A PROCESS FOR THE PRODUCTION OF A LIQUID CRYSTALLINE EXTENDED CHAIN POLYMER COMPOSITION

Abstract: Novel liquid crystalline extended chain polymer compositions comprising a high concentration of one or more extended chain homopolymers, copolymers or block polymers and certain strong acids are prepared by admixing a high concentration of one or more selected monomers with or without oxidation protecting moieties and one or more of substantially non-oxidizing strong acid(s) containing P2O5. Such compositions, which are prepared by polymerization in a reaction vessel maximizing surface-to-volume ratio, are capable of exhibiting high cohesive strength, and are especially suited to the production of high molecular weight ordered polymer fibers. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

Description: A PROCESS FOR THE PRODUCTION OF A LIQUID CRYSTALLINE EXTENDED CHAIN POLYMER COMPOSITION Technical Field of Invention The present invention relates to a process for the synthesis of high molecular weight extended chain crystalline polymers, to the preparation of novel liquid-crystalline extended chain polymer-strong acid compositions, and to the production of industrially useful polymeric articles such as fibers, fibrids. films and the like. Background Art The invention described herein was made with Government support under U.S. Department of Defense contract Nos. F33615-81-K-5070. F49620-81-K-0003. F33615-82-C-5079. F59620-83-K-0036. and/or F33615-84-C-5005 awarded by the United States Air Force. The Government has certain rights in this invention. Reference is made to other co-pending PCT International and corresponding United States patent applications, all assigned to SRI International and having as one of their inventors James F.Wolfe. Said other PCT applications are entitled: "Liquid Crystalline Poly(2.6-benzothiazole) Compositions, Process, and Products". No. PCT/US82/01286. publication No. WO84/01161, published with international search report, corresponding U.S. Patent No. 4,533,724 issued August 6. 1985; "Liquid Crystalline Polymer Compositions. Process, and Products", No. PCT/US82/01285. publication No. WO84/01160. published with international search report, corresponding U.S. Patent No. 4,533,692 issued August 6, 1985; "Liquid Crystalline Polymer Compositions, Process, and Products". No. PCT/US83/01437. publication No. WO84/01162 published with international search report (in addition, a supplementary European Search Report conducted at the Hague was completed on July 2, 1985). corresponding U.S. Patent No. 4.533.6.93 issued August 6, , 1985; and "Liquid Crystalline Polymer Compositions. Process, and Products". No. PCT/US85/00258. U.S. application Serial No. 590,292. filed March 16, 1984. It is believed that the following references are also relevant to the instant application: (1) Choe. U.S. Patent No. 4.423.202; (2) Choe et al.. Macromolecules 14. pp. 920-24 (1981); (3) Wolfe et al., Macromolecules 14. pp. 915-20 (1981); (4) Wolfe et al.. Macromolecules 14. pp. 909-914 (1981); (5) U.S. Patent No. 4.225.700 to Wolfe et al.; (6) Cotts et al., Macromolecules 14. pp. 930-34 (1981); (7) U.S. Patent No. 3.632.414 to Arnold et al.; (8) U.S. Patent No. 4.131.748 to Arnold et al.; (9) U.S. Patent No. 4.108.835 to Arnold et al.; (10) U.S. Patent No. 4.207,407 to Helminiak et al.; (11) U.S. Patent No. 3,449.296 to Angelo et al.; (12) U.S. Patent No. 4,359.567 to Evers; (13) U.S. Patent No. 3.424.720 to Rudner et al.; (14) Allen et al.. Macromolecules 14. pp. 1135-38 (1981); (15) Teijin. Japanese Patent No. 4.219.270; (16) Teijin. French Patent No. 1,363.757; and (17) U.S. Patent No. 4.054.633 to Richardson. In general, the class of aromatic heterocyclic extended chain polymers are well-known for their outstanding thermal, physical and chemical properties. Unfo tunately, these polymers are essentially non- elting and have proven very difficult to process economically into articles. In order to fashion such polymers into desired articles of commerce, e.g. fibers, films, fibrids . and the like, it is necessary that they be in solution or dope form. Although such polymers can be dissolved to some extent in various acidic solvents, such as sulfuric acid (SA). methanesulfonic acid (MSA), chlorosulfonic acid (CSA). polyphosphoric acid (PPA) and the like, the relatively poor solubility of the polymers in these acids has created problems with preparation and use. Normally, a precipitated or dried particulate form of the polymer is dissolved in a strong acidic solvent by admixing at elevated temperature and/or elevated pressure a period of at least several hours. If the polymer is insoluble in the particular solvent, other solvents or solvent mixtures are employed. Usually, heating and cooling cycle ' s are applied and " repeated to obtain a useful dope. The resulting dopes often contain undissolved polymer, however, and must be filtered before further processing. It is most desirable, therefore, to be able to polymerize such polymers in the liquid crystalline state starting from monomer solutions. With the exception of the polymerization of polybenzobisthiazole (PBT) as reported in references (3) and (5) cited above, it has not been heretofore possible to polymerize this class of polymers in the liquid crystalline state using prior art processes. The polymers and dopes provided by prior art methods, with the exception of PBT dopes, can be characterized as being low molecular weight and in some instances lacking full chain extension (assuming a flexible coil conformation). With the mentioned exception, all polymer dopes produced by prior art polymerization methods are of low polymer concentration. and isotropic in character. It is possible to synthesize PBT in the liquid crystalline state from monomers to give a resultant polymer concentration in the final polymerization mixture near 10% with an intrinsic viscosity of about 26 dL/g (see, e.g.. reference (3)). The synthesis of high molecular weight PBT at 10% or greater polymer concentration was, however, unknown. High molecular weight PBT could only be synthesized at low monomer levels. One difficulty encountered was the viscosity of the 2,5-diamino-l.4-benzenedithiol onomer/polyphosphoric acid solution, which resulted in considerable foaming and corresponding difficulty with dehydrohalogenation. Attempts by those skilled in the art to synthesize PBT at high monomer levels resulted in low molecular weight PBT. In sum. prior art polymers and dopes are severely limited in their potential utility for the production of highly ordered molecular weight crystalline polymeric articles. Disclosure of the Invention Accordingly, it is a primary object of the present invention to prepare extended chain crystalline polymers, liquid crystalline compositions of such polymers, and crystalline polymeric articles such as fibers, fibrids. films and the like, by a process substantially free of one or more of the aforementioned disadvantages of the prior art. It is another object of the invention to provide a process for preparing liquid crystalline extended chain polymer compositions of high phosphorus pentoxide content from one or more selected monomers. It is still another object of the invention to provide a process for preparing high solids content liquid crystalline extended chain polymer compositions exhibiting excellent properties for fiber spinning. it is still another object to provide a process for preparing high solids content liquid crystalline extended chain homopolymer. copolymer. and block polymer compositions. Yet another object is to provide a process for preparing high molecular weight extended chain crystalline homopolymers. copolymers and block polymers which are substantially free of amorphous regions. A further object is to provide a method whereby the dehydrohalogenation of one or more hydrohalide monomers in a substantially non-oxidizing strong acid can be carried out more easily and rapidly in a controlled manner. A still further object is to provide a method for the dehydrohalogenation of a high concentration of one or more hydrohalide monomers in the presence of a substantially non-oxidizing strong acid having a high phosphorus pentoxide content, whereby the foaming difficulties previously encountered during dehydrohalogenation are substantially reduced. i is a further object to provide a method for controlling the viscosity of an admixture of one or more hydrohalide monomers in a substantially non-oxidizing strong acid while increasing the phosphorus pentoxide content of the admixture. Still another object is to provide a method for controllably removing monomer oxidation protecting moieties under selected dehydrohalogenation conditions. A further object 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. Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art on examination of the following, or may be learned by practice of the invention. In accordance with our discovery, the process of this invention now makes it possible to prepare high molecular weight extended chain crystalline polymers, liquid-crystalline compositions of such polymers, and crystalline polymeric articles from viscous solutions of monomer(s). In general, the process involves preparing a liquid crystalline extended chain polymer composition of workable viscosity, including: (a) preparing a monomer reaction medium suitable for polymerization by incorporating a high concentration of at least one selected monomer in a substantially non-oxidizing strong acid, said reaction medium containing at least about 80% by weight phosphorus pentoxide: (b) introducing said reaction medium into a reaction vessel selected so that a sur ace-to-volume ratio greater than about 0.2 cm " is achieved; and (c) heating said reaction medium to a temperature sufficient to effect polymerization of said at least one monomer. More specifically, the process comprises: (a) mixing at least one of a selected first homo— or hetero— bifunctional monomer(s) with or without oxidation protecting atoms or groups with a preliminary solvent of a substantially non-oxidizing strong acid having a high phosphorus pentoxide content, (b) heating and optionally placing the resulting mixture under reduced pressure to promote the removal of any volatilized protecting atoms or groups present and to provide a first mixture of the first monomer(s) in the preliminary solvent, said mixing and heating steps (a) and (b) being performed sequentially or simultanously at a selected same or different surface-to-volume ratio(s), said steps (a) and (b) being performed under a selected same or different set of conditions of time, temperature, pressure, rate and amount of said monomer(s) addition, and rate and amount of phosphorus pentoxide addition, said temρerature(s) of steps (a) and (b) being sufficient to maintain said mixture at a workable viscosity under said selected set of conditions, said selected surface-to-volume ratio(s) of steps (a) and (b) being sufficient to control the removal of said volatilized protecting atoms or groups under said selected set of conditions, said selected surface-to-volume ratio being greater than 0.2 cm "1 , said rate and amount of said monomer(s) addition of steps (a) and (b) being controlled to facilitate the removal of said volatilized protecting atoms or groups under said selected set of conditions, said rate and amount of phosphorus pentoxide addition being controlled to facilitate the removal of said volatilized protecting atoms or groups and prevent decomposition of said monomer(s) due to heating under said selected set of conditions, (c) adding at least one of a selected second monomer(s) in the resulting mixture of step (b) when said selected first monomer(s) is a homo—bifunctional monomer so as to provide a first mixture of the first and second monomers in the preliminary solvent while maintaining said first mixture of the first and second monomers at a workable viscosity, (d) then adjusting the phosphorus pentoxide content of the mixture resulting from step (b) or (c) as necessary to provide a first or a first and second monomer reaction medium of sufficient phosphorus pentoxide content suitable for polymerization and for achieving a degree of polymerization greater than about 40 while maintaining said reaction medium at a workable viscosity, (e) causing polymerization of the first or the first and second monomer(s) 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 intrinsic viscosity, . or (f) causing polymerization of the first or the first and second monomer(s) at a temperature sufficient to effect reaction at a rate to form a first homo-polymeric product or a first copolymeric 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, said second homo-oligomeric product being formed by like steps (a) and (b) followed by: (lg) adding at least one of a selected second monomer(s) in the resulting mixture of step (b) when said selected first monomer is a homo-bifunctional monomer so as to provide a mixture of a first and second monomers in the preliminary solvent, (2g) then adjusting , the phosphorus pentoxide content of the mixture resulting from step (b) or (lg) to provide a first or a first and second monomer reaction medium of sufficient phosphorus pentoxide content suitable for polymerization, (3g) causing polymerization of the first or first and second monomer(s) 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(s) of step (a) or (lg) which forms the second homo- oligomeric product be different from at least one of the selected monomer(s) 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 monomer(s) or a first and second monomers in the preliminary solvent so as to form a monomer-oligomer mixture, and then adjusting the phosphorus pentoxide content of said monomer-oligomer mixture as necessary to provide a monomer-oligomer reaction medium of sufficient phosphorus pentoxide content suitable for polymerization, said first monomer of said second mixture being formed by like steps (a) and (b) and said first and second monomer of said second mixture being formed by like steps (a), (b) and (c), with the overall proviso that at least one of the selected monomer of step (a) or (c) which forms the first or first and second monomer(s) of said second mixture be different from at least one of the selected monomer(s) of step (a) or (c) which forms the first homo-oligomeric product, (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 blockpolymeric product, (j) spinning, drawing, extruding, or casting an article from said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said first poly-oligomeric product, said second homo-oligomeriα product, said first block-oligomeric product, said first block-polymeric product, or mixtures thereof. In another embodiment of the invention, the molecular weight (characterized by intrinsic viscosity) of said first homo-oligomeric product, said first co-oligoraeric 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 discontinuing steps (e), (f), (3g), and (i) (which forms said respective products) at an early stage of reaction so as to achieve a preselected low intrinsic viscosity or said seeps are continued at a temperature sufficient to effect further reaction to obtain a preselected higher intrinsic viscosity or further heating said products to achieve an intrinsic viscosity 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 copolymeric product, said first poly-oligomeric product, said second homo-oligomeric product, said first block-oligomeric product, and said first block-polymeric product which are formed by the respective reaction steps (e) (f) » (3g) » and (*) involving the reaction of a selected first and second monomer is controlled by adding a selected excess molar amount of said selected second monomer or more preferably a selected excess molar amount of said selected first monomer or allowing the loss of a small proportion of said selected 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 of one or more selected monofunctional reactants (as described hereinafter) having a single functional group in steps (a), (b), (c), and (lg) to achieve an intrinsic viscosity less than the maximum attainable. Brief Description of the Drawings The invention will be more fully explained with reference to the Figures wherein: FIG. 1 graphically illustrates the relationship of the maximum amount of usable PPA and Pώ~0_b content for a polymer yield (P ) = 100 grams required to achieve a final PPA concentration (P ) of 0.822 for selected polymer concentrations (plot of equation a*) showing a region (shaded dash area) of poor solubility for monomer la; FIGS. 2, 3, 4 and 5 are percent P _.0 c b content profile diagrams giving the profile area bounded by ABCDEFGHI of percent P 0_ for achieving the advantages of this invention; and FIG. 6 graphically illustrates various regions (A through E requiring consideration of process parameters) over a family of curves of maximum amount of usable PPA vs. P <£0_b content for Py = 100 grams required to achieve a P of 0.822 for selected polymer concentrations (P s). c Mode * a. of Carrying 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 1 of the polymer. In the case of a rigid rod polymer. p is essentially infinite and the axial ratio is 1/d. By the method of the present invention, 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 compositions of lower polymer concentration but there are special advantages to preparing compositions of high concentration. Extended chain polymer—strong 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 - 1055)..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 5 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 is spun by a dry- jet-wet spinning technique into a polyphosphoric acid-solvent/polymer-nonsolvent such as methanol. ,lb _ water, or dilute aqueous acidCs) . If the polymer is one. such as poly (2,6- benzothiazole) that is less rodlike in structure than polybenzobisthiazole-or polybenzobisoxazole and thus possesses a critical concentration for 20 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 25 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. 