0.4845 mol). The mixture was then stirred under reduced pressure at 50C overnight. The temperature was then raised to 70C for 8h. Phosphorus pentoxide (138.62g) ~as then added in one portion to increase the effective P205 content to 86.4%.
After heating at 100C with stirring overnight the reaction product was stir-opalescent. After placing the mixture, which still contained undissolved monomer, under reduced pressure for -~
3h, a sample was removed and ~as placed between a microscope slide and a cover glass. The unprecipitated product depolarized plane- -polarized light. The reaction mixture was then heated under argon as follows: an additional 2.5h at 100C; 2h at 120C; l~h at 130C; 31h at 170C; 43.5h at 200C. A sample of the green, opalescent polymer reaction product yielded gold-orange ~ibers upon precipitation in water.
The sample was extracted in water for 24h and dried under vacuum at 140C for 24h. The intrinsic viscosity was determined to be 8.2 dL/g ~\
~2S973 ,l in MSA a~ 30.1C. The reaction product is characterized as having a final effective P205 content of 82.2% with the polymer ~T~n having a concentration of 15.1% by weight.

A mixture of 125.8g of 115% PPA and 53.9g of concentrated phosphoric acid (85.7% H3P04) was heated to 100C for 4h under reduced pressure in a 500 mL 3-necked flask. The % P205 content profile for this Example is illu~trated in Figure 12. To a 500 ~L resin kettle was added 91.85g (0.44B6 mol) of 3a. The kettle containing the monomer wias deaerated.
108.17g of the PPA prepared above (having a P205 content of 77.2%) was then added. The kettle was then heated with an oil bath at 50C under a thin ;`
stream of argon overnight. The kettle was then placed under reduced pressure again and heated to 70C for 23h. P205 (108.32g) was then added in three portions to increase the effective P205 content to 88.5%. Reduced pressure was applied .
to degas the P205 and to cause foaming that aided in mixing. After 3h of stirring the temperature was raised to 100C and maintained at that temperature under reduced pressure for 21h. The mixture was stir-opalescent and depolarized plane-polarized light. The mixture was then ' --~L~59~

heated as follows: 115C under argon for 3h;
130C under reduced pressure for 2h; 170C for 0.5h; 190C for 17h. A sample of the green, opalescent reaction product was removed and gave a fibrillar, golden-colored fiber upon drawing followed by precipitation in water. After extracting with water in a Soxhlet apparatus for 24h the sample was dried for 24h at 110C under reduced pressure. The intrinsic viscosity of this sample was 15.8 dL/g in ~SA at 30.0C. An additional 7.5h of heating gave a sample with an ir.trinsic viscosity of 16.7 dL/g. The reaction product thus obtained was 20.3% by weight of polymer ~T~n in PPA with a final P205 content of 82.4%.

The procedure of Example 27 is essentially repeated. Instead of monomer 3a, 146.9123g (0.4305753 mol) of monomer 3k iE~
dehydrochlorinated in an ~initial" ~olution of 265~9g of PPA having a P205 content of 77.3%
(prepared by mixing 78.6g of ~5.4% H3P04 with 187.4g of 115% PPA). When dehydrochlorination is substantially complete, an additional 144.85g of P205 is gradually added to the mixture and ~59~736 dissolved by stirring and heating essentially according to the schedule given in Example 27.
The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 85.3~ prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further .
characterized as having a polymer concentration of 19%; fibers are readily formed by direct spinning, or draNing from the reaction product.
15 The polymer obtained is of the follo~Ning ~ :
structure: .

~CI~n characterized by an intrinsic viscosity of 15 dL/g in MSA at 30C which corresponds to an average n value of polymerization of about 70.

The procedure of Example 27 is essentially repeated. Instead of monomer 3a, 161.90g t, '' ',' ' ~' '; , .'; ,','''';; ' - ''''` ..'" ;.`''' ` ' , ' `' ',, ' . 'j ' ' . ' " '' . ' ' .. , ',, ". .: . ' ," . ' .: ".' "''. ';:' ' .' "'' . . ` , ' .. ' ~;~S9~6 (0.85391 mol) of monomer 3c is dehydrochlorinated in an ~initial~ solution of 198.~g of PPA having a P205 content of 77.3% (prepared by mixing 58.7g of 85.4% H3P04 with 140.0g of 115% PPA). When dehydrochlorination is substantially complete, an - additional 196.8g of P205 is gradually added to the mixture and dissolved by stirring and heating essentially according to Example 27. The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 88.6%
prior to the start of polymerization and an effective P205 content of approximately 82.2%
subsequent to substantial complete poiymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 19%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the iollowing structure:

~U~n characterized by an intrlnsic ~iscosity of 12 dL/g in MSA at 30C.

