US4668762A
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Polycondensation catalyst
Assignee: Shell USA Inc
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Filing: 1986-05-09
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Granted: 1987-05-26
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Expires: 2006-05-09
Abstract
Abstract Condensation polymers of high molecular weight, such as polyesters, polyureas, and polyamides, are usually prepared at temperatures of 200 DEG C. or greater. However, by utilizing the catalyst system of the present invention condensation polymers can be synthesized at much lower temperatures. These catalyst systems are comprised of (1) a silicon-phosphorus composition which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom; and (2) at least one acid acceptor. For example, P(OSiR3)3 wherein R can be an aliphatic or aromatic hydrocarbon radical, can be used in conjunction with a basic solvent as a catalyst system. Polymeric agents having pendant diphenylphosphine dichloride groups can also be used in conjunction with an acid acceptor as a catalyst system.
Inventors
- 👤 Naoya Ogata
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 08:11
CPC Classifications
C; C08; C08G; C08G69/00; C08G69/02; C08G69/04; C08G18/00; C08G18/06; C08G18/08; C08G18/16; C08G18/166; C08G18/168; C08G63/00; C08G63/78; C08G63/82; C08G63/87
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
57 words
A catalyst system which is particularly useful for the synthesis of condensation polymers which is comprised of (1) at least one silicon-phosphorus compound which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom; (2) an acid acceptor; and (3) a halogenated organic compound.
Claim 2
Dependent Claim
57 words
A catalyst system which is particularly useful for the synthesis of condensation polymers which is comprised of (1) at least one silicon-phosphorus compound which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom; (2) an acid acceptor; and (3) a halogenated organic compound.
Claim 3
Dependent Claim
34 words
A catalyst system which is particularly useful in synthesizing condensation polymers which is comprised of (1) at least one polymeric agent having pendant diphenyl phosphine dihalide groups; and (2) at least one acid acceptor.
Claim 4
Dependent Claim
34 words
A catalyst system which is particularly useful in synthesizing condensation polymers which is comprised of (1) at least one polymeric agent having pendant diphenyl phosphine dihalide groups; and (2) at least one acid acceptor.
Claim 5
Dependent Claim
65 words
A process for the synthesis of a polyester comprising polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (1) a silicon-phosphorus composition which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom; (2) an acid acceptor: and (3) at least one halogenated organic compound.
Claim 6
Dependent Claim
65 words
A process for the synthesis of a polyester comprising polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (1) a silicon-phosphorus composition which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom; (2) an acid acceptor: and (3) at least one halogenated organic compound.
Claim 7
Dependent Claim
63 words
A process for the synthesis of a polyamide which comprises polymerizing at least one dicarboxylic acid with at least one diamine in the presence of (1) a silicon-phosphorus composition which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom: (2) an acid acceptor: and (3) a halogenated organic compound.
Claim 8
Dependent Claim
63 words
A process for the synthesis of a polyamide which comprises polymerizing at least one dicarboxylic acid with at least one diamine in the presence of (1) a silicon-phosphorus composition which contains at least one divalent oxygen atom which is bonded directly to a tetravalent silicon atom and a trivalent or pentavalent phosphorus atom: (2) an acid acceptor: and (3) a halogenated organic compound.
Claim 9
Dependent Claim
143 words
A process for the semi-continuous synthesis of a polyester which comprises (1) polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (a) at least one substrate having pendant diphenylphosphine dichloride groups and (b) at least one acid acceptor, at a temperature between about 0° C. and 150° C.: (2) allowing said polymerization to continue until a polyester is formed with a substantial amount of the pendant diphenylphosphine dichloride groups being converted to pendant diphenylphosphine oxide groups; (3) treating the pendant diphenylphosphine oxide groups produced with a member selected from the group consisting of oxalyl chloride and phosgene under conditions which are sufficient to convert the pendant diphenylphosphine oxide groups back to regenerated pendant diphenylphosphine dichloride groups: and (4) polymerizing additional dicarboxylic acids with additional aromatic glycols in the presence of the regenerated pendant diphenylphosphine dichloride groups.
Claim 10
Dependent Claim
143 words
A process for the semi-continuous synthesis of a polyester which comprises (1) polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (a) at least one substrate having pendant diphenylphosphine dichloride groups and (b) at least one acid acceptor, at a temperature between about 0° C. and 150° C.: (2) allowing said polymerization to continue until a polyester is formed with a substantial amount of the pendant diphenylphosphine dichloride groups being converted to pendant diphenylphosphine oxide groups; (3) treating the pendant diphenylphosphine oxide groups produced with a member selected from the group consisting of oxalyl chloride and phosgene under conditions which are sufficient to convert the pendant diphenylphosphine oxide groups back to regenerated pendant diphenylphosphine dichloride groups: and (4) polymerizing additional dicarboxylic acids with additional aromatic glycols in the presence of the regenerated pendant diphenylphosphine dichloride groups.
