US4312976A
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Single-stage melt polymerization process for the production of high molecular weight polybenzimidazole
Assignee: Celanese Corp
•
Filing: 1980-07-15
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Granted: 1982-01-26
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Expires: 2000-07-15
Abstract
Abstract A single-stage melt polymerization process for the production of high molecular weight polybenzimidazole is provided. The process comprises reacting a monomeric reactant or reactants, which are capable of reacting to form a polybenzimidazole, at a temperature above the melting temperature of the monomeric reactant or reactants in the presence of a catalyst selected from the group consisting of organic sulfonic acids, halogenated acetic acids, and non-oxidizing inorganic acids. The polybenzimidazole is preferably produced by the reaction of 3,3',4,4'-tetraaminobiphenyl with isophthalic acid at a temperature within the range of approximately 360° C. to 425° C. for a period of time within the range of approximately 3 to 5 hours in the presence of approximately 0.25 to 0.5 percent by weight, based upon the weight of the isophthalic acid, of p-toluenesulfonic acid. The process of the present invention is conducted in the absence of a solvent, generates only a small amount of foam, and forms water as the sole, readily removable by-product.
Inventors
- 👤 Eui W. Choe
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 20:07
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/18
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
127 words
A single-stage melt polymerization process for the production of high molecular weight polybenzimidazole which comprises reacting a member of the class consisting of: (A) 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 dicarboxylic acid, and (B) at least one aromatic compound having a pair of amine substituents in an ortho position relative to each other and a carboxylic acid group positioned upon an aromatic nucleus at a temperature above the melting temperature of the monomeric reactant or reactants in the presence of a catalyst selected from the group consisting of organic sulfonic acids, halogenated acetic acids, and non-oxidizing inorganic acids.
Claim 2
Dependent Claim
127 words
A single-stage melt polymerization process for the production of high molecular weight polybenzimidazole which comprises reacting a member of the class consisting of: (A) 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 dicarboxylic acid, and (B) at least one aromatic compound having a pair of amine substituents in an ortho position relative to each other and a carboxylic acid group positioned upon an aromatic nucleus at a temperature above the melting temperature of the monomeric reactant or reactants in the presence of a catalyst selected from the group consisting of organic sulfonic acids, halogenated acetic acids, and non-oxidizing inorganic acids.
Claim 3
Dependent Claim
43 words
The process of claim 1 wherein said high molecular weight polybenzimidazole exhibits an inherent viscosity of at least approximately 0.5 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
54 words
The process of claim 1 wherein said high molecular weight polybenzimidazole is produced by the reaction of 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 dicarboxylic acid.
Claim 5
Dependent Claim
46 words
The process of claim 1 wherein said high molecular weight polybenzimidazole is produced by the reaction of at least one aromatic compound having a pair of amine substituents in an ortho position relative to each other and a carboxylic acid group positioned upon an aromatic nucleus.
Claim 6
Dependent Claim
12 words
The process of claim 4 wherein said aromatic compound comprises 4-carboxy-3',4'-diaminodiphenyl ether.
Claim 7
Dependent Claim
21 words
The process of claim 1 wherein said melt polymerization process is conducted at a temperature of at least approximately 340° C.
Claim 8
Dependent Claim
23 words
The process of claim 1 wherein said melt polymerization process is conducted for a period of time of at least approximately 3 hours.
Claim 9
Dependent Claim
16 words
The process of claim 1 wherein said melt polymerization process is conducted under an inert atmosphere.
Claim 10
Dependent Claim
30 words
The process of claim 1 wherein said catalyst is an organic sulfonic acid selected from the group consisting of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and mixtures thereof.
Claim 11
Dependent Claim
11 words
The process of claim 9 wherein said catalyst is p-toluenesulfonic acid.
Claim 12
Dependent Claim
26 words
The process of claim 1 wherein said catalyst is a halogenated acetic acid selected from the group consisting of trifluoroacetic acid, trichloroacetic acid, and mixtures thereof.
Claim 13
Dependent Claim
26 words
The process of claim 1 wherein said catalyst is a non-oxidizing inorganic acid selected from the group consisting of sulfuric acid, phosphoric acid, and hydrochloric acid.
Claim 14
Dependent Claim
32 words
The process of claim 3 wherein said catalyst is present in an amount within the range of approximately 0.01 to 2 percent by weight, based upon the weight of said dicarboxylic acid.