265 _ ~ ~:5~736 The procedure of Example 27 is essentially repeated. Instead of monomer 3a, 161.90g (0.85391 mol) of monomer 3d is dehydrochlorinated in an ~initial~ solution of 221.7g of PPA having :
a P205 content of 77.3% (prepared by mixing 65.50g of 85.4% H3P04 ~ith 156.2g of 115~ PPA).
When dehydrochlorination is substantially complete, an additional 203.lg of P205 is gradually added to the mixture and dissolved by stirring and heating essentially according to Example 27. The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 88.2% prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymeri~ation. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 18%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of t~e following structure:
; .

, ~ ~59~6 ~V~
characterized by an intrinsic viscosity of 12 dL/g in ~SA at 30C.
, i Analogous to the foregoing Examples 26-30, other 5 Type II extended chain polymers may be synthesized to yield liquid-crystalline compositions having varying proportions of polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present invention.
The synthesis is illustrated by the reaction systems in Table 19. The e------> denotes especially preferred selected monomer reactions.

267 --- :
: `
,:

9~3~
.

~ TABLE 19 '' ' Polymers of Type II, Class 2 ' 5 . :
Polymerization Reactions:

z3~NH2 ~N~

~ Monomer (3,2) ------> Polymer II(2) `

3f e------> ~X~n 3g e----~~> ~Y~n 3h e------> ~TI~n 3i e------> ~UI~n ., The procedure of Example 8 i6 essentially repeated. Instead of monomers la and 2a, 99.923g .:

. . 268 ~., ~519~36 (0.35182 mol) of monomer lc i6 dehydrochlorinated in an ~initial~ solution of B02.0g of PPA having a P205 content of 77.3% (prepared by mixing 177.9g of 85.4% H3P04 with 424.1g of 115% PPA).
When dehydrochlorination is substantially complete, 76.740g (0.35182 mol) of monomer 4a is added followed by the gradual addition of 272.7g of P205. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 84.4%
prior to the start of polymerization and an effective P205 content of approximately 82.0% `
subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 10%; fibers are readily formed by direct spinning, or drawing from the r~!action product.
The polymer obtained is of the rollowing structure:
~ZB'A'B'3n characterized by an intrinsic viscosity of 10 dL/g in MSA at 30C. ;
:
.

. 269 ' :

~59~736 , Analogous to the foregoing Example 31, other Type :, III extended chain polymers may be synthesized to yield liquid-crystalline compositions having varying proportions of polymer concentration, P205 content and polymer intrinsic viscosity in .- accordance with the present invention.

The synthesis is illustrated by the reaction .i systems in Table 20. The e~ --> denotes especia11y preierred selected moDomer reactiors.

.

:
,. ~

:

., :

i9~36 Poly~ers of Type III, Class 1 Polymerization Reactions:
o ~\N~N~
Monomer ~l,l)+Monomer (4,1) ------> Polymer III(1) . . .

lc + 4b e------> ~B'A'F'Z~n le + 4a e------> ~C'A'B'Z~n le ~ 4b e------> ~C'A'F'Z~

EXAMPLE 32 :
The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 109.94g ..
(0.27752 ~ol) of monomer 11 is dehydrochlorinated ~
~.

271 -= ~

,.

1~:5973~
.
:;
in an ~initial~ solution of 317.2g of PPA haYing a P205 content of 77.3% ~prepared by mixing 93.7g of 85.4% H3P04 with 223.5g of 115% PPA). ~hen dehydrochlorination is substantially complete, 60.533g (0.27752 mol) of monomer 4a is added followed by the gradual addition of 219.5g of P205. The mixture is then stirred and heated essentially according to Example 8. The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 86.6 prior to the start of polymerization and an effective P205 content of approximately 82.0%
subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and i5 further characterized as having a polymer concentration of 15%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure: ;
~ZD'A'B'~n characterized by an intrinsic viscosity o~ 7dL/g ir. MSA at 30C. :

' ii:: . ': ' -' .' . : :: . . . , : . ' : ' ' ., : . .:, . ' : , . ~ . .

