US4808694A
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Poly(arylene sulfide sulfone) polymer containing ether groups
Assignee: Phillips Petroleum Co
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Filing: 1988-03-14
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Granted: 1989-02-28
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Expires: 2008-03-14
Abstract
Abstract A two-step process to make a poly(arylene sulfide sulfone) polymer exhibiting improved high temperature properties is described. In the first step a prepolymer characterized as dihalo-terminated polyethersulfone oligomers is prepared by reacting an aromatic diphenol with an excess of a dihalo aromatic sulfone. In the second step the excess dihalo aromatic sulfone and the oligomers are copolymerized in the presence of a sulfur source to form a poly(arylene sulfide sulfone) polymer. An alkali metal carboxylate is present in the second step. The polymers exhibit improved softening temperature and glass transition temperature and are useful in high temperature applications.
Inventors
- 👤 James T. Edmonds, Jr.
- 👤 Jon Geibel
- 👤 Rex L. Bobsein
- 👤 Jim J. Straw
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 19:15
CPC Classifications
C; C08; C08G; C08G63/00; C08G63/02; C08G63/12; C08G63/46; C08G63/48; C08G65/00; C08G65/34; C08G65/48; C08G75/00; C08G75/20
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
106 words
A process comprising: (a) reacting in an organic solvent a dihalo aromatic sulfone with an aromatic diphenol at a mole ratio of about 8/1 to about 20/1 in the presence of an alkali metal base to form a mixture comprising dihalo-terminated oligomers, and subsequently (b) adding a sulfur source selected from the group consisting of hydrogen sulfide, alkali metal hydrosulfides, alkali metal sulfides, acyclic and cyclic thioamides and mixtures, thereof, to the mixture resulting from (a) and continuing the reaction at a temperature and for a sufficient time to form a recoverable polymeric solid, characterized as having a polymer melt temperature in excess of 250° C.
Claim 2
Dependent Claim
106 words
A process comprising: (a) reacting in an organic solvent a dihalo aromatic sulfone with an aromatic diphenol at a mole ratio of about 8/1 to about 20/1 in the presence of an alkali metal base to form a mixture comprising dihalo-terminated oligomers, and subsequently (b) adding a sulfur source selected from the group consisting of hydrogen sulfide, alkali metal hydrosulfides, alkali metal sulfides, acyclic and cyclic thioamides and mixtures, thereof, to the mixture resulting from (a) and continuing the reaction at a temperature and for a sufficient time to form a recoverable polymeric solid, characterized as having a polymer melt temperature in excess of 250° C.
Claim 3
Dependent Claim
57 words
The process of claim 1 wherein (b) further an alkali metal carboxylate is added, said alkali metal carboxylate being represented by R'COOM, where R' is a hydrocarbyl radical selected from the group consisting of alkyl, cycloalkyl, aryl and combinations thereof with carbon atoms in the range of 1 to about 20 and M is an alkali metal.
Claim 4
Dependent Claim
26 words
The process of claim 2 wherein R' is an alkyl radical having 1 to about 6 carbon atoms or a phenyl radical and M is sodium.
Claim 5
Dependent Claim
45 words
The process of claim 2 wherein (b) further water is added to bring the total water, including water of hydration, present to an amount of at least about 3.5 moles per mole of sulfur source and greater than about 0.5 moles per mole organic solvent.
Claim 6
Dependent Claim
37 words
The process of claim 2 wherein (b) N-methyl-2-pyrrolidone and water are added in amounts such that the ratio: (moles total water including water of hydration)/(total moles NMP) is within the range from about 0.75 to about 2.5.
Claim 7
Dependent Claim
18 words
The process of claim 5 wherein the ratio is within the range from about 1 to about 2.
Claim 8
Dependent Claim
29 words
The process of claim 1 wherein the aromatic diphenol is characterized by having an alkylene radical link between two phenolic groups and the dihalo aromatic sulfone is a bis(halophenyl)sulfone.
Claim 9
Dependent Claim
16 words
The process of claim 7 wherein the aromatic diphenol is 2,2-bis(p-hydroxyphenyl)propane and the bis(halophenyl)sulfone is bis(p-chlorophenyl)sulfone.
Claim 10
Dependent Claim
26 words
The process of claim 1 wherein the alkali metal base is selected from the group consisting of an alkali metal hydroxide and an alkali metal carbonate.
Claim 11
Dependent Claim
15 words
The process of claim 9 wherein the alkali metal base is an alkali metal carbonate.