30 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 , medium molecular weight, or ultra-high molecular weight (up to the maximum obtainable) are desired, the present invention is most advantageous. Extended chain polymers of essentially any desired molecular weight (characterized by intrinsic viscosity) up to the maximum attainable can be prepared in the liquid crystalline phase without substantial difficulty. Pref erably , molecular weight is controlled by discontinuing said polymer ization at a selected degree of polymerization, more pref erably , by of f -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 polymer ization, and most pref erably, by the addition of one or more suitable monofunctional reactants in selected amounts and at a selected stage of polymer ization. The following convention is utilized to characterize the molecular weights (in terms of intrinsic viscosity) of polymers produced by the process of the invention: intrinsic viscosity in MSA at 30 °C <4 dL/g very low 4 to <10 dL/g low 10 to <20 dL/g medium 20 to <25 dL/g high 25 to 50 dL/g very high > 50 dL/g Ultra-high In instances where the extended chain polymer molecular weight must be maintained at a level below the maximum attainable, 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 induce further polymerization which may be undesirable, then preparation of suαh polymers in accordance with the practice of the invention is advantageous. The liquid crystalline compositions prepared by the process of the invention exhibit special properties which make them very useful as dopes in the production of fibers, films, fibrids, and the like. In addition, the compositions have 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 low, as well as exceptionally high, draw ratios. It is believed that these properties can be attributed to the combination of high polymer concentration, substantially high polymer molecular weight, and a high phosphorus pentoxide content. The polymer concentration of the compositions of the invention can range from about 10% or less to about 30% or more based on the weight of the composition. The process can be use to prepare liquid crystalline compositions of any desired viscosity. In accordance with the practice of the invention, the liquid crystalline compositions (depending on polymer concentration and molecular weight) can have (bulk) viscosities over a wide range from about 3,000 to about 1,500,000 poise, preferrably from about 10 ι " 000 to about 150,000 poise, more preferrably from about 20,000 to about 80,000, and most preferrably between about 20,000 to about 40,000 poise. The bulk viscosities of the compositions of the invention can be measured, over a broad range, using a RMS-605 Mechanical Spectrometer with a 2.5-αn Hastelloy cone and plate under N2 in a suitable oven modified to prevent the introduction of » water vapor. The modified cone and plate can be utilized to measure viscosities from 0.1 poise to 5,000,000 poise. The cone and plate includes a "moat" containing silicone oil built into the plate, onto which a concentric ring is attached to the cone assembly. The torque generated by viscous drag on the vapor barrier is less than 1 g cm. Measurement of the viscosity of neat PPA using the modified cone and plate shows no change over an 8 h period, confirming that this device does successfully exclude moisture when the sample is introduced anhydrously. Steady-state and dynamic viscosity measurements can be made over a range of shear rates. Strong acids are generally characterized as highly polar solvents. Although various strong acids may be used as solvents to carry out the dehydrohalogenation of some of the monomers of the process, the resultant acid-monomer solutions, in most instances, can not be converted or converted with great difficulty into reaction mediums suitable for polymerization. As a practical matter and an essential aspect of the invention, the strong acids selected for use in the process of the invention must not only be effective as a dehydrohalogenation solvent but also must be able to be converted into an effective reaction medium suitable for polymerization. Polyphosphoric acid has been found to be suitable for the process of the invention and is the most preferred because of its compatibility ■ with the preferred monomers, its effectiveness as solvent for carrying out the various steps.of the i ention, and its substantially non-oxidative nature for the preferred monomers and resultant polymers of polycondensation. For a discussion of the chemistry of phosphoric and polyphosphoric acids relevant to the instant invention, see U. S . Patent No . 4.532. 692 to Wolf e et al . at columns 6-7. the disclosure of which patent is hereby, incorporated by reference in its entirety. In certain Instances one or more alkanesulfonic acids (e.g. , methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, trifluoromethanesulfonic acid and the like) will work as a suitable dehydrohalogenation solvent. We have found, however, that before the alkanesulfonic acids can be converted into a reaction medium and utilized, phosphorus pentoxide must be added in sufficient amounts for polyαondensation. We have found that when any of the alkanesulfonic acids are employed, the proportion of phosphorus pentoxide should be at least about 30% by weight of the alkanesulfonic acid(s) and may range from between about 30% to about 70%, preferrably between about 35% to about 60%, more preferrably between about 35% to about 50% and most preferrably between about 35% to about 45%. Alkanesulfonic acids are especially suited for use in the polymerization of some of the more oxidation resistant monomers of the invention. The use of alkanesulfonic adds should be avoided when polymerizing certain monomers such as 2 5-diamino-l,4-benzenedithiol dihydroβhloride and the like. These monomers are highly susceptible to thermal oxidation in the c presence of a major amount of alkanesulfonic acids when heated above 100"C. When preparing a reaction medium of a heat sensitive monomer, the amount of any of the alkanesulfonic acids present should be less than about 10%, preferrably less than 5%, and most preferrably less than 2%. 0 Solvent mixtures of one or more alkanesulfonic acid(s) and polyphosphoric acid having an effective P 2 °5 content are also contemplated as useful in the present process. The alkanesulfonic acids employed in the process of the invention 5 are available from various sources such as Stepan Chemical Co., Onyx Chemical Go., Conoco Chemical Co., Richardson Co., Kodak laboratory Chemicals, etc. The chemistry for making these acids are well known to those skilled in the art (e.g., Kirk-Othmer, "Encyclopedia of Chemical Technology", 3rd Ed., Vol. 22, pp. 45-63, 1982.). The alkane- 0 sulfonic acids should be technical grade, preferrably reagent grade and should be distilled before use. Distillation under vacuum is especially preferred to avoid thermal decomposition at high temperatures. In using alkanesulfonic acids, the volatility of these acids must be 5 must be controlled during polymerization, but can be of advantage in the spinning of fibers and the extrusion of films. The alkanesulfonic acids can be removed, for example, during dry spinning before coagulation is initiated (i.e., in the air gap). The two-stage removal of the solvent can improve the skin-core formation to begin before the fiber enters the 0 coagulation bath and accelerate the collapse of the polymer on itself, which would give better mechanical properties such as compressive strength, and would provide a method to recycle the acids. A common factor of the (suitable) strong acids "systems" (i.e., (1) polyphosphoric acid/alkanesulfonic acids, (2) alkanesulfonic a id(s -P2θ-, and (3) polyphosphoric acid) employed in the process of the invention which makes them effective as solvents for carrying out the various steps of the invention is the "total" concentration of solvent reactive species and monomer reactive species; they must be high enough to give a rate of polymerization that can effectively compete with side reactions. . • In the absence of side reactions lower concentrations of the solvent reactive species leads to a lower rate of polymerization and longer times to achieve the desired polymer molecular weight. In all three systems, dehydrohalogenation (which activates the monomer reactive spcecies) can take place irrespective of the P.O c content of the solvent. The preliminary solvent, however, must be converted ±n_ situ to a reaction medium suitable for polymerization in which there is a sufficient concentration of the solvent reactive species. From a theoretical point of view, the relationship of P^O- content on the effectiveness of the three systems to carry out polymerization is not well understood. This difficulty, we believe, is due in part to the differences in solvent reactive species presence in the three systems. The three systems undoubtedly have different rate constants for the polymerization step and have different side reactions (such as oxidation of sensitive monomers in alkanesulfonic acids) with different reaction rates. We have found, however, PPA must have a concentration of solvent reactive species (i.e., triphosphoric acid and higher oligoraers such as tetra-, penta-, hexa-, heptaphosphoric acid etc. ) of greater than 60% at the end of polymerization in order to obtain sufficient reaction rate. PPA loses its solvent power at a higher ^_^5 content than does alkanesuflfonic acid/P-O (e.g., MSA/P-Oc) because H 3 P0, is not a good solvent for polymers of the invention whereas MSA is. If we assume that the reactive species in MSA/P^O,- is a mixed anhydride of P 2 ° an< MSA with a molecular weight of 334.16 then a 30-40 wt % P 2 0 5 in MSA ■ mixture contains 70 to 94% of the solvent reactive species at the beginning of the reaction and with the water of condensation this goes to comparable levels of the solvent reactive species at the end of the polymerization. In any case , there must be a sufficiently high level of solvent reactive species at the end of the polymerization, and that level is near about 60 wt %. Monomers In general, any monoπteric material or mixture of monomeric materials having the ability to react in polyphosphoric acid and mixtures of polyphosphoric acid and alkanesulfonic acids to form the extended chain polymers of the present invention can be utilized herein. Suitable monomeric materials useful in forming the liquid-crystalline extended chain polymer compositions of the present invention are of nine types as described below. Types 1. 2. 4. 6, 7 and 8 are homo-bifunctional monomers. Types 3. 5 and 9 are hetero-bifunctional monomers. Type 1 monomers have the general formula wherein Ar is an aromatic moiety; X. and X2 are the same or different atoms or groups selected from the class 0. S. and NR: R is hydrogen or an organic group attached to N; the R's on the two nitrogen atoms where both X, and X„ are NR may be the same or different: NH 2# X^ and X-H are bonded to aromatic carbon atoms of Ar ; the groups on the left side of Ar are ortho with respect to one another and the groups on the right side of Ar are ortho with respect to one another. The two sets of NH„ and XH are each considered a functional group and are positioned on A 1 such that they do not both interact partially with the appropriate condensing moiety of another monomer. Monomer 1 is typically isolated as a hydrohalide salt of the monomer. Type 1 monomers are homobifunctiional. by definition, whether or not X. and X„ are the same of different. In general, Ar may be any aromatic moiety (carbocyclic or heterocyclic) and it may be a sin le rin such as or it may comprise a plurality of aromatic rings connected by valence bonds or by linking atoms or groups such as where ?ι§ β r-is * ©a e bond as in diphenyl) or a divalent atom (-0- or -S-) or group such as -NR-(R=H or an organic group). -(CH«)- (n=l or a higher integer) . Specific examples of Ar 1 are as follows: The aromatic ring or rings of Ar . 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.. ^ to C.- straight chain and branched chain alkyl. benzyl, etc.). phenyl. chloro substituted alkyl. phenyl and benzyl. 5 Among permissible hetero substituents are chloro. bromo. nitro. alkoxy. aryloxy. S0.-H. SR. and -NR.Rrt R j and 2 being organic groups) . Formula 1 monomers useful in preparing the extended chain polymers and novel liquid- 10 crystalline compositions of the instant invention 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 ** - 5 denotes the monomer class. The preferred (1.1) monomers are those wherein Ar is a six-membered aromatic ring with the four valence positions being on carbon atoms having a 1. 2. 4. 5 relationship to each other, such as 1. 20 2. 4, 5-benzene or 2. 3. 5. S-pyridine; R is H or a monovalent aromatic radical, such as phenyl. or a monovalent heteroaromatic radical, such as 2- pyridyl. or a monovalent aliphatic radical, such as methyl. Monomers (1.1) which when reacted 25 with a diacid or a diacid derivative give two substantially collinear bonds are most preferred. The preferred (1.2) monomers are those wherein Ar is two six-membered aromatic rings attached by a covalent carbon-carbon bond each with 30 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 Ar is two fused six- membered rings with valence positions being on carbon atoms and having a 1.2.5.6 relationship to each other, such as 1 ,2,5.6-naDhthalene. The four functional groups attached to the valence positions of Ar by covalent bonds comprise two amino groups and the groups -X^H and -X-H such that one amino group is ortho to -X.H and the other amino group is ortho to X«H and X^H is attached to either the 3 or 4 position in the first case or the 1 or 2 position in the second case and -XnH is attached to either the 3* or 4 * position in the first case and the 5 or 6 position in the second .case. X. and X« are defined as above. The preferred (1.3) monomers are those wherein Ar is any aromatic moiety with two sets of _ ortho-valences at carbon atoms, such as wherein β is a bivalent aromatic or heteroaromatic moiety. Q. S. SCL. C=0. - H 2 CH 2 -. etc. The four functional groups attached to the valence positions of Ar are divided into two sets (NH„ and X^) and (NH 2 and X 2 H) with the functional groups within each set being positioned ortho to each other and the two sets positioned on Ar such that they cannot simultaneously react with the same functional ggrroouupp ooff ;another monomer. 1 and X„ are defined as above. Type 2 monomers have the general formula wherein Y is a bivalent organic group and Z. and Z are electron-deficient carbon groups and may be the same or different groups selected from the following class: -cαoH -CSSH -COBr - SI -CSOH -C0C1 -CSBr -CONHR -COSH -CSC1 - OI -CSNHR -CN (R. = H or an organic group bonded to N by a carbon atom) The only requirement of Z. and Z« is that they react with the X.H and X 2 H and with the two hydrogen atoms of the primary amino groups of Type 1 monomers to form suitable leaving entities, such as water, hydrogen sulfide, hydrogen halide, ammonia, etc. Type two monomers are homobifunctional, by definition, whether or not Z 1 and Z 2 are the same or different. The bivalent group Y may be an aromatic group, an acyclic aliphatic group, or a cycloaliphatic -27a- 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 Ar 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 invention 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. 2 The preferred (2.1) monomers are those wherein Y is nil. or Y„ comprise at least two carbon atoms to which are attached Z. and Z« such that the two exocyclic bonds between Y 2 and Z. and between Y2 and Z„ have a rigid and fixed relationship to each other and are substantially collinear. or Y 2 may also be a cycloaliphatic group that has at least two carbon atoms to which are attached Z. and Z« such that the two bonds between Y 2 and Z. and between Y 2 and Z« have a highly preferred relationship to each other that is substantially collinear. Carboxylic acid derivatives of 2j-2q -28- 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. 2 The preferred (2.2) monomers are those wherein Y. 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 * -biphenyl or 3.3'-biphenyl, 2 or Y comprise two fused six-membered rings with valence positions being on carbon atoms and having a 1.5 relationship to each other, such as 2 2.6-naphthalene or 2.6-quinoline. or Y is a cycloaliphatic divalent moiety with valences on carbon atoms and in a 1.2-trans configuration, or 2 Y is a variety of condensed aromatic and heteroaromatic ring systems attached only by carbon-carbon bonds and having 2 valences. Z. and Z 2 are the same as defined above. 