US4748231A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Reprecipitation of poly(arylene sulfide) to increase molecular weight thereof
Assignee: Phillips Petroleum Co
•
Filing: 1986-11-21
•
Granted: 1988-05-31
•
Expires: 2006-11-21
Abstract
Abstract The molecular weight of linear and non-linear poly(arylene sulfide) PAS is increased by reprecipitation. The reprecipitation is accomplished by heating PAS to its dispersion temperature in a mixture of polar organic solvent, water, and alkali metal carboxylate until the PAS is dispersed in the mixture. Water is then added to cause a phase separation, then the total mixture is slowly cooled and a PAS of increased molecular weight is recovered. PAS slime, a waste product of some polymerization processes, can also be reprecipitated, as above, to recover useful particulate PAS that would normally be discarded.
Inventors
- 👤 Afif M. Nesheiwat
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 19:52
CPC Classifications
C; C08; C08G; C08G75/00; C08G75/02; C08G75/0204; C08G75/0277; C08G75/0281; C08G75/0209; C08G75/0213; C08G75/0231; C08G75/025; C08G75/0254; C08G75/14
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
120 words
A method for increasing the molecular weight of linear poly(arylene sulfide) comprising: (a) heating a mixture comprising linear poly(arylene sulfide), polar organic solvent, and alkali metal carboxylate, with or without water, to at least the dispersion temperature of said linear poly(arylene sulfide) in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said linear poly(arylene sulfide) to disperse in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispersion temperature to cause a phase separation; (d) slowly cooling said mixture and water to at least about 200° C.; and (e) recovering a linear poly(arylene sulfide) of increased molecular weight from said mixture.
Claim 2
Independent Claim
120 words
A method for increasing the molecular weight of linear poly(arylene sulfide) comprising: (a) heating a mixture comprising linear poly(arylene sulfide), polar organic solvent, and alkali metal carboxylate, with or without water, to at least the dispersion temperature of said linear poly(arylene sulfide) in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said linear poly(arylene sulfide) to disperse in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispersion temperature to cause a phase separation; (d) slowly cooling said mixture and water to at least about 200° C.; and (e) recovering a linear poly(arylene sulfide) of increased molecular weight from said mixture.
Claim 3
Dependent Claim
31 words
A method according to claim 1 wherein said mixture of (a) contains a sufficient amount of water to stabilize said linear poly(arylene sulfide) but yet not sufficient to cause phase separation.
Claim 4
Dependent Claim
15 words
A method according to claim 1 wherein said polar organic solvent is an organic amide.
Claim 5
Dependent Claim
27 words
A method according to claim 3 wherein said organic amide is N-methyl-2-pyrrolidone and said dispersion temperature of said linear poly(arylene sulfide) in N-methyl-2-pyrrolidone is about 260° C.
Claim 6
Dependent Claim
16 words
A method according to claim 1 wherein said alkali metal carboxylate is an alkali metal acetate.
Claim 7
Dependent Claim
14 words
A method according to claim 5 wherein said alkali metal acetate is sodium acetate.
Claim 8
Dependent Claim
24 words
A method according to claim 1 wherein said heating is effected under sufficient pressure to maintain said polar organic solvent substantially in liquid phase.
Claim 9
Dependent Claim
20 words
A method according to claim 1 wherein said mixture of (d) is slowly cooled until at least about 150° C.
Claim 10
Dependent Claim
29 words
A method according to claim 1 wherein said mixture of (d) is slowly cooled at a rate in the range of about 0.2° to about 1° C. per minute.
Claim 11
Dependent Claim
20 words
A method according to claim 9 wherein said mixture of (d) is slowly cooled until at least about 100° C.
Claim 12
Dependent Claim
39 words
A method according to claim 1 wherein said sufficient length of time for said linear poly(arylene sulfide) to melt and be dispersed in the balance of the mixture is within the range of about 1 minute to 1 hour.
Claim 13
Dependent Claim
31 words
A method according to claim 1 wherein the amount of water added in (c) is within the range of about 1 to 9 moles water per mole of linear poly(arylene sulfide).
Claim 14
Dependent Claim
48 words
A method according to claim 1 wherein the molar ratio of polar organic solvent to linear poly(arylene sulfide) is within the range of about 2:1 to 6:1 and the molar ratio of alkali metal carboxylate to linear poly(arylene sulfide) is within the range of about 0.1:1 to 1:1.
Claim 15
Dependent Claim
16 words
A method according to claim 1 wherein said linear poly(arylene sulfide) is untreated linear poly(phenylene sulfide).
