US4157337A
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Process for the polymerization of cyclic diorganopolysiloxanes with cation-complex catalysts
Assignee: General Electric Co
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Filing: 1977-07-06
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Granted: 1979-06-05
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Expires: 1997-07-06
Abstract
Abstract Diorganopolysiloxane homo- and copolymers having a viscosity from 50 to 200,000,000 centipoise at 25° C., are produced by (A) reacting a composition of (i) a first cyclic siloxane having 3 to 6 units alone or admixed with (ii) a second cyclic tetrasiloxane having 3 to 6 units, (i) being present in an amount of 30 to 100 mol % of the composition, at a temperature in the range of 90° to 150° C. and in the presence of 5 to 500, preferably 5 to 50 parts per million, as KOH, of a catalyst comprising (a) KOH complexed with a molar equivalent of a cyclic polyesther, or (b) a silanolate of KOH complexed with a molar equivalent of a cyclic polyether and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached. Especially useful products of the process are homopolymers and copolymers including siloxane chain units of the formula R R 1 SiO wherein R 1 is alkyl, halogenated alkyl or cycloalkyl, and preferably, perfluoroalkyl, and R is the same as R 1 and, in addition, methyl, ethyl, vinyl or phenyl.
Inventors
- 👤 Edwin R. Evans
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 03:18
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/04; C08G77/06; C08G77/08; C08G77/22; C08G77/24
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
192 words
A process for producing a diorganopolysiloxane having a viscosity of from 50 to 200,000,000 centipoise at 25° C. comprising (A) reacting a composition comprising (i) a cyclic polysiloxane of the formula, (R R.sup.1 SiO).sub.x or a mixed such polysiloxane wherein R is methyl, ethyl, vinyl or phenyl and R 1 is as defined for R and in addition, alkyl, halogenated alkyl, or cycloalkyl, each of 3 to 8 carbon atoms and x is from 3 to 6, and (ii) a cyclic polysiloxane of the formula, (R.sub.2.sup.2 SiO).sub.y wherein R 2 is, independently, methyl, ethyl, vinyl or phenyl and y is from 3 to 6, or a mixed such polysiloxane, (i) being present in an amount of from 30 to 100 mol % of the composition, at a temperature in the range of 20° to 160° C. in the presence of 5 to 500 parts per million, as KOH, of a catalyst comprising (a) KOH complexed with a molar equivalent of a cyclic polyether, or (b) a silanolate of KOH complexed with a molar equivalent of a cyclic polyether and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 2
Dependent Claim
192 words
A process for producing a diorganopolysiloxane having a viscosity of from 50 to 200,000,000 centipoise at 25° C. comprising (A) reacting a composition comprising (i) a cyclic polysiloxane of the formula, (R R.sup.1 SiO).sub.x or a mixed such polysiloxane wherein R is methyl, ethyl, vinyl or phenyl and R 1 is as defined for R and in addition, alkyl, halogenated alkyl, or cycloalkyl, each of 3 to 8 carbon atoms and x is from 3 to 6, and (ii) a cyclic polysiloxane of the formula, (R.sub.2.sup.2 SiO).sub.y wherein R 2 is, independently, methyl, ethyl, vinyl or phenyl and y is from 3 to 6, or a mixed such polysiloxane, (i) being present in an amount of from 30 to 100 mol % of the composition, at a temperature in the range of 20° to 160° C. in the presence of 5 to 500 parts per million, as KOH, of a catalyst comprising (a) KOH complexed with a molar equivalent of a cyclic polyether, or (b) a silanolate of KOH complexed with a molar equivalent of a cyclic polyether and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 3
Dependent Claim
17 words
A process as defined in claim 1 wherein the cyclic polyether is 1,4,7,10,13,16-hexaoxacyclooctadecane or 2,5,8,15,18,21-hexaoxatricyclo[20,4,0,0 9:14 ]-hexacosane.
Claim 4
Dependent Claim
44 words
A process as defined in claim 1 wherein the silanolate includes units of the formula R 2 4 SiO wherein the R 4 groups, independently, are alkyl of from 1 to 8 carbon atoms, cycloalkyl of from 4 to 8 carbon atoms or phenyl.
Claim 5
Dependent Claim
12 words
A process as defined in claim 3 wherein R 4 is methyl.
Claim 6
Dependent Claim
48 words
A process as defined in claim 1 wherein the catalyst is neutralized with phosphoric acid or a compound of the formula, R b 6 SiX 4-b , where R 6 is alkyl, cycloalkyl, vinyl or phenyl, X is bromine or chlorine, and b is from 0 to 3.
