Claims
- 1. In 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, the improvement comprises the following steps:
- (a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABEFG of FIG. 16, said concentration of monomer(s) being present in said reaction medium in sufficient amounts to achieve a polymer concentration greater than about 10 percent by weight based on the total weight of said composition;
- (b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 16.
- 2. In 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, the improvement comprises the following steps:
- (a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid having a phosphorus pentoxide content of at least about 80 percent by weight based on the total weight of said strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABEFG of FIG. 17, said concentration of monomer(s) in said reaction medium being present in sufficient amounts to achieve a polymer concentration greater than about 10 percent by weight based on the total weight of said composition;
- (b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 17.
- 3. In 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, the improvement comprises the following steps:
- (a) preparing a reaction medium suitable for polymerization by incorporating a high concentration of one or more of a selected monomer(s) in a substantially non-oxidizing strong acid having a phosphorus pentoxide content of at least about 85 percent by weight based on the total weight of said strong acid, said reaction medium being prepared at a preselected surface-to-volume ratio greater than about 0.2 cm.sup.-1 and substantially within the shaded phosphorus pentoxide content profile area bounded by ABFG of FIG. 18, said monomer(s) in said reaction medium being present in sufficient polymerizable concentration so as to produce a liquid crystalline polymer phase in said composition;
- (b) conducting polymerization of said monomer(s) substantially within the shaded phosphorus pentoxide content profile area bounded by BCDE of FIG. 18.
- 4. A process according to claim 1 wherein said polymerization is conducted under conditions to exercise control of molecular weight
- (a) by the addition of one or more suitable monofunctional reactants in selected amounts and at a selected stage of polymerization,
- (b) by off-balancing the stoichiometric proportion of monomers at a selected stage of polymerization, or
- (c) by discontinuing said polymerization at a selected degree of polymerization.
- 5. A process according to claim 2 or 3, wherein said polymerization is conducted under conditions to exercise control of molecular weight
- (a) by the addition of one or more suitable monofunctional reactants in selected amounts and at a selected stage of polymerization,
- (b) by off-balancing the stoichiometric proportion of monomers at a selected stage of polymerization, or
- (c) by discontinuing said polymerization at a selected degree of polymerization.
- 6. In 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, the improvement comprises the following steps:
- (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 preselected 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 simultaneously 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 temperature(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.sup.-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:
- (1g) 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 (1g) 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 (1g) 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.
- 7. A process according to claim 6 wherein said selected first monomer is selected from the group consisting of:
- 2,5-diamino-1,4-benzenedithiol dihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzene 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-1,8-dicarboxylic anhydride, 2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene, 2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline, or 2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride.
- 8. A process according to claim 6 wherein said selected second monomer is selected from the group consisting of:
- terephthalic acid, terephthaloyl chloride, terephthalonitrile, or trans-1,4-cyclohexanedicarboxylic acid.
- 9. A process according to claim 6 wherein said selected first monomer is selected from the group consisting of:
- 2,5-diamino-1,4-benzenedithiol dihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzene 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 dihydrochoride, 3-hydroxy-4-aminobenzoic acid hydrochloride, 3-amino-4-hydroxybenzoic acid hydrochloride, 3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 2,3,5,6-tetraaminopyridine trihydrochloride, 1,5-diamino-2,6-naphthalenedithiol dihydrochloride, 1,5-diamino-2,6-naphthalenediol dihydrochloride, 1,2,5,6-tetraminonaphthalene tetrahydrochloride, 3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3',4,4'-tetraaminodiphenyl sulfone, 3,3'-dimercapto-4,4'-diaminodiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3',4,4'-tetraaminobenzophenone, 3,6-diamino-1,2-benzenedithiol dihydrochloride, 3-mercapto-4-aminobenzoic acid hydrochloride, 3-mercapto-4-aminobenzoic acid, or 3,4-diaminobenzoic acid.