2 The preferred (2,3) monomers are those wherein Y may be any aromatic, heteroaromatic and aliphatic divalent species not previously described. Type 3 monomers have the general formula wherein Ar is a trivalent aromatic or heteroaromatic moiety, and X 3 is 0. S. or N-R (R = H or an organic group) . Type 3 monomers are neterobifunctional, by definition. -29- Formula 2 monomers useful in preparing the extended chain polymers and novel liquid- crystalline compositions of the instant invention may also further be classified into two groups: Class 1 (3.1) and Class 2 (3.2). The first number of the number pairs denotes the monomer type and the second number of the pairs denotes the monomer class. The preferred (3.1) monomers are those wherein Z, 3 is the same as defined for Z.. Ar is a trivalent aromatic or heteroaromatic moiety with the three valence positions being on carbon atoms and having the relationship that the valence bond 3 between Z 3 and Ar is nearly collinear with the same valence bond in subsequently condensed monomers, and X 3 is defined as for X. in Table 1. X 3 and NH 2 are positioned ortho to each other on Ar 3 . The preferred (3.2) monomers are those wherein 3 Z 3 . Ar . and X 3 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°. Type 4 monomers have the general formula -30- wherein Z 4 . Z g . Z β . and Z-, are the same or different and are chosen from the list of carboxylic acid derivatives given for Z. in Table 4. z. and Z ς . or Z- and Z- , or both sets can also be carboxylic acid anhydride groups.Z, and Z e are defined as one functional group (as are Zg and Zη) and thus Type 4 monomers are homobif nctional by definition, whether or not Z^, Z^, Zg and Zη are the same or different. Ar is an aromatic or aromatic heterocyclic moiety having four valence positions at carbon atoms. Ar can be a six-member ring with the valence positions having 1, 2, 4, 5 relationship, or Ar can be two condensed six-member rings, such as naphthalene. Z, and Ze as one set and Zg and Zη 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 Z. and Ze must be collinear with the corresponding (imaginary) line for Zg and Z-,. Formula 4_ monomers useful in preparing the extended chain polymers and novel liquid- crystalline compositions of the instant invention are classified as Class 1 (4.1). * The first number of the number pairs denotes the monomer t ype and the second number of the pairs denotes t he monomer class. Type 5 monomers have the general formula wherein Z g and Z g are defined as for Z 4 and Z g in Table 9. Ar is defined as in Table 9. the two amino groups are ortho to each other, and Z g . Z g . and the two amino groups are positioned such that two imaginary lines drawn perpendicular to the -31- bonds between their valence carbons are collinear. Type 5 monomers are heterobi- functional, by definition. Formula £ 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. Type 6 monomers have the general formula wherein Ar represents an aromatic moiety and is a tetrahydroxy fused ring system. Z. Q . Z... Z. 2 . Z. _ are the same HO atoms bonded to carbon atoms of Ar 6. Type 6 monomers are defined as homobifunctional monomers. In general. Ar 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 _, 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. -32- The preferred ( 6.1 ) monomers are those wherein Ar comprise a single center aromatic ring in the center of the fused ring system. The preferred ( 6.2 ) monomers are those wherein Ar comprise at least two center aromatic rings in the center of the fused ring system. Type 7 monomer has the general formula wherein Y represents an aromatic or heteroaromatic moiety and is a fused ring carbon group, the X_'s are double bonded to carbon. toms of Y . Type 7 monomers are homobifunctional, by definition. Formula _ 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. Type 8 monomer has the general formula -33- wherein Y 8 is a single carbon cyclic moiety. X 1Q and X.. are HO and 0 atoms respectively, bonded to carbon atoms of Y 8 . Type 8 monomers are homobifunctional, by definition. Formula S 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 Type 9 monomer has the general formula Q wherein Ar represents an aromatic moiety and is a partially fused ring system. Z, . and Z. 5 are OH atoms. X. are selected from the class 0. S. and NR; R is H or an organic group attached to N; m Z ' 4 H« Z 14' and Z 15 * re bonded to carbon atoms 9 of Ar ; NH- and X,H are positioned ortho; Z., and Z. _ are positioned ortho. Type 9 monomers are heterofunctional, by definition. Formula 2 monomers useful in preparing the extended chain 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. -34- The preferred (2,3) monomers are those wherein Y 2 ""^ ^* anv aromatic heteroaromatic and aliphatic divalent species not previously described. The preferred (3,2) monomers are those wherein Z^, r^, and Xj are defined above. The bonds that are formed in homopolymerization of (3,2) monomers are defined in their spatial relationship as having an angle of catenation of less than about 150 to 180°. Specific examples of preferred (1,1), (1,2), (1,3), (2,1), (2,2), (2,3), (5,1), (3,2), (4,1), (5,1), (6,1), (6,2), (7,1), (8,1), and (9,1) monomers suitable for use in the process of the invention inσlude: (la) 2,5-diamino-l,4-benzenedithiol dihydrochloride, (lb) 4,6—diamino-l,3-benzenediol dihydrochloride, (lc) 1,2,4,5-tetraaminobenzene tetrahydrochloride, (Id) 2,5-diamino * —1,4-benzenediol dihydrochloride, (le) 2,3,5,6-tetraaminoρyridine trihydrochloride, (If) 3,5-diamino-2,6-pyridinediol trihydrochloride, (lg) 3,6-diamino-2,5-pyridinedithiol dihydrochloride, (lh) Nl,N5-diphenyl-l,2,4,5-tetraaminobenzene dihydrochloride, (li) 3,3*-dimercaptobenzidine dihydrochloride, (lj) 3,3'-dihydroxybenzidine dihydrochloride, lk ) 3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride, (11) 3,3'-diaminobeπzidine tetrahydrochloride dihydrate, (lm) 3,3'-diamino-4,4*-dianilinobiphenyl dihydrochloride, (In) l,5-diamino-2,6-naρthalenedithiol dihydrochloride, (lo) l,5-diamino-2,6-napthalenediol dihydrochloride, (lp) 1,2,5,6-tetraminonapthalene tetrahydrochloride, (lq) S^'-dimercapto^^'-diaminodiphenyl ether dihydrochloride, Or) S.S'^^'-tetraaminodiphen l ether tetrahydrochloride, (Is) S^'-dihydroxy-^^'-diaminodiphenyl ether, (It) 3,3'-diamino-4,4'-dihydroxydiphenyl ether, -35- (lu) sulfone, (lv) 3,3*-dimercapto-4,4'-diaπιinodiphenyl sulfone, (lw) 3,3'-dihydroxy-A, '-diaminodiphenyl sulfone, (lx) 3,3*-diamino-4,4•-dihydroxydiphenyl sulfone, (ly) 3,3 , ,4,4 , -tetraaιαinobenzophenone, (lz) 3,6-diamino-l,2-benzenedithiol dihydrochloride, (2a) terephthalic acid, (2b) terephthaloyl chloride, (2c) 1,4-benzenedicarboxamide, (2d) terephthalonitrile, (2e) trans-1,4-cyclohexanedicarboxylic acid, (2f) trans-l,4-cyclohexanedicarboxylic acid chloride, (2g) trans-l,4-cyclohexanedicarboxamide, (2h) trans-1, -dicyanocyclohexane, (21) 2,5-pyridinedicarboxylic acid, (2j) 2,6-benzo[l,2-d:4,5-d' ]bisthiazoledinitrile, (2k) 2,6-benzo[l,2-d:5,4-d* Jbisoxazoledinitrile, (21) 2,6-benzobisimidazoledinitrile, (2m) 2,6-benzo[l,2-d: ,5-d'Jbisoxazoledinitrile, (2n) 2,6-pyridobisimidazoledinitrile, (2o) 2,6-pyrido[2,3-d:6,5-d'Jbisoxazoledinitrile, (2p) 2,6-pyrido[2,3-d:5,6-d' ]bisthiazoleinitrile, (2q) l,7-diphenyl-2,6-benzobisimidazoledinitrile, (2r) 2,6-bis(4-carboxyphenyl)benzo[l,2-d:4,5-d' ]bisthiazole, (2s) 2,6-bis(4-carboxyphenyl)benzo[1,2-d:5, -d'Jbisoxazole, (2t) 2,6-bis(4-carboxyphenyl)benzobisimidazole, (2u) 2,6-bis(4-carboxyphenyl)benzo(l,2-d:4,5-d' Jbisoxazole, (2v) 2,6-bis(4-carboxyphenyl)pyridobisimidazole, (2w) 2,6-bis(4-carboxyphenyl)pyrido{2,3-d:6,5-d'Jbisoxazole, (2x) 2,6-bis(4-carboxyphenyl)pyrido[2,3-d:6,5-d' Jbisthiazole, (2y) l,7-diphenyl-2,6-bi(4-carboxyphenyl)benzobisimidazole, (2z) oxamide, (2aa) 4,4'-biphenyldicarboxylic acid, (2bb) 4,4'-biphenyldicarboxylic acid chloride, (2cc) 2,6-naphthalenedicarboxylic acid, (2dd) 2,6-naphthalenedicarboxylic acid chloride, (2ee) 2,6-quinolinedicarboxylic acid, (2ff) 3,3'-biphenyldicarboxylic acid, -36- (2gg) trans-l,2-cyclohexanedicarboxylic acid, (2hh) 1,4-bis(5-carboxybenzoxazole-2-yl)benzene, (2ii) l,4-bis(6-carboxybenzothiazole-2-yl)benzene, (2jj) 2,5-bis(6-carboxybenzothiazole-2-yl)pyridine, (2kk) 4,4'-bis(p-phenylenedioxy)dibenzoyl chloride, (211) 4,4'-bis(p-phenylenedioxy)dibenzonitrile, (2mm) 4,4'-bis(m-phenylenedioxy)dibenzoic acid, (2nn) 4,4'-bis(m-phenylenedioxy)dibenzoyl chloride, (2oo) 4,4 , -bis(m-phenylenedioxy)dibenzonitril, (2pp) 3,3 * -bis(m-phenylenedioxy)dibenzoyl chloride, (2qq) 3,3,'-bis(p—phenylenedioxy)dibenzonitrile, (2rr) 4,4'-bis(o-phenylenedioxy)dibenzonitrile, (2ss) isophthalic acid, (2tt) 4,4*-dicarboxydiphenyl ether, (2uu) 3,3'-dicarboxydiphenyl ether, (2vv) succinic acid, (2ww) glutaric acid, (2xx) adipic acid, (2yy) pimelic acid, (2zz) sebacic acid, (3a) 3-mercapto-4-aminobenzoic acid hydrochloride, (3b) 3-mercapto-4-aminobenzoic acid, (3c) 3-hydroxy-4-aminobenzoic acid hydrochloride, (3d) 3-amino-4-hydroxybenzoic acid hydrochloride, (3e) 3,4-diaminobenzoic acid, (3f) N3-phenyl-3,4-diaminobenzoic acid, (3g) N4-phenyl-3,4-diaminobenzoic acid, (3h) 4-carboxy-3 '-mercap o- '-aminobipheny , ' i) 4-carboxy-3 '-amino-4'-hydroxybiphenyL, j 4-carboxy-3' , '-diaminobiphenyl, (3k) 2(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochlor :-. (4a) pyromellitic dianhydride, (4b) 1,4,5,8-naphthalenetetracarboxylic dianhydride, (5a) 4,5-diaminonaphthalene-l,8-dicarboxylic anhydride, (6a) 2,3,7,8-tetrahydroxy-l,4,6,9-tetraazaanthracene, (6b) 2,2',3,3 * -tetrahydroxy-6,6 * -biquinoxaline, (7a) 1,2,6,7-tetraketopyrene, (8a) 2,5-dihydroxy-l,4-benzoquinone, (9a) 2,3-dihydroxy-6,7-diarainoquinoxaline dihydrochloride, and the like. -37- These monomers, their structures and methods of preparation are disclosed in applicants' above-cited U.S. Patent Nos. 4,533,692 and 4,533,693. Any onofunctional reactaπt or mixture of monofunctional reactants having the ability to react in polyphosphoric acid to form the heterocyclic ring structures of this invention ' , can be utilized. Monofunctional ' reactants may be used in the amounts of 0.025 mole percent or less to about 3 mole percent or more. Amounts substantially greater than 3 mole percent should be avoided in order to prevent formation of low molecular weight polymer and/or the formation -of isotropic solutions. Polymers that have chain ends made non-reactive by reaction of a monofunctional reactaπt are called end-capped or chain-terminated polymers. In general, suitable monofunctional reactants selected for use in controlling the molecular weight of the extended chain polymers of the present invention are of three types as described below. Type 10 monofunctional reactants have the general formula wherein Ar ,ϋ i s _ n aromatic moiety; X 1 is selected from the class 0, S, and NR; ?. is hydrogen or an organic group attached to N; K2, and X.H are bonded to aromatic carbon atoms of Ar ; the groups on Ar are ortho with respect to one another. -38- Xcπofur-ctioπal reactant 10 is typically isolated as a T .- i r ' -s.- ' * '- salt. "r. ceπarai, Ar 10 may te ar.y aromatic mciety (carbocycli: cr J i ezerocyclic) and it may be 'a sir.gl * ring su: as or it may comprise a plurality of aromatic rings connects*: :y valence bcr.ds or by linking atoms or groups such as where S is a valence bond (as in dipher.yi) or a divalent atom (-0- or -S-) or group such as -NP.-(R=K or an organic group), -(CH 2 ) n - (n=1 or a higher integer). Specific examr'. * .10 are as follows: NAL -39- ΓOTOT- roro: 3® • © -40- The aromatic ring or rings of Ar 10 , 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 above), with the solvent (PPA) cr with the oligoraeric or polymeric products are to be avoided. Among permissible hydrocarbon substituents are alkyl (e.g., C 1 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, SO H, SR, and -NR 1 R 2 (Hi a d R 2 being organic groups). Specific examples of Type 10 monofunctional reactants preferred for use in the invention include those compounds (s.own as free amines or hydrohalides) in Table 1 below. Table 1 Monofunctional Reactants of Type 10 2-aminothiophenol obtained from Aldrich Chemical Co. and purified by distilation under reduced pressure. -41- o-aminophenol obtained from Aldrich Chemical Co. and purified by distillation under reduced pressure. _o-phenylenediamine obtained from Aldrich Chemical Co . and purified by sublimation . 2,3-diaminopyridine obtained Aldrich Chemical Co. and purif: by recrystallization from benzene. -amir.o-3-merca?tobipher.yl prepared from -amir.cbip enyl by- methods analogous to Monomers 1a and 1i. 3-amino-U-hycroxybiphenyl was obtained from CT Orgar.ics ar.c used as obtained. -42- 1-amino-2-naphthalenethiol prepared by methods analogous to Monomers 1a and 1i. 1-amino-2-naphthol obtained from Aldrich Chemical Co. and purified by recrystallization from dilute HC1 containing stannous chloride by adding concentrated KC1. 2,3-diaminonaphthalene was obtained from Aldrich Chemical Co. and purified by recrystallization from water. 3,^-diaminobenzophenone obtained from Aldrich Chemical Co. a: was purified by recrystallization from dilute HC1 cor. ai.-.ir.ϊ stannous chloride by adding concentrated KC1. " y?e 11 monofunctional reactants have Ϊ 9 -Z- ■ r f - β rsin i ' is 2 soncvalβπ ;=πi - g ous n Z - - - -•■ -43- electron-deficient carbon group selected from the following class: -C00H -CSSH -COBr -CSI -CS0H -C0C1 -CSBr -C0NHR-, -COSH -CSC1 -COI -CSNHR-, -CN (R = H or an organic group bonded to N by a carbon atom) The only requirement of Z 1 s that it react with the X^ and x H and with the two hydrogen atoms of the primary amino groups of Type 1 monomers to form suitable leaving entities, such as water, hydrogen sulfide, hydrogen halide, ammonia, etc. The monovalent group ϊ^ Qa y be an aromatic group, an acyclic aliphatic group, or a cycloaliphatic group, ana 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 Ar 1 may be used subject to the.same restrictions. Specific examples of Type 11 monofunctional reactants preferred for use in the invention include these compounds in Table 2 below. Table Monofunctional Reactants of Type 11 11a HOOC ^g> -44- CIOC →g> 1 1 b b enzoyl chloride obtained from Aldrich Chemical Co . and purified by distillation . * *-© 1 1 c enzonitrile obtained from Aldrich Chemical Co. and purified by distillation. cyclohexanecarboxylic acid obtained from Aldrich Chemical Co. and purified by recrystallization from water. cyclohexanecarboxylic acid chloride obtained from Aldrich Chemical Co. and purified by distillation. Picoiinic acid obtained from Aldrich Chemical Co . and purified sublimation. AD ORIGINAL / U-biphenylcarboxylic acid obtained from Aldrich Chemical Co. 2-naphthoic acid obtained from Aldrich Chemical Co. CH 3 C0 2 H 1 glacial acetic acid obtained from Aldrich Chemical Co. CH^COCl 11j acetyl chloride obtained from Aldrich Chemical Co. CH 3 CK 2 C0 2 H 11k propionic acid obtained from Aldrich Chemical Co. CH 3 -(CH 2 -) 2 C0 2 H 111 n-butyric acid obtained from Aldrich Chemical Co. CH 3 -(CK 2 -^ 3 C0 2 K 11m valeric acid obtained from Aldrich Chemical Co. caproic acid obtained form Al-rich Chemical Co. / -46- ι>., fw» 1 2 monofunctional reactants have the general formula wherein Zι< and Z5, are chosen from the list of carboxylic acid derivatives given for ! ■< as defined for monomers of Type 2. Z n and Zc, can also be a carboxylic acid anhydride group. Ar 11 is an aromatic or aromatic heterocyclic moiety ' having two valence positions at -carbon atoms. Ar can be a six-member ring or Ar 11 can be two condensed six-member rings, such as naphthalene. Z4 and Ze must either be ortho-positionec within each set or bear a 1,8-relationship (if A is a naphthalene nucleus) to each other. Specific examples of Type 12 monofunctional reactants preferred for use in the invention include those ' compounds in Table 3 : below. Table Monofunctional Reactants of Type 12 p hthalic anhydride obtained from Aldrich Chemical Co , 1 ■3-naphthalic anhydride obtained from Aldrich Chemical Co. D ORIGINAL -47- Homopolvmeric Compositions and Preparation Homopolymeric compositions which may be prepared by the method of the present invention are described in U. S . Patent No . 4.533.692. previously incorporated by reference, at columns 7-14 (and represented by Formulae I-VI I I and XX-XXXII therein) . Reaction mechanisms for the formation of these homopolymeric compositions are discussed at columns 36-37 of that patent. In the formation of these homopolymeric compositions . The intermediate P-0- content , P , is operative at the ini t ia t ion of polycondensation and is calculated so as to give a th ird (or final) P.,0 5 content, P f , that accounts for p olyphosphoric acid hydrolysis by 100% of the theoretical water of polycondensation. The intermediate P 2°5 content » p m » in accordance with the practice with the instant invention may range between about 82% and about 90%. The final P-,0 5 content , P f , must be above some minimum value if the solution is to maintain its effectiveness as a reaction medium at the late stages of polymerization. The final P ^ Oe content should be between about 80.5% to about 86%, preferably between about 82% to about 86%, and most preferably between about 82% to about 84%. In accordance with the present invention a liquid .crystalline extended chain polymer composition of any desired polymer concentration and intrinsic viscosity (e.g., between 10 - 20% and / dL/g - 18 dL/g) can be obtained by selecting and controlling the conditions under which the process is carried out (batch, semi-continuous, continuous or intermittent-continuous). Tbe various important general process steps for preparing liquid crystalline polymer compositions -48- of the present invention may include one or more of the following stages which are considered to be within the process parameters described above. These stages are: Stage One—One or more of a selected first monomers selected from the group consisting of ' — (amino-group-containing) monomer^ i . 3 . £ , or 2 is added to a specified initial weight in grams (given by a ) of a polyphosphoric acid with a P„0g content P. according to the empirical equation a* = {[l-P f ]([P y /P c ]-P y ) - [n o (18.02)/M w ]P y }(l-P i ) -1 where P is the weight in grams of the theoretical yield of polymer. P c is the weight fraction of polymer in the total weight of the final liquid crystalline polymer composition (and is chosen to be above the critical concentration of the polymer necessary for liquid crystalline phase formation in the resulting poly er- polyphosphoric acid composition) , n Q is an integer giving the number of moles of condensation by-product per mole of polymer repeating unit. The number 18.02 is the molecular weight of the condensation by-product. M^ is molecular weight of the polymer repeating unit. and P f is the final P-O content that must be above a minimum value as defined by this invention. -49- Stage Two — Once the f irst monomer(s) are ' combined with polyphosphoric acid , and protecting groups , if present , released , (optionally , depending on the particular polymer and reaction mechanism chosen) a stoichioπetric amount of one or more of a selected second monomer selected from the group consisting of 2 . i . fi . Z or S is next added and the chosen value of f is achieved by adding b* (an intermediate weight in grams of ?r _) to the mixture according to the equation . b* = CP y V /P c " P y " n o (18.02) /M ] P v j - a* Stage Three — The resulting mixture (containing the f irst monomer (s) and/or the second monomer (s) ) i s then heated to a temperature suitable for polycondensation and maintained for a time to achieve the desired molecular weight ( characterized by intrinsic viscosity) . Optionally, where the resultant extended chain polymer is formed from a selected f irst and second " monomer, a selected excess molar amount ( from 0.02-5 molar or less to 3 molar or more percent) of said selected second monomer can be added in Stage Two or more preferably a selected excess molar amount of said selected first monomer can be added in S tage One or allowing the loss of a small proportion of said selected first or said selected second monomer during polymerization Stage Three thereby off-balancing the stoichiometry of the monomers to obtain a desired intrinsic viscosity value less than the maximum attainable . Alternatively , one or more monofunctional reactants selected from Tables 1 , 2 , and 3 . can be added during Stage One thereby limiting the maximum intrinsic viscosity attainable at Stage Three . The monofunct ional reactants described herein are ef fective when added at the beginning of the polymerization Stage . -50- reac t ion temperature may range from about 100 β C to about fl O'C preferably about 160 β C to about 190"C, and most preferably about 185 * C._ The initial P„O r content. P. should be low enough to: 2 5 i ( 1 ) achieve efficient dehydrohalogenation and/or (2) achieve sufficient monomer leading to achieve desired P without foaming problem or unusually high bulk viscosity. P f should be high enough to: (2a) maintain a polyphosphoric acid composition that is an effective reaction medium at late stages of polycondensation. (2b) provide an effective phosphcrylating medium as described in N. Yoda and M. Kurihara, "New Polymers of Aromatic Keterocycles by Polyphosphoric Acid Solution Methods", J. Polymer Science. acromolecular Reviews. Volume 5, (1971). p. 159 at initial stage of polymerization. The subject matter of the paper by Yoda and et. al .. is specifically incorporated herein by reference. ( 2c ) provide a. effective solvent for the polymer s- the end of polycondensation. For purpose of illustration, a plot of equation a is presented in Figure 1 showing regions (shaded dash area ) of poor monomer la solubility. In the case of polymer AI-f n , the family of ? curves can be utilized as follows 1 !