Claim 7
Dependent Claim
39 words
A process as defined in claim 1 including after step (b) the further step comprising heating the reaction mixture to 150° to 200° C. at a vacuum of 1 to 100 mm of Hg to strip off all volatiles.
Claim 8
Dependent Claim
23 words
A process as defined in claim 1 wherein the cyclic polysiloxanes are reacted with the catalyst for from 1/2 hour to 20 hours.
Claim 9
Dependent Claim
42 words
A process as defined in claim 1 wherein the cyclic polysiloxanes and mixtures thereof contain less than 20 parts per million of trifunctional siloxanes, less than 200 parts per million of monofunctional siloxanes, and less than 10 parts per million of water.
Claim 10
Dependent Claim
28 words
A process as defined in claim 1 wherein R 1 is R 7 CH 2 CH 2 --and R 7 is perfluoroalkyl of 1 to 6 carbon atoms.
Claim 11
Dependent Claim
33 words
A process as defined in claim 1 wherein R 1 is CF 3 CH 2 CH 2 --; R and R 2 are each methyl; and x and y are 3 or 4.
Claim 12
Dependent Claim
17 words
A process as defined in claim 10 wherein x is 4 and y is 3 or 4.
Claim 13
Dependent Claim
17 words
A process as defined in claim 1 wherein component (i) comprises 100 mol % of the composition.
Claim 14
Dependent Claim
26 words
A process as defined in claim 1 wherein cyclic polysiloxane (i) is present in an amount of from 30 to 96 mol % of the composition.
Claim 15
Dependent Claim
26 words
A process as defined in claim 1 wherein cyclic polysiloxane (i) is present in an amount of from 30 to 85 mole % of the compositon.
Claim 16
Dependent Claim
25 words
A process as defined in claim 1 wherein step (A) is carried out at a temperature in the range of 90° C. to 150° C.
Claim 17
Dependent Claim
192 words
A process for producing a diorganopolysiloxane having a viscosity of from 50 to 200,000,000 centipoise at 25° C. comprising (A) reacting a composition comprising (i) a cyclic polysiloxane of the formula, (R R.sup.1 SiO).sub.x or a mixed such polysiloxane wherein R is methyl, ethyl, vinyl or phenyl and R 1 is as defined for R and in addition, alkyl, halogenated alkyl, or cycloalkyl, each of 3 to 8 carbon atoms and x is from 3 to 6, and (ii) a cyclic polysiloxane of the formula, (R.sub.2.sup.2 SiO).sub.y wherein R 2 is, independently, methyl, ethyl, vinyl or phenyl and y is from 3 to 6, or a mixed such polysiloxane, (i) being present in an amount of from 30 to 100 mol % of the composition, at a temperature in the range of 20° to 160° C. in the presence of 5 to 50 parts per million, as KOH, of a catalyst comprising (a) KOH complexed with a molar equivalent of a cyclic polyether, or (b) a silanolate of KOH complexed with a molar equivalent of a cyclic polyether and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 18
Dependent Claim
192 words
A process for producing a diorganopolysiloxane having a viscosity of from 50 to 200,000,000 centipoise at 25° C. comprising (A) reacting a composition comprising (i) a cyclic polysiloxane of the formula, (R R.sup.1 SiO).sub.x or a mixed such polysiloxane wherein R is methyl, ethyl, vinyl or phenyl and R 1 is as defined for R and in addition, alkyl, halogenated alkyl, or cycloalkyl, each of 3 to 8 carbon atoms and x is from 3 to 6, and (ii) a cyclic polysiloxane of the formula, (R.sub.2.sup.2 SiO).sub.y wherein R 2 is, independently, methyl, ethyl, vinyl or phenyl and y is from 3 to 6, or a mixed such polysiloxane, (i) being present in an amount of from 30 to 100 mol % of the composition, at a temperature in the range of 20° to 160° C. in the presence of 5 to 50 parts per million, as KOH, of a catalyst comprising (a) KOH complexed with a molar equivalent of a cyclic polyether, or (b) a silanolate of KOH complexed with a molar equivalent of a cyclic polyether and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 19
Dependent Claim
17 words
A process as defined in claim 16 wherein the cyclic polyether is 1,4,7,10,13,16-hexaoxacyclooctadecane or 2,5,8,15,18,21-hexaoxatricyclo[20,4,0,0 9:14 ]-hexacosane.
