US4831081A
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Method for crosslinking reactive polyolefins via a rhodium catalyzed hydrosilation reaction using polyorganosiloxane crosslinkers
Assignee: Union Carbide Corp
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Filing: 1987-09-30
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Granted: 1989-05-16
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Expires: 2007-09-30
Abstract
Abstract The present invention is directed to a method for crosslinking reactive polyolefins using a rhodium catalyzed hydrosilation reaction and novel siloxanes as crosslinkers. Also disclosed are novel siloxane compounds which are useful in the crosslinking of polyolefins and polyolefin compositions which have been crosslinked through use of the claimed process and siloxane crosslinkers.
Inventors
- 👤 Roswell E. King, III
- 👤 Herbert E. Petty
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 12:41
CPC Classifications
C; C08; C08L; C08L43/00; C08L43/04; C08K; C08K5/00; C08K5/54; C08K5/541; C08K5/5415; C08K5/5419; C08L23/00; C08L23/02
Claims Analysis
Total Claims: 54
Claim 1
Independent Claim
189 words
A process of crosslinking reactive polyolefins comprising admixing a reactive polyolefin with (a) a polyorganosiloxane of the formula: ##STR12## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR13## D' represents the group ##STR14## T represents the group ##STR15## Q represents the group ##STR16## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z of T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6; and (b) a hydrosilation catalyst of the formula L.sub.1 L.sub.2 RhX wherein L 1 and L 2 are neutral coordinating ligands and X is a halide atom or pseudo-halide ligand; and exposing the resultant mixture to an elevated temperature sufficient to initiate a hydrosilation reaction therein.
Claim 2
Dependent Claim
189 words
A process of crosslinking reactive polyolefins comprising admixing a reactive polyolefin with (a) a polyorganosiloxane of the formula: ##STR12## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR13## D' represents the group ##STR14## T represents the group ##STR15## Q represents the group ##STR16## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z of T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6; and (b) a hydrosilation catalyst of the formula L.sub.1 L.sub.2 RhX wherein L 1 and L 2 are neutral coordinating ligands and X is a halide atom or pseudo-halide ligand; and exposing the resultant mixture to an elevated temperature sufficient to initiate a hydrosilation reaction therein.
Claim 3
Dependent Claim
39 words
The process of claim 1 wherein x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 1.
Claim 4
Dependent Claim
65 words
The process of claim 1 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having from about 8 to about 16 carbon atoms, R" represents a methyl group, x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 1.
Claim 5
Dependent Claim
61 words
The process of claim 1 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having about 12 carbon atoms, R" represents a methyl group, x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 1.
Claim 6
Dependent Claim
20 words
The process of claim 1 wherein the rhodium containing hydrosilation catalyst is in admixture with a platinum containing hydrosilation catalyst.
Claim 7
Dependent Claim
90 words
The process of claim 1 wherein L 1 and L 2 of the hydrosilation catalyst are selected from the group consisting of linear olefinic groups having from 2 to about 8 carbon atoms, cycloaliphatic groups containing at least two double bonds and having from about 6 to about 12 carbon atoms, carbon monoxide, phosphine and phosphite compounds of the formula P(R"') 3 and P(OR"') 3 , respectively, wherein R"' represents a phenyl group or an alkyl-substituted phenyl group wherein the alkyl group contains from 1 to about 6 carbon atoms.
Claim 8
Dependent Claim
28 words
The process of claim 6 wherein L 1 and L 2 of the hydrosilation catalyst represent linear olefinic groups having from about 4 to about 8 carbon atoms.
Claim 9
Dependent Claim
15 words
The process of claim 1 wherein X of the hydrosilation catalyst is a chlorine atom.
Claim 10
Dependent Claim
15 words
The process of claim 6 wherein X of the hydrosilation catalyst is a chlorine atom.
Claim 11
Dependent Claim
23 words
The process of claim 6 wherein L 1 and L 2 of the hydrosilation catalyst represent cyclooctadiene and X represents a chlorine atom.
Claim 12
Dependent Claim
27 words
The process of claim 1 wherein the hydrosilation catalyst is present in amounts ranging from about 25 to about 1000 ppm based upon the total polyolefin composition.