Claim 16
Independent Claim
180 words
A method for increasing the molecular weight of linear poly(arylene sulfide) comprising: (a) heating a mixture of linear poly(arylene sulfide), N-methyl-2-pyrrolidone, water, and alkali metal acetate to at least the dispersion temperature of said linear poly(arylene sulfide) in said N-methyl-2-pyrrolidone; (b) maintaining said mixture at about said dispersion temperature for at least about 1 minute to 1 hour, time sufficient for said linear poly(arylene sulfide) to be dispersed in the balance of the mixture; (c) adding at least about 1 to 9 moles additional water per mole of linear poly(arylene sulfide) while maintaining said mixture at about said dispesion temperature; (d) slowly cooling said mixture at a rate in the range of about 0.2° to 1° C. per minute until at least about 150° C.; and (e) recovering a linear poly(arylene sulfide) of increased molecular weight from said mixture; wherein the amount of water in the mixture of (a) is sufficient to stabilize said linear poly(arylene sulfide) but yet not sufficient to cause phase separation and wherein the amount of water added in (c) is sufficient to cause phase separation.
Claim 17
Independent Claim
180 words
A method for increasing the molecular weight of linear poly(arylene sulfide) comprising: (a) heating a mixture of linear poly(arylene sulfide), N-methyl-2-pyrrolidone, water, and alkali metal acetate to at least the dispersion temperature of said linear poly(arylene sulfide) in said N-methyl-2-pyrrolidone; (b) maintaining said mixture at about said dispersion temperature for at least about 1 minute to 1 hour, time sufficient for said linear poly(arylene sulfide) to be dispersed in the balance of the mixture; (c) adding at least about 1 to 9 moles additional water per mole of linear poly(arylene sulfide) while maintaining said mixture at about said dispesion temperature; (d) slowly cooling said mixture at a rate in the range of about 0.2° to 1° C. per minute until at least about 150° C.; and (e) recovering a linear poly(arylene sulfide) of increased molecular weight from said mixture; wherein the amount of water in the mixture of (a) is sufficient to stabilize said linear poly(arylene sulfide) but yet not sufficient to cause phase separation and wherein the amount of water added in (c) is sufficient to cause phase separation.
Claim 18
Dependent Claim
24 words
A method according to claim 15 wherein said alkali metal acetate is sodium acetate and said linear poly(arylene sulfide) is untreated linear poly(phenylene sulfide).
Claim 19
Dependent Claim
19 words
A method according to claim 15 wherein said mixture of (d) is cooled to at least about 100° C.
Claim 20
Dependent Claim
20 words
A method according to claim 15 wherein said linear poly(arylene sulfide) recovered in (e) is then treated with calcium cations.
Claim 21
Dependent Claim
49 words
A method according to claim 15 wherein after said linear linear poly(arylene sulfide) of (e) is recovered from said mixture, poly(arylene sulfide) slime which contains poly(arylene sulfide) fines is taken from said mixture and processed through said steps (a)-(e) to recover more linear poly(arylene sulfide) of increased molecular weight.
Claim 22
Dependent Claim
101 words
A method according to claim 15 wherein said heating is affected under sufficient pressure to maintain said N-methyl-2-pyrrolidone substantially in liquid phase, the molar ratio of N-methyl-2-pyrrolidone to linear poly(arylene sulfide) is within the range of about 2:1 to 6:1, the molar ratio of alkali metal acetate to linear poly(arylene sulfide) is within the range of about 0.1:1 to 1:1, the molar ratio of water to linear poly(arylene sulfide) in (a) is within the range of about 0:1 to 3:1, and the molar ratio of water to linear poly(arylene sulfide) of (c) is within the range of about 1:1 to 9:1.
Claim 23
Dependent Claim
76 words
A method according to claim 20 wherein the molar ratio of water to linear poly(arylene sulfide) in (a) is within the range of about 0.1:1 to 2:1, the molar ratio of water to linear poly(arylene sulfide) of (c) is within the range of about 2:1 to 4:1, and said time sufficient for said linear poly(arylene sulfide) to be dispersed in the balance of the mixture is within the range of about 5 minutes to 30 minutes.
Claim 24
Dependent Claim
62 words
A method according to claim 21 wherein the molar ratio of N-methyl-2-pyrrolidone to linear poly(arylene sulfide) is about 3:1, the molar ratio of alkali metal acetate to linear poly(arylene sulfide) is about 0.3:1, the molar ratio of water to linear poly(arylene sulfide)in (a) is about 1:1, and the molar ratio of water to linear poly(arylene sulfide) present in (c) is about 3:1.
Claim 25
Dependent Claim
23 words
A method according to claim 22 wherein said linear poly(arylene sulfide) is linear poly(phenylene sulfide), and said alkali metal acetate is sodium acetate.
Claim 26
Independent Claim
112 words
A method for recovering particulate poly(arylene sulfide) from poly(arylene sulfide) fines comprising: (a) heating a mixture of poly(arylene sulfide) fines, polar organic solvent, alkali metal carboxylate, with or without, to at least the dispersion temperature of said poly(arylene sulfide) fines in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said poly(arylene sulfide) fines to be dispersed in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispersion temperature to cause a phase separation; (d) slowly cooling said mixture until at least about 200° C.; and (e) recovering particulate poly(arylene sulfide) from said mixture.
