US4064114A
Expired / Lapsed
US
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Production of arylene sulfide polymers
Assignee: Phillips Petroleum Co
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Filing: 1976-01-19
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Granted: 1977-12-20
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Expires: 1996-01-19
Abstract
Abstract A method is provided for producing arylene sulfide polymers employing a p-dihalobenzene, an alkali metal sulfide, lithium acetate, an N-alkyl-2-pyrrolidone, and optionally a polyhalo aromatic compound having more than two halogen substituents per molecule, preferably with the addition of a base selected from alkali metal hydroxides and alkali metal carbonates at polymerization conditions. A first composition comprising N-alkyl-2-pyrrolidone, lithium acetate and water is prepared and subjected to dehydration conditions after which a composition containing at least 50 weight percent water, an alkali metal sulfide and preferably containing a base is added to the first dehydrated composition and a second dehydration performed. A composition resulting from the second dehydration is then contacted with a p-dihalobenzene, and optionally a polyhalo aromatic compound having more than two halogen substituents per molecule, at polymerization conditions to form arylene sulfide polymers of higher molecular weight than produced without the two-step dehydration. The two-step dehydration also results in less foaming and flooding of the distillation column as compared with the process using a single dehydration.
Inventors
- 👤 James T. Edmonds, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 12:47
CPC Classifications
C; C08; C08G; C08G75/00; C08G75/02; C08G75/0204; C08G75/025; C08G75/0254
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
93 words
A method for producing polymers comprising: a. forming a first composition by contacting N-alkyl-2-pyrrolidone, lithium acetate and water; b. dehydrating said first composition to form a first dehydrated composition; c. contacting said first dehydrated composition with a second composition containing at least about 50 weight percent water and an alkali metal sulfide to form a third composition; d. dehydrating said third composition to form a third dehydrated composition; and e. contacting said third dehydrated composition with a p-dichlorobenzene at polymerization conditions for a period of time sufficient to form a p-phenylene sulfide polymer.
Claim 2
Independent Claim
93 words
A method for producing polymers comprising: a. forming a first composition by contacting N-alkyl-2-pyrrolidone, lithium acetate and water; b. dehydrating said first composition to form a first dehydrated composition; c. contacting said first dehydrated composition with a second composition containing at least about 50 weight percent water and an alkali metal sulfide to form a third composition; d. dehydrating said third composition to form a third dehydrated composition; and e. contacting said third dehydrated composition with a p-dichlorobenzene at polymerization conditions for a period of time sufficient to form a p-phenylene sulfide polymer.
Claim 3
Dependent Claim
22 words
A method of claim 1 wherein said second composition also comprises a base selected from alkali metal hydroxides and alkali metal carbonates.
Claim 4
Dependent Claim
35 words
A method of claim 1 wherein said water in said first composition is in a form selected from among an aqueous solution of lithium acetate, an aqueous slurry of lithium acetate and lithium acetate dihydrate.
Claim 5
Dependent Claim
35 words
A method of claim 2 wherein said water in said first composition is in a form selected from among an aqueous solution of lithium acetate, an aqueous slurry of lithium acetate and lithium acetate dihydrate.
Claim 6
Dependent Claim
100 words
A method of claim 3 wherein said p-dihalobenzene is represented by the formula ##STR3## where each X is selected from the group consisting of chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and hydrocarbyl in which the hydrocarbyl can be an alkyl, cycloalkyl, or aryl radical or combination thereof such as alkaryl, aralkyl, or the like, the total number of carbon atoms in each molecule being within the range of 6 to about 24, with the proviso that in at least 50 mole percent of the p-dihalobenzene employed each R must be hydrogen.
Claim 7
Dependent Claim
100 words
A method of claim 4 wherein said p-dihalobenzene is represented by the formula ##STR4## where each X is selected from the group consisting of chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and hydrocarbyl in which the hydrocarbyl can be an alkyl, cycloalkyl, or aryl radical or combination thereof such as alkaryl, aralkyl, or the like, the total number of carbon atoms in each molecule being within the range of 6 to about 24, with the proviso that in at least 50 mole percent of the p-dihalobenzene employed each R must be hydrogen.