Claim 20
Dependent Claim
44 words
A process as defined in claim 16 wherein the silanolate includes units of the formula R 2 4 SiO wherein the R 4 groups, independently, are alkyl of from 1 to 8 carbon atoms, cycloalkyl of from 4 to 8 carbon atoms or phenyl.
Claim 21
Dependent Claim
12 words
A process as defined in claim 18 wherein R 4 is methyl.
Claim 22
Dependent Claim
48 words
A process as defined in claim 16 wherein the catalyst is neutralized with phosphoric acid or a compound of the formula, R b 6 SiX 4-b , where R 6 is alkyl, cycloalkyl, vinyl or phenyl, X is bromine or chlorine, and b is from 0 to 3.
Claim 23
Dependent Claim
39 words
A process as defined in claim 16 including after step (b) the further step comprising heating the reaction mixture to 150° to 200° C. at a vacuum of 1 to 100 mm of Hg to strip off all volatiles.
Claim 24
Dependent Claim
22 words
A process as defined in claim 16 wherein the cyclic polysiloxanes are reacted with catalyst for from 1/2 hour to 20 hours.
Claim 25
Dependent Claim
42 words
A process as defined in claim 16 wherein the cyclic polysiloxanes and mixtures thereof contain less than 20 parts per million of trifunctional siloxanes, less than 200 parts per million of monofunctional siloanes, and less than 10 parts per million of water.
Claim 26
Dependent Claim
28 words
A process as defined in claim 16 wherein R 1 is R 7 CH 2 CH 2 --and R 7 is perfluoroalkyl of 1 to 6 carbon atoms.
Claim 27
Dependent Claim
33 words
A process as defined in claim 16 wherein R 1 is CF 3 CH 2 CH 2 --; R and R 2 are each methyl; and x and y are 3 or 4.
Claim 28
Dependent Claim
17 words
A process as defined in claim 25 wherein x is 4 and y is 3 or 4.
Claim 29
Dependent Claim
17 words
A process as defined in claim 16 wherein component (i) comprises 100 mol % of the composition.
Claim 30
Dependent Claim
26 words
A process as defined in claim 16 wherein cyclic polysiloxane (i) is present in an amount of from 30 to 96 mol % of the composition.
Claim 31
Dependent Claim
26 words
A process as defined in claim 16 wherein cyclic polysiloxane (i) is present in an amount of from 30 to 85 mole % of the composition.
Claim 32
Dependent Claim
25 words
A process as defined in claim 16 wherein step (A) is carried out at a temperature in the range of 90° C. to 150° C.
Claim 33
Dependent Claim
78 words
A process for producing an organopolysiloxane copolymer comprising (A) reacting a composition comprising: (i) from 70 to 50 mol % of 1,3,5,7-tetramethyl-tetrakis-1,3,5,7-(3,3,3-trifluoropropyl) cyclotetrasiloxane, and (ii) from 30 to 50 mol % of octamethylcyclotetrasiloxane, at a temperature of 120° C. for 12 hours in the presence of 20 parts per million, as KOH, of a catalyst comprising KOH complexed with a molar equivalent of 1,4,7,10,13,16-hexaoxacyclooctadecane, and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 34
Dependent Claim
78 words
A process for producing an organopolysiloxane copolymer comprising (A) reacting a composition comprising: (i) from 70 to 50 mol % of 1,3,5,7-tetramethyl-tetrakis-1,3,5,7-(3,3,3-trifluoropropyl) cyclotetrasiloxane, and (ii) from 30 to 50 mol % of octamethylcyclotetrasiloxane, at a temperature of 120° C. for 12 hours in the presence of 20 parts per million, as KOH, of a catalyst comprising KOH complexed with a molar equivalent of 1,4,7,10,13,16-hexaoxacyclooctadecane, and (B) neutralizing the catalyst in the reaction mixture after equilibrium has been reached.
Claim 35
Dependent Claim
21 words
A process as defined in claim 31 wherein the copolymer reaction product has a viscosity of 65,000-70,000 centipoise at 25° C.
Claim 36
Dependent Claim
38 words
A process as defined in claim 31 including after step (B) the further step comprising heating the reaction mixture at a temperature of 155°-160° C. and a vacuum of 1-2 mm of Hg, to strip off all volatiles.
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) | 1982-06-04 | 1982-12-04 | 1983-06-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-06-04 | 1986-12-04 | 1987-06-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-06-04 | 1990-12-04 | 1991-06-05 | $7700.00 | Window Closed / Lapsed |