- 10. A process according to claim 6 wherein said selected second monomer is 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, 4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenyl ether, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, pyromellitic dianhydride, or 1,4,5,8-naphthalenetetracarboxylic dianhydride.
- 11. A process according to claim 6 wherein said selected first monomer is selected from the group consisting of:
- 2,5-diamino-1,4-benzenedithiol dihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzene 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-1,8-dicarboxylic anhydride, 2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene, 2,2',3,3'-tetrahydroxy-6,6'biquinoxaline, 3-mercapto-4-aminobenzoic acid hydrochloride, 3-mercapto-4-aminobenzoic acid, or 2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride.
- 12. A process according to claim 6, wherein said phosphorus pentoxide in said preliminary solvent is present in an amount at least above about 80% by weight.
- 13. A process according to claim 6 wherein said selected first monomer of said second homo-oligomeric product is selected from the group consisting of:
- 2,5-diamino-1,4-benzenedithiol dihydrochloride, 4,6-diamino-1,3-benzenediol dihydrochloride, 1,2,4,5-tetraaminobenzene 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, 3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 2,3,5,6-tetraaminopyridine trihydrochloride, 1,5-diamino-2,6-naphthalenedithiol dihydrochloride, 1,5-diamino-2,6-naphthalenediol dihydrochloride, 1,2,5,6-tetraminonaphthalene tetrahydrochloride, 3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride, 3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3',4,4'-tetraaminodiphenyl sulfone, 3,3'-dimercapto-4,4'-diaminodiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3',4,4'-tetraaminobenzophenone, 3,6-diamino-1,2-benzenedithiol dihydrochloride, 3-mercapto-4-aminobenzoic acid hydrochloride, 3-mercapto-4-aminobenzoic acid, or 3,4-diaminobenzoic acid.
- 14. A process according to claim 6, wherein said selected second monomer of said second homo-oligomeric product is selected from the group consisting of:
- terephthalic acid, terephthaloyl chloride, 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, 4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenyl ether, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, pyromellitic dianhydride, or 1,4,5,8-naphthalenetetracarboxylic dianhydride.
- 15. A process according to claim 6, wherein said selected first monomer is 2,5-diamino-1,4-benzenedithiol dihydrochloride or 4,6-diamino-1,3-benzenediol dihydrochloride.
- 16. A process according to claim 6, wherein said selected first monomer is 3-amino-4-hydroxy benzoic acid hydrochloride or 3-mercapto-4-aminobenzoic acid hydrochloride.
- 17. A process according to claim 6, wherein said phosphorus pentoxide in said preliminary solvent is present in an amount between about 63% and 88% by weight.
- 18. A composition prepared by the process of claim 6, wherein said composition is characterized as having a total polymer concentration of at least about 10% by weight based on the total weight of said composition.
- 19. A process according to claim 6, wherein said phosphorus pentoxide content of said first homo-oligomeric product, said first co-oligomeric product, said second homo-oligomeric product, said second co-oligomeric product, said first block-oligomeric product, or said first blockpolymeric product formed by said polymerization reaction is between about 80.5% and about 86% by weight.
- 20. A process according to claim 6, wherein said phosphorus pentoxide content of said first homo-oligomeric product, said first co-oligomeric product, said second homo-oligomeric product, said second co-oligomeric product, said first block-oligomeric product, or said first blockpolymeric product formed by said polymerization reaction is between about 80.5% and about 84% by weight.
- 21. A process according to claim 6 further comprising spinning said first homo-oligomeric product, said first co-oligomeric product, said first homo-polymeric product, said first copolymeric product, said second homo-oligomeric product, said second co-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product through an air-gap and into a coagulation bath thereby forming a fiber.
- 22. A process according to claim 6, further comprising extruding said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said second homo-oligomeric product, said second co-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product into a coagulation bath thereby forming a film.
- 23. A process according to claim 6, further comprising extruding said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said second homo-oligomeric product, said second co-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product into a coagulation bath thereby forming an article.