Claim 12
Dependent Claim
13 words
The process of claim 10 wherein the alkali metal carbonate is sodium carbonate.
Claim 13
Dependent Claim
15 words
The process of claim 1 wherein the dihalo-terminated oligomers are characterized as dihalo-terminated polyethersulfone oligomers.
Claim 14
Dependent Claim
29 words
The process of claim 12 wherein the dihalo-terminated polyethersulfone oligomers comprise the oligomer from the reaction of one mole of aromatic diphenol with two moles of a bis(halophenyl) sulfone.
Claim 15
Dependent Claim
13 words
The process of claim 7 wherein the alkali metal hydrosulfide is sodium hydrosulfide.
Claim 16
Dependent Claim
100 words
The process of claim 7 wherein (a) the alkali metal base to the aromatic diphenol mole ratio is within the range of about 2/1 to 25/1 and wherein (b) the ratio of the moles of bis(halophenyl)sulfone minus the moles of aromatic diphenol in (a) to moles of added sulfur source is within the range of about 1.05/1 to about 0.95/1, the mole ratio of alkali metal base to sulfur source is within the range of about 1.1/1 to about 2.2/1, and the mole ratio of alkali metal carboxylate to bis(halophenyl)sulfone is within the range of about 1/1 to about 2/1.
Claim 17
Dependent Claim
50 words
The process of claim 8 wherein the recoverable polymeric solid is characterized as having a polymer melt temperature in excess of 275° C. and an inherent viscosity in excess of 0.30 dL/g measured at 30° C. using as solvent N-methyl-2-pyrrolidone at a solids concentration of 0.5 grams per 100 mL.
Claim 18
Dependent Claim
65 words
The process of claim 8 wherein the recoverable polymeric solid is characterized as having a polymer melt temperature in excess of 290° C., a measurable melt flow rate of less than 5000 grams per 10 minutes and an inherent viscosity from about 0.30 to about 0.60 dL/g measured at 30° C. using as solvent N-methyl-2-pyrrolidone at a solids concentration of 0.5 grams per 100 mL.
Claim 19
Dependent Claim
19 words
The process of claim 1 wherein further an organic amide is present as a solvent in (a) and (b).
Claim 20
Dependent Claim
27 words
The process of claim 18 wherein the organic amide is selected from the group consisting of formamide, acetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and epsilon-caprolactam, dimethylbenzamide and mixtures thereof.
Claim 21
Dependent Claim
11 words
The process of claim 19 wherein the organic amide is N-methyl-2-pyrrolidone.
Claim 22
Dependent Claim
29 words
The process of claim 1 wherein (a) and (b) are conducted in the presence of a solvent selected from among the group consisting of dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and tetramethylurea.
Claim 23
Dependent Claim
53 words
The process of claim 1 wherein (a) and (b) are conducted in the presence of a solvent mixture comprising an organic amide selected from the group consisting of formamide, acetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and epsilon-caprolactam, dimethylbenzamide and mixtures thereof and a compound selected from the group consisting of dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and tetramethylurea.
Claim 24
Dependent Claim
18 words
The process of claim 1 wherein further a quench fluid is added to cool the mixture from (b).
Claim 25
Dependent Claim
21 words
The process of claim 23 wherein the quench fluid is selected from the group consisting of N-methyl-2-pyrrolidone, water, or mixtures thereof.
Claim 26
Dependent Claim
9 words
A polymer produced by the process of claim 1.
Claim 27
Dependent Claim
9 words
A polymer produced by the process of claim 8.
Claim 28
Dependent Claim
9 words
A polymer produced by the process of claim 15.
References Cited (Backward Citations)
GB1078234A
Cited
US4175175A
Cited
US4108837A
Cited
US3354129A
Cited
US3400065A
Cited
US3432468A
Cited
DE1909441A1
Cited
US3634355A
Cited
GB1264900A
Cited
US3657385A
Cited
US3655822A
Cited
US3809682A
Cited
US3919177A
Cited
US4016145A
Cited
FR2331584A1
Cited
US4125525A
Cited
US4127713A
Cited
US4268647A
Cited
US4301274A
Cited
EP0185317A2
Cited
US4654410A
Cited
EP0237593A1
Cited
EP0210377A1
Cited
DE3614602A1
Cited
DE3714583A1
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-02-28 | 1992-08-29 | 1993-02-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-02-28 | 1996-08-29 | 1997-02-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-02-28 | 2000-08-29 | 2001-02-28 | $7700.00 | Window Closed / Lapsed |