Claim 15
Dependent Claim
32 words
The process of claim 5 wherein said catalyst is present in an amount within the range of approximately 0.01 to 2 percent by weight, based upon the weight of said aromatic compound.
Claim 16
Dependent Claim
87 words
A single-stage melt polymerization process for the production of high molecular weight aromatic polybenzimidazole which comprises reacting 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 dicarboxylic acid at a temperature above the melting point of said dicarboxylic acid in the presence of a catalyst selected from the group consisting of organic sulfonic acids, halogenated acetic acids, and non-oxidizing inorganic acids.
Claim 17
Dependent Claim
87 words
A single-stage melt polymerization process for the production of high molecular weight aromatic polybenzimidazole which comprises reacting 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 dicarboxylic acid at a temperature above the melting point of said dicarboxylic acid in the presence of a catalyst selected from the group consisting of organic sulfonic acids, halogenated acetic acids, and non-oxidizing inorganic acids.
Claim 18
Dependent Claim
44 words
The process of claim 15 wherein said high molecular weight aromatic polybenzimidazole exhibits an inherent viscosity of at least approximately 0.5 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 19
Dependent Claim
11 words
The process of claim 15 wherein said aromatic tetraamine comprises 3,3',4,4'-tetraaminobiphenyl.
Claim 20
Dependent Claim
52 words
The process of claim 15 wherein said dicarboxylic acid is selected from the group consisting of aromatic dicarboxylic acids; aliphatic dicarboxylic acids; and heterocyclic dicarboxylic acids wherein the carboxyl groups are substituents upon carbon atoms in a ring compound selected from the group consisting of pyridine, pyrazine, furan, quinoline, thiophene, and pyran.
Claim 21
Dependent Claim
14 words
The process of claim 18 wherein said dicarboxylic acid comprises an aromatic dicarboxylic acid.
Claim 22
Dependent Claim
12 words
The process of claim 19 wherein said dicarboxylic acid comprises isophthalic acid.
Claim 23
Dependent Claim
21 words
The process of claim 15 wherein said melt polymerization process is conducted at a temperature of at least approximately 340° C.
Claim 24
Dependent Claim
23 words
The process of claim 15 wherein said melt polymerization process is conducted for a period of time of at least approximately 3 hours.
Claim 25
Dependent Claim
15 words
The process of claim 15 wherein said melt polymerization process is conducted at atmospheric pressure.
Claim 26
Dependent Claim
16 words
The process of claim 15 wherein said melt polymerization process is conducted under an inert atmosphere.
Claim 27
Dependent Claim
30 words
The process of claim 15 wherein said catalyst is an organic sulfonic acid selected from the group consisting of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and mixtures thereof.
Claim 28
Dependent Claim
11 words
The process of claim 25 wherein said catalyst is p-toluenesulfonic acid.
Claim 29
Dependent Claim
26 words
The process of claim 15 wherein said catalyst is a halogenated acetic acid selected from the group consisting of trifluoroacetic acid, trichloroacetic acid, and mixtures thereof.
Claim 30
Dependent Claim
26 words
The process of claim 15 wherein said catalyst is a non-oxidizing inorganic acid selected from the group consisting of sulfuric acid, phosphoric acid, and hydrochloric acid.
Claim 31
Dependent Claim
32 words
The process of claim 15 wherein said catalyst is present in an amount within the range of approximately 0.01 to 2 percent by weight, based upon the weight of said dicarboxylic acid.
Claim 32
Dependent Claim
113 words
A single-stage melt polymerization process for the production of high molecular weight aromatic polybenzimidazole having an inherent viscosity of at least approximately 0.5 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., said process comprising reacting a mixture of (1) at least one aromatic tetraamine containing two groups of amine substituents, said amine substituents in each group being in ortho position relative to each other, and (2) at least one aromatic dicarboxylic acid at a temperature of at least approximately 340° C. for a period of time of at least approximately 3 hours in the presence of p-toluenesulfonic acid.
Claim 33
Dependent Claim
113 words
A single-stage melt polymerization process for the production of high molecular weight aromatic polybenzimidazole having an inherent viscosity of at least approximately 0.5 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., said process comprising reacting a mixture of (1) at least one aromatic tetraamine containing two groups of amine substituents, said amine substituents in each group being in ortho position relative to each other, and (2) at least one aromatic dicarboxylic acid at a temperature of at least approximately 340° C. for a period of time of at least approximately 3 hours in the presence of p-toluenesulfonic acid.