« • cchhoooossee a τAI} polymer concentration, P , as an example 0.16; select a point on the curve ? » 0.16 above :ne snaded dash area Lndicatir-.g poor monomer la sol biiiry; -51- 3. from that point selected, the weight in grams of PPA (a*) of the corresponding P_0_ content (P . ) 2 5 1 should be added to 2.06g of monomer la can be determined; 5 4. after dehydrochlorination is complete, the amount of monomer 2a to be added is 62.38 g; and 5. if the final P_0 5 content (f) has been chosen to be 82.22, then the amount of P.O. to be added (b ) is the ^■0 difference between the amount of PPA used in step 3 above and the weight of PPA at the end of the curve for p - 0.16. c The choice of the optimal P. is dependent on the 15 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 exhibit different solubility limits. Solubility rankings of some representive monomers are listed 20 below. monomers with solubilities greater than la; If, lg, 3a, 3b, 3c, and 3d; 25 monomers with solubilities comparable to la: Id, and 3e; 30 -52- monomers with solubilities less than la: lb, lc, le, li, Ik, 3f, 3g, 3h, 3i, and 3j; and monomers with solubilities much less than la: lh, 11, lm, In, lo, Ip, 5a, and 9a. Some process and product benefits ΛS a result of better control of certain process parameters such as shear and temperature in a continuous process are: (1) a more homogeneous products of reaction as a result of a much higher order of magnitude of mixing; (2) higher throughputs; (3) and improved economics. Another advantage of continuous processing is that the resulting reaction products can be blended in essentially all portions with other reaction products of different polymer type and/or reaction products at different stages of reaction. In a continuous process, the aforementioned dehydrochlorination step of "Stage One" and aonomer—P 0, addition of "Stage Two" are conducted at a temperature not to exceed about 100 # C in a batch reactor. Stage Three" of the invention can be conducted in a motionless (static) mixer. -53- Tta« reaction mixture of "Stage Two" lβ fed from an outlet of the batch reactor through « constant displacement pump to a static mixer (tubular reactor) preferably of the type described In U.S. _ 3,800,985 where the first mixing element is heated at a temperature * between about 140*C to about 185*C. The second and subsequent Intermediate mixing elements are heated at temperatures between about 165*C and about 200*C. The last mixing elements are heated at temperatures between about 80*C and about 200"C 0 depending on the desired temperature selected for spinning the particular extended chain polymer employed. In order to avoid Interruptions in the continuous process, two or more batch reactors (for conducting "Stage One" and "Stage Two") are connected to the static mixer (tubular reactor) in parallel array fashion so as to feed said tubular reactor in time-wise sequence. Preferably, "Stage One'and "Stage Two" can 0 b e conducted in an emptied batch reactor without the need for clean-up. The volume requirement of the tubular reactor is a function of the size and number of the batch reactor array, the desired (mixing elements) residence time, and the desired flow rate. 5 Such a continuous process is especially suitable for the preparation of block copolymers of the present Invention. Block copolymers can be made by admixing a second reaction mixture after the first reaction mixture has passed through an intermediate number of 0 mixing elements. -54- f_ vey important aspect of the continuous process an veil as for the batch process which βuβt be emphasi ed is that "Stage One", "Stage Two", and "Stage Three" of the Invention must be conducted within the shaded 5 phosphorus pentoxide content profile area bounded by ABCDEFGHI of Figures 2, 3, 4, or 5. The high P p O_ content of Figure 5, in particular, is unrealized by the art. ~_ Q In accordance with the process of the invention, it is possible to dehydrohalogenate a high concentration of selected hydrohalide monomers more rapidly in extremely high P 9 O 5 content (viscous and highly viscous) strong acid solutions. In addition, the process is applicable to the dehydrohalogenation of monomers . _ more rapidly in a solution of lesser P^^s content than that of U.S. Patent 4,225,700. 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. 20 r 25 30 -55- While the process of this invention can be used to prepare any of the class of extended chain polymers described herein, the process steps can be varied depending on the composition and polymer properties desired. Tits monomer(s) and strong acid(s) of stages One .and TWo as set forth above can be combined and the protecting atoms or groups released by: (1) admixing a high concentration of monomer(s) in a strong acid such as polyphosphoric acid having a low P 2 0- content followed by dehydrohalogenation, or (2) admixing a high concentration of monomer(s) in a strong acid such as polyphosphoric acid having a high P-0 5 content followed by dehydrohalogenation at a sufficiently high surface-to-volume ratio (S/V). Both methods (1) and (2) of dehydrohalogenation will avoid the uncontrollable (runaway) foaming inherent in prior art processes and provide reaction mediums suitable for polymerization. The effect of various parameters such as temperature, surface-to-volume ratio, P~0_. content, agitation (stir rate), andreduced pressure on monomer dehydrohalogenation is shown in the table below. In the ta led means increases, means decreases, and C means no change. T A B L E (Monomer Dehydrohalogenation) Gas(HCL) evolution ♦ + T T Monomer-acid viscosity T NC j NC NC Monomer decomposition NC L NC NC A = Temperature C = P CL Content B = Surface-to-Volume Ratio D = Stir Rate E = Pressure -56- Xhe empirical relationship: ■ in S/V - {[2 exp((P c /0.5) - 1)] exp(P i /0.9) 15 + 3(100 exp[a*/(a*+ b*) -1]) + lO^/O.Θ 15 } -1 Is used to estimate the size of resin kettle required to give an efficient and manageable dehydrochlorination when conducted at 100 β C and under reduced pressure. The relationship shows the strong dependency of required S/V on the P 2 0 5 content of medium, which follows mainly from the strong dependency of the bulk viscosity on the P 2 0g content. When the value of the radius required exceeds the practical limit, cylindrical resin kettles cannot be used and a reactor of higher S/V should be used. Standard laboratory resin kettles have a cylindrical configuration and may range in capacity from 50 cubic centimeters to many hundreds of cubic meters. However, as the capacity is increased the surface area does not increase proportionally. This results in a decrease of the surface-to-volume ratio. Laboratory kettles have a fairly constant ratio of depth to diameter, which generally lies between 1.2 and 1.4. A 100-gallon stirred reactor filled to capacity has a surface-to-volume ratio of only about 0.012 cm , but this could be effectively increased to about 0.048 cm -1 if the reactor were filled to only one-quarter capacity. It is impractical to use less than about one-fourth of the capacity of a standard laboratory resin kettle due to the inefficient stirring which results and due to the high percentage of material which is effectively lost on the sides of the vessel. -57- The p rocess of the invention can be performed in any reactor, oro p erly equipped with a. stirrer, thienoometer, inert gas inlet, *nd inlet points for the introduction of reactants. The configurations of suitable batch and continuous reactors that can be engineered are many and are well known to those skilled in the art. Reactors and process equipment suitable for use In the process of the invention should have the following requirements: (1) the mixing apparatus of whatever engineering arrangement selected, is made from a material which is nonreactive with the reaction medium of the process, (2) the apparatus must be able to withstand the temperatures required at the various stages of the process, (3) the mixing mechanism must be able to operate under the conditions of high bulk viscosity of the reaction medium, *r (4) the fltlxing must be conducted within a closed system so that no external reactants may intrude upon the reaction, and ( 5 ) the procedure must be conducted under an atmosphere of inert gases. -58- In accordance with the present invention, the various orocess considerations for controlling the conditions under which Stages One, Two, and Three of the process are carried out are described below. The process steps, in more detail, are as follows: Step 1: Preparation of monomer for mixing with PPA Step 2: Admix a first monomer with PPA having an initial P 9 0 ς content of P. (in accordance with dehydrohalogenation .Tuthod (1) or (2)) teρ 3: Dehydrohalogenation in a reactor of sufficient surface-to-volume ratio Step 4: Addition of second monomer to the product of Step 3 ( omitted in the case of AB-type polymers) Step 5: Addition of P-0- to the product of Step 4 (or 3) to raise the P- ' .' z-onιc-. t to a value of P so as to achieve a final P 2 0 5 content, P , above about 0.805 (method (2)) Step 6: Addition of mono-functional reagent to control raoLecular weight of the resulting polymer (omitted in the case of block copolymers) •Step 7: Polymerization to completion for the production of horaopol mers and copolymers; or, for the production of block polymers, two sets of monomers mixtures are prepared by conducting Steps 1-5 twice and the two reaction mixtures are allowed to react to predetermined values of molecular weight before they are mixed and further polymerized to join the two blocks together -59- Step 8: Processing into articles such as fiber, film, fibrids, and.the like The major process consideration involving steps 1-8 are as ollows: Step 1 " The purity of monomers is essential for the quality control necessary to achieve reproducibllity in polymer molecular weight and the resulting dope rheology. If the monomer contains any water of crystallization this must be taken into account in the following step by adding the term W to the a* equation: a* -[P y £-l-P f N(l/P c )-l] " (n o 18.02/M w )}- Wj/(1- Pi ) where W is the water of crystallization in grams and is calculated from the assay of the monomer and the amount of monomer added in Step 2. Step 2 - P P P and P f are selected at the beginning of this step and a* is calculated using the a* equation above. Figure 19 graphically illustrates various regions (A-E) for a P f value of 0.822 and a P of 100 g. The regions being A-less preferred, B-preferred, C-most preferred, D-less preferred (for different reasons than A), and E-least preferred. Region A - An advantage of selecting a P. in this region is the low bulk viscosity of the PPA which ranges from approximately IQQ ~ ^20 ceπCi P°i se C P) (where the subscript is the temperature in °C)at 622 P-,0 5 content to 50 100 - 1000 2Q Cp at a P 2°5 con tent of 762. The disadvantage of this region is that -60- as the choice of P increases the monomer concentration required becomes so high that monomer insolubility becomes a problem. There are further disadvantages that the viscosity of the mixture becomes high because of the high solids content and relatively large quantities of P-0, must be added after dehydrochlorination (Step 5). Region B - The bulk viscosity of the PPAs in this region are in the range of 10 - 1,200 Cp in the temperature range of 20 - 100°C and are thus advantageous in providing a workable viscosity for the dehydrochlorination mixture. Region C - Selections of P in this region are most desirable because of the low viscosity of the PPA (50 1Q0 - 1500 20 Cp) and the remaining P-,o 5 to be added (b*) is a convenient ratio to the amount of the preliminary solvent (a*). If the P is high such that the monomer is difficultly soluble then the dehydrochlorination can be initiated at an P. in this region and P 0^ added before the dehydrochlorination is complete (This applies for all regions, but is most applicable for Regions A, B, and C). Region D - The S/V of the reactor must be increased if a P in region D is selected. The bulk viscosity of the medium is dramatically increased over region C. Region E - For a P. to be selected in this region requires the use of very high S/V reactors so that high temperatures may be employed in the dehydrochlorination step. The following general guidelines should be followed in order to select an appropriate reactor in which to conduct Steps 2 and 3« When any of the following conditions exist, it is -61- advantageouβ and necessary to increase the surface-to-volume ratio (S/V) above that obtained by using a practical percentage of the capacity of a normal resin kettle: * * Condition 1. Final Polymer concentration, P , is above about 15 wt 2 and the initial P 2 0 5 content, P^ is above about 772. Condition 2. Final Polymer concentration, P , is above about 10 wt 2 and the initial P 2 0 5 content, P., is above about 802. 0 Condition 3. Final Polymer concentration, P , is above about 8 wt 2 and the initial P 2 0c content, P., is above about 842. Condition 4. The polymer yield, P , is above about 50 kg. 5 The appropriate amount of monomer to give the desired polymer yield, P , is mixed with a* grams of the initial PPA having a P 2 0c content of P.. P. is selected to be a convenient value that is above 622 and below P where P is the maximum intermediate m m 0 P 2°5 content allowable by the a* equation if the value of P f is to be achieved. P m = l ~ {fU-P f ] t(l /P c ) -l ]-x}/ [ (l /P c ) -l ]-x} 0 where x is (n o 18.02/M ) , which is equal to the moles of water of condensation per gram of polymer. Figure 6 shows that the P ' s for P ' s of 0.10. 0 . 12 Λ C * 0.13. 0.15. 0.17 and 0.20 are 0.847. 0.853. 0.8635, 0.871. and 0.8816. respectively. -62- M ineral acids such as any of the alkanesulfonic acids that do oxidize the monomer may be added at this point to lower the i scosi t y and decrease the time required . , for dehydrohalogenation. T h e p referred method for this addition is to treat the mineral c __ as an inert diluent by calculating the values of a* and b* for a selected value of P that is 3 to 102 higher than the ac t ual desired P and then add the acid in the amount necessary t o bring the actual value of the concentration (once b* is also added) to this desired value. The rate of the polymerization ( St ep 7) will be substantially decreased as the amount of the inert diluent is increased. Step 3 - Although the S/V must be above some minimum value for t his step, it is preferred that the dehydrohalogenation be conducted at a maximum S/V by using one of the following two procedures: (1) Passing the dehydrochlorination mixture through a mechanically agitated thin film evaporator (2) Sparging the dehydrochlorination mixture with an inert gas (thereby creating a foam) and passing the resulting foam through a static mixer into a evacuated chamber where the foam can settle. Procedure 1 - Use of an agitated thin film evaporator (ATFE) The first monomer is mixed with the preliminary solvent (i.e., a PPA of P 0c content between 62 and 842) and heated at a t emperature between 50 and 100°C until dehydrohalogenation is substantially complete. The product is then metered into a stirred vessel to conduct Step 4 by a pseudo-batch method. -63- The above-mentioned formulas I , III , V , VII , and VIII homopolymer compositions may be prepared in accordance Tith the above process parameters by : (a) mixing a selected first monomer (for example , a selected first monomer selected from the group consisting of ( 1 , 1 ) , ( 1 ,2) , or ( 1 ,3 ) with or without oxidation protecting atoms or groups • ffith a preliminary solvent of phosphoric acid having a relatively lox 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 froα 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 froα step (c) to provide a first and second moncαer reaction medium c: greater phosphcrus pentoxide content suitable for polymerization. (e) causing polymerization of t e first and second mor.oαer at a temperature sufficient to effect reaction at a rate to form a first hcmc- oiigomeric product having a preselected intrinsic viscosity or a first hoaopolyπieric product, -64- (f) optionally adding a preselected excess molar amount of said selected first monomer in step (a) thereby off-balancing the stoichiometry proportion of said selected first and second monomers in said first and second monomer reaction medium so as to provide a said first homo-oligomeric product or a said first homopolymeric product following polymerization step (e) having a predetermined intrinsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both said selected first and second monomers, (g) optionally adding a preselected excess molar amount of said selected second monomer in step (c) thereby off-balancing the stoichiometry proportion of said selected first and second monomers in said first and second monomer reaction medium so as to provide a said first homo-oligomeric product or a said first homopolymeric product following polymerization step (e) having a predetermined intrinsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both said selected first and second monomers, (h) optionally adding one or more of a selected monofunctional reactants in step (a) so as to provide a said first homo-oligomeric product or a said first homopolymeric product following polymerization step (e) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants. Formulas II, IV, and VI hcmopclymer compositions may 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)) • sit-, or wi ho t oxidation protecting atoms or groups xith a -65- preliπinary solvent of phosphoric acid having a relatively lo 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) 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 suff icient to effect reaction at a rate to form a first homo- ol igomeric product having a preselected intrinsic viscosity or a first homopolymeric product , ( e) optionally adding one or more of a selected monofunctional reactants in step (a) so as to provide a said first homo-oligomeric product or a said first homopolymeric product following polymerization step (d) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants. -66- Copolymeric Compositions and Preparation Copolymeric compositions which may be prepared by the method of the present invention are described in U.S. Patent No. 4,533.692, previously incorporated by reference, at columns 42-45 (and represented by Formulae IX-XVIII therein) . Reaction mechanisms for the formation of these copolymeric compositions are proposed at columns 45-46 of that patent. Copolyraer compositions represented by Formulae IX, 10 X, XII. XV. XVI. XVII and XVIII as designated in the aforementioned patent can be prepared in accordance with the method of the present invention by: (a) mixing at leas * , t o of a selected first ■ j _5 monomers (for example, t~.'o or more of a monomer selected from the group consisting of (1.1). 