~L~59~736 .
Analogous to the foregoing Example 32, other Type ~ III extended chain polymer~ may be synthesized to ., yield liquid-crystallinc compositions having : varying proportions o~ polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present inrention.
The synthesis is illustrated by the reactions in Table 21. The e~ --> denotes especially preferred selected monomer reactions.

.':
, .
: `
.:

273 - ~

~IL25973~i _ Polymers of Type III, Class 2 Polymerization Reactions:

~onomer (1,2)+~onomer (4,1) ------~ Polymer III(2) ~ . . .

11 + 4a e---~ D'A'B'Z~
11 + 4b e------> ~D A F Z~n lp + 4a e------> ~E'A'B'2~n :
lp + ~b e------> ~E'A F Z~n .. . ~

The procedure of Example 27 is ~sssentially repeated. Instead of mor.omer 3a, 117.S156g (0.51494~3 mol) of monomer 5a is dissolved in an ``` 2-/4 . : . ~ : .;. .;.,. :,i , . :: i? : - . . , . ~ .`"., . . ' S~t736 :.' ninitial~ solution of 623.7g of PPA having a P205 content of 77.0% (prepared by mixing 192.8g of 85.4% H3P04 with 430.9g of 115% PPA~. ~hen dissolution is substantially complete, an additional 257.8g of P205 is gradually added to the mixture and dissolved by stirring and heating essentially according to Example 27. The amount `:
of P205 added is preselected (as determined in ' accord with the aforementioned formulae a* and b*) to provide the reaction mixture ~ith an :`
effective P205 content of approximately 83.7% : :
prior ~o the start of polymerization and an effective P205 content of approximately 82.0%
subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further :
characterized as having a polymer concentration of 10%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the follo~ing structure:
~F'A'3n characteri~ed by an intrinsic viscosity of 10 dL/g in MSA at 30C.

2~5 , ... ~

'` ; C 4 ;

125~7~

,, The pr~cedure of Example B is essentially repeated. Instead of monomers la and 2a, 70.'784g (0.28869 mol) of monomer la is dehydrochlorinated in an ~initial~ solution of 242.6g of PPA having a P205 content of 77.3% (prepared by mixing 71.7g of 85.4% H3P04 ~ith 171.0g of 115% PPA). When dehydrochlorination is substanti lly complete, 71.070g (0.28869 mol) of monomer 6a is added followed by the gradual addition of 162.9~ of P205. The mixture is then stirred and heated according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effecti~e P205 content of `
approximately 86.4% prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent 1;o substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polyme~r concentration of 19%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:

276 ` .~
-. ~ . .

`:
~25~'73~ :

: ~B'G'~
, characterized by an intrinsic viscosity of 7 dL/g ; in ~SA at 30C.
. EXAMPLE 35 5 The procedure of Example 13 iB essentially repeated. Instead of monomers lb and 2a, B7.798g (0.31820 mol) of monomer lb is dehydrochlorinated in an ~initial" mixture of 343.3g of PPA having a P205 content of 77.3% (prepared by mixing 101.4g of 85.4% H3P04 with 241.9g of 115% PPA). When dehydrochlorination is substantially complete, 78.336g (0.31820 mol) of monomer 6a is added followed by the gradual addition of 200.4g o~
P205. The mixture is then stirred and heated ~5 according to a schedule similar to Example 13.
The amount of P205 added is preselected (as determined in accord ~ith the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 c:ontent of approximately 85.7% prior to thel 6tart of - .
polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. Tha re~action product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration .

..., ,:.

.,, ,~ .