- 24. A process according to claim 1 or 5 further comprising extruding said liquid crystalline extended chain polymer composition through an air-gap and into a coagulation bath thereby forming a film.
- 25. A process according to claim 21 wherein said spinning is conducted at an initial draw ratio of from about 5:1 to about 50:1.
- 26. A process according to claim 21, wherein said spinning is conducted at a temperature between about 60.degree. C. to about 200.degree. C.
- 27. A process according to claim 21, wherein said spinning is conducted through an air-gap separation distance of from about 1 cm to about 100 cm before allowing said fiber to enter into a coagulation bath.
- 28. A process according to claim 6, wherein said composition is characterized as having a total polymer concentration of at least about 14% by weight based on the total weight of said composition.
- 29. A process according to claim 6, wherein said composition is characterized as having a total polymer concentration of at least about 10% by weight based on the total weight of said composition.
- 30. A process according to claim 6, wherein said phosphorus pentoxide in said preliminary solvent is present in an amount between about 80% and 88% by weight.
- 31. A process according to claim 6, wherein said phosphorus pentoxide in said preliminary solvent is present in an amount at least about 85% by weight.
- 32. A process according to claim 6 further comprising spinning said first homo-oligomeric product, said first co-oligomeric product, said first homo-polymeric product, said first copolymeric product, said second homo-oligomeric product, said second co-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product through an air-gap and into a coagulation bath thereby forming a fiber.
- 33. A process according to claim 6, wherein a selected weight in grams, a* of said preliminary solvent of a substantially non-oxidizing strong acid having a substantially high phosphorus pentoxide content, P.sub.i, is added in accordance with the empirical equation:
- a*={[1-P.sub.f] ([P.sub.y /P.sub.c ]-P.sub.y)-[n.sub.o (18.02)/M.sub.w ]P.sub.y }(1-P.sub.i).sup.-1
- where P.sub.y =weight in grams of a predetermined theoretical yield of said extended chain homopolymer, copolymer, or blockpolymer;
- P.sub.c =preselected weight fraction of said extended chain homopolymer, copolymer, or blockpolymer of the total weight of said first homopolymeric product, said first copolymeric product, or said first block-polymeric product following polymerization;
- n.sub.o =integer number of moles of polycondensation by-product per moles of repeating unit of said extended chain homopolymer, copolymer, or blockpolymer;
- 18.02=molecular weight of polycondensation by-product;
- M.sub.w =molecular weight of said extended chain homopolymer, copolymer, or blockpolymer recurring unit; and
- P.sub.f =preselected phosphorus pentoxide content of said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said second homo-oligomeric product, said second co-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product,
- said P.sub.f being achieved by incorporating a selected intermediate weight in grams, b* of phosphorus pentoxide in said increasing phosphorus pentoxide content step forming said first monomer reaction medium, said first and second monomer reaction medium, said monomer-oligomer reaction medium, or said first oligomer-monomer reaction medium of greater phosphorus pentoxide content in accordance with the empirical equation:
- b*=[P.sub.y /P.sub.c ]-P.sub.y -[{n.sub.o (18.02)/M.sub.w }]P.sub.y -a*.
- 34. A crystalline polymer composition prepared by the process of claim 6, wherein said polymer composition is characterized as having a molecular weight with an n value corresponding to an intrinsic viscosity of at least about 7 dL/g as determined in methanesulfonic acid at 30.degree. C.
- 35. An article formed from the liquid crystalline polymer composition prepared by the process of claim 6 in admixture with a flexible aromatic heterocyclic polymer.
- 36. A process according to claim 6 further comprising spinning said liquid crystalline extended chain polymer composition through an air-gap and into a coagulation bath thereby forming a fiber.
- 37. A process according to claim 6 further comprising extruding said liquid crystalline extended chain polymer composition through an air-gap and into a coagulation bath thereby forming a film.
- 38. A process according to claim 6, wherein said phosphorus pentoxide in said preliminary solvent is present in an amount at least about 85% by weight.
