US4463167A
Expired / Lapsed
US
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Two stage high molecular weight polybenzimidazole production with phosphorus containing catalyst
Assignee: Hoechst AG
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Filing: 1983-03-21
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Granted: 1984-07-31
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Expires: 2003-03-21
Abstract
Abstract This invention provides a two stage melt polymerization process for the production of an improved type of high molecular weight polybenzimidazole, which involves the use of an arylphosphine or arylphosphite polymerization catalyst. The process provides poly-2,2'-(m-phenylene)-5-5'-bibenzimidazole of improved color and Plugging Value, and is further characterized by an inherent viscosity of at least about 0.9 dl/g, and a weight average molecular weight of at least about 140,000.
Inventors
- 👤 Eui W. Choe
- 👤 Anthony B. Conciatori
- 👤 Bennett C. Ward
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 21:47
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/18
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
142 words
A two stage polymerization process for the production of high molecular weight polybenzimidazole from a mixture of ( 1) at least one aromatic tetraamine containing two groups of amine substituents, said amine substituents in each group being in an ortho position relative to each other, and (2) at least one dicarboxylate ester corresponding to the formula: ##STR10## where R 1 is a substituent selected from aromatic, alkylene or heterocyclic groups, and R 2 is a substituent selected from aliphatic, alicyclic or aromatic groups, which comprises heating the mixture above its melting temperature in a first stage melt polymerization zone in contact with a phosphorus-containing polymerization catalyst selected from arylphosphines or arylphosphites, to provide a foamed prepolymer; and heating the prepolymer in a second stage solid state polymerization zone at a temperature above about 250° C. to produce high molecular weight polybenzimidazole product.
Claim 2
Dependent Claim
142 words
A two stage polymerization process for the production of high molecular weight polybenzimidazole from a mixture of ( 1) at least one aromatic tetraamine containing two groups of amine substituents, said amine substituents in each group being in an ortho position relative to each other, and (2) at least one dicarboxylate ester corresponding to the formula: ##STR10## where R 1 is a substituent selected from aromatic, alkylene or heterocyclic groups, and R 2 is a substituent selected from aliphatic, alicyclic or aromatic groups, which comprises heating the mixture above its melting temperature in a first stage melt polymerization zone in contact with a phosphorus-containing polymerization catalyst selected from arylphosphines or arylphosphites, to provide a foamed prepolymer; and heating the prepolymer in a second stage solid state polymerization zone at a temperature above about 250° C. to produce high molecular weight polybenzimidazole product.
Claim 3
Dependent Claim
45 words
A process in accordance with claim 1 wherein the high molecular weight polybenzimidazole exhibits an inherent viscosity of at least about 0.9 dl/g when measured at a concentration of 0.4 g of said polybenzimidazole in 100 ml of 97 percent sulfuric acid at 25° C.
Claim 4
Dependent Claim
40 words
A process in accordance with claim 1 wherein the first stage melt polymerization reaction is conducted at a temperature between about 200°-300° C., and the second stage solid state polymerization reaction is conducted at a temperature between about 320°-420° C.
Claim 5
Dependent Claim
20 words
A process in accordance with claim 1 wherein the two stages of polymerization reaction are conducted under an inert atmosphere.
Claim 6
Dependent Claim
29 words
A process in accordance with claim 1 wherein the polymerization catalyst is present in a quantity between about 0.01-5 weight percent, based on the weight of the monomeric reactants.
Claim 7
Dependent Claim
19 words
A process in accordance with claim 1 wherein the monomeric dicarboxylate ester reactant has an aromatic dicarboxylic acid structure.
Claim 8
Dependent Claim
15 words
A process in accordance with claim 1 wherein the monomeric aromatic tetraamine reactant is 3,3',4,4'-tetraaminobiphenyl.
Claim 9
Dependent Claim
16 words
A process in accordance with claim 1 wherein the monomeric dicarboxylate ester reactant is diphenyl isophthlate
Claim 10
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is diphenylphosphine.
Claim 11
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is tri(p-methoxyphenyl)phosphine.
Claim 12
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is dimethoxy-phenylphosphine.
Claim 13
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is di-n-butoxy-phenylphosphine.
Claim 14
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is diphenylphosphite.
Claim 15
Dependent Claim
13 words
A process in accordance with claim 1 wherein the polymerization catalyst is triphenylphosphite.
Claim 16
Dependent Claim
130 words
A two stage polymerization process for the production of high molecular weight polybenzimidazole from a mixture of 3,3',4,4'-tetraaminobiphenyl and diphenyl isophthalate which comprises heating the mixture above its melting temperature in a first stage melt polymerization zone in the presence of a phosphorus-containing polymerization catalyst selected from arylphosphines and arylphosphites to provide a foamed prepolymer; and heating the prepolymer in a second stage solid state polymerization zone at a temperature above about 250° C. to produce high molecular weight polybenzimidazole product; wherein the polybenzimidazole exhibits an inherent viscosity of at least about 0.9 dl/g when measured at a concentration of 0.4 g of said polybenzimidazole in 100 ml of 97 percent sulfuric acid at 25° C., and the polybenzimidazole has a weight average molecular weight of at least about 140,000.
Claim 17
Dependent Claim
130 words
A two stage polymerization process for the production of high molecular weight polybenzimidazole from a mixture of 3,3',4,4'-tetraaminobiphenyl and diphenyl isophthalate which comprises heating the mixture above its melting temperature in a first stage melt polymerization zone in the presence of a phosphorus-containing polymerization catalyst selected from arylphosphines and arylphosphites to provide a foamed prepolymer; and heating the prepolymer in a second stage solid state polymerization zone at a temperature above about 250° C. to produce high molecular weight polybenzimidazole product; wherein the polybenzimidazole exhibits an inherent viscosity of at least about 0.9 dl/g when measured at a concentration of 0.4 g of said polybenzimidazole in 100 ml of 97 percent sulfuric acid at 25° C., and the polybenzimidazole has a weight average molecular weight of at least about 140,000.
Claim 18
Dependent Claim
50 words
A process in accordance with claim 15 wherein the polybenzimidazole has a Plugging Value of greater than about 1.5; a Gardner Color of less than about 10; and which polybenzimidazole is capable of forming a 15 weight percent solution when heated at 240° C. for two hours in dimethylacetamide solvent.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-07-31 | 1988-01-30 | 1988-07-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-07-31 | 1992-01-30 | 1992-07-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-07-31 | 1996-01-30 | 1996-07-31 | $7700.00 | Window Closed / Lapsed |