5~7;3~

~.

of 15%; libers are readily formed by direct spinning, or drawing ~rom the reaction product.
. The polymer obtained is of the following structure:
~B'H'~n characterized by an intrinsic viscosity of 7 dL/g in MSA at 30C. .-The procednre of Example 8 is essentially repeated. Instead of monomers la and 2a, 90.945g (0.32021 mol) of monomer lc is dehydrochlorinated in an n initial~ solution of 402.5g of PPA ha~ing a P205 content of 77.3% (prepared by mixing 192.lg of 85.4% H3P04 with 210.4g of 115% PPA).
When dehydrochlorination is su~stantially complete, 78.830g (0.32021 mol) of monomer 6a is added followed by the gradual a.ddition of 307.8g o~ P205. The mixture is then stirred and heated according to a schedule similar to Exampl~ 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned formnlae a* and b*) to provide the reaction mixture with an effecti~e P205 content of approximately 84.9% prior to the start of polymerization and an effective P205 content of ~, .

approximately 82.2% ~ubsequent to substantial complete polymerization. The reaction product obtained exhibits ~tir-opalescence and is further characterized as having a polymer concentration of 12%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
~B'I'~n characterized by an intrinsic viscosity of 7 dL/g in ~lSA at 30C.
Analogous to the fcregoing Examples 34-36, other Type V extended chain polymers may be synthesized to yield liquid-crystalline compositions having varying proportions of polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present invention.
The synthesis is illustrated by the reaction systems in Table 23. The e---~ denotes especially preferred selected monomer reactions.

2~9 . ~ . ~ . ~

' . 1, i . ! . . ..

2t;~9~73~ :

, TABLE 23 ,, Polymers of Type V, Class 1 - Polymerization Reactioni~:

H2N 3~ 2 Zl~ 1~< 2~n .~ 10 ~onomer (1,1) +Monomer (6,1) ------> Polymer V(1) ld + 6a e------> ~B'H'3n*
~ 15 le + 6a e------> ~C'I'3n ! lf ~ 6a e------> ~C H 3n . lg + 6a e------> ~C'G'~n lh ~ 6a e------> ~B'M'~n *Note: Oxygens always para on B' . . .

.. .

~,. 280 ~ ~ . ', ' . . ~

; ^\
:
~ 2~973~;
,.;, ;
` EXAMPLE 37 , The procedure of Example 8 i~ essentially repeated. Instead of monomers la and 2a, 58.035g (0.23669 mol) of mono~er la is dehydrochlorinated in an ~initial~ solution of 307.7g of PPA having a P205 content of 77.3% (prepared by mixing ~0.9g i~ of 85.4~ H3P04 with 216.8g of 115~ PPA). When dehydrochlorination is substantially complete, 76.281g (0.23669 mol) of monomer 6b is added followed by the gradual addition of 163.5g of P205. The mixture is then stirred and heated accordi~g to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of - approximately 85.2% prior to the start of polymerization and an effecti~e P205 contant o~
approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as ha~ing a polymer concentration of 17%; fibers are readily formed by direct spinnin~, or drawing from tbe reaction product.
The polymer obtained is of the following structure:

' .

.~:
. .

_ ~ . . . .... .. ... . . .

~259~3~
~:
: ~B'J'~
n characterized by an intrinsic YiæcoSity of 7 dL/g in MSA at 30C.
.

~, 5 The procedure of Example 13 is essentially i repeated. Instead of monomers lb and 2a, 54.581g .: (0.25617 mol) of monomer lb is dehydrochlorinated in an ~initial~ solution of 330.4g of PPA having ~ a P205 content of 77.3% (prepared by mixing 97.6g ,~ 10 of 85.4% H3P04 with 232.7g of 115% PPA). When dehydrochlorination is substantially complete, 82.559g (0.25617 mol) of monomer 6b is added followed by the gradual addition of 17B.2g of ~ P205. The mixture is then stirred and heated 1 15 according to a schedule similar to Example 13.
The amount of P205 added is preselected (as determined in accord with the laforementioned formulae a* and b*) to pro~ide the reaction mixture with an effective P205 content of approximately 85.2% prior to the start of polymerization and ~n effectiYe P205 content of :~
approximately 82.2% suhsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration :.~ 2~2 :: - , . .- : ., . .. . : : :: : : ~ ~ . : , : : : .:: :

iL25973~

of 16%; fibers are readily formed by direct SpiDniDg, or drawing from the reaction product.
1 The polymer obtained is of the following ., structurs:
, 5 ~B'K'~n ., .
;~ characterized by an intrinsic viscosity of 7 dL/g ~: in MSA at 30C.
` - EXAMPLE 39 The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 73.126g .
(0.25747 mol) of monomer lc is dehydrochlorinated in an ~initial~ solution of 362.6g of PPA ha~ing ,~ a P205 content of 77.3% (prepared by mixing 107.lg of 85.4% H3P04 with 255.5g of 115% PPA).
When dehydrochlorination is substan~ially complete, 82.978g (0.25747 mol~ of monomer 6b is added followed by the gradual :Iddition of 185.5g of P205. The mixture is then E;tirred and heated according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned A formulae a* and b*) to provide the reaction ; mixture uith an effectiYe P205 content of approximately 85.0% prior to the ~tart of polymerization and an effective P20~ content of .