20 25 30 -67- ( 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 (3,1)) 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 froα 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 eirec: :tιcn at a rat form a first co- -68- oligomeric product having a preselected intrinsic viscosity 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 stoichiometry proportion of said selected first and second monomers in said first and second monomer reaction 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 first and second monomers, (g) optionally adding a preselected excess molar amount of said selected second monomer in step (c) thereby off-balancing the stoichiometry proportion of said selected first and second monomers in said first and second monomer reaction 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 first and second monomers, (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 polymerization step (e) having a predetermined intrinsic viscosity less than the maxirauπi attainable in the absence of said selected aonof nctior.al reactants. -69- Copoly ers represented by Formulae IX. XII. XVI, and XVIII copolymer compositions can also be prepared by replacing the above steps (g) and (h) with the following: (g) optionally adding one or more of a selected monofunctional reactants in step (a) so as to provide a said firs t co-oligomeric product or a said first copolymeric p roduct following polymerization step (e) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants. 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 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. -70- (d) causing polymerization of the said two of a selected first monomer at a temperature sufficient to effect reaction at a rate to form a first co-oligomeric product having a reselected intrinsic viscosity or a first copolymeric product, (e) 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 polymerization step (d) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants. -71- Block Polymeric Compositions and Preparation Block polymeric compositions which may be prepared by the method of the present invention are described in U.S. Patent No. 4.533,692. previously incorporated by reference, at columns 56-61 (and represented by Formulae IX-XIX therein) . Reaction mechanisms for the formation of these block polymeric compositions are proposed at columns 61-63 of that patent. Block polymeric compositions given by Formulae IX. XII. XVI. XVIII and XIX may be prepared according to the method of the present invention by carrying out steps (a) through (g) as set forth in previously referenced U.S. Patent No. 4,533,692. at column 63. line 44 et seq.. or according to steps (a) through (h) set forth at column 64, line 17 et seq. of that patent, with the exception that, prior to polymerization, one or more monofunctional reactants is added so as to provide a block polymeric product having a predetermined intrinsic viscosity less than the maximum attainable in the absence of that monofunctional reactant. Polymers given by Formulae X. XV and XVII are prepared similarly to the method set forth above, i.e. according to the disclosure of U.S. Patent 4.533.692. with the addition of a suitable monofunctional reagent added prior to polymerization so that a block polymeric product is provided having an intrinsic viscosity less than that otherwise attainable. Preferred characteristics of block polymers prepared according to the method of the present invention are set forth in U.S. Patent 4.533.692 at columns 64-66. -72- Intrinsic Viscosity Intrinsic viscositiy is determined by extrap r olation of η*» re.l - 1/c and In 1"- re,l/c to zero concentration in methane sulfonic acid at 30°C. Anisotropic Character of the Compositions The extended chain polymer compositions of this invention are optically anisotropic . i.e. , microscopic regions of a given extended chain composition are birefringen ; 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 cr mesomorphic state. The extended chain polymer compositions of this invention that exhibit optical anisotropy do so 7. * hile 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 when subjected to appreciable shear. The extended chain polymer concentration cf the compositions of the instant invention is -73- above the "critical 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 the vessel containing the extended chain polymer compositions or by only siow 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. This may be described as being a pearly or opalescent quality of the extended chain polymer compositions of this invention. Compositions which are disturbed as described above often give the appearance of having snriations and or graininess in the surface. These visual effects are observed in the liquid crystalline extended chain polymer -74- compcsitions of this invention. This may commonly be referred to as "stir opalescence. " 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 be formed into fibers of high quality by spinning them into suitable baths such as by wet 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 nay range from less than about 1 cm to about 150 cm or longer, preferably from about 2 cm to about 3C0 cm, more preferably from about 10 cm to about 200 cm. and most preferably from about 10 cm to about 1C0 cm. -75- accordance with the practice of the invention, the initial draw ratio is approximately from about 1:1 to about 500:1 or 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 300:1. The t erm "draw ratio", as is well known, is a measure of the degree of stretching during the orientation of the fibrous material. In the -resent invention, the initial draw ratio is a measure of the degree of stretching of the filaments which occurs between 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 which 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. Tie exit velocity is tie speed at which the filaments leave the coagulation bath. Although any means of measurement may be used, the exit velocity is conveniently determined by the surface sneed cf the rolls which take UD the -76- fiiaments after their exit from the bath. Thus, the speed of the wash rolls is preferably measured for this purpose. Spinning of polybenziαidazole fibers by one working of this general technique is described in. e.g.. Tan U.S. 4.253.245. A variety of baths may be used to coagulate the extruded dope into fibers. The baths may be. e.g.. water or αethanol 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 cay be used 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.. saturated sodium bicarbonate), remove the surface liquid from the threadline # wχth a wiping device (e.g. , a sponge) or a jet, wash with water and/or aqueous alkaline solutions to reduce the acid content. and wind UD the fibers on bobbins. T?-.e fibers -77- αay 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 110°C. They can also be conveniently dried on heated rolls. The liquid crystalline compositions are' especially suitable for extruding. This and other methods of article frabication are fully described in J. S. Robinson, "Spinning, Extruding, and Processing of Fibers"; Chemical Technology Review No. 159. oyes Data Corp.. 1930. The above cited patents and/or publications are incorporated herein by reference . The fibers prepared from the polymers of this invention exhibit high values of tensile nrooerties. 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 -78- 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. Yam 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 environment. 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 averaged. Yarns are given 3 turns per inch (2.54 cm.) twist (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 extension (ID'S elongation/ minute for fibers having an E of under 8%. and 60 elongation/minute for fibers with Ξ of 8 to 100%) until t e sample breaks. ιe άenier of a single filament ( .p.f.) is <2 i " uncticnal resonan -79- 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 known 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. -80- AdditiTβs It will be understood that the usual additives such as dyes, fillers, antioxidants, and the like can be incorporated into the compositions of the present invention for the purpose intended, before preparation of * the shaped article. Uineral acids that are solvents for the extended chain polymers of the instant compositions such as polyphosphoric acid, methane sulfonic acid. 100% sul uric acid, chlorosul onic 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-soluble polymers described 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. The rigid rod polymers (polymers of Class 1) of this invention may be employed as additives in the monomer-acid solutions or reaction mediums so as to induce polymerization in the liquid crystalline phase of flexible and semi-flexible polymers at extremely low or low monomer concentrations. The above cited p atent and thesis are incorporated herein by reference. -81- The fa b rica t ion of composites made with the compounds produced by th e method of the present invention may be manufactured using T echniques described in "Fabrication of Advanced Composites" , Handbook of Composites, edited by George Lubin, 1982, which h and b ook is herein incorporated by reference. j y π ri ι<;τ.ri a i Appl icabi l it y The liquid crystalline extended chain polymer compositions are extremely suitable for spinning into highly ordered and high strength fibers . S uch fibers are useful as reinforcement substitutes for other inorganic or organic products . Various examples include glass f ibers , asbestos, boron fibers . carbon and graphite fibers , whiskers , quartz and sil ica fibers , ceramic fibers , metal fibers . natural organic fibers , and synthetic organic f ibers . 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 thermoplastic materials , such as metal replacements and those areas where high performance is necessary. Extended chain polymer compositions may be employed for use in -82- forming nigh strength films suitable in the pro¬ duction of composites, belts, 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. 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. It is to be understood that while the invention has been described in conjunction with the preferred specific embodiment thereof, that the foregoing description as well as the examples which follow are intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains. _ 83_ Example 1 PBO (poly-p-phenylenebenzobisoxazole) is prepared from t erephthaloyl chloride and 4,6-diaminoresorcinol dihydrochloride (lb) in polyphosphoric acid (PPA) . 5 The two monomers are dehydrochlorinated together. 115% PPA (132.I3g) is deoxygenated by heating under nitrogen at 150°C overnight. It is then added under N_ flow to a 500mL resin kettle containing 11.47017g (0.056496 mol) of , n t erephthaloyl chloride that is previously purified by sublimation followed by recrystallization from dry hexane. The acid chloride is mixed into the PPA, then monomer (lb) (12.03727g, 0.056496 mol) is added and mixed under N 2 flow. The mixture is heated over 0.5h to 87°C, and at 87 to 90°C for 5h. Considerable foaming occurs at 55 and 87 C. A 15 large surface-to-volume ratio is required for these steps, to allow excape of HC1 and thus prevent uncontrollable foaming. The following heating schedule is used for the 20 polymerization: 130°C for 2h, 150°C for 16h (during this time the polymer forms a liquid crystalline solution), 170°C for 2h, 185°C for lh, and 200°C for 45h. A sample is removed. The intrinsic viscosity of this sample in MSA at 30 β C is 17.1 dL/g. 25 30 - 84- Example 2 PBO (poly-p-phenylenebenzobisoxazole) is prepared from ephthaloyl chloride and ,6-diaminoresorcinol dihydrochloride (lb) in polyphosphoric acid (PPA). The acid chloride monomer is dehydrochlorinated first, followed by the diamine monomer (lb). 1152 PPA (124.05g) is eoxygenated by heating at 150 C under , flow overnight. I t is then added to a 500mL resin kettle at 0 β C containing I2.74822g (0.062791 mol) of terephthaloyl chloride, previously purified by sublimation and recrystallization from dry hexane. The kettle is stirred and slowly heated as follows to dehydrochlorinate: 0°C to 60°C over 2.5h, at 60°C for 66.5h, 60° to 90°C over Ih, and at 90°C for 5h. The kettle is cooled overnight, and (lb) is then added under N flow. The stirred mixture is heated to 70°C over 5.5h, at 70°C for 2h, and at 83 β C for 15h. Dehydrochlorination appears complete at this time. A large surface-to-volume ratio is required for these steps, to allow escape of HC1 and thus prevent uncontrollable foaming. Deaerated PPA (7.49g) is then added under N_ flow to decrease the final polymer concentration from 10.4 wt% to 9.9 wt . The mixture is then polymerized by heating from 83°C to 130°C over 1.6h, from 130° to 150°C over 3h, at 150°C for 19.5h (during this time the polymer forms a stir-opalescent solution which relaxes to a hazy solution at rest), at 170°C for 5.5h, at 185"C for 2h, and at 200°C for 23.5h. The anisotropic polymer is removed and stored in a bottle under N_. A sample is removed, precipitated in H-O, and dried. The intrinsic viscosity of this sample in MSA at 30°C is 17.6 dL/g. - 85- Example 3 The reaction products of Examples 1 and 2 are drawn many times their lengths to give highly fibrillar fibers. A portion of the solution is removed from the reaction flask and placed in a KBr press equipped with a die with a circular orifice of 0.13 mm in diameter. The solution is extruded into the air and stretched by pulling manually and the fiber is then dipped in water. The fiber thus produced is washed with water and then dried under tension in an air oven overnight at 110"C. High orientation is evident from fibrils which split from the surface of the fiber and by the complete extinction of light transmitted through the fiber when a single polaroid is placed in a perpendicular direction only between the source and the fiber. l r ier la was prepared according to the method of Wolfe Arnold, Macromolecules. Vol. 14. 809 (1981). recrystallized from aqueous hydrochloric acid containing 3 wt% stannous chloride, and dried for 20h at 63°C under reduced pressure immediately before use. The mixture is stirred at 53°C for I5h and 62 C for 4h under reduced pressure. Upon heating to 70 C, the monomer precipitates . Addition of 16.6g of PgOg results in redissolution of the monomer. The solution is then heated at 100 C for 3h under reduced pressure to complete the dehydrochlorination. Monomer 2a (8.9761g. 0.05403 mol) i s then added under an argon flow. Additional P-Og (19.Og) is then added. The solution is then heated as follows: 100°C for 48h; 150°C for 2.5h; 160°C for 10b (the dark green solution becomes stir- opalescent during th < s period); and 180°C for 25h. The resulting reaction product is deep - 8-5 purple- with a metallic luster, exhibits 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 Po^ e content of 82Sδ with the -fBI} polymer concentration being 13.3*3 by weight. The intrinsic viscosity of the polymer iBIχ isolated from the reaction product is 23.9 dL/g in MSA at 10 30 C. which corresponds to an average number of recurring units, n. of approximately 110. Example 4 15 182. g of a PPA solution with an effective P_ s content of 77.255 (prepared by mixing 30 wt55 of H P0 4 and 70 *t% of 11555 PPA) is add.ed to ' a 500 πL resin kettle containing 52.62853g (0.21460 mol) of la. (Monomer la of large crystal size 20 s prepared with a final recrystallization according to the method of Wolfe. Loo, and Arnold. Macrop l ules. 14. 915 " (1981) using the final isolation procedure involving a transfer of the dipotassium salt of monomer la as solid into 6N hydrochloric acid.) After stirring to 25 incorporate the solid monomer into the PPA. the mixture is substantially dehydrochlorinated by heating the mixture at 55-70°C under reduced pressure for approximately 31h. Monomer 2a (35.6522g. 0.21460 mol) is added to the resin 30 kettle and incorporated as described in the previous Example. Powdered l23.35g) is then added to increase the effective P Λ *.0 o e content to approximately 8β .455 and resulting mixture is _ 87_ stirred at 100°C for I7h under an argon flow. The polymerization mixture is then heated with stirring as follows: 100-Ϊ70°C in lh. 170°C for 23h. and 200°C for 24h. The intrinsic viscosities (in dL/g) are determined for the • tAI} • polymer from samples withdrawn at the indicated times: 17.2 (7b). 