- 39. A process according to claim 6, wherein said removal of volatilized protecting atoms or groups is conducted at a temperature less than about 100.degree. C.
- 40. A process according to claim 6, wherein said polymerization reaction is conducted at a temperature within the range of from about 100.degree. C. to about 220.degree. C.
- 41. A process according to claim 6, wherein said polymerization is conducted at a temperature of from about 100.degree. C. to greater than about 185.degree. C.
- 42. A process according to claim 6 wherein said polymerization is conducted under conditions to exercise control of molecular weight:
- (j) by 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 said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, or said second homo-oligomeric product following polymerization steps (e), (f) and (3g) having a predetermined intrinsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both said selected first and second monomers;
- (k) by 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 said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, or said second homo-oligomeric product following polymerization steps (e), (f) and (3g) having a predetermined intrinsic viscosity less than the maximum attainable for a stoichiometric equivalent amount of both said selected first and second monomers;
- (l) by adding one or more of a selected mono-functional reactants at a selected step following step (b) or (d) and prior to forming said first homopolymeric product or said copolymeric product so as to provide said first homo-oligomeric product, said first co-oligomeric product, said first homo-polymeric product, said first copolymeric product, or said second homo-oligomeric product following polymerization steps (e), (f) and (3g) having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants; or
- (m) by adding one or more of a selected mono-functional reactants prior to end of polymerization in step (i) so as to provide said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product having a predetermined intrinsic viscosity less than the maximum attainable in the absence of said selected monofunctional reactants;
- (n) spinning said first homo-oligomeric product, said first co-oligomeric product, said first homopolymeric product, said first copolymeric product, said second homo-oligomeric product, said poly-oligomeric product, said first block-oligomeric product or said first block-polymeric product of step (j), (k), (l), or (m) through an air-gap and into a coagulation bath thereby forming a fiber.
- 43. A process according to claim 42 wherein said selected monofunctional reactant is selected from the group consisting of:
- 2-aminothiophenol, o-aminophenol, o-phenylenediamine, benzoic acid, acetic acid, phthalic anhydride, 2,3-diaminopyridine, 4-amino-3-mercaptobiphenyl, 3-amino-4-hydroxybiphenyl, 1-amino-2-naphthalenethiol, 1-amino-2-naphthol, 2,3-diaminonaphthalene, 3,4-diaminobenzophenone, benzoyl chloride, benzonitrile, cyclohexanecarboxylic acid, cyclohexanecarboxylic acid chloride, picolinic acid, 4-biphenylcarboxylic acid, 2-naphthoic acid, acetyl chloride, propionic acid, n-butyric acid, valeric acid, caproic acid, or 1,8-naphthalic anhydride.
- 44. A process according to claim 38 wherein said selected mono-functional reactant is selected from the group consisting of:
- 2-aminothiophenol, o-aminophenol, o-phenylenediamine, benzoic acid, acetic acid, or phthalic anhydride.
- 45. A crystalline polymer composition prepared by the process of claim 6 in the form of a fiber, film, or fibrids.
- 46. An article comprising a crystalline polymer composition prepared by the process of claim 6 in a resinous matrix.
- 47. A crystalline polymer made by the process of claim 6.
- 48. A composition article comprising a resinous matrix reinforced with the crystalline polymer of claim 47.