Claim 8
Dependent Claim
57 words
A method of claim 5 wherein the N-alkyl-2-pyrrolidone is represented by the formula ##STR5## where each R' is selected from the group consisting of hydrogen and R", and R" is an alkyl radical having 1 to about 3 carbon atoms, the total number of carbon atoms in each molecule of the N-alkyl-2-pyrrolidone being 5 to about 8.
Claim 9
Dependent Claim
57 words
A method of claim 6 wherein the N-alkyl-2-pyrrolidone is represented by the formula ##STR6## where each R' is selected from the group consisting of hydrogen and R", and R" is an alkyl radical having 1 to about 3 carbon atoms, the total number of carbon atoms in each molecule of the N-alkyl-2-pyrrolidone being 5 to about 8.
Claim 10
Dependent Claim
46 words
A method of claim 7 wherein the mole ratio of p-dihalobenzene to alkali metal sulfide is within the range of about 0.9:1 to about 2:1 and the mole ratio of lithium acetate to alkali metal sulfide is within the range of about 0.7:1 to about 4:1.
Claim 11
Dependent Claim
64 words
A method of claim 8 wherein the mole ratio of p-dihalobenzene to alkali metal sulfide is within the range of about 0.9:1 to about 2:1, the mole ratio of lithium acetate to alkali metal sulfide is within the range of about 0.7:1 to about 4:1; the mole ratio of base to alkali metal sulfide is within the range of about 0.01:1 to about 0.8:1.
Claim 12
Dependent Claim
54 words
A method of claim 9 wherein polymerization conditions comprise a reaction temperature within the range of about 125° C to about 450° C, a pressure sufficient to maintain the p-dihalobenzene and organic amide substantially in the liquid phase, and the reaction time is within the range of about 10 minutes to about 72 hours.
Claim 13
Dependent Claim
54 words
A method of claim 10 wherein polymerization conditions comprise a reaction temperature within the range of about 125° C to about 450° C, a pressure sufficient to maintain the p-dihalobenzene and organic amide substantially in the liquid phase, and the reaction time is within the range of about 10 minutes to about 72 hours.
Claim 14
Dependent Claim
69 words
A method of claim 12 wherein the N-alkyl-2-pyrrolidone is N-methyl-2-pyrrolidone, the water in the first composition is contained in lithium acetate dihydrate, the base is sodium hydroxide, the alkali metal sulfide is sodium sulfide, said p-dihalobenzene is p-dichlorobenzene, the reaction temperature is within the range of about 175° C to about 350° C and the reaction time is within the range of about 1 hour to about 8 hours.
Claim 15
Dependent Claim
44 words
A method of claim 1 wherein said third dehydrated composition is contacted with a polyhalo aromatic compound having more than two halogen substituents per molecule and a p-dihalobenzene at polymerization conditions for a period of time sufficient to form a branched arylene sulfide polymer.
Claim 16
Dependent Claim
22 words
A method of claim 14 wherein said second composition also comprises a base selected from alkali metal hydroxides and alkali metal carbonates.
Claim 17
Dependent Claim
35 words
A method of claim 14 wherein said water in said first composition is in a form selected from among an aqueous solution of lithium acetate, an aqueous slurry of lithium acetate and lithium acetate dihydrate.
Claim 18
Dependent Claim
35 words
A method of claim 15 wherein said water in said first composition is in a form selected from among an aqueous solution in lithium acetate, an aqueous slurry of lithium acetate and lithium acetate dihydrate.
Claim 19
Dependent Claim
179 words
A method of claim 16 wherein said p-dihalobenzene is represented by the formula ##STR7## where each X is selected from the group consisting of chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and hydrocarbyl in which the hydrocarbyl can be an alkyl, cycloalkyl, or aryl radical or combination thereof such as alkaryl, aralkyl, or the like, the total number of carbon atoms in each molecule being within the range of 6 to about 24, with the proviso that in at least 50 mole percent of the p-dihalobenzene employed each R must be hydrogen and said polyhalo aromatic compounds having more than two halogen substituents per molecule are represented by the formula R'''X n , where each X is selected from the group consisting of chlorine, bromine, and iodine, n is an integer of 3 to 6, and R''' is a polyvalent aromatic radical of valence n which can have up to about 4 methyl substituents, the total number of carbon atoms in R''' being within the range of 6 to about 16.