Claim 27
Independent Claim
112 words
A method for recovering particulate poly(arylene sulfide) from poly(arylene sulfide) fines comprising: (a) heating a mixture of poly(arylene sulfide) fines, polar organic solvent, alkali metal carboxylate, with or without, to at least the dispersion temperature of said poly(arylene sulfide) fines in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said poly(arylene sulfide) fines to be dispersed in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispersion temperature to cause a phase separation; (d) slowly cooling said mixture until at least about 200° C.; and (e) recovering particulate poly(arylene sulfide) from said mixture.
Claim 28
Dependent Claim
31 words
A method according to claim 24 wherein said mixture of (a) contains a sufficient amount of water to stabilize said poly(arylene sulfide) fines but yet not sufficient to cuase phase separation.
Claim 29
Dependent Claim
15 words
A method according to claim 24 wherein said polar organic solvent is an organic amide.
Claim 30
Dependent Claim
27 words
A method according to claim 26 wherein said organic amide is N-methyl-2-pyrrolidone and said dispersion temperature of said poly(arylene sulfide) fines in N-methyl-2-pyrrolidone is about 260° C.
Claim 31
Dependent Claim
16 words
A method according to claim 24 wherein said alkali metal carboxylate is an alkali metal acetate.
Claim 32
Dependent Claim
14 words
A method according to claim 28 wherein said alkali metal acetate is sodium acetate.
Claim 33
Dependent Claim
24 words
A method according to claim 24 wherein said heating is effected under sufficient pressure to maintain said polar organic solvent substantially in liquid phase.
Claim 34
Dependent Claim
20 words
A method according to claim 24 wherein said mixture of (d) is slowly cooled until at least about 150° C.
Claim 35
Dependent Claim
29 words
A method according to claim 24 wherein said mixture of (d) is slowly cooled at a rate in the range of about 0.2° to about 1° C. per minute.
Claim 36
Dependent Claim
20 words
A method according to claim 32 wherein said mixture of (d) is slowly cooled until at least about 100° C.
Claim 37
Dependent Claim
37 words
A method according to claim 24 wherein said sufficient length of time for said poly(arylene sulfide) fines to be dispersed in the balance of the mixture is within the range of about 1 minute to 1 hour.
Claim 38
Dependent Claim
31 words
A method according to claim 24 wherein the amount of water added in (c) is within the range of about 1 to 9 moles water per mole of poly(arylene sulfide) fines.
Claim 39
Dependent Claim
48 words
A method according to claim 24 wherein the molar ratio of polar organic solvent to poly(arylene sulfide) fines is within the range of about 2:1 to 6:1 and the molar ratio of alkali metal carboxylate to poly(arylene sulfide) fines is within the range of about 0.1:1 to 1:1.
Claim 40
Dependent Claim
16 words
A method according to claim 24 wherein said poly(arylene sulfide) fines are untreated poly(phenylene sulfide) fines.
Claim 41
Independent Claim
174 words
A method for converting poly(arylene sulfide) fines to particulate poly(arylene sulfide) fines comprising: (a) heating a mixture of poly(arylene sulfide) fines, N-methyl-2-pyrrolidone, water, and alkali metal acetate to at least the dispersion temperature of said poly(arylene sulfide) fines in said N-methyl-2-pyrrolidone; (b) maintaining said mixture at about said dispersion temperature for at least about 1 minute to 1 hour, time sufficient for said poly(arylene sulfide) fines to be dispersed in the balance of the mixture; (c) adding at least about 1 to 9 moles additional water per mole of poly(arylene sulfide) fines while maintaining said mixture at about said dispersion temperature; (d) slowly cooling said mixture at a rate in the range of about 0.2° to 1° C. per minute to about 150° C.; and (e) recovering particulate poly(arylene sulfide) from said mixture; wherein the amount of water in the mixture of (a) is sufficient to stabilize said poly(arylene sulfide) fines but yet not sufficient to cause phase separation and wherein the amount of water added in (c) is sufficient to cause phase separation.
Claim 42
Independent Claim
174 words
A method for converting poly(arylene sulfide) fines to particulate poly(arylene sulfide) fines comprising: (a) heating a mixture of poly(arylene sulfide) fines, N-methyl-2-pyrrolidone, water, and alkali metal acetate to at least the dispersion temperature of said poly(arylene sulfide) fines in said N-methyl-2-pyrrolidone; (b) maintaining said mixture at about said dispersion temperature for at least about 1 minute to 1 hour, time sufficient for said poly(arylene sulfide) fines to be dispersed in the balance of the mixture; (c) adding at least about 1 to 9 moles additional water per mole of poly(arylene sulfide) fines while maintaining said mixture at about said dispersion temperature; (d) slowly cooling said mixture at a rate in the range of about 0.2° to 1° C. per minute to about 150° C.; and (e) recovering particulate poly(arylene sulfide) from said mixture; wherein the amount of water in the mixture of (a) is sufficient to stabilize said poly(arylene sulfide) fines but yet not sufficient to cause phase separation and wherein the amount of water added in (c) is sufficient to cause phase separation.