- 49. An extended chain crystalline polymer composition prepared by the process of claim 1, 5, or 6 selected from the group consisting of a homopolymer, a copolymer, or a block polymer, said homopolymer having the formulas: ##STR783## wherein Ar.sup.1 is ##STR784## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR785## n being a positive integer; ##STR786## wherein Ar.sup.3 is ##STR787## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of each hetero ring are disposed ortho to one another, n being a positive integer; ##STR788## wherein Ar.sup.1 is ##STR789## and Ar.sup.4 is ##STR790## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1 and the carbon atoms being bonded to aromatic carbon atoms of Ar.sup.4, n being a positive integer; ##STR791## wherein Ar.sup.5 is ##STR792## the nitrogen atoms being bonded to Ar.sup.5, n being a positive integer; ##STR793## wherein Ar.sup.6 is ##STR794## Ar.sup.1 is ##STR795## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.1, NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, n being a positive integer; ##STR796## wherein Ar.sup.9 is ##STR797## X.sub.4 is sulfur, oxygen, or NR (R being hydrogen or an aromatic group), the NH group and X.sub.4 being bonded to aromatic carbon atoms of Ar.sup.9, n being a positive integer; ##STR798## wherein Ar.sup.1 is ##STR799## Y.sup.7 is ##STR800## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1 and bonded to adjacent carbon atoms of Y.sup.7, n being a positive integer; or ##STR801## wherein Ar.sup.1 is ##STR802## Y.sup.8 is ##STR803## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1 and adjacent carbon atoms of Y.sup.8, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, n being a positive integer; wherein said I, II, III, IV, V, VI, VII, and VIII polymers are characterized as having a molecular weight with an n value corresponding to an intrinsic viscosity of at least about 7 dL/g as determined in methanesulfonic acid at 30.degree. C., with the proviso that when said polymer is poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene) that the molecular weight of said poly([benzo-(1,2-d:4,5-d')bisthiazole-2,6-diyl]-1,4-phenylene correspond to an intrinsic viscosity greater than 30.3 dL/g as determined in methanesulfonic acid at 30.degree. C.; said copolymer having the formulas: ##STR804## wherein Ar.sup.1 is ##STR805## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR806## a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; ##STR807## wherein Ar.sup.1 is ##STR808## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group) the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR809## a.sub.i b.sub.j /m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, Ar.sup.3 is ##STR810## the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.k represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; ##STR811## wherein Ar.sup.3 is ##STR812## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of the hetero ring are disposed ortho to one another, c.sub.k represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.k represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; ##STR813## wherein Ar.sup.1 is ##STR814## Ar.sup.4 is ##STR815## the nitrogen atoms being bonded to Ar.sup.1 and the carbon atoms being bonded to Ar.sup.4, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; ##STR816## wherein Ar.sup.4 is ##STR817## Ar.sup.1 is ##STR818## and Ar.sup.5 is ##STR819## the carbon atoms being bonded to Ar.sup.4 and Ar.sup.5 and the nitrogen atoms being bonded to Ar.sup.1 and Ar.sup.5, n being a positive integer; c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.k represents an average number of the respective different sequential recurring units present in said copolymer, a.sub.i b.sub.j m/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; ##STR820## wherein Ar.sup.1 is ##STR821## Ar.sup.6 is ##STR822## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an oranic group), the NH groups and X.sub.1 and X.sub.2 being bonded to NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units represent in said copolymer, n being a positive integer; ##STR823## wherein Ar.sup.6 is ##STR824## Ar.sup.1 is ##STR825## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.1, NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, a.sub.i b.sub.j m/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, Ar.sup.9 is ##STR826## X.sub.4 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH group and X.sub.4 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.9, c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.k represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; or ##STR827## wherein Ar.sup.1 is ##STR828## Y.sup.7 is ##STR829## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1 and bonded to adjacent carbon atoms of Y.sup.7, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said copolymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said copolymer, n being a positive integer; wherein said copolymers X, XI, XII, XV, XVI, XVII, and XVIII are characterized as having a molecular weight with an n value corresponding to an intrinsic viscosity of at least about 5 dL/g as determined in methanesulfonic acid at 30.degree. C. with the proviso that when said copolymer is IX that the molecular weight of said