, :

':' ' :
~259736 , . . .
.
approximately 82.2% subsequent to substantial ~ complete polymerization. The reaction product - obtained exhibits stir-opalescence and is further , characterized as having a polymer concentration ,i 5 of 15%; fibers are readily formed by direct spinning, or drawing from the reaction product.
; The polymer obtained is of the following structure:
Z~ ~B'L'~
characterized by aD intrinsic viscosity of 6 dL/g in MSA at 30C.
Analogous to the foregoing Examples 37-39, other Type V extended chain polymers may be synthesized to yield liquid-crystalline compositions having varying proportions of polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present invention.
The synthe~is is illustrated by the reaction systems in Table 24a. The e-- ---> denotes especially preferred selected monomer reactions.

.. ~._ .. . .. .. . . .. . .

`~

. r--~
12S9~3~i TA~LE 24a , . .
Polymers of Type V, Class 2 Polymerization Reactions:

H2N3~ , 3~ Z12 ~H H~ :`

HX, X2H ~11 Z-3 ~ X~ 2~bn , 10 ~onomer (l,l)~Monomer (6,2) ------> Polymer V(2) ~ ---ld + 6b e------> ~B'K'~n* .
15 le + Bb e----~ C L ~n lf ~ 6b e------> ~C'K'~n lg ~ 6b e------> ~C'J 3n lh + Bb e------> ~B'N'~n *Note: Oxygens always para on B' . ~, , ~ ~25~73~
i, ":' .` The procedure of Example 8 is essentially ~` repeated. Instead of monomers ia and 2a, 76.047g (0.23369 mol) of monomer li is dehydrochlorinated in an ~initial~solution of 3~9.2g of PPA having a P205 content of 77.3% (prepared by mixing lO9.lg of 85.4% H3P04 with 280.1g of 115~ PPA). When dehydrochlorination is substantially complete, 58.269g (0.23369 mol) of monomer 6a is added followed by the gradual addition of 180.4g of P205. The mixture is then stirred and heated according to a schedule similar to Example 8.
; The amount of P205 added is preselected (as determined in accord with the aforementioned ( 15 formulae a* and b*) to provide the reaction ; mixture ~ith an effective P205 content of approximately 84.8% prior to the start of ~, polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration o~ 15%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the follo~ing structure:

.
... .

~59 ~'36 ;
~D'C'~
characterized by an intrinsic ~iscosity of 10 dL/g in ~SA at 30C.

, 5 The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 74.075g (0.25617 mol) of monomer lj is dehydrochlorinated in an ~initial~ solution of 493.7g of PPA having a P205 content of 77.3% (prepared by mixing 145.9g of 85.4% H3P04 with 347.8g of 115% PPA).
When dehydrochlorination is substantfally complete, 63.065g (0.25B17 mol) of monomer 6a is added follo~ed by the gradual addition of 221.2g of P205. The mixture is then stirred and heated according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of ~' approximately 84.3% prior to the start of polymerization and an effective P~05 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits ~tir-opalescen~e and is further characterized as having a polymer concentration , ~87 ` ~L25973$
, .
of 12%; fibers are readily formed by direct spinning, or drawing from the reaction product.
: The polymer obtained is of the following ~tructure:
. 5 ~D'H'~
characterized by an intrinsic viscosity of 6 dL/g in MSA at 30C.

The procedure of Example 8 i6 essentially repeated. Instead of monomers la and 2a, 74.075g (0.25617 mol) of monomer lk is dehydrochlorinated in an ~initial~ solution of 493.7g o~ PPA having a P205 content of 77.3% (prepared by mixing 145.9g of 85.4% H3P04 with 347.8g of 115~ PPA).
When dehydrochlorination is substantially complete, 63.065g (0.25617 mol) of monomer ôa is added followed by the gradual additio~ of 221.2g of P205. The mixture is then stirred and heated according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforeme~tioned formulae a* and b*~ to pro~ide the reaction mixture with an effective P205 content of approximately 84.3% prior to the start of polymerization and an effective P205 content of 28~

~259736 approximately 82.2% 6ubsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 12%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
~D H 3n ; 10 characterized by an intrinsic viscosity of 5 dL~g in MSA at 30C.