Claim 43
Dependent Claim
23 words
A method according to claim 38 wherein said alkali metal acetate is sodium acetate and said poly(arylene sulfide) fines are poly(phenylene sulfide) fines.
Claim 44
Dependent Claim
19 words
A method according to claim 38 wherein said mixture of (d) is cooled to at least about 100° C.
Claim 45
Dependent Claim
20 words
A method according to claim 38 wherein said linear poly(arylene sulfide) recovered in (e) is then treated with calcium cations.
Claim 46
Dependent Claim
44 words
A method according to claim 38 wherein after said particulate poly(arylene sulfide) of (e) is recovered from said mixture, poly(arylene sulfide) slime which contains poly(arylene sulfide) fines is taken from said mixture and processed through said steps (a)-(e) to recover more particulate poly(arylene sulfide).
Claim 47
Dependent Claim
101 words
A method according to claim 38 wherein said heating is effected under sufficient pressure to maintain said N-methyl-2-pyrrolidone substantially in liquid phase, the molar ratio of N-methyl-2-pyrrolidone to poly(arylene sulfide) fines is within the range of about 2:1 to 6:1, the molar ratio of alkali metal acetate to poly(arylene sulfide) fines is within the range of about 0.1:1 to 1:1, the molar ratio of water to poly(arylene sulfide) fines in (a) is within the range of about 0:1 to 3:1, and the molar ratio of water to poly(arylene sulfide) fines of (c) is within the range of about 1:1 to 9:1.
Claim 48
Dependent Claim
76 words
A method according to claim 43 wherein the molar ratio of water to poly(arylene sulfide) fines in (a) is within the range of about 0.1:1 to 2:1, the molar ratio of water to poly(arylene sulfide) fines of (c) is within the range of about 2:1 to 4:1, and said time sufficient for said poly(arylene sulflide) fines to be dispersed in the balance of the mixture is within the range of about 5 minutes to 30 minutes.
Claim 49
Dependent Claim
63 words
A method according to claim 44 wherein the molar ratio of N-methyl-2-pyrrolidone to poly(arylene sulfide) fines is about 3:1, the molar ratio of alkali metal acetate to poly(arylene sulfide) fines in about 0.3:1, the molar ratio of water to poly(arylene sulfide) fines in (a) is about 1:1, and the molar ratio of water to poly(arylene sulfide) fines present in (c) is about 3:1.
Claim 50
Dependent Claim
23 words
A method according to claim 45 wherein said poly(arylene sulfide) fines are poly(phenylene sulfide) fines, and said alkali metal acetate is sodium acetate.
Claim 51
Independent Claim
120 words
A method for increasing the molar weight of non-linear poly(arylene sulfide) comprising: (a) heating a mixture comprising non-linear poly(arylene sulfide), polar organic solvent, and alkali metal carboxylate, with or without water, to at least the dispersion temperature of said non-linear poly(arylene sulfide) in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said non-linear poly(arylene sulfide) to disperse in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispesion temperature to cause a phase separation; (d) slowly cooling said mixture and water to at least about 200° C.; and (e) recovering a non-linear poly(arylene sulfide) of increased molecular weight from said mixture.
Claim 52
Independent Claim
120 words
A method for increasing the molar weight of non-linear poly(arylene sulfide) comprising: (a) heating a mixture comprising non-linear poly(arylene sulfide), polar organic solvent, and alkali metal carboxylate, with or without water, to at least the dispersion temperature of said non-linear poly(arylene sulfide) in said polar organic solvent; (b) maintaining said mixture at about said dispersion temperature for a sufficient length of time for said non-linear poly(arylene sulfide) to disperse in the balance of the mixture; (c) adding sufficient water while maintaining said mixture at about said dispesion temperature to cause a phase separation; (d) slowly cooling said mixture and water to at least about 200° C.; and (e) recovering a non-linear poly(arylene sulfide) of increased molecular weight from said mixture.
References Cited (Backward Citations)
GB166368A
Cited
US3919177A
Cited
US4089847A
Cited
US4071509A
Cited
US4415729A
Cited
US4524200A
Cited
JPS60235838A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1991-05-31 | 1991-11-30 | 1992-05-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-05-31 | 1995-11-30 | 1996-05-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-05-31 | 1999-11-30 | 2000-05-31 | $7700.00 | Window Closed / Lapsed |