copolymer IX corresponds to an intrinsic viscosity greater than 16 dL/g as determined in methanesulfonic acid at 30.degree. C.; said block polymer having the formulas: ##STR830## wherein Ar.sup.1 is ##STR831## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR832## a.sub.1 b.sub.j reprersents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR833## wherein Ar.sup.3 is ##STR834## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of each hetero ring are disposed ortho to one another, c.sub.k represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.k represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR835## wherein Ar.sup.1 is ##STR836## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR837## a.sub.i b.sub.j m/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, Ar.sup.3 is ##STR838## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of each hetero ring are disposed ortho to one another, c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.k represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR839## wherein Ar.sup.1 is ##STR840## Ar.sup.4 is ##STR841## the nitrogen atoms being bonded to Ar.sup.1 and the carbon atoms being bonded to Ar.sup.4, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR842## wherein Ar.sup.1 is ##STR843## when bonded to nitrogen atoms; and when Ar.sup.1 is bonded to both nitrogen atoms and X.sub.1 and X.sub.2, Ar.sup.1 is ##STR844## Ar.sup.4 is ##STR845## the nitrogen atoms being bonded to Ar.sup.1 and the carbon atoms being bonded to Ar.sup.4, m'/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y' represents an average number of the respective different sequential recurring units present in said block polymer, X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atoms and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.1, N and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another and Y.sup.2 is nil or is ##STR846## m/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR847## wherein Ar.sup.3 is ##STR848## X.sub.3 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the nitrogen atom and X.sub.3 being bonded to aromatic carbon atoms of Ar.sup.3, N and X.sub.3 of the hetero ring are disposed ortho to one another, p represents the molar proportions of the respective different recurring units present in said block polymer, y'/2 represents an average number of the respective different sequential recurring units present in said block polymer, Ar.sup.1 is ##STR849## Ar.sup.4 is ##STR850## the nitrogen atoms being bonded to Ar.sup.1 and the carbon atoms being bonded to Ar.sup.4, q represents the molar proportions of the respective different recurring units present in said block polymer, y represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR851## wherein Ar.sup.4 is ##STR852## Ar.sup.1 is ##STR853## and Ar.sup.5 is ##STR854## the carbon atoms being bonded to Ar.sup.4 and Ar.sup.5, and the nitrogen atoms being bonded to Ar.sup.1 and Ar.sup.5, n being a positive integer; c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.k represents an average number of the respective different sequential recurring units present in said block polymer, a.sub.i b.sub.j m/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR855## wherein Ar.sup.1 is ##STR856## Ar.sup.6 is ##STR857## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.1, NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; ##STR858## wherein Ar.sup.1 is ##STR859## Ar.sup.6 is ##STR860## X.sub.1 and X.sub.2 are the same or different and are sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.1 and X.sub.2 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.1, NH and X.sub.1 or X.sub.2 of each hetero ring are disposed ortho to one another, a.sub.i b.sub.j m/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, Ar.sup.9 is ##STR861## X.sub.4 is sulfur, oxygen, or NR (R being hydrogen or an organic group), the NH groups and X.sub.4 being bonded to aromatic carbon atoms of Ar.sup.6 and Ar.sup.9, c.sub.k m'/m+m' represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.k represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer; or ##STR862## wherein Ar.sup.1 is ##STR863## Y .sup.7 is ##STR864## the nitrogen atoms being bonded to aromatic carbon atoms of Ar.sup.1, and bonded to adjacent carbon atoms of Y.sup.7, a.sub.i b.sub.j represents the molar proportions of the respective different recurring units present in said block polymer, y.sub.ij represents an average number of the respective different sequential recurring units present in said block polymer, n being a positive integer.
- 50. A polymer composition prepared by the process of claim 7 wherein said polymer is ##STR865##
- 51. A polymer composition prepared by the process of claim 50 wherein said polymer has an intrinsic viscosity of from about 15 dL/g to about 48 dL/g.
- 52. A polymer composition prepared by the process of claim 7 wherein said polymer is ##STR866##
- 53. A polymer composition prepared by the process of claim 52 wherein said polymer has an intrinsic viscosity of from about 9 dL/g to about 24 dL/g.
- 54. A polymer composition prepared by the process of claim 7 wherein said polymer is ##STR867##
- 55. A polymer composition prepared by the process of claim 54 wherein said polymer has an intrinsic viscosity of about 15 dL/g.
