US3870685A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Catalytic method for producing aromatic polyamides
Assignee: Celanese Corp
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Filing: 1973-06-15
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Granted: 1975-03-11
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Expires: 1993-06-15
Abstract
Abstract High molecular weight wholly aromatic linear polyamides of film and fiber-forming grade are prepared by direct condensation of monomeric aromatic dicarboxylic acids and aromatic diamines in about a mole to mole ratio in the presence of an aromatic sulfone and a catalytic amount of a boric acid and/or a sulfonic acid or derivatives thereof. The condensation product using the noted catalyst is polymerized to higher inherent viscosities than that obtained without a catalyst under similar conditions. The described process is particularly advantageous because substantially shorter polymerization times are required to obtain film and fiber-forming polymers.
Inventors
- 👤 Rufus S Jones
- 👤 Anthony B Conciatori
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 18:32
CPC Classifications
C; C08; C08G; C08G69/00; C08G69/02; C08G69/26; C08G69/32
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
174 words
A METHOD FOR PREPARING HIGH MOLECULAR WEIGHT AROMATIC CARBOXYLIC POLYAMIDES COMPRISING HEATING IN THE SUSTANTIAL ABSENCE OF OXYGEN AN AROMATIC CARBOXYLIC DICARBOXYLIC ACID AND AN AROMATIC CARBOCYCLIC DIAMINE IN ABOUT A MOLE TO MOLE RATIO IN THE PRESENCE OF ABOUT 2,500 TO 2500 PERCENT, BY WEIGHT, BASED ON THE POLYMER WEIGHT, OF AN ARYL SULFONE AND ABOUT 0.2 TO 15 MOLE PERCENT, BASED ON THE REACTANTS, OF A COMBINATION OF BORIC ACID AND AN, ARYL OR ALKYL SULFONIC ACID OF FROM 1 TO 16 CARBON ATOMS WHEREIN THE MOLAR RATIO OF THE BORIC ACID TO ORGANIC SULFONIC ACID IS BETWEEN ABOUT 10:1 AND 1:10, TO A TEMPERATURE ABOVE THE MELTING POINT OF SAID SULFONE TO JUST BELOW THE DECOMPOSITION TEMPERATURE OF THE REACTANTS AND CONTINUING SAID HEATING WITH THE REMOVAL OF CONDENSATION BY-PRODUCTS FOR A PERIOD OF TIME SUFFICIENT TO FORM A PRODUCT HAVING AN INHERENT VISCOSITY OF AT LEAST 0.4 AS MEASURED USING A SOLUTION OF 0.4 GRAMS OF PRODUCT PER 100 MILLILITERS OF CONCENTRATE, 97-99% BY WEIGHT, AQUEOUS SULFURIC ACID AT 25*C.
Claim 2
Independent Claim
174 words
A METHOD FOR PREPARING HIGH MOLECULAR WEIGHT AROMATIC CARBOXYLIC POLYAMIDES COMPRISING HEATING IN THE SUSTANTIAL ABSENCE OF OXYGEN AN AROMATIC CARBOXYLIC DICARBOXYLIC ACID AND AN AROMATIC CARBOCYCLIC DIAMINE IN ABOUT A MOLE TO MOLE RATIO IN THE PRESENCE OF ABOUT 2,500 TO 2500 PERCENT, BY WEIGHT, BASED ON THE POLYMER WEIGHT, OF AN ARYL SULFONE AND ABOUT 0.2 TO 15 MOLE PERCENT, BASED ON THE REACTANTS, OF A COMBINATION OF BORIC ACID AND AN, ARYL OR ALKYL SULFONIC ACID OF FROM 1 TO 16 CARBON ATOMS WHEREIN THE MOLAR RATIO OF THE BORIC ACID TO ORGANIC SULFONIC ACID IS BETWEEN ABOUT 10:1 AND 1:10, TO A TEMPERATURE ABOVE THE MELTING POINT OF SAID SULFONE TO JUST BELOW THE DECOMPOSITION TEMPERATURE OF THE REACTANTS AND CONTINUING SAID HEATING WITH THE REMOVAL OF CONDENSATION BY-PRODUCTS FOR A PERIOD OF TIME SUFFICIENT TO FORM A PRODUCT HAVING AN INHERENT VISCOSITY OF AT LEAST 0.4 AS MEASURED USING A SOLUTION OF 0.4 GRAMS OF PRODUCT PER 100 MILLILITERS OF CONCENTRATE, 97-99% BY WEIGHT, AQUEOUS SULFURIC ACID AT 25*C.