Claim 20
Dependent Claim
179 words
A method of claim 17 wherein said p-dihalobenzene is represented by the formula ##STR8## where each X is selected from the group consisting of chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and hydrocarbyl in which the hydrocarbyl can be an alkyl, cycloalkyl, or aryl radical or combination thereof such as alkaryl, aralkyl, or the like, the total number of carbon atoms in each molecule being within the range of 6 to about 24, with the proviso that in at least 50 mole percent of the p-dihalobenzene employed each R must be hydrogen and said polyhalo aromatic compounds having more than two halogen substituents per molecule are represented by the formula R'''X n , where each X is selected from the group consisting of chlorine, bromine, and iodine, n is an integer of 3 to 6, and R''' is a polyvalent aromatic radical of valence n which can have up to about 4 methyl substituents, the total number of carbon atoms in R''' being within the range of 6 to about 16.
Claim 21
Dependent Claim
57 words
A method of claim 18 wherein the N-alkyl-2-pyrrolidone is represented by the formula ##STR9## where each R' is selected from the group consisting of hydrogen and R", and R" is an alkyl radical having 1 to about 3 carbon atoms, the total number of carbon atoms in each molecule of the N-alkyl-2-pyrrolidone being 5 to about 8.
Claim 22
Dependent Claim
57 words
A method of claim 19 wherein the N-alkyl-2-pyrrolidone is represented by the formula ##STR10## where each R' is selected from the group consisting of hydrogen and R", and R" is an alkyl radical having 1 to about 3 carbon atoms, the total number of carbon atoms in each molecule of the N-alkyl-2-pyrrolidone being 5 to about 8.
Claim 23
Dependent Claim
77 words
A method of claim 18 wherein the mole ratio of p-dihalobenzene to alkali metal sulfide is within the range of about 0.9:1 to about 2:1, the mole ratio of lithium acetate to alkali metal sulfide is within the range of about 0.7:1 to about 4:1 and the polyhalo aromatic compound having more than two halogen substituents per molecule is present in an amount up to about 0.6 part by weight per 100 parts by weight of p-dihalobenzene.
Claim 24
Dependent Claim
96 words
A method of claim 21 wherein the mole ratio of p-dihalobenzene to alkali metal sulfide is within the range of about 0.9:1 to about 2:1, the mole ratio of lithium acetate to alkali metal sulfide is within the range of about 0.7:1 to about 4:1; the mole ratio of base to alkali metal sulfide is within the range of about 0.01:1 to about 0.8:1 and the polyhalo aromatic compound having more than two halogen substituents per molecule is present in an amount up to about 0.6 part by weight per 100 parts by weight of p-dihalobenzene.
Claim 25
Dependent Claim
66 words
A method of claim 22 wherein polymerization conditions comprise a reaction temperature within the range of about 125° C to about 450° C, a pressure sufficient to maintain the p-dihalobenzene, the polyhalo aromatic compound having more than two halogen substituents per molecule, and organic amide substantially in the liquid phase, and the reaction time is within the range of about 10 minutes to about 72 hours.
Claim 26
Dependent Claim
66 words
A method of claim 23 wherein polymerization conditions comprise a reaction temperature within the range of about 125° C to about 450° C, a pressure sufficient to maintain the p-dihalobenzene, the polyhalo aromatic compound having more than two halogen substituents per molecule, and organic amide substantially in the liquid phase, and the reaction time is within the range of about 10 minutes to about 72 hours.
Claim 27
Dependent Claim
82 words
A method of claim 25 wherein the N-alkyl-2-pyrrolidone is N-methyl-2-pyrrolidone, the water in the first composition is contained in lithium acetate dihydrate, the base is sodium hydroxide, the alkali metal sulfide is sodium sulfide, the p-dihalobenzene is p-dichlorobenzene, the polyhalo aromatic compound having more than two halogen substituents per molecule is 1,2,4-trichlorobenzene, the reaction is within the range of about 175° C to about 350° C and the reaction time is within the range of about 1 hour to about 8 hours.
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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) | 1980-12-19 | 1981-06-20 | 1981-12-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-12-19 | 1985-06-20 | 1985-12-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-12-19 | 1989-06-20 | 1989-12-20 | $7700.00 | Window Closed / Lapsed |