22.8 (24h) . and 35.4 (48h) . Heating without stirring for an additional 24h does not increase the intrinsic viscosity of the ΕAIJ^ polymer. The green reaction product exhibits stir-opalescence and is characterized as having a final effective P_Q ς content of 82.25 with * τAI_* polymer concentration being approximately 15.1wt55. EXAMPLE 5 The procedure of Example 4 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 PgOg content of 77.2% ( prepared by mixing 80.9g of 85.455 K 3 P0 4 with 188.3g of 11555 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 P 2 °5- The mixture is then stirred and heated essentially according to Example 8. The amount of P 2 Q c s preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P~ _ content of approximately 85.0755 prior to the start of polymerization and an effective P_p~ content of -88 - approximately 82.255 subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 1955; fibers are readily formed by direct spinning, or drawing from the reaction product. The polymer obtained is of the following structure: • EAIBI*n characterized by an intrinsic viscosity of 20 dL/g in MSA at 30°C which corresponds to an n value of average polymerization of about 50. Heating the reaction mixture for 5 hours gives an intrinsic viscosity of 12 dL/g in MSA at 30°C heating the reaction mixture .or a total of 7 hours gives an intrinsic viscosity of 15 dL/g in MSA at 30°C, heating the reaction mixture for a total of 12 hours lives an intrinsic viscosity of 18 dL/g in MSA at 30°C. The above procedure is followed with the exception that the P 2 0 5 con t ent during the dehydrochlorination begins at 80% and is incrementally increased to an intermediate P 2 0 5 content of 85.072 prior to polymerization. - 8g- EXAMPLE 6 A mixture of 125.8g of 11555 PPA and 53.9g of concentrated phosphoric acid (85.755 H 3 P0 4 ) is heated to 100°C for 4h under reduced pressure in a 500 aL 3-nec ed flask. The X P,0- content profile for this Example is illustrated in Figure 12. To a 500 aL resin kettle is added 91.85g (0.4465 mol) of 3a. The kettle containing the monomer is deaerated. 108.17g of the PPA prepared above (having a 2 °5 content of 77.2%) is then added. The kettle was then heated with an oil bath at 50°C under a thin stream of argon overnight. The kettle is then placed under reduced pressure again and heated to 70°C for 23h. P 2 0 5 (108.32g) is then added in three portions to increase the effective 0c content to 88.555. Reduced pressure is applied to degas the P^C and to cause foaming that aids in mixing. After 3h of stirring the temperature is raised to 100°C and maintained at that temperature under reduced pressure for 21h. The mixture is stir-opalescent and depolarizes plane-polarized light. The mixture is then neated as follows: 115°C under argon for 3h: 130°C under reduced pressure for 2h: 170°C for 0.5b: 190°C for 17h. A sample of the green, opalescent reaction product is removed and gives a fibrillar. golden-colored fiber upon drawing followed by precipitation in water. After extracting with water in a Soxhlet apparatus for 24h the sample is dried for 24h at 110°C under reduced pressure. The intrinsic viscosity of this sample is 15.8 dL/g in MSA at 30.0°C. An " 90 " additional 7.5h of heating gives a sample with an intrinsic viscosity of 16.7 dL/g. The reaction product thus obtained is 20.355 by weight of polymer -tT} in PPA with a final P-Og content of 82.455. EXAMPLE 7 The procedure of Example 4 is essentially repeated. Instead of monomers la and 2a. 99.923g (0.35182 mol) of monomer lc is dehydrochlorinated in an "initial" solution of 602.Og of PPA having a P rj C content of 77.355 (prepared by mixing 177.9g of 85.455 H 3 P0 4 with 424. lg of 11555 PPA). When dehydrochlorination is substantially complete. 76.740g (0.35182 mol) of monomer 4a is added followed by the gradual addition of 272. g of ^ - T e mixture is then stirred and heated essentially according to Example 8. The amount of P_0 ς added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P P_ content of approximately 84.455 prior to the start of polymerization and an effective P^C 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 1055; fibers are readily formed by direct spinning, or drawing from the reaction product. -91- The polymer obtained is of the following structure: -EZB * A'B * τ n characterized by an intrinsic viscosity of 10 dL/g in MSA at 30°C. W en the intermediate P 2 0 5 content is increased such that he final P 2 0 5 content is 83.02 and the reaction mixture is hUI ed for 5 hours, an intrinsic viscosity of 10 dL/g in MSA at 30°.Tis obtained; heating the reaction mixture for a total^of 7 u . s gives an intrinsic viscosity of 12 dL/g in MSA at 30°C; hou _a ng the reaction mixture for a total of 12 hours gives an he n t rinsic viscosity of 16 dL/g in MSA at 30°C. EXAMPLE 8 The procedure of Example 4 is essentially repeated. Instead of monomers la and 2a. 58.035g (0.23559 mol) of monomer la is dehydrochlorinated in an "initial" solution of 307.7g of PPA having a P 0,- content of 77.355 (prepared by mixing 90.9g ■_ * - of 85.455 H 3 P0 4 with 216.8g of 11555 PPA). When dehydrochlorination is substantially complete. 75.281g (0.23669 mol) of monomer 6b is added followed by the gradual addition of 163.5g of P-Q.- . The mixture is then stirred and heated according to a schedule similar to Example 8. The amount of P ^ C added is preselected (as determined in accord with the aforementioned formulae a* and b*) to provide the reaction mixture with an effective P 2 0 5 content of approximately 85.255 prior to the start of polymerization and an effective Pr ) 0_ content of -92- approximately 82.255 subsequent to substantial complete polymerization. The reaction product obtained exhibits stir-opalescence and is further characterized as having a polymer concentration of 1755: fibers are readily formed by direct spinning, or drawing from the reaction product " . The polymer obtained is of the following structure : characterized by an intrinsic viscosity of 7 dL/g in MSA at 30°C. The above procedure is followed with the exception that the P o content during the dehydrochlorination begins at 822 and chen is incrementally increased to an intermediate P 2 U < : content of 85.2% prior to polymerization. When the intermediate o 0 ? content is increased such that the final P 2 0^ content is 83.0% and the reaction mixture is heated for 5 hours at 185°C, an intrinsic viscosity of 4 dL/g in MSA at 30 C is obtained; heating the reaction mixture for a total of 7 hours at 185°C gives an intrinsic viscosity of 7 dL/g in MSA a t 30 C; heating the reaction mixture for a total of 12 hours at 185°C gives an intrinsic viscosity of 10 dL/g in MSA at 30°C. -93- EXAMPLE 9 Two polymerizations (Step A and Step B) were conducted simultaneously in separate resin kettles and combined at a later stage (Step C) to give a product of a block copolymer believed to have the following structure: where a.b. is 0.793 and a b„ is 0.207 and y.. is greater than about 30. Step r A: Prep r aration of τAIrn• A mixture of 92.06g of 11555 PPA and 39.45g of concentrated orthophosphoric acid (85.755 H ^ PO.) was stirred at 100 C for 2h under reduced pressure. A portion ( 128.63g ) of the hot PPA ( 77.355 τas added under a flow of argon to a resin kettle containing 41.42682g (0.16896 mol) of la. The mixture was stirred at 50 C under argon flow for 15h, then under reduced pressure at 60 C for 23.5h. 70°C for 6h. and 80°C for 8.5h to effect dehydrochlorination. Terephthalic acid (2a) (28.0688g, 0.16S25 mol) was then added in four -ap¬ portions. The mixture was cooled to approximately 40°C and 92.22g of P 2 0g was added. The mixture was stirred at the following temperatures for the specified times under a flow of argon: 100°C for 42.5h: 120°C to 160°C in increments of 10°C per 0.5h: 170°C for 2.5h. At this time the mixture became stir-opalescent and a sample of the dope exhibited birefringence under plane-polarized light. After an additional 3h at 170°C the polymer from Step B was added (See Step C) . The intrinsic viscosity of Polymer -EAIr isolated from the reaction mixture immediately before Step C was 2.3 dL/g which corresponds to an n value (average number of recurring units) of 30 and a p value (extent of ' reaction) of 0.983. Step B: Preparation of -EAG"r . A mixture of 30.72g of 11555 PPA and 13.13g of concentrated orthophosphoric acid (85.755 I-UPC was stirred at 100°C for 2h under reduced pressure. The PPA (41.66g; 77.355 P o ° c ) as added without cooling under a flow of argon to a resin kettle containing 13.80877g (0.05632 mol) of la. The mixture was stirred at 50 C under argon flow ffoor 15h. then under reduced pressure at 60 C for 23.5h, 70°C for 6h, and 80°C for 35.5h. Isophthalic acid C2ss) (9.3569g, 0.05632 mol) that had been obtained from Aldrich Chemical Company in 9955 purity was twice recrystallized from 9055 aqueous ethanol and dried at 110°C for 24h and was then added in two portions incorporating the solid after each addition. The mixture was cooled to approximately 40°C and then -95- 31.59g of P 2 0 'as added. The mixture was then heated simultaneously and at the same heating schedule as the solution in Step A. Step C: Block Copoiymerization. After 5.5h at 170°C. 72g of the viscous, red. optically isotropic product from Step B was added to the kettle from Step A under an argon atmosphere at the time indicated in Step A. Both kettles were heated under an argon flex as follows: 170°C for 12.8h; 190°C for 2h; 200°C for 26h. The resulting mixture remained stir-opalescent and continued to polymerize as indicated by intrinsic viscosities of samples removed at various times. Upon precipitation in H 0. the final sample of the resulting copolymer had an intrinsic * viscosity of 17.5 dL/g in MSA at 30°C. The final precipitated sample of the portion of the product from Step 3 that had not been added to the product from Step A (but had been heated according to the same schedule as the mixture) had an intrinsic viscosity of 1.8 dL/g in V.SA at 30 C. The weight percent of polymer iAIτ in the product from Step A was 16.2 : the weight percent of polymer "tAG"τ in the product from Step B was 16.3. The weight percent of block copolymer " 96 " was therefore cal culated to be 16 . 2 : the weight percents of the individual "tAIr and £AG" 3- n segments of the block copolymer in the final product were 12. 9 and 3 . 4 , respectively , as calculated f rom the we ights of the constituent polymers added and the total weight of the resulting product . The mol percent of mesogenic - AIr and f l exible -fAG" } units were 79 . 3 and n n 20 .7 . respectively , as cal culated from the weights of the constituent polymers added . The above procedure is essentially repeated using 100 times the amounts of all of the reagents and monomers with the following modifications. The dehydrochlorination mixtures of both Steps A and B are mixed in separate Atlantic mixers o maintained at 60 C and circulated through separate Tef lon-coated, 6-inch-diameter, Pope wiped-film evaporators at 100°C ( to ef fect the dehydrochlorinations ) and then are returned to the original mixers . The appropriate amounts of terephthalic acid and isophthalic acid are then added and incorporated into the dehydrochlorinated mixtures at 100°C. Both of the mixers are then cooled to 50°C and the appropriate amounts of P 2 °5 are ac *ded. Tne mi ure from Step A is then polymerized to give the polymer -£A.I * L with an intrinsic viscosity (in MSA at 30°C) of approximately 10 dL/g by passing the reaction mixture through a static mixer of the Kenics type with a residence time at 185°C of 1.5 hours . The mixture from Step B is simultaneously polymerized to give the polymer AG"-}^ with an intrinsic viscosity (in MSA at 30°C of approximately 0.4 dL/g by passing the reaction mixture through a separate static mixer of the Kenics type with a residence time at 175°C of 1. 5 hours . The two oligoraeric reaction products are then mixed in the same proportions as above by feeding the intermediate products into the same mixer at 185°C and continuing the polymerization by heating at 185-190°C for an -97- additional 15 hours. The resulting block polymer has an intrinsic viscosity in MSA at 30°C (at the indicated times) of 12.5 dL/g (at 4 hours), of 16.7 dL/g (at 6 hours), and of 20 dl */.S (at 15 hours). Example 10 The reaction product of Example 2 is placed in a constant displacement spinning apparatus and extruded 0 at about 3.4 MPa (500 psi) through a 0.381 mm (0.015 in.) diameter orifice and passed through a 20.96 cm (8.25 in.) air gap at a selected take up rate to give a spin draw ratio of about 6.12:1. The extrusion temperature is about 63°C. The coagulation medium is _5 water. The average tensile properties of seven single filaments (ASTM D 3379, 2.54 cm (1.0 in.) gage length) are 2.96 GPa (4.3X10 psi) tensile strength, 89.6 GPa (13X10 psi) modulus, and elongation at break range from 4.2 - 62. The fiber diameters range from 33-37 micrometer (0.00129 to 0.00146 inches). Heat treated 0 filaments (conditioned under tension at 500°C for 60 seconds in a nitrogen atmosphere) give average values of tensile strength 3.45 GPa (5.0X10 psi), modulus 317 GPa (46X10 psi), and elongation at break 1.8 -2. 2. The heat treated fiber diameters range from 29.7-33.3 5 micrometer (0.00117 to 0.00133 inches). Example 11 0 The procedure of Example 2 i≤ essentially repeated using 21.0018 g (0.09857 mol) of lb and 16.3768g (0.09858 mol) of 2a. The P 2 0, content during " 98 dahydrochlorination is 75.162 for S hours and is increased to 81 * 371 by the addition of dβaerated P.O. for an additional 24 hours. The concentration of monomer lb during dehydrochlorination is initially 5 21.942. After Che addition of 2a, P-O. is added so as to raise the l*_°_ content to 87.52 before polymerization and to give a ^Q* content after substantial polymerization of 83.172. The mixture is then heated at 185°C for 28 hours. The concentration of polymer fBI-} is 13.8 -, Q weight percent. The isolated polymer t B *i has an intrinsic viscosity of 24.4 dL/g. Example 12 15 1__ reaction product from Example __ is dry-jeC-vec spun as in Example 10 except that Che extrusion temperature is 70*0. Che jet diameter is 0.254 mm (0.010 in.), Che air gap is 20.3 cm (8 in.) and che required extrusion pressure is 1.17 MPa (170 pel). Q The average tensile strength of nine single filaaencs is 3.12 GPa (453,000 psi) vhich ranges from about 2.82 Co about 3.35 GPa (410,000 to 486,000 psi). The average tensile modulus is 303 GPa (43.9X10 pel). After creacing this fiber ac 450*C in air for 30 seconds with a 22 stretch the scrength is unchanged and the modulus has increased Co an average of 410 GPa (59.5X10 6 psi). Repeating these conditions with a 2.82 screech give identical scrength and a modulus of 394 GPa (57.09X10 psi). After creacing che as spun fiber at 500*C in air for 30 seconds with a 2.52 screech the 0 tensile scrength increases to an average of 3.58 GPa (519,000 psi) and the modulus Increases to 467 GPa (67.8X10 6 psi). - 99- Example 13 _ mixture of 13.35 g of 1152 PPA and 8.89 g of 85.92 H-PO. is scirred under reduced pressure for 3.3 h at 5 100*C. To a 100-mL resin kettle is added 17.76096 g (0.09368 mol) of 3-a__in*_-4-hydroxybenzoic acid hydrochloride (3d). The kectle is flushed with argon, and 20.45 g of Che above PPA ( 2 0 5 concent - 75.22) is added * This mixture is stirred under reduced 10 pressure; however, the mixture solidifies overnight. 1152 PPA (8.20 g, P^ content - 83.82) is added to ob ain a βcirrable mixture with a P_,0_ concent of 77.62. Afcer 8 h, 10.17 g of PJOJ is added as a powder, giving a P 2 ° c concent of 83.492. __ Dehydrochlorination is substantially complete afcer stirring for an addiclonal 15 h aC 80*C. Additional P,0- (12.65 g) is then added at 100 # C in accordance vich equation b Co give a ~P of 82.22 and an incermediace P-0- concenc of 87.552. The keCtle is placed under reduced pressure before incorporating che 0 P.O. by scirring. The ixcure is Chen scirred for 2.4 h ac 100*C, and Che temperature is increased to 140 * C. After 1 h at Chis temperature, a clear amber solution is ob alned. The Cemperacure is raised co 150*C for 1 b and Chen raised Co 185 β C. Afcer 1 h aC 185*C, Che 5 reaction mixcure shows a Can pearlescence when scirred and is birefringenc when viewed ac rest under crossed polars. The reaccion mixcure is Chen heaced ac 185 'C for an addiclonal 40 h. Nearly colorless, high βcrengch fibers are readily formed by drawing che 0 reaccion produc . The concencracion of polymer τ?*τn in Che prodnct is calculated to be 16.672. The intrinsic ▼iβcoβicy of polymer τV n isolated from cbe produce is -100- measured Co be 13.84 dL/g in USA at 30*C. The dried polymer has a TGA break in air at lO'C/ ln of 640*C. Anal. Calcd. for C^NO: C, 71.80; H, 2.58; H, 11.96. Found: C, 71.09; H, 2.64; N, 11.67; Residue, 0.8. Example 14 The reaccion mixture of Example 13 is placed in a conetanC displacement spinning apparatus and extruded at abouc 3.4 HPa (500 psi) through a 0.381 mm (0.015 is.) diameter orifice into a 31.75 cm (12.5 in.) air gap with a cake-up race co supply a spin draw ratio of 6.6:1. The temperature of the spinning dope is 65"*C. The as spun fiber is of poor quality and very ooo-unlform. The as-spun properties are (340X10 psi) Censile scrength, 41.3-96.5 GPa (6-14X10 psi) modulus, with no elongaclon to break determined. After heat treatment under tension at 500°C for 60 seconds in nitrogen, the Example 15 The procedure of Example 13 is essentially repeaced using 80.95 g (0.4269 mol) of aonoaer 3d, 34.37 g of 85.92 EjPO^, 80.13 g of 1152 PPA and 118.06g of ? 