Claim 3
Independent Claim
174 words
A method for preparing high molecular weight aromatic carbocyclic polyamides comprising heating in the substantial absence of oxygen an aromatic carbocyclic dicarboxylic acid and an aromatic carbocyclic diamine in about a mole to mole ratio in the presence of about 100 to 2500 percent, by weight, based on the polymer weight, of an aryl sulfone and about 0.2 to 15 mole percent, based on the reactants, of a combination of boric acid and an, aryl or alkyl sulfonic acid of from 1 to 16 carbon atoms wherein the molar ratio of the boric acid to organic sulfonic acid is between about 10:1 and 1:10, to a temperature above the melting point of said sulfone to just below the decomposition temperature of the reactants and continuing said heating with the removal of condensation by-products for a period of time sufficIent to form a product having an inherent viscosity of at least 0.4 as measured using a solution of 0.4 grams of product per 100 milliliters of concentrate, 97-99% by weight, aqueous sulfuric acid at 25*C.
Claim 4
Independent Claim
174 words
A method for preparing high molecular weight aromatic carbocyclic polyamides comprising heating in the substantial absence of oxygen an aromatic carbocyclic dicarboxylic acid and an aromatic carbocyclic diamine in about a mole to mole ratio in the presence of about 100 to 2500 percent, by weight, based on the polymer weight, of an aryl sulfone and about 0.2 to 15 mole percent, based on the reactants, of a combination of boric acid and an, aryl or alkyl sulfonic acid of from 1 to 16 carbon atoms wherein the molar ratio of the boric acid to organic sulfonic acid is between about 10:1 and 1:10, to a temperature above the melting point of said sulfone to just below the decomposition temperature of the reactants and continuing said heating with the removal of condensation by-products for a period of time sufficIent to form a product having an inherent viscosity of at least 0.4 as measured using a solution of 0.4 grams of product per 100 milliliters of concentrate, 97-99% by weight, aqueous sulfuric acid at 25*C.
Claim 5
Dependent Claim
39 words
The method of claim 1 wherein the catalyst is a combination of boric acid and an organic sulfonic acid or acid forming derivatives thereof in a molar ratio of about 2:1 to 6:1 boric acid to organic sulfonic acid.
Claim 6
Dependent Claim
23 words
The method of claim 2 wherein the boric acid and organic sulfonic acid are in a molar ratio of between 10:1 and 1:10.
Claim 7
Dependent Claim
21 words
The method of claim 3 wherein boric acid to organic sulfonic acid is in a molar ratio of 2:1 to 6:1.
Claim 8
Dependent Claim
24 words
The method of claim 1, wherein the organic sulfonic acid is selected from the group consisting of paratoluene sulfonic acid and benzene sulfonic acid.
Claim 9
Dependent Claim
27 words
The method of claim 1, wherein the resulting product is further polymerized to increase the inherent viscosity to a value in the range of 1.0 to 5.0.
Claim 10
Dependent Claim
34 words
The method of claim 1, wherein the dicarboxylic acid is of the formula HOOCArCOOH and the diamine is of the formula H2NArNH2, wherein Ar is selected from the group consisting of meta and para
Claim 11
Dependent Claim
23 words
The method of claim 7 wherein the dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof.
Claim 12
Dependent Claim
20 words
The method of claim 7 wherein the diamine is selected from the group consisting of metaphenylenediamine, paraphenylenediamine and mixtures thereof.
Claim 13
Dependent Claim
31 words
The method of claim 1, wherein a nonreactive diulent is present in addition to the sulfone in an amount of 50 to 1,500 percent based on the weight of the polymer.
Claim 14
Dependent Claim
13 words
The method of claim 1, wherein the aryl sulfone is of the formula
Claim 15
Dependent Claim
11 words
The method of claim 11 wherein the sulfone is diphenyl sulfone.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-03-10 | 1978-09-09 | 1979-03-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-03-10 | 1982-09-09 | 1983-03-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-03-10 | 1986-09-09 | 1987-03-11 | $7700.00 | Window Closed / Lapsed |