Claim 11
Dependent Claim
24 words
A catalyst system as specified in claim 1 wherein said acid acceptor is an organic base which has a pKa of at least 5.
Claim 12
Dependent Claim
30 words
A catalyst system as specified in claim 6 wherein said halogenated organic compound contains at least one carbon atom which has at least two halogen atoms bonded directly to it.
Claim 13
Dependent Claim
143 words
A catalyst system as specified in claim 7 wherein said silicon-phosphorus compound has a structural formula selected from the group consisting of: ##STR10## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are selected from the group consisting of alkyl groups which contain from 1 to 20 carbon atoms, aryl groups which contain from 1 to 20 carbon atoms, alkylaryl groups which contain from 1 to 20 carbon atoms, hydrogen atoms, organometallic groups, and inorganic moieties; and wherein R 4 , R 5 , R 6 and R 7 can further be selected from the group consisting of halogen atoms with the proviso that no more than 2 of the members selected from the group consisting of R 4 , R 5 , R 6 and R 7 are halogen atoms.
Claim 14
Dependent Claim
45 words
A catalyst system as specified in claim 8 wherein said organic base has a pKa within the range of 5 to 12 and wherein said halogenated organic compound contains at least one carbon atom which has at least 3 halogen atoms bonded directly to it.
Claim 15
Dependent Claim
33 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has the structural formula P(OSiR 3 ) 3 wherein R is an alkyl group containing from 1 to 20 carbon atoms.
Claim 16
Dependent Claim
21 words
A catalyst system as specified in claim 10 wherein R is an alkyl group containing from 1 to 8 carbon atoms.
Claim 17
Dependent Claim
72 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has a structural formula selected from the group consisting of: ##STR11## wherein R, R 1 and R 2 can be the same or different and are selected from the group consisting of alkyl groups containing from 1 to 20 carbon atoms, aryl groups containing from 1 to 20 carbon atoms, and alkylaryl groups containing from 1 to 20 carbon atoms.
Claim 18
Dependent Claim
57 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has the structural formula O═P(OSiR 3 ) 3 wherein R is selected from the group consisting of alkyl groups containing from 1 to 20 carbon atoms, aryl groups containing from 1 to 20 carbon atoms, and alkylaryl groups containing from 1 to 20 carbon atoms.
Claim 19
Dependent Claim
77 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has a structural formula selected from the group consisting of X 2 P(OSiR 3 ) 3 and X 2 P-OSiR 3 wherein X represents a halogen atom and wherein R is selected from the group consisting of alkyl groups containing from 1 to 20 carbon atoms, aryl groups containing from 1 to 20 carbon atoms, and alkylaryl groups containing from 1 to 20 carbon atoms.
Claim 20
Dependent Claim
26 words
A catalyst system as specified in claim 14 wherein said halogen atom is selected from the group consisting of chlorine atoms, bromine atoms and iodine atoms.
Claim 21
Dependent Claim
66 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has the structural formula: ##STR12## wherein R is selected from the group consisting of alkyl groups containing from 1 to 20 carbon atom, aryl groups containing from 1 to 20 carbon atoms, and alkylaryl groups containing from 1 to 20 carbon atoms; and wherein n is an integer from about 10 to about 1,000.
Claim 22
Dependent Claim
21 words
A catalyst system as specified in claim 16 wherein R represents an alkyl group containing from 1 to 8 carbon atoms.
Claim 23
Dependent Claim
89 words
A catalyst system as specified in claim 9 wherein said silicon-phosphorus compound has the structural formula: ##STR13## wherein n is an integer from about 10 to about 1000 and wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be the same or different and are selected from the group consisting of alkyl groups containing from 1 to 20 carbon atoms, aryl groups containing from 1 to 20 carbon atoms, and alkylaryl groups containing from 1 to 20 carbon atoms.
Claim 24
Dependent Claim
21 words
A catalyst system as specified in claim 18 wherein R represents an alkyl group containing from 1 to 8 carbon atoms.
Claim 25
Dependent Claim
29 words
A catalyst system as specified in claim 2 wherein said polymeric agent has the structural formula: ##STR14## werein n is an integer and wherein X represents a halogen atom.
Claim 26
Dependent Claim
19 words
A catalyst system as specified in claim 20 wherein n is an integer from about 10 to about 1,000.
Claim 27
Dependent Claim
37 words
A process as specified in claim 3 wherein said process is conducted at a temperature from 50° C. to 80° C. and wherein said acid acceptor is an organic base having a pKa of at least 5.
