Process for the production of polyarenazole polymer
View Patent ↗The present invention concerns a process for making a polyareneazole polymer comprising the steps of: a) contacting azole-forming monomers, metal powder, and optionally P 2 O 5 , in polyphosphoric acid to form a mixture; b) blending the mixture at a temperature of from about 50° C. to about 110° C.; c) further blending the mixture at a temperature of up to about 145° C. to form a solution comprising an oligomer; d) optionally, degassing the solution; and e) reacting the oligomer solution at a temperature of about 160° C. to about 250° C. for a time sufficient to form a polymer.
1. A process for making a polyareneazole polymer, comprising the steps of:
a) contacting areneazole-forming monomers, metal powder, and optionally P 2 O 5 , in polyphosphoric acid to form a mixture; wherein the metal powder is iron powder and wherein said mixture comprises 0.1 to 0.5 wt % iron based on the weight of said monomers;
b) blending the mixture at a temperature of from about 50° C. to about 110° C.;
c) further blending the mixture at a temperature of up to about 145° C. to form a solution comprising an oligomer;
d) optionally, degassing the solution; and
e) reacting the oligomer solution at a temperature of about 160° C. to about 250° C. for a time sufficient to form a polymer.
2. The process of claim 1 wherein the areneazole-forming monomers include 2,5-dimercapto-p-phenylene diamine, terephthalic acid, bis-(4-benzoic acid), oxy-bis-(4-benzoic acid), 2,5-dihydroxyterephthalic acid, isophthalic acid, 2,5-pyridodicarboxylic acid, 2,6-napthalenedicarboxylic acid, 2,6-quinolinedicarboxylic acid, 2,6-bis(4-carboxyphenyl) pyridobisimidazole, 2,3,5,6-tetraaminopyridine, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, 2,5-diamino-4,6-dithiobenzene, or any combination thereof.
3. The process of claim 1 wherein the areneazole-forming monomers are 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid.
4. The process of claim 3 wherein the areneazole-forming monomers are in the form of a complex of 2,3,5,6-tetraaminopyridine and 2,5-dihydroxyterephthalic acid.
5. The process of claim 1 wherein step a) further comprises a chain terminator for the polymer.
6. The process of claim 5 wherein the chain terminator is benzoic acid, phenyl benzoate, or orthophenylene diamine.
7. The process of claim 1 wherein the polyphosphoric acid has an equivalent P 2 O 5 content of at least about 81 percent after polymerization.
8. The process of claim 1 wherein the polyphosphoric acid has an equivalent P 2 O 5 content of at least about 82 percent after polymerization.
9. The process of claim 1 wherein step c) is performed in a controlled shear environment.
10. The process of claim 9 wherein the controlled shear environment is one or more static mixers.
11. The process of claim 9 wherein the controlled shear environment is an extruder.
12. The process of claim 1 wherein phosphoric acid is added to the solution after step c).
13. The process of claim 12 wherein the phosphoric acid is superphosphoric acid or polyphosphoric acid.
14. The process of claim 11 wherein the shear rate imparted in the controlled shear environment in step c) is up to 8 reciprocal seconds.
15. The process of claim 1 wherein the temperature in step e) is from about 180° C. to about 200° C.
16. The process of claim 1 wherein the time in step e) is from about 1 to about 6 hours.
17. The process of claim 1 wherein step e) comprises a plurality of reaction steps, each step having an increasing temperature.
18. The process of claim 1 wherein the solution in step e) has a percent solids concentration of about 10 to about 21 percent by weight.
19. The process of claim 1 further comprising the step:
f) spinning a filament from the solution comprising polymer of step e).