Claim 13
Dependent Claim
27 words
The process of claim 11 wherein the hydrosilation catalyst is present in amounts ranging from about 50 to about 200 ppm based upon the total polyolefin composition.
Claim 14
Dependent Claim
27 words
The process of claim 10 wherein the hydrosilation catalyst is present in amounts ranging from about 50 to about 200 ppm based upon the total polyolefin composition.
Claim 15
Dependent Claim
23 words
The process of claim 5 wherein the ratio of rhodium-containing hydrosilation catalyst to platinum-containing hydrosilation catalyst ranges from about 1:10 to about 10:1.
Claim 16
Dependent Claim
19 words
The process of claim 14 wherein the ratio of rhodium-containing hydrosilation catalyst to platinum-containing hydrosilation catalyst is about 1:1.
Claim 17
Dependent Claim
19 words
The process of claim 5 wherein the platinum-containing catalyst comprises (C 2 H 5 S) 2 PtCl 2 .
Claim 18
Dependent Claim
19 words
The process of claim 14 wherein the platinum-containing catalyst comprises (C 2 H 5 S) 2 PtCl 2 .
Claim 19
Dependent Claim
13 words
The process of claim 1 wherein the reactive polyolefin comprises ethylene/propylene/diene monomer polymers.
Claim 20
Dependent Claim
41 words
The process of claim 18 wherein the ethylene/propylene/diene monomer polymers contain from about 60 to about 80 wt. % of ethylene and the diene component thereof is selected from the group consisting of 1,4 hexadiene, dicyclopentadiene, ethylidene norbornene, 4(5)-methyl-1,4-hexadiene and 1,5-cyclooctadiene.
Claim 21
Dependent Claim
33 words
The process of claim 1 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having from about 8 to about 16 carbon atoms, and R" represents a methyl group.
Claim 22
Dependent Claim
16 words
A process as defined in claim 1 wherein the rhodium hydrosilation catalyst has the formula: [(cyclooctadiene)RhCl].sub.2.
Claim 23
Dependent Claim
17 words
A process as defined in claim 1 wherein the rhodium hydrosilation catalyst has the formula: [(CO).sub.2 RhCl].sub.
Claim 24
Dependent Claim
17 words
A process as defined in claim 1 wherein the rhodium hydrosilation catalyst has the formula: (PPh.sub.3).sub.2 CORhCl
Claim 25
Dependent Claim
169 words
A polyolefin composition comprising (a) a reactive polyolefin, (b) a polyorganosiloxane of the formula: ##STR17## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR18## D' represents the group ##STR19## T represents the group ##STR20## Q represents the group ##STR21## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z of T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6; and (c) a hydrosilation catalyst of the formula L.sub.1 L.sub.2 RhX wherein L 1 and L 2 are neutral coordinating ligands and X is a halide atom or pseudo-halide ligand.
Claim 26
Dependent Claim
169 words
A polyolefin composition comprising (a) a reactive polyolefin, (b) a polyorganosiloxane of the formula: ##STR17## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR18## D' represents the group ##STR19## T represents the group ##STR20## Q represents the group ##STR21## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z of T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6; and (c) a hydrosilation catalyst of the formula L.sub.1 L.sub.2 RhX wherein L 1 and L 2 are neutral coordinating ligands and X is a halide atom or pseudo-halide ligand.
Claim 27
Dependent Claim
39 words
The composition of claim 24 wherein x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 24.
Claim 28
Dependent Claim
65 words
The composition of claim 24 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having from about 8 to about 16 carbon atoms, R" represents a methyl group, x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 24.
Claim 29
Dependent Claim
61 words
The composition of claim 24 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having about 12 carbon atoms, R" represents a methyl group, x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 24.
Claim 30
Dependent Claim
20 words
The composition of claim 24 wherein the rhodium containing hydrosilation catalyst is in admixture with a platinum containing hydrosilation catalyst.
Claim 31
Dependent Claim
33 words
The composition of claim 24 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having from about 8 to about 16 carbon atoms, and R" represents a methyl group.