The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 101.996g (0.25747 mol) of monomer 11 is dehydrochlorinated in an rinitialY solution of 493.3g of PPA having a P205 content of 77.3%
(prepared by mixing 145.7g of 8Ei.4% H3P04 with 347.6g of 115% PPA). When dehydrochlorination is substantially complete, 63.385g (0.25747 mol) of monomer 6a is added followed by t.he gradual addition of 221.5g of P206. The m~xture is then ~tirred and heated according to a schedule similar to Example 8. The amou~t of P205 added is preselected (as determined in ~ccord ~ith the :
, . ~

~,, ' . ., , , " , ~, , ;,, : .

: - `
~2S9~36 aforementioned formulae a* and b*) to provide the`
reaction mixture with an effective P205 content of approximately 84.3% prior ts the start of polymerization and an effective P~05 content of '~ 5 approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibi~s stir-opalescence and is further characterized as having a polymer concentration of 12%; fibers are readily formed by direct spinning, or drawing from the reaction product.
~, The polymer obtaineB is of the following structure:
~D' I '~n characterized by an intrinsic viscosity of 7 dL/g in MSA at 30C.
Analogous to the foregoir,g Examples 40-43, other Type V extended chain polymers ~ay be synthesized to yield liquid-crystalline com~positions having ~arying proportions of ]polymer concentration, P205 content and polymer intrinsic viscosity in accordance with the present inv~3ntion.
The synthesis i6 illustrated by the reaction systems in Tables 24b and 24c. The e------> and p--~---> denote especially preferred and preferred selected mo~omer reactions respectively.

` ~L259736 . TABLE 24b , Polymers of Type Y, Class 2 ? Polymerization Reactions: :
.
H2N3~ ~ 3~ Z12 ~N~N~
HX~ X2H Z1~ Z13 X2 ~ ' .
~ 10 ~onomer (1,2)+Monomer (B,1) ------> Polymer V(2) __ _ lm + 6a e------> ~D'M'~n ln t 6a e------> ~E'G'~n ;~
lo + 6a e------> ~E'H'~n lp + 6a e------> ~E'I'~n . . _ . .

TABLE 24c ~onomer (1,2)+Monomer (B,2) ------> Polymer V~2) li + Bb P~~~~~~' ~J~n ~ .

r ~: ~25973 lj ~ B~ p~ --> ~D'K'~n*
lk ~ Bb p------> ~D'K'~n**
~ b p~ D'L'~n lm + 6b p------> ~D'N'~n ln + Bb P~~~~~~~ ~E~J~n lo + 6b p------> ~E'K'~n lp + 6b p------> ~E'L'~n . . _ . . .

*Note: Oxygen always in 3,3'-positions on D' **Note: Oxygens al~ays in 4,4'-positions on D' The procedure of Example 27 is essentially repeated. Instead of monomer 3a,, 123.074g ~0.64042 mol) of monomer 9a is dissolved in an "initial n solution of 423.lg of PPA having a P205 content of 77.3% (prepared by mixing 125.0g of 85.4% H3P04 with 298.lg of 115% PPA). ~hen .
dissolution is substantially complete, an additional 223.0g of P205 is gradually added to the mixture and dissolved by stirring and heating ,-' -. . , ,:
., ;.
. 292 '~ '' ''.'' ~ ' ': .

r,, . ; . ' ~ '` " ' ' ' ' ' ' ' ' ~ ';

:
125~7~;

essentially according to Example 27. The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a~ and b*) to provide the reaction mixture with an effective P205 content of approximately 85.1 prior to the start of polymerization and an effecti~e P205 content of approximately 82.2%
subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opilescence and is further characterized as having a polymer concentration of 13%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The polymer obtained is of the following structure:
~B'P'~
characterized by an intrinsic viscosity of 10 dL/g in ~SA at 30C.

The procedure of Example 8 is essentially repeat~d. Instead of monomers la and 2a, 86.502g (0.30457 mol) of monomer lc is dehydrochlorinated in an "initial~ solution of 478.4g of PPA having a P205 content of 77.3% (prepared by mixing 141.3g of 85.4% H3P04 with 337.0g of 115% PPA).