2 Q These amounes give a P. of 77.322, an incermediace P-0- content of 88.832, and (because of the loss of 1.5 g of water during polycondensacion) a P, of 83.82. The concencracion of polymer fV * τ α la the reaccion produce is calculaced Co be 16.87 weighc 2. The Cocal reaccion eime above lOO'C is 43.5 hours. The scir-opalescenc reaccion produce is birefringenc ac rear and live colorless fibers afcer drawing and prβe±piεaeing in wacer. The incrinβic viβcoβicy of isolaeed polymer τ V-τ a is 12.0 dL/g. ' J.Q1- Examplβ 16 The raaecloa produce of Example 15 is placed In a conβeane dlsplaeemenc spinning apparaCus and extruded ac about 3.4 HPa (500 pel) through a 0.25 ma (0.010 in.) diameter orifice into a 20.3 cm (8 In.) air gap with a Cake up race to supply a spin draw raclo of 145:1. The temperature of che spinning dope is 90*C. The tensile screngch of fibers (average of nine breaks) spun from said dope is 3.57 GPa (518,000 psi). The average Censlle modulus Is 133 GPa (19.3110 p*D * This value does noc cake inco accounc Che machine compliance. The average serais ac break is 3.32. The fiber diameter is 16 alcromeeers (0.630X10 "3 in.). -102- The physical properties of spun and heat-treated fibers formed from c rpositions of Examples 10, 12, .14 and 16.are shown in Table 4 below. T A B L E EXAMPLES τBI* *Bl fV4 τ V+ π π a a CONDITION Example No. : 10 12 14 16 Polymer dope 1. Intrinsic Viscosity (dL/g) 23.9 24.4 13.8 12.0 2. P 2 0 5 Content (Z) 82.3 83.2 82.2 83.8 3. Polymer Concentration (2) 13.3 13.8 16.7 16.9 Spinning Conditions 4. Spin Draw Ratio 6.1:1 53:1 6.6:1 145:1 5. Spin Temperature ("C) 63 70 65 90 6. Air Gap Distance (cm) 21 20.3 31.7 20.3 7. Jet Diameter ( π) 0.381 0.25 0.381 0.25 8. Dope pressure (MPa) *2 1.17 *3.4 *3.4 Aβ Spun Fiber Properties 9. Tensile Strength (GPa) 2.96 3.12 2.34 3.57 10. Single break Tensile Strength (GPa) -highest value - 5.01 11. Modulus (GPa) 89.6 303 41-96 133 12. Elongation 2 4.2-6 3.3 13. Fiber diameter (micrometer) 33 37-76 16 -103- Heat Treatment Conditions 14. Temperature ( * C) 500 450 500 15. Time (seconds) 60 30 60 16. Screech faccor (2) - 2 7.5 17. Atmosphere condition Nitrogen Air Nitrogen Post Heat Treatment Fiber Properties 18. Tensile Strength (GPa) 3.45 3.07 2.34 19. Modulus (GPa) 317 410 136 20. Elongation (2) 1.8-2.4 21. Fiber Diameter (micrometer) 31.4 22. Visual uniform non-uniform - * denotes approximate values - 104. Example 17 The procedure of Example 2 is essentially repeated with the following modifications. Instead of the molar amounts of 2a 5 given in Example 13, 8.953 1 * g, 0.05389 mols of 2a was added. Benzoic acid (Matheson primary standard, 0.0330 g, 0.2701 mmol) was then added under a stream of argon and incorporated under reduced pressure. _ Q The resulting reaction product is characterized as having a final ef ective P j Oς content of 82U with the τ BI n polymer concentration being 13-3% by weight. The intrinsic viscosity of the end-capped polymer -fBI isolated from the reaction product i3 20 dL/g in MSA at 30°C, which corresponds to an , c average number of recurring units, n, of approximately 100. Example 18 0 The procedure of Example 6 is essentially repeated with the following modification. After dehydrochlorination is substantially complete and the P2O5 is added, benzoic acid (Matheson primary standard, 1.6365 g, 0.013U0 mol) is added under a 3tream of argon and incorporated under reduced 5 pressure. The intrinsic viscosity of end-capped polymer • fT-_ n isolated from the reaction product is 5.2 dL/g. The reaction product thus obtained is 20.3J by weight of polymer -ETi n in PPA with a final P 2 0 5 content of 82. ~i . 0 - 105 Example 19 The procedure of Example 6 is essentially repeated with the following modifications. After dehydrochlorination is substantially complete and the P 2 0g is added, benzoic acid (Matheson primary standard, 0.8181 g, 6.699 mmol) is added under a stream of argon and incorporated under reduced pressure. The intrinsic viscosity of polyme τ T n isolated from the reaction product is 10.2 dL/g. The reaction product thus obtained is 20.3% by weight of end-capped polymer -£ -} n in PPA with a final P 2 0 5 content of 82.U*. Example 20 The procedure of Example 6 is essentially repeated with the following modifications. After dehydrochlorination is substantially complete and the P 2 °5 is added, benzoic acid (Matheson primary standard, 0.1364 g, 1.117 mmol) is added under a stream of argon and incorporated under reduced pressure. The intrinsic viscosity of polymer -,T n isolated from the reaction product is 16.4 dL/g. The reaction product thus obtained is 20.3% by weight of end-capped polymer -fc n in PPA with a final P 2 0 5 content of 82.4J. Example 21 The procedure of Example 7 is essentially repeated with the following modifications. After dehydrochlorination is substantially complete and the P 0ς is added, benzoic acid -ιoe- (Matheson primary standard, 3 * 1285 g, 25.02 mmol) is added under a stream of argon and incorporated under reduced pressure. The intrinsic viscosity of polymer i Vf n isolated from the reaction product is 4.0 dL/g. The reaction product thus obtained is 18% by weight of end-capped polymer V-} n in PPA with a final P 2 0 5 content of 82.2%. Example 22 The procedure of Example 7 is essentially repeated with the following modi ications. After dehydrochlorination is substantially complete and the P 2 0 5 is added, benzoic acid (Matheson primary standard, 1.5642 g, 12.81 mmol) is added under a stream of argon and incorporated under reduced pressure. The intrinsic viscosity of polymer -f -J n isolated from the reaction product is 9-6 dL/g. The reaction product thus obtained is 20.3% by weight of end-capped polymer τV-_ n in PPA with a final P 2 θ5 content of 82.2%. Example 23 The procedure of Example 7 is essentially repeated with the following modi ications. After dehydrochlorination is substantially complete and the P 2 θ5 i3 added, benzoic acid (Matheson primary standard, 0.2607 g, 2.135 mmol) i3 added under a stream of argon and incorporated under reduced pressure. The intrinsic viscosity of polymer τ isolated from the reaction product is 14.2 dL/g. The reaction product thus obtained i3 20.3% by weight of end-capped polymer n in PPA with a final P2O5 content of 82.2%. -107. The following nonlimitive examples are given to further illustrate the invention, especially the effect of bulk viscosity on the conditions necessary for dehy rochlorination. One of the parameters that confr ' bu.es to the bulk, viscosity . > f the dehydro-rhlor-inar'.or. mixture is the P„0_. content of the PPA employed. The empirical relation lάp minimum S/V shows the strong dependence of the minimum surface-to- volume IΛ ratio on the initial F-'Jr content. This dependence is a direct result of the strong dependence of the viscosity on the content. Examples 24 through 59 illustrate the preparation of 100 grams of poly (benzo[l,2-d * :5,4-d' ]bisoxazole-2,6-diyl)- ,4- 5 phenylene) (PBO). 90.966 grams of 4,6-diamino-l,3-benzenediol dihydrochloride is added to a* grams of PPA having a 2 ° c content of P. to form the dehydrochlorination mixture. In those examples where the selected P. is greater than that commercially or readily "available PPA" the monomer is added to the appropriate 0 amount of available PPA and then add a sufficient amount of ? 0ς to achieve the selected P.. In this case the weight of che PPA employed upon mixing, a**, is given by a** = a* (P.-1)/(P„0, content of available PPA - 1) 5 l 2 5 and the amount of - j O, co be added during the mixing procedure i' given by a*-a**. The viscosity of the dehydrochlorination mixture is dependent on whether the PPA is equilibrated by prior heating above 100°C or is a mixture of a PPA of lower P 9 0_- 0 content and solid p _ r- The latter situation is preferred when the P. is greater than about 86% P-0,- because of the high viscosity of these PPAs. BAD ORIGI -108- In Examples 24 through 59 , 70.932 grams of ? 2 0_ (b* grams) is added when the dehydrochlorination is substantially complete. In those examples in which a monofunctional reactant is employed the indicated mole per cent (based on 4,6-diamino-l,3-benzenediol dihydrochloride) is also added, and the amount of terephthalic acid is reduced by half of the moles of nonofunctional reactant used. Examples 60 through 95 illustrate the preparation of 100 grams of poly (benzo.1,2-d' :4,5-d' ]bisthiazole-2,6-diyl)-l,4- -phenylene) (PBT). 92.062 grams of 2,5-diamino-l,4-benzenedithiol dihydrochloride is added to a * grams of PPA having a P 2 0 5 content of ? L to form the dehydrochlorination mixture. The same considerations in the preparation of high P-O ^ content P 's as given for Examples 156-191 are employed in these Examples. When the maximum solubility listed in the Example exceeds the actual concentration in the Example this indicates that the monomer is only partially soluble at the initial P-O- content and thus dehydrochlorination will proceed with the advantages of the lower viscosity of the low P 0 content PPA, but the content must be incrementally increased by the addition of 2 °5 (which has the effect of increasing the solubility and decreasing the actual concentration) to the value of the intermediate P-.0 C content, P , during the i. o m dehydrochlorination step. -103" Examples 24 25 27 28 29 wt fraction 0.15 0.15 0.15 0.15 0.15 c * p. wt fraction 0.84 0.84 0.84 0.84 0.84 P . wt fraction 0.888 0.888 0.888 0.888 0.888 tn . , wt fraction 0.888 0.858 0.828 0.798 0.768 a*, grams of PPA 535.891 422.482 348.690 296.842 258.418 b*, grams of P 2 0 5 .000 113.409 187.201 239.048 277.473 a*/(a* + b*) 1.000 0.788 0.651 0.554 0.482 First Monomer cone (wt %) 14.511 17.717 20.690 23.456 26.036 Maximum solubilitym 23.31 22.08 20.96 19.93 18.99 Minimum S/V (cm ) 13.330 7.009 3.966 2. 296 1. 345 Radius required (in) 13.275 8.547 5.841 4. 100 2. 928 Reactor Selection a a a a b DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 18 20 23 8 8 Monofunct. reactant (mol %) ' 1.4 1.3 1.1 0 0 Polymerization conditions e e e f f Process j j j a.) High surface to volume ratio reactor required for Dehydrochlorinatioi b. ) 6-inch diameter resin kettle is used c) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100°C and reduced pressure 185°C for 5 h f.) 185 C for 2 h, the oligomer thus obtained is used in a block polymerization 185°C for 12 h 185°C for 8 h Dry-jet wet-spin into fiber Extrude into film Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole per cent)/2 1.) Determined from equations a* and b* . ) Maximum solubility of First Monomer = 9+20expP ^ . n.) Minimum radius required to obtain desired S/V -110- Examples 30 . 31 32 33 34 ? , tft fraction 0.15 0.15 0.15 0.15 0.15 fraction 0.84 0.84 0.84 0.84 0.83 r p , t fraction 0.888 0.888 0.888 0.888 0.878 3 • J . t fraction 0.738 0.708 0.678 0.648 0.878 , ι* , grams of PPA 228. 801 205. 274 186. 135 170. 260 535. 891 _.*, grams of 307.090 330.616 349.756 365.630 .000 ,*/( a * + b*) 0.427 0.383 0.347 0.318 1.000 First Monomer cone (wt %) 28.448 30.707 32.828 34.823 14.511 Maximum solubility 18.13 17.35 16.63 15.97 22.86 Minimum S/V, cm 0.800 0.489 0.312 0.213 11.448 Radius required (in) 2.125 1.573 1.197 0.945 12.302 Reactor Selection b b b b a DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 8 8 8 8 18 Monofunct. reactant (mol Z ) k 0 0 0 0 1.35 Polymerization conditions f f f f e rocess ) High surface to volume ratio reactor required for Dehydrochlorinati ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ■) 185 C for 2 h, the oligo er thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h •) Dry-jet wet-spin into fiber ■ ) Extrude into film ■ ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant per cent)/2 ■ ) Determined from equations a* and b* ■ ) Maximum solubility of First Monomer - 9+20expP,. • ) Minimum radius required to obtain desired S/V "Ill- Examples 35 36 37 38 39 p . wt fraction 0.125 0.1 0.075 0.05 0.13 p . wt fraction 0.83 0.83 0.83 0.83 0.82 p wt f raction 0.868 0.859 0.851 0.844 0.860 πr p. , wt fraction 0.868 0.859 0.851 0.844 0.860 a*, grams of PPA 669. 224 869. 224 1202. 557 1869. 224 638. 455 b *» S rams of P 2°5 .000 - . 000 . 000 .000 . 000 a*/(a* + b* ) 1. 000 1. 000 1. 000 1. 000 1. 000 First Monomer cone (wt % ) 1 1. 966 9.474 7. 032 4. 641 12. 471 Maximum solubility m 22. 47 22. 12 21. 81 21. 52 22. 13 Minimum S/V, cm 9.660 8.417 7.499 6.792 8.759 Radius required (in) n 12.628 13.435 14.915 17.698 11.745 Reactor Selection a a a a a DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 23 27 27 23 18 Monofunct. reactant (mol ) 1 1..11 0.8 0.8 1.1 1.35 Polymerization conditions e g g g e Process i j j i i ) High surface Co volume ratio reactor required for Dehydrochlorination ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ) 185°C for 2 h, the oligomer thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h ) Dry-jet wet-spin into fiber ) Extrude into film ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole per cent)/2 ) Determined from equations a* and b* ) Maximum solubility of First Monomer = 9+20exρP,. ) Minimum radius required to obtain desired S/V -LU. Examples 40 41 42 43 44 p C| wt fraction 0.13 0.13 0.13 0.13 0.13 p wt fraction 0.82 0.82 0.82 0.82 0.82 p wt fraction 0.860 0.860 0.860 0.860 0.860 m P.-. wt fraction 0.830 0.800 0.770 0.740 0.710 a*, grams of PPA 526.099 447.370 389.137 344.318 308.757 b*, grams of P 2 0 5 112.356 191.085 249.318 294.137 329.698 a*/(a* + b*) 0.824 0.701 0.609 0.539 0.484 First Monomer cone (wt %) 14.742 16.898 18.947 20.898 22.757 Maximum solubility 21.00 19.97 19.03 18.17 17.38 Minimum S/V, cm 4.663 2.656 1. ,563 0. 945 0.592 Radius required (in) 7.780 5.415 3. ,873 2. ,833 2.124 Reactor Selection a a c b b DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 18 22 8 8 20 Monofunct. reactant (mol %) k 1 1..3355 1.1 0 0 1.3 Polymerization conditions e e f f e Process i ) High surface to volume ratio reactor required for Dehydrochlorination ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ) 185°C for 2 h, the oligomer thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h ) Dry-jet wet-spin into fiber ) Extrude into film ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole per cent)/2 ) Determined from equations a* and b* ) Maximum solubility of First Monomer = 9+20expP. ) Minimum radius required to obtain desired S/V -113- Examples 45 46 47 48 49 p wt fraction 0. 13 0. 13 0. 13 0. 1 0. 1 c' •j wt fraction 0.82 0.82 0.82 0.83 0.83 P wt fraction 0.860 0.860 0.860 0.859 0.859 rn' P. wt fraction 0.680 0.650 0. 620 0. 859 0.829 3 * , grams of PPA 279.854 255.899 235.721 869.224 716.382 b*, grams of 2 °5 358.601 382.556 402.734 .000 152. 842 a */(a* + b* ) 0.438 0.401 0.369 1.000 0.824 First Monomer cone (wt %) 24.531 26.225 27.845 9.474 11.267 Maximum solubilitym 16.66 16.00 15.40 22. 12 21.00 Minimum S/V, cm 0. 390 0. 273 0. 205 8.417 4.496 Radius required (in) n 1. 641 1. 314 1. 093 13. 435 8. 914 Reactor Selection b b b a a DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 20 20 22 22 22 Monofunct . reactant , ( mol % . ) k 1. 3 1.3 1.1 1.1 1.1 Polymerization conditions e e e h h Process i i i ) High surface to volume ratio reactor required for Dehydrochlorinatio ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ) 185°C for 2 h, the oligomer thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h ) Dry-jet wet-spin into fiber ) Extrude into film ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole pe cent)/2 ) Determined from equations a* and b* ) Maximum solubility of First Monomer = 9 ' +20expP„. ) Minimum radius required to obtain desired S/V -114- Exa ples 50 51 52 53 54 wt fraction 0.1 0.1 0.1 0.1 0.1 P c' . wt fraction 0.83 0.83 0.83 0.83 0.83 P wt fraction 0.859 0.859 0.859 0.859 0.859 nr p wt fraction 0.799 0.769 0.739 0.709 0.679 a*, grams of PPA 609.253 529.997 468.987 420.573 381.220 b*, grams of ?_ _ 259.971 339.227 400.237 448.651 488.004 a*/(a* + b*) 0.701 0.610 0.540 0.484 0.439 First Monomer cone (wt Z 12.991 14.649 16.245 17.783 19.265 Maximum solubility 19.97 19.02 18.16 17.37 16.65 Minimum S/V, cm 2.570 1.517 0.921 0.580 0.384 Radius required (in) 6.215 4.454 3.264 2.453 1.899 Reactor Selection a c b b b DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 22 22 22 22 22 Monofunct. reactant, (mol ) k 1.1 1.1 1.1 1.1 1.1 Polymerization conditions h h h h h Process i i i i ) High surface to volume ratio reactor required for Dehydrochlorinatio ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ) 185°C for 2 h, the oligomer thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h ) Dry-jet wet-spin into fiber ) Extrude into film ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole pe cent)/2 ) Determined from equations a* and b* ) Maximum solubility of First Monomer = 9+20expP.. ) Minimum radius required to obtain desired S/V -115- Examples 55 56 57 58 59 P . wt fraction 0.1 0.1 0.08 0.08 0.08 c' p wt fraction 0.83 0.83 0.82 0.82 0.82 p , wt fraction 0.859 0.859 0.843 0.843 0.843 m' p , wt fraction 0.649 0.619 0.843 0.813 0.783 a*, grams of PPA 348.601 321.124 1119.224 940.102 810.404 b*, grams of p 2 °5 520.623 548.100 .000 179..122 308.820 a*/(a* + b*) 0.401 0.369 1.000 0.840 0.724 First Monomer cone (wt %) 20.694 22.074 7.517 8.823 10.092 Maximum solubilitym 16.00 15.40 21.48 20.41 19.43 Minimum S/V, cm 0.270 0.204 6.885 3.688 2.122 Radius required (in) n 1.524 1.271 13.788 9.248 6.513 Reactor Selection b b a a a DeHCl conditions d d d d d Intrinsic Viscosity (dL/g) 22 22 30 24 24 Monofunct. reactant, (mol %) : 11..11 1.1 0.2 0.9 0.9 Polymerization conditions h h g g g Process i __ . ) High surface to volume ratio reactor required for Dehydrochlorination ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ) 185°C for 5 h ) 185°C for 2 h, the oligomer thus obtained is used in a block polymerization ) 185°C for 12 h ) 185°C for 8 h ) Dry-jet wet-spin into fiber ) Extrude into film ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole ur cent)/2 ) Determined from equations a* and b* ) Maximum solubility of First Monomer = 9+20expP. ) Minimum radius required to obtain desired S/V -116- Examples 60 p wt fraction 0. 08 P . wt fraction 0. 82 p wt fraction 0. 843 m' p wt fraction 0. 753 i' a*, grams of PPA 712. 154 b*. grams of P 2 0 5 407. , 070 a */(a* + b*) 0. , 636 First Monomer cone (wt Z ) ) 11. , 327 Maximum solubility 18. , 53 Minimum S/V (cm ) 1. , 274 Radius required ( in) 4. , 730 Reactor selection a DeHCl conditions d. Intrinsic Viscosity (dL/g) 24 l Monofunct . reactant , (mol ) 0. 9 Polymerization conditions g Process i a.) High surface to volume ratio reactor required for Dehydrochlorinatio b.) 6-inch diameter resin kettle is used -•) 8-inch diameter resin kettle is used *■ !•) Conduct dehydrochlorination at 100°C and reduced pressure a - - ) 185°C for 5 h ϊ - ) 185°C for 2 h, the oligomer product obtained is used in a block polymerization • J.) 185°C for 12 h h.) 185°C for 8 h ! • ) Dry-jet wet-spin into fiber • ) Extrude into film "* - • ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole p cent)/2 ! • ) Determined from equations a* and b* **• ) Maximum solubility of First Monomer = 9+20expP. n -) Minimum radius required to obtain desired S/V -117- Examples 61 62 63 64 65 P wt fraction 0. 175 0. 175 0. 175 0. 175 0. 175 c' P . wt fraction 0.84 0. 84 0.84 0.84 0.84 P wt fraction 0. 891 0. 891 0. 891 0.891 0. 891 tn p , wt fraction 0. 891 0.861 0. 831 0. 801 0. 771 a*, grams of PPA 444.364 348.348 286.452 243.233 211.346 b*. rams of P 2 0 5 .000 96.017 157.912 201.131 233.018 a*/(a* + b*) 1.000 0.784 0.645 0.547 0.476 First Monomer cone (wt Z ) 17.162 20.904 24.322 27.457 30.343 Maximum solubilitym 29.44 28.19 27.06 26.02 25.08 Minimum S/V (cm ) 15.081 7.714 4.306 2.473 1.440 Radius required (in) 12.857 8.142 5.516 3.852 2.740 Reactor Selection a a a a b DeHCl conditions d d d d d Intrinsic Viscosity , dL/g 20 22 25 10 10 k Monofunct. reactant , (mol % ) 1. 4 4 1.3 1.1 0 0 Polymerization conditions e e e f f Process j j j a.) High surface to volume ratio reactor required for Dehydrochlorination b. ) 6-inch diameter resin kettle is used c) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100°C and reduced pressure e.) 185°C for 4 h f.) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g.) 185°C for 10 h h. ) 185°C for 6h i») Dry-jet wet-spin into fiber j-) Extrude into film k..) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole pe cent)/2 !