- 56. A polymer composition prepared by the process of claim 7 wherein said polymer is ##STR868##
- 57. A polymer composition prepared by the process of claim 52 wherein said polymer has an intrinsic viscosity of about 12 dL/g.
- 58. A polymer composition prepared by the process of claim 7 wherein said polymer is ##STR869##
- 59. A polymer composition prepared by the process of claim 58 wherein said polymer has an intrinsic viscosity of about 12 dL/g.
- 60. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR870##
- 61. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR871##
- 62. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR872##
- 63. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR873##
- 64. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR874##
- 65. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR875##
- 66. A polymer composition prepared by the process of claim 9 wherein said polymer contains the moiety ##STR876##
- 67. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR877##
- 68. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR878##
- 69. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR879##
- 70. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR880##
- 71. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR881##
- 72. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR882##
- 73. A polymer composition prepared by the process of claim 11 wherein said polymer contains the moiety ##STR883##
- 74. A composition prepared by the process of claim 49, wherein said extended chain polymer includes at least one homopolymer having the formula: ##STR884##
- 75. A composition prepared by the process of claim 49, wherein said extended chain polymer includes at least one homopolymer having the formula: ##STR885##
- 76. A composition prepared by the process of claim 49, wherein said extended chain polymer includes at least one homopolymer having the formula: ##STR886##
- 77. A composition prepared by the process of claim 49, wherein said extended chain polymer includes at least one homopolymer having the formula: ##STR887##
- 78. A composition prepared by the process of claim 49, wherein said extended chain polymer includes at least one homopolymer having the formula: ##STR888##
- 79. A composition prepared by the process of claim 49, wherein said extended chain polymer present is characterized as having a molecular weight corresponding to an intrinsic viscosity of at least about 12 dL/g as determined in methanesulfonic acid at 30.degree. C.
- 80. A polymer composition prepared by the process of claim 53 wherein said polymer ##STR889##
- 81. A polymer composition prepared by the process of claim 80 wherein said polymer has an intrinsic viscosity of from about 15 dL/g to about 42 dL/g.
- 82. The polymer of claim 80 having an intrinsic viscosity of from about 20 dL/g to about 25 dL/g.
- 83. A polymer composition prepared by the process of claim 49 wherein said polymer is ##STR890##
- 84. A polymer according to claim 83 wherein said polymer has an intrinsic viscosity of from about 9 dL/g to about 24 dL/g.
- 85. The polymer of claim 83 having an intrinsic viscosity of from about 18 dL/g to about 23 dL/g.
- 86. A polymer composition prepared by the process of claim 49 wherein said polymer is ##STR891##
- 87. A polymer composition according to claim 86 wherein said polymer has an intrinsic viscosity of about 12 dL/g.
- 88. A polymer composition according to claim 82 having an intrinsic viscosity of from about 13 dL/g to about 17 dL/g.
- 89. A polymer according to claim 49 wherein said polymer is ##STR892##
- 90. A polymer composition according to claim 89 wherein said polymer has an intrinsic viscosity of about 12 dL/g.
- 91. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR893##
- 92. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR894##
- 93. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR895##
- 94. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR896##
- 95. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR897##
- 96. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR898##
- 97. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR899##
- 98. A polymer composition prepared by the process of claim 49 wherein said polymer contains the moiety ##STR900##
- 99. A polymer composition prepared by the process of claim 49 wherein said polymer is ##STR901##
- 100. A polymer polymerized in the presence of a selected monofunctional reactant composition prepared by the process of claim 99 wherein said polymer has an intrinsic viscosity of from about 11 dL/g to about 16 dL/g.
- 101. A crystalline polymer made by the process of claim 6 wherein said polymer contains one or more phenyl, pyridyl, or methyl organic substituent group.
- 102. A process according to claim 53 wherein said phosphorus pentoxide content of step (d) is increased by adding phosphorus pentoxide in two or more portions to provide said monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization.
