Processes for increasing polymer inherent viscosity
View Patent ↗Disclosed are processes for preparing polyareneazole polymers including contacting a molar excess of a free base in water with a terephthalic acid salt to form an aqueous mixture, adjusting the pH to precipitate a monomer complex, contacting the monomer complex with metal powder, and polymerizing the monomer complex. Polyareneazoles, filaments and yarns are also disclosed.
1. A process for preparing a poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d′]bisimidazole polymer comprising:
contacting a molar excess of a 2,3,5,6-tetraamino pyridine free base in water with a 2,5-dihydroxy terephthalic acid salt to form an aqueous mixture,
adjusting the pH of the aqueous mixture to within the range of from about 3 to about 5 to precipitate a monomer complex composed of 2,3,5,6-tetraamino pyridine and 2,5-dihydroxy terephthalic acid monomers,
contacting, in polyphosphoric acid, the monomer complex with about 0.05 to about 0.9 weight percent metal powder based on the total weight of the monomers, and
polymerizing the monomer complex in polyphosphoric acid to form the polymer.
2. The process of claim 1 wherein the molar ratio of the 2,3,5,6-tetraamino pyridine to the 2,5-dihydroxy terephthalic acid monomers is in excess of about 1.05 to 1.
3. The process of claim 1 wherein the pH is adjusted by adding orthophosphoric acid to the aqueous mixture.
4. 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.
5. The process of claim 1 wherein the metal powder comprises iron powder, tin powder, vanadium powder, chromium powder, or any combination thereof.
6. The process of claim 5 , wherein the metal powder comprises iron.
7. The process of claim 1 , wherein the 2,5-dihydroxy terephthalic acid salt is an alkaline salt or an ammonium salt of 2,5-dihydroxy terephthalic acid.
8. The process of claim 7 , wherein the alkaline salt is 2,5-dihydroxy terephthalic acid dipotassium salt.
9. The process of claim 1 including the additional step of forming a fiber from the polymer.
10. The process of claim 1 , wherein the poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d′]bisimidazole) is characterized as providing a polymer solution having an inherent viscosity of at least about 22 dl/g at 30° C. at a polymer concentration of 0.05 g/dl in methane sulfonic acid.
11. A process for preparing a poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d′]bisimidazole) polymer comprising:
contacting 2,3,5,6-tetraamino pyridine free base in water with 2,5-dihydroxy terephthalic acid dipotassium salt to form an aqueous mixture,
adjusting the pH of the aqueous mixture to within the range of from about 3 to about 5 to precipitate a monomer complex composed of 2,3,5,6-tetraamino pyridine and 2,5-dihydroxy terephthalic acid monomers,
contacting, in polyphosphoric acid, the monomer complex with about 0.05 to about 0.9 weight percent metal powder based on the total weight of the monomers, and
polymerizing the monomer complex in polyphosphoric acid to form the polymer.
12. The process of claim 11 wherein the molar ratio of the 2,3,5,6-tetraamino pyridine to the 2,5-dihydroxy terephthalic acid monomers is in excess of about 1 to 1.
13. The process of claim 12 wherein the molar ratio of the 2,3,5,6-tetraamino pyridine to the 2,5-dihydroxy terephthalic acid monomers is in excess of about 1.05 to 1.
14. The process of claim 11 wherein the pH is adjusted by adding orthophosphoric acid to the aqueous mixture.
15. The process of claim 11 wherein the polyphosphoric acid has an equivalent P 2 O 5 content of at least about 81 percent after polymerization.
16. The process of claim 15 wherein the polyphosphoric acid has an equivalent P 2 O 5 content of at least about 82 percent after polymerization.
17. The process of claim 11 wherein the metal powder comprises iron powder, tin powder, vanadium powder, chromium powder, or any combination thereof.
18. The process of claim 17 wherein the metal powder comprises iron.
19. The process of claim 11 including the additional step of forming a fiber from the polymer.
20. The process of claim 11 , wherein the poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d′]bisimidazole) is characterized as providing a polymer solution having an inherent viscosity of at least about 22 dl/g at 30° C. at a polymer concentration of 0.05 g/dl in methane sulfonic acid.