. , .
293 .

125973~

When dehydrochlorination is substantially complete, 79.864g (0.30457 mol) of monomer 7a is added followed by the gradual addition of 233.0g of P205. The mixture is then stirred and heated . 5 according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord ~ith the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P205 content of approximately 84.7% prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 12%; fibers are readily formed by direct spinning, or drawing from the reaction product.
The poly~er obtained is of the following structure: -~B'O'~n characterized by an intrinsic v:iscosity of 10 dL/g in USA at 30C.
Analogous to the foregoing Example 45, other Type : .
VII extended chain polymers may be synthesized to :~
yield liquid-crystalline compositions having .. , ~'' ~'.
' ~.
-: :, 294 :

1 .

~ 5~73~
~ .

.. varying proportions of polymer concentration, - P205 content and polymer intrinsic viscosity in accordance with the present invention.
The synthesis is illustrated by the reaction .' 5 systems in Tables 26 and 27. The e~ ->
denotes especially preferred selected monomsr reactions.

~! _ , TABLE 26 Polymers of Type VII, Class 1 Polymerization Reactions:

H2N3~NH2 X7~ ~-- ~N~N~

112N NH2 X7 ~ N N~

Uonomer (l,l)~onomer ~7,1) ------> Polymer VII(1) le + 7a e~ C''~n _ _ .1 ~ 29~i r :' .
5~736 :
; TABLE 27 .: Polymers of Type VII, Class 2 Polymerization Reactions:
S H2 N 3~ N H2 X7 ~ ~ ~ N ~ N~

H2N NH2 X7 X7 ~N~N~

~onomer (1,2)+Uonomer (7,1) ~ > Polymer VII(2) 11 + 7a e------> ~D'O'~
lp + 7a e------> ~E'0'3n .
~ . . :

, '~
~`:
:` ~25~73~
., -The procedure of Example 8 i6 essentially repeated. Instead o~ monomers la and 2a, 102.35g (0.48036 mol) of monomer lb is dehydrochlorinated . 5 in an ~initial" solution of 329.2g of PPA having a P205 content of 77.3% (prepared by mixing 97.3g . of 85.4% H3P04 ~ith 231.9g of 115% PPA). When i dehydrochlorination is substantially complete, 67.296g (0.48036 mol) of monomer 8a is added follo~ed by the gradual addition of 250.5g of P205. The mixture i~ then stirred and heated according to a schedule similar to Example 8.
The amount of P205 added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction ' ' '',,' ' :

'' ' ' ' i' ' 'i'~ '' ~ ' '', '` .'' ' ' . . '~", ' . , ` ~59736 :' mixture with an effective P205 content of approximately 87.1% prior to the start of polymerization and an effective P205 content of approximately 82.2% subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 14%; fibers are readily formed by direct ~! spinning, or drawing from the reaction product.
~ 10 The polymer obtained is of the following :, structure:
~B ~ 3n characterized by an intrinsic viscosity of 7 dL/g in MSA at 30C.

The procedure of Example 8 is essentially repeated. Instead of monomers la and 2a, 137.73g (0.48494 mol) of monomer lc is dehydrochlorinated in an ~initial~ solution of 370.8g of PPA having a P205 content of 77.3% (prepared by mixing 109.6g of 85.4% H3P04 with 261.3g of 115% PPA).
When dehydrochlorination is substantially complete, 67.939g (0.48494 mol) of monomer 8a is added follo~ed by the gradual addition of 263.5g of P205. The mixture is then stirred and heated ., ....... ... . _ , .

~ "

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. . .
' `~ .

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Claims (22)

CLAIMS:

1. A process for preparing an extended chain polymer composition of workable viscosity which is useful as a dope in the production of fibers and films, said composition comprising liquid crystalline poly(2,6-benzothiazole), said process comprises the following steps:

(a) mixing a selected monomer with or without oxidation protecting atoms or groups with a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to remove any volatilized protecting atoms or groups present and provide a solution of the monomer in the preliminary solvent, (c) then increasing the phosphorus pentoxide content of the mixture resulting from step (b) by adding phosphorus pentoxide in two or more portions to provide a monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (d) causing polymerization of the monomer at a temperature sufficient to effect reaction at a rate to form a homo-oligomeric product having a preselected intrinsic viscosity or a homopolymeric product.