- 103. A process according to claim 6 wherein said strong acid is polyphosphoric acid.
- 104. A process according to claim 6 wherein said strong acid is methanesulfonic acid.
- 105. A process for preparing a liquid crystalline extended chain block polymer composition of workable viscosity which is useful in the production of fibers and films comprising the following steps:
- (a) mixing at least one of a selected first homo- or hetero-bifunctional monomer with or without oxidation protecting atoms or groups with a preliminary solvent of a substantially non-oxidizing strong acid having a preselected phosphorus pentoxide content,
- (b) heating and optionally placing the resulting mixture under reduced pressure to promote the removal 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 temperature(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.sup.-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) to 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 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,
- (e) causing polymerization of the first or the first and second monomer at a temperature sufficient to effect reaction at a rate to form a first homo-oligomeric product or a first co-oligomeric product having a preselected intrinsic viscosity, or
- (f) 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:
- (1f) adding at least one of a selected second monomer 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 monomer in the preliminary solvent,
- (2f) then adjusting the phosphorus pentoxide content of the mixture resulting from step (b) or (1f) to provide a first or a first and second monomer reaction medium of greater phosphorus pentoxide content suitable for polymerization,
- (3f) 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 (1f) which forms the second homo-oligomeric product be different from at least one of the selected monomer of step (a) or (c) which forms the first homo-oligomeric product, or
- (g) 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(s) of step (a) or (c) which forms the first or first and second monomer 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,
- (h) causing polymerization of the poly-oligomeric product resulting from step (f) or the monomer-oligomer resulting from step (g) at a temperature sufficient to effect reaction at a rate to form a first block-oligomeric product having a preselected intrinsic viscosity or a first block-polymeric product.
- 106. A process according to claim 1, 2, 3, 33 or 105 wherein said strong acid is polyphosphoric acid.
- 107. A process according to claim 1, 2, 3, 33 or 105 wherein said strong acid is methanesulfonic acid.
- 108. A process according to claim 1, 2, 3, 33 or 105 wherein said strong acid is methanesulfonic acid, polyphosphoric acid, or an admixture thereof.
- 109. A process according to claim 6 wherein said strong acid is methanesulfonic acid, polyphosphoric acid, or an admixture thereof.
- 110. An article made from the polymer composition prepared by the process of claim 6.
- 111. An article specified in claim 110 wherein said article is selected from the group consisting of flywheels, radomes, engine parts, housings, moldings, tires, belts, fishing rods, tennis racquets, skis, ski poles, bicycle frames, boat hulls, ropes, cloths, protective clothing, helmets, cables, and composites.
- 112. A fiber spun according to the process of claim 21.
- 113. The fiber of claim 112 being characterized as having a tensile strength greater than 1.37 GPa.
- 114. A crystalline polymer composition prepared by the process of claim 49 wherein said organic group is phenyl, pyridyl or methyl.
REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of application Ser. No. 616,469 filed Sept. 15, 1983 now issued as U.S. Pat. No. 4,533,693, originally filed as PCT application No. PCT/US83/01437 on Sept. 15, 1983 and published as W0 84/01162 on Mar. 29, 1984. Ser. No. 616,469 in turn is a continuation-in-part of Ser. No. 433,831 filed as PCT 83/012285 Sept. 17, 1982, now U.S. Pat. No. 4,533,692, published as W0 84/01160 on Mar. 29, 1984, Section 102(e) date Sept. 17, 1982.
ORIGIN OF INVENTION
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, F49620-83-K-0036, and/or F33615-84-C-5005 awarded by the United States Air Force. The Government has certain rights in this invention.
US Referenced Citations (14)
Foreign Referenced Citations (2)
Number |
Date |
Country |
1363757 |
May 1964 |
FRX |
4219270 |
Jul 1964 |
JPX |
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Entry |
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Continuation in Parts (2)
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Number |
Date |
Country |
Parent |
616469 |
Sep 1983 |
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Parent |
433831 |
Sep 1982 |
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