Claim 34
Dependent Claim
41 words
The process of claim 30 wherein said high molecular weight aromatic polybenzimidazole exhibits an inherent viscosity of at least approximately 0.6 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid.
Claim 35
Dependent Claim
44 words
The process of claim 31 wherein said high molecular weight aromatic polybenzimidazole exhibits an inherent viscosity within the range of approximately 0.7 to 0.75 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid.
Claim 36
Dependent Claim
11 words
The process of claim 30 wherein said aromatic tetraamine comprises 3,3+,4,4'-tetraaminobiphenyl.
Claim 37
Dependent Claim
14 words
The process of claim 30 wherein said aromatic dicarboxyli acid and comprises isophthalic acid.
Claim 38
Dependent Claim
24 words
The process of claim 30 wherein said melt polymerization is conducted at a temperature within the range of approximately 340° C. to 450° C.
Claim 39
Dependent Claim
25 words
The process of claim 35 wherein said melt polymerization process is conducted at a temperature within the range of approximately 360° C. to 425° C.
Claim 40
Dependent Claim
19 words
The process of claim 36 wherein said melt polymerization process is conducted at a temperature of approximately 425° C.
Claim 41
Dependent Claim
26 words
The process of claim 30 wherein said melt polymerization process is conducted for an period of time within the range of approximately 3 to 10 hours.
Claim 42
Dependent Claim
26 words
The process of claim 38 wherein said melt polymerization process is conducted for a period of time within the range of approximately 3 to 5 hours.
Claim 43
Dependent Claim
15 words
The process of claim 30 wherein said melt polymerization process is conducted at atmospheric pressure.
Claim 44
Dependent Claim
16 words
The process of claim 30 wherein said melt polymerization process is conducted under an inert atmosphere.
Claim 45
Dependent Claim
34 words
The process of claim 30 wherein said p-toluenesulfonic acid is present in an amount within the range of approximately 0.01 to 2 percent by weight, based upon the weight of said aromatic dicarboxylic acid.
Claim 46
Dependent Claim
34 words
The process of claim 26 wherein said p-toluenesulfonic acid is present in an amount within the range of approximately 0.25 to 0.5 percent by weight, based upon the weight of said aromatic dicarboxylic acid.
Claim 47
Dependent Claim
105 words
A single-stage melt polymerization process for the production of a high molecular weight aromatic polybenzimidazole having an inherent viscosity of at least approximately 0.5 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid, said process comprising reacting under an inert atmosphere 3,3',4,4'-tetraaminobiphenyl and isophthalic acid at a temperature within the range of approximately 360° C. to 425° C. for a period of time within the range of approximately 3 to 5 hours in the presence of approximately 0.25 to 0.5 percent by weight, based upon the weight of said isophthalic acid, of p-toluenesulfonic acid.
Claim 48
Dependent Claim
105 words
A single-stage melt polymerization process for the production of a high molecular weight aromatic polybenzimidazole having an inherent viscosity of at least approximately 0.5 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid, said process comprising reacting under an inert atmosphere 3,3',4,4'-tetraaminobiphenyl and isophthalic acid at a temperature within the range of approximately 360° C. to 425° C. for a period of time within the range of approximately 3 to 5 hours in the presence of approximately 0.25 to 0.5 percent by weight, based upon the weight of said isophthalic acid, of p-toluenesulfonic acid.
Claim 49
Dependent Claim
41 words
The process of claim 44 wherein said high molecular weight aromatic polybenzimidazole exhibits an inherent viscosity of at least approximately 0.6 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid.
Claim 50
Dependent Claim
44 words
The process of claim 45 wherein said high molecular weight aromatic polybenzimidazole exhibits an inherent viscosity within the range of approximately 0.7 to 0.75 dl./g. when measured at a concentration of 0.4 g. of said polybenzimidazole in 100 ml. of 97 percent sulfuric acid.
Claim 51
Dependent Claim
19 words
The process of claim 44 wherein said melt polymerization process is conducted at a temperature of approximately 425° C.
Claim 52
Dependent Claim
15 words
The process of claim 44 wherein said melt polymerization process is conducted at atmospheric pressure.
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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) | 1985-01-25 | 1985-07-27 | 1986-01-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-01-25 | 1989-07-27 | 1990-01-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-01-25 | 1993-07-27 | 1994-01-26 | $7700.00 | Window Closed / Lapsed |