2. A process for preparing an extended chain polymer composition of workable viscosity which is useful as a dope in the production of fibers and films, said composition comprising a liquid crystalline poly(2,6-benzothiazole), and said process comprises:

(a) incorporating a selected monomer in a preliminary solvent of phosphoric acid having a relatively low phosphorus pentoxide content, (b) increasing the phosphorus pentoxide content of the resultant preliminary solvent by adding phosphorus pentoxide in two or more portions to provide a monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization, (c) causing polymerization of the monomer at a temperature sufficient to effect reaction at a rate to form a polymer having a preselected intrinsic viscosity.

3. A process according to claim 1 or 2 wherein said selected monomer is 3-mercapto-4-aminobenzoic acid hydrochloride.

4. A process according to claim 1 or 2 wherein said selected monomer is 3-mercapto-4-aminobenzoic acid.

5. A process according to claim 1 wherein said phosphorus pentoxide content of step (a) is present in said preliminary solvent in an amount below about 77% by weight.

6. A process according to claim 2 wherein said phosphorus pentoxide content of step (a) is present in said preliminary solvent in an amount below about 77% by weight.

7. A process according to claim 5 wherein said phosphorus pentoxide content of said monomer reaction medium of step (c) is of an amount suitable for polymeriza-tion to provide a homopolymeric product of said polymerization reaction having a phosphorus pentoxide content between about 82% and about 86% by weight.

8. A process according to claim 6 wherein said phosphorus pentoxide content of said monomer reaction medium of step (c) is of an amount suitable for polymerization to provide a homopolymeric product of said polymerization reaction having a phosphorus pentoxide content between about 82% and about 86% by weight.

9. A process according to claim 7 wherein said phosphorus pentoxide content of step (d) is present in said homopolymeric product in an amount between about 82% and about 84% by weight.

10. A process according to claim 8 wherein said phosphorus pentoxide content of step (d) is present in said homopolymeric product in an amount between about 82% and about 84% by weight.

11. A process according to claims 9 or 10 further comprising the step of spinning said homo-oligomeric pro-duct or said homopolymeric product through an air-gap and into a coagulation bath thereby forming a fiber, said spinning being performed at high draw ratios.

12. A process according to claims 9 or 10 further comprising the step of spinning said homo-oligomeric product or said homopolymeric product through an air-gap of from about 1 cm to about 200 cm before entering a coagulation bath thereby forming a fiber.

13. A process according to claims 7 or 8 wherein said phosphorus pentoxide content of step (d) is present in said homo-oligomeric product in an amount between about 82%
and about 84% by weight.

14. A process according to claims 7 or 8 wherein said phosphorus pentoxide content of step (c) is increased by adding phosphorus pentoxide in two or more portions to provide said monomer reaction medium of greater phosphorus pentoxide content between about 82% and about 84% by weight.

15. A process according to claims 9 or 10 further comprising the step of drawing said homo-oligomeric product or said homo-polymeric product and passing said product through a coagulation bath so as to extract substantially all the phosphoric acid thereby forming an article.

16. A process according to claims 9 or 10 further comprising the step of extruding said homo-oligomeric product or said homopolymeric product and passing said product through a coagulation bath so as to extract substantially all the phosphoric acid thereby forming a film.

17. A process according to claims 9 or 10 further comprising the step of casting said homo-oligomeric product or said homopolymeric product and passing said product through a coagulation bath so as to extract substantially all the phosphoric acid thereby forming an article.

18. A process according to claim 2 wherein said phosphorus pentoxide content following polymerization is present in an amount between about 82% and about 84% by weight.

19. A process according to claim 2 wherein said phosphorus pentoxide content of step (b) is present in said monomer reaction medium in an amount between about 82% and about 86% by weight.

20. A process according to claim 1 wherein said polymer is wherein n corresponds to a molecular weight of at least about 7 dL/g as determined in methanesulfonic acid at 30°C.

21. A process according to claim 2 wherein said polymer is wherein n corresponds to a molecular weight of at least about 7 dL/g as determined in methanesulfonic acid at 30°C.

22. A process according to claims 20 or 21 wherein said polymer is crystalline poly(2,6-benzothiazole).