•) Determined from equations a* and b* m. ) Maximum solubility of First Monomer = 20+20expP. n.) Minimum radius required to obtain desired S/V -118- Examples 66 67 68 69 70 wt fraction 0.175 0.175 0.175 0.175 0.15 p , wt fraction 0.84 0.84 0.84 0.84 0.83 • _l wt fraction 0.891 0.891 0.891 0.891 0.872 p , wt fraction 0.741 0.7U 0.681 0.651 0.872 a*, grams of PPA 186.851 167.444 151.689 138.644 539.602 b*, grams of P^ 257.513 276.921 292.676 305.721 .000 a*/(a* + b*) 0.420 0.377 0.341 0.312 I.000 First Monomer cone (wt %) 33.008 35.476 37.769 39.905 14.575 Maximum solubility 24.21 23.42 22.70 22.03 28.61 Minimum S/V (cm ) 0.850 0. ,514 0. 325 0. 218 10.542 Radius required (in) 1.979 1. ,458 1. ,102 0. ,863 11.846 Reactor Selection b b b b a DeHCl conditions d d d d d Intrinsic Viscosity, dL/g 10 10 10 10 20 Monofunct. reactant, (mol %) ; 0 0 0 0 1.35 Polymerization conditions f f f f e Process i a. ) High surface to volume ratio reactor required for Dehydrochlorinatio b. ) 6-inch diameter resin kettle is used c. ) 8-inch diameter resin kettle is used d. ) Conduct dehydrochlorination at 100°C and reduced pressure e. ) 185°C for 4 h f. ) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g- ) 185°C for 10 h h. ) 185°C for 6h i. ) Dry-jet wet-spin into fiber !• ■ ) Extrude into film k.') Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole pe cent)/2 •) Determined from equations a* and b* ■) Maximum solubility of First Monomer ■ 20+20expP. •) Minimum radius required to obtain desired S/V -119- Examples 71 72 73 74 75 p , wt fraction 0.125 0.1 0.075 0.05 0.13 c' p , wt fraction 0.83 0.83 0.83 0.83 0.82 P , wt fraction 0.863 0.856 0.849 0.842 0.855 πr p , wt fraction 0.863 0.856 0.849 0.842 0.855 i * a*, grams of PPA 672.936 872.936 1206.269 1872.936 642.167 b*. grams of P 2 0 5 .000 .000 .000 .000 .000 a*/(a* + b*) 1.000 1.000 1.000 1.000 1.000 First Monomer cone (wt %) 12.034 9. 540 7.091 4. 685 12.539 Maximum solubilitym 28. 28 27. 98 27. 71 27. 46 27. 94 Minimum S/V ( cm ) 9.109 8.077 7.295 6.681 8.262 Radius required (in) 2.297 13.189 14.734 17.570 11.441 Reactor Selection a a a a a DeHCl conditions d d d • d d Intrinsic Viscosity , dL/g 25 30 30 25 20 Monofunct . reactant , (mol % ) k ' 11..11 0.8 0.8 1.1 1.35 Polymerization conditions e g g g e Process i j j i i a.) High surface to volume ratio reactor required for Dehydrochlorinatio b.) 6-inch diameter resin kettle is used c.) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100°C and reduced pressure e.) 185°C for 4 h f-) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g.) 185°C for 10 h h -) 185°C for 6h i«) Dry-jet wet-spin into fiber j«) Extrude into film k.) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole pe cent)/2 *•- ) Determined from equations a* and b* m «) Maximum solubility of First Monomer = 20+20expP. n -) Minimum radius required to obtain desired S/V -120- Examples 76 77 78 79 80 P wt fraction 0.13 0.13 0.13 0.13 0.13 c p _, wt fraction 0.82 0.82 0.82 0.82 0.82 *£' p , wt fraction 0.855 0.855 0.855 0.855 0.855 p f wt fraction 0.825 0.795 0.765 0.735 0.705 a*, grams of PPA 532.358 454.619 396.691 351.857 316.129 b*, grams of P 2 0 5 109.809 187.548 245.475 290.309 326.038 a*/(a* + b*) 0.829 0.708 0.618 0.548 0.492 First Monomer cone (wt Z ) 14.744 16.840 18.836 20.739 22.554 Maximum solubility 26. 82 25. 81 24. 88 24.03 23. 25 Minimum S/V (cm ) 4.402 2.511 I. ,483 0. 903 0.572 Radius required (in) 7.603 5.307 3. ,809 2. ,800 2.113 Reactor Selection a a c b b DeHCl conditions d d d d d Intrinsic Viscosity, dL/g 20 25 10 10 22 Monofunct. reactant, (mol %) k l.35 1.1 0 0 1.3 Polymerization conditions e e f f e Process i i i a. ) High surface to volume ratio reactor required for Dehydrochlorinati b. ) 6-inch diameter resin kettle is used c. ) 8-inch diameter resin kettle is used d. ) Conduct dehydrochlorination at 100°C and reduced pressure e. ) 185°C for 4 h f. ) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g. ) 185°C for 10 h h. ) 185°C for 6h i. , ) Dry-jet wet-spin into fiber j. ) Extrude into film k.•) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole p cent)/2 • ) Determined from equations a* and b* •) Maximum solubility of First Monomer =» 20+20expP. • ) Minimum radius required to obtain desired S/V -121- Exa ples 81 82 83 84 85 p , wt fraction 0.13 0.13 0.13 0.1 0.1 c p . wt fraction 0.82 0.82 0.82 0.83 0.83 p . wt fraction 0.855 0.855 0.855 0.856 0.856 m' , wt fraction 0.675 0.645 0.615 0.856 0.826 a*, grams of PPA 286.987 262.765 242.313 872.936 722.660 b*, grams of 2 0c 355.180 379.402 399.854 .000 150.276 a */(a* + b*) 0.447 0.409 0.377 1.000 ' 0.828 First Monomer cone (wt %) 24.288 25.946 27.533 9.540 11.300 .Maximum solubility *31 22.54 21.90 21.30 27.98 26.87 Minimum S/V (cm ) 0.382 0.272 0.207 8.077 4.315 Radius required (in) Cl 1.645 1.327 1.112 13.189 8.771 Reactor Selection b b b a a DeHCl conditions d d d d. d Intrinsic Viscosity, dL/g 22 22 25 25 25 Monofunct. reactant, (mol %) k 1.3 1.3 1.1 1.1 1.1 Polymerization conditions e e e h h Process i i i i i a.) High surface to volume ratio reactor required for Dehydrochlorination b. ) 6-inch diameter resin kettle is used c.) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100°C and reduced pressure e.) 185°C for 4 h f.) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g.) 185°C for 10 h h.) 185°C for 6h !•) Dry-jet wet-spin into fiber j-) Extrude into film ιc.) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole per cent)/2 !•) Determined from equations a* and b* m.) Maximum solubility of First Monomer = 20+20expP. n -) Minimum radius required to obtain desired S/V " 122 " Examples 86 87 88 89 90 Pc, wt fraction 0. 1 0. 1 0. 1 0. 1 0. 1 p wt fraction 0.83 0.83 0.83 0.83 0.83 P , wt fraction 0. 856 0. 856 0.856 0. 856 0.856 m' P . wt fraction 0. 796 0. 766 0. 736 0. 706 0. 676 , J. a*, grams of PPA 616.526 537.574 476.548 427.965 388.371 b*, grams of P 2 0 5 256.410 335.362 396.388 444.971 484.565 a*/(a* + b*) 0.706 0.616 0.546 0.490 0.445 First Monomer cone (wt %) 12.992 14.622 16.191 17.703 19.162 m Maximum solubility 25.85 24.91 24.06 23.28 22.57 Minimum S/V (cm " ) 2.468 1.461 0.892 0.566 0.378 Radius required (in) 6. 127 4. 402 3. 237 2. 444 1. 903 Reactor Selection a c b b b DeHCl conditions d d d d d Intrinsic Viscosity, dL/g 25 25 25 25 • 25 Monofunct. reactant, (mol ) t* * 11..11 1. 1 1. 1 1. 1 1. 1 Polymerization conditions h h h h h Process i i i i i ) High surface to volume ratio reactor required for Dehydrochlorinatio ) 6-inch diameter resin kettle is used ) 8-inch diameter resin kettle is used ) Conduct dehydrochlorination at 100°C and reduced pressure ■) 185°C for 4 h 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization ■) 185°C for 10 h .) 185°C for 6h .) Dry-jet wet-spin into fiber •) Extrude into film ■ ) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole p cent)/2 •) Determined from equations a* and b* •) Maximum solubility of First Monomer * 20+20expP. •) Minimum radius required to obtain desired S/V " 12T Exa ples 91 92 93 94 95 P wt fraction 0.1 0.1 0.08 0.08 0.08 c' p . wt fraction 0.83 0.83 0.82 0.82 0.82 p , wt fraction 0.856 0.856 0.840 0.840 0.840 m p , wt fraction 0.646 0.620 0.840 0.810 0.780 i a*, grams of PPA 355.483 331.410 1122.936 945.851 817.010 b*, grams of P 2 0 5 517.453 541.526 .000 177.085 305.926 a*/(a* + b*) 0.407 0.380 1.000 0.842 0.728 First Monomer cone (wt %) 20.571 21.740 7.577 8.870 10.127 Maximum solubility ,m 21.92 21.41 27.38 26.31 25.34 Minimum S/V (cm ) 0.269 0.212 6.696 3. 590 2.069 Radius required (in) 1.536 1.317 13.620 9. 152 6.457 Reactor Selection b b a a a DeHCl conditions d - d d d d Intrinsic Viscosity, dL/g 25 25 36 28 28 Monofunct. reactant, (mol %) κ" * 11..1I 1.1 0.5 1 1 Polymerization conditions h h g g g Process i i i i i a.) High surface to volume ratio reactor required for Dehydrochlorinatio b.) 6-inch diameter resin kettle is used c.) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100" * C and reduced pressure e.) 185°C for 4 h f.) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g.) 185°C for 10 h h.) 185°C for 6h i.) Dry-jet wet-spin into fiber j-) Extrude into film k.) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole per cent)/2 1-) Determined from equations a* and b* m.) Maximum solubility of First Monomer *» 20+20expP. n -) Minimum radius required to obtain desired * S/V -124- Examples 96 P , wt fraction 0.08 p wt fraction 0.82 p . wt fraction 0.840 p. , wt fraction 0.750 l' a*, grams of PPA 719.062 b*, grams of P„0c 403.874 a*/(a* + b*) 0.640 First Monomer cone (wt %) 11.350 Maximum solubility 24.45 Minimum S/V (cm ) 1.246 Radius required (in) 4.701 Reactor Selection a DeHCl conditions d Intrinsic Viscosity, dL/g 28 Monofunct. reactant, (mol %) k 1 Polymerization conditions g Process i a.) High surface to volume ratio reactor required for Dehydrochlorinati b.) 6-inch diameter resin kettle is used c.) 8-inch diameter resin kettle is used d.) Conduct dehydrochlorination at 100°C and reduced pressure e.) 185°C for 4 h f.) 185°C for 1.5 h, the oligomer product obtained is used in a block polymerization g.) 185°C for 10 h h.) 185°C for 6h i.) Dry-jet wet-spin Into fiber j.) Extrude into film k.) Mole per cent (based on First Monomer) of benzoic acid; Second Monomer mole per cent is reduced by (Monofunctional reactant mole p cent)/2 1.) Determined from equations a* and b* m.) Maximum solubility of First Monomer == 20+20expP. n.) Minimum radius required to obtain desired S/V -125- Example 97 A homogeneous solution is prepared by adding 10 wt % of P-O c to freshly distilled methanesulfonic acid (MSA) and heating according to the procedure of Eaton et al (J. Org. Chem., 38, 4071, 1973). To a 100 mL resin kettle is added 24.28 grams of 3-amino-4-hydroxybenzoic acid hydrochloride and 38.36 grams of the above solution. The mixture is stirred at 50-70 C for 47 hours to effect dehydrochlorination. p 0 c (27.65 grams) is then added and the mixture is stirred for 64 hours at 100 C. The polymerization is then initiated by raising the temperature to 150 C. The reaction mixture is optically anisotropic during the polymerization and is highly birefringent when viewed under crossed polars at room temperature. The reaction product is removed from the reactor after 48.5 hours at 150°C and can be stretched into white fibers that do not have noticeable microfibrillar morphology. The reaction product before coagulation is characterized as containing 17.52 wt Z of homopolymer -.V n and having a 7 0, content (i. e. , total wt of P 2 0 < - / total wt of the solvent) of 44.6%. The isolated polymer has an intrinsic viscosity in MSA at 30°C of 16.0 dL/g. The above procedure is essentially repeated with the following modifications. The wt% of P^O c in the dehydro¬ chlorination solvent is 9.26% and the dehydrochlorination time at 50-70°C is 18 hours. The equilibration time at 100°C Is 5 hours. The polymerization time at 150°C is 43 hours. The concentration of homopolymer Vj* n in the reaction product is 17.6 wt % and the P-0- content is 35.7%. The isolated polymer has an intrinsic viscosity in MSA at 30 C of 4.75 dL/g. -126- Example 98 The procedure of Example 97 is essentially repeated with the following modifications. The wt% of P 2 0c in the dehydrochlorination solvent is 9.11% and 4,6-diamino-l,3- benzenediol dihydrochloride is used as the first monomer. The dehydrochlorination time at 30°C is 18 hours. The equilibration time at 100°C is 1 hour. A stoichiometric amount of terephthalic acid is added and the polymerization time is 2.5 hours at 120°C (at which time the reaction mixture is stir-opalescent) and then 15 hours at 140 C. The concentration of homopolymer -fBIfcin the reaction product is 13.0 wt% and the P 2 0 5 content is 27.7%. The isolated polymer has an intrinsic viscosity in MSA at 30 C of 4.12 dL/g. Example 99 When the procedure of Example 98 is followed except that the 4,6-diamino-l,3-benzenediol dihydrochloride is replaced by 2,5-diaraino-l,4-benzenedithiol dihydrochloride polymerization does not proceed at 140 C, presumably owing to decomposition of the oxidatively sensitive monomer.

Claims: -127- Claims 1. A process for the production of a liquid crystalline extended chain polymer composition of workable viscosity which is useful in the production of polymer articles, comprising the steps of: (a) preparing a monomer reaction medium suitable for polymerization by incorporating a high concentration of at least one selected monomer in a substantially non-oxidizing strong acid, said reaction medium containing at least about 80 percent by weight phosphorus pentoxide: (b) introducing said reaction medium into a reaction vessel selected so that a surface-to-volume ratio greater than about 0.2 cm " is achieved; and (c) heating said reaction medium to a temperature sufficient to effect polymerization of said at least one monomer. 2. The process of claim 1, wherein said polymerization is conducted under conditions to exercise control of molecular weight, said conditions comprising: (a) adding at least one suitable monofunctional reactant in a predetermined amount at a selected stage of polymerization: (b) adjusting the stoichiometric proportion of said at least one monomer at a selected stage of polymerization: or (c) discontinuing polymerization at a selected degree thereof. 3. A process for the production of a liquid crystalline extended chain polymer composition of workable viscosity which is useful in the production of polymer articles, comprising the steps of: -128- (a) initially admixing in a reaction vessel selected so as to provide a surface-to-volume ratio of at least 0.2 cm " at least one homo- or hetero- bifunctional monomer with a preliminary solvent to provide an initial monomer reaction mixture, said at least one monomer optionally provided with oxidation protecting moieties and present in said reaction medium in sufficient quantity to achieve a polymer concentration greater than about 10 percent by weight of the total composition, said solvent comprising a substantially non-oxidizing strong acid having an initial phosphorus pentoxide content of between about 63 and 92 weight percent: (b) heating and optionally placing said mixture under reduced pressure, whereby any protecting moieties present are removed. said temperature of said initial admixing and heating steps (a) and (b) being sufficient to maintain said mixture at a workable viscosity; (c) adjusting the phosphorus pentoxide content of said mixture as necessary to provide a final phosphorus pentoxide concentration suitable for polymerization and for achieving a degree of polymerization greater than about 40 while maintaining said reaction medium at a workable viscosity: and (d) causing polymerization of said at least one monomer at a temperature sufficient to effect formation of a polymeric composition that is homo-oligomeric. co-polymeric, or block polymeric. 4. The process of claim 3. wherein said at least one monomer comprises an initially present first monomer selected from the group consisting of 2.5-diamino-1.4-benzenedithiol dihydrochloride. -129- 4,6-diamino-1.3-benzenediol dihydrochloride. 1.2.4,5-tetraminobenzene tetrahydrochloride. 3.3--dimercaptobenzidine dihydrochloride. 3.3'-dihydroxybenzidine dihydrochloride, 3,3'-diamino-4.4'-dihydroxybiphenyl dihydrochloride, 3,3'-diaminobenzidine tetrahydrochloride dihydrate, 2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochloride. 3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoic acid hydrochloride, 4,5-diaminonaphthalene-l,8-dicarboxylic anhydride, 2,3.7.8-tetrahydroxγ-l.4.6.9-tetraazaanthracene. 2,2' ,3,3'-tetrahydroxy-6.6'-biquinoxaline. 2.3-dihydroxy-6.7-diaminoquinoxaline dihydrochloride, 3.3'-dimercapto-4.4'-diaminodiphenyl ether dihydrochloride. 3.3' .4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3'-dihγdroxγ-4.4'-diaminodiphenyl ether, 2.3.5,6-tetraaminopyridine trihydrochloride. 1.5-diamino-2,6-naphthalenedithiol dihydrochloride, l.5-diamino-2.6-naphthalenediol dihydrochloride, 1,2,5,6- etraaminonaphthalene tetrahydrochloride, 3,3'-dimercapto-4.4'-diaminodiphenyl ether dihydrochloride, 3.3' .4.4'-tetraaminodiphenyl ether tetrahydrochlorid'e, 3.3'-dihydroxy-4.4'-dihydroxydiphenyl ether. 3,3' .4,4'-tetraaminodiphenyl sulfone. 3.3'-dimercapto-4.4' -diaminodiphenyl sulfone. 3,3'-diamino-4. '-dihydroxydiphenyl sulfone. 3.3' ,4'-tetraaminobenzophenone, 3,6-diamino-1.2-benzenedithiol dihydrochloride. 3-mercapto-4-aminobenzoic acid hydrochloride. 3-mercapto-4-aminobenzoic acid and 3,4-diaminobenzoic acid. -130- 5. The process of claim 4. wherein said at least one monomer further comprises a second monomer added after said admixing step and prior to said heating step, said second monomer selected from the group consisting of terephthalic acid, terephthaloyl chloride, terephthalonitrile, trans-1.4-cyclohexanedicarboxylic acid, 2,5-pyridinedicarboxylic acid. 4.4'-biphenyldicarboxylic acid. 4.4'-biphenyldicarboxylic acid chloride. 2.6-naphthalenedicarboxylic acid, 3.3'-biphenyldicarboxylic acid, trans-1.2-cyclohexanedicarboxylic acid. 1,4-bis(5-carboxybenzoxazole-2-yl)benzene, 2.5-bis(6-carboxybenzothiazole-2-yl)pyridine. isophthalic acid. 4, '-dicarboxydiphenyl ether. 3.3'-dicarboxydiphenyl ether, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid. pyromellitic dianhydride and 1,4,5,8-naphthalenetetracarboxylie dianhydride. 6. The process of claim 3, wherein said final phosphorus pentoxide concentration is between about 80.5% and 86% by weight. 7. The process of claim 3, wherein said removal of oxidation protecting moieties is conducted at a temperature of less than about 100°C, 8. The process of claim 3. wherein siad polymerization is effected at a temperature between about 100°C and 220°C. 9. The process of claim 3. further including spinning said polymeric composition through an air-gap -131- having a separation distance of from about 1 cm to 100 cm and into a coagulation bath, whereby a fiber is formed. 10. The fiber produced by the process of claim 9. 11. The process of claim 3.. further including extruding said polymeric composition into a coagulation bath thereby forming a film. 12. The film produced by the process of claim 11. 13. A liquid crystalline polymer made by the process of claim 3. 14. A composite article comprising a resinous matrix reinforced with the liquid crystalline polymer of claim 13.

Inventors: SYBERT JOANNE R, SYBERT PAUL D, WILSON BLAKE, WOLFE JAMES F, SYBERT, JOANNE, R., SYBERT, PAUL, D., WILSON, BLAKE, WOLFE, JAMES, F.
Applicants: COMMTECH INT, COMMTECH INTERNATIONAL
Application year: 1986
Main classification: C08G69
IPC codes: C08G73, C08G75, C08J5, C08L79, D01F6