Claim 28
Dependent Claim
29 words
A process as specified in claim 22 wherein said halogenated organic compound contains at least one carbon atom which has at least three halogen atoms bonded directly to it.
Claim 29
Dependent Claim
144 words
A process for the semi-continuous synthesis of a polyester which comprises (1) polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (a) at least one substrate having pendant diphenylphosphine dihalide groups and (b) at least one acid acceptor, at a temperature between about 0° C. and 150° C.; (2) allowing said polymerization to continue until a polyester is formed with a substantial amount of the pendant diphenylphosphine dihalide groups being converted to pendant diphenylphosphine oxide groups: (3) treating the pendant diphenylphosphine oxide groups produced with a member selected from the group consisting of oxalyl halides and carbonyl dihalides under conditions which are sufficient to convert the pendant diphenylphosphine oxide groups back to regenerated pendant diphenylphosphine dihalide groups; and (4) polymerizing additional dicarboxylic acids with additional aromatic glycols in the presence of the regenerated pendant diphenylphosphine dihalide groups.
Claim 30
Dependent Claim
144 words
A process for the semi-continuous synthesis of a polyester which comprises (1) polymerizing at least one dicarboxylic acid with at least one aromatic glycol in the presence of (a) at least one substrate having pendant diphenylphosphine dihalide groups and (b) at least one acid acceptor, at a temperature between about 0° C. and 150° C.; (2) allowing said polymerization to continue until a polyester is formed with a substantial amount of the pendant diphenylphosphine dihalide groups being converted to pendant diphenylphosphine oxide groups: (3) treating the pendant diphenylphosphine oxide groups produced with a member selected from the group consisting of oxalyl halides and carbonyl dihalides under conditions which are sufficient to convert the pendant diphenylphosphine oxide groups back to regenerated pendant diphenylphosphine dihalide groups; and (4) polymerizing additional dicarboxylic acids with additional aromatic glycols in the presence of the regenerated pendant diphenylphosphine dihalide groups.
Claim 31
Dependent Claim
22 words
A process as specified in claim 24 wherein said acid acceptor is an organic base having a pKa of at least 5.
Claim 32
Dependent Claim
31 words
A catalyst system which is particularly useful in synthesizing condensation polymers which is comprised of (1) glass beads having pendant diphenyl phosphine dihalide groups: and (2) at least one acid acceptor.
Claim 33
Dependent Claim
31 words
A catalyst system which is particularly useful in synthesizing condensation polymers which is comprised of (1) glass beads having pendant diphenyl phosphine dihalide groups: and (2) at least one acid acceptor.
Claim 34
Dependent Claim
44 words
A catalyst system as specified in claim 1 wherein the molar ratio of the acid acceptor to the silicon-phosphorus compound is trom 0.8 to 1.5 and wherein the molar ratio of the halogenated organic compound to the silicon-phosphorus compound is from 0.8 to 1.5.
Claim 35
Dependent Claim
81 words
A process as provided in claim 3 wherein the molar ratio of the silicon-phosphorus composition to the total amount of dicarboxylic acids and aromatic glycols present is from 1.0 to 1.5; wherein the molar ratio of the acid acceptor to the total amount of dicarboxylic acids and aromatic glycols present is from 1.0 to 1.5; and wherein the molar ratio of said halogenated organic compounds to the total amount of dicarboxylic acids and aromatic glycols present is from 1.0 to 1.5.
Claim 36
Dependent Claim
78 words
A process as provided in claim 4 wherein the molar ratio of the silicon-phosphorus composition to the total amount of dicarboxylic acids and diamines present is from 1.0 to 1.5; wherein the molar ratio of the acid acceptor to the total amount of dicarboxylic acids and diamines present is from 1.0 to 1.5: and wherein the molar ratio of said halogenated organic compounds to the total amount of dicarboxylic acids and diamines present is from 1.0 to 1.5.
Claim 37
Dependent Claim
29 words
A catalyst system as specified in claim 2 wherein the molar ratio of acid acceptor to pendant diphenyl phosphine dihalide groups is within the range of 0.8 to 1.5.
Claim 38
Dependent Claim
63 words
A process as specified in claim 24 wherein the molar ratio of pendant diphenyl phosphine dihalide groups to the total molar amount of dicarboxylic acids and aromatic glycols is within the range of 1.0 to 1.5 and wherein the molar ratio of acid acceptor to the total molar amount of dicarboxylic acids and aromatic glycols is within the range of 1.0 to 1.5.
References Cited (Backward Citations)
US4077944A
Cited
US4156072A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-05-25 | 1990-11-24 | 1991-05-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-05-25 | 1994-11-24 | 1995-05-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-05-25 | 1998-11-24 | 1999-05-26 | $7700.00 | Window Closed / Lapsed |