Claim 32
Dependent Claim
90 words
The composition of claim 24 wherein L 1 and L 2 of the hydrosilation catalyst are selected from the group consisting of linear olefinic groups having from two to about 8 Carbon atoms, cycloaliphatic groups containing at least two double bonds and having from about 6 to about 12 carbon atoms, carbon monoxide, phosphine and phosphite compounds of the formula P(R"') 3 and P(OR"') 3 , respectively, wherein R"' represents a phenyl group or an alkyl-substituted phenyl group wherein the alkyl group contains from 1 to about 6 carbon atoms.
Claim 33
Dependent Claim
28 words
The composition of claim 30 wherein L 1 and L 2 of the hydrosilation catalyst represent linear olefinic groups having from about 4 to about 8 carbon atoms.
Claim 34
Dependent Claim
15 words
The composition of claim 24 wherein X of the hydrosilation catalyst is a chlorine atom.
Claim 35
Dependent Claim
15 words
The composition of claim 30 wherein X of the hydrosilation catalyst is a chlorine atom.
Claim 36
Dependent Claim
23 words
The composition of claim 30 wherein L 1 and L 2 of the hydrosilation catalyst represent cyclooctadiene and X represents a chlorine atom.
Claim 37
Dependent Claim
27 words
The composition of claim 24 wherein the hydrosilation catalyst is present in amounts ranging from about 25 to about 1000 ppm based upon the total polyolefin composition.
Claim 38
Dependent Claim
27 words
The composition of claim 35 wherein the hydrosilation catalyst is present in amounts ranging from about 50 to about 200 ppm based upon the total polyolefin composition.
Claim 39
Dependent Claim
27 words
The composition of claim 34 wherein the hydrosilation catalyst is present in amounts ranging from about 50 to about 200 ppm based upon the total polyolefin composition.
Claim 40
Dependent Claim
23 words
The composition of claim 28 wherein the ratio of rhodium-containing hydrosilation catalyst to platinum-containing hydrosilation catalyst ranges from about 1:10 to about 10:1.
Claim 41
Dependent Claim
19 words
The composition of claim 38 wherein the ratio of rhodium-containing hydrosilation catalyst to platinum-containing hydrosilation catalyst is about 1:1.
Claim 42
Dependent Claim
19 words
The composition of claim 28 wherein the platinum-containing catalyst comprises (C 2 H 5 S) 2 PtCl 2 .
Claim 43
Dependent Claim
19 words
The composition of claim 38 wherein the platinum-containing catalyst comprises (C 2 H 5 S) 2 PtCl 2 .
Claim 44
Dependent Claim
13 words
The composition of claim 24 wherein the reactive polyolefin comprises ethylene/propylene/diene monomer polymers.
Claim 45
Dependent Claim
41 words
The composition of claim 42 wherein the ethylene/propylene/diene monomer polymers contain from about 60 to about 80 wt. % of ethylene and the diene component thereof is selected from the group consisting of 1,4 hexadiene, dicylcopentadiene, ethylidene norbornene, 4(5)-methyl-1,4-hexadiene and 1,5-cyclooctadiene.
Claim 46
Dependent Claim
16 words
A composition as defined in claim 24 wherein the rhodium hydrosilation catalyst has the formula: [(cyclooctadiene)RhCl].sub.2.
Claim 47
Dependent Claim
17 words
A composition as defined in claim 24 wherein the rhodium hydrosilation catalyst has the formula: [(CO).sub.2 RhCl].sub.2.
Claim 48
Dependent Claim
17 words
A composition as defined in claim 24 wherein the rhodium hydrosilation catalyst has the formula: (PPh.sub.3).sub.2 CORhCl.
Claim 49
Dependent Claim
141 words
A poylorganosiloxane useful in the crosslinking of reactive polyolefin compositions, said polyorganosiloxane being of the formula: ##STR22## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR23## D' represents the group ##STR24## T represents the group ##STR25## Q represents the group ##STR26## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z in T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6.
Claim 50
Dependent Claim
141 words
A poylorganosiloxane useful in the crosslinking of reactive polyolefin compositions, said polyorganosiloxane being of the formula: ##STR22## or mixtures thereof R represents an alkyl group having from 1 to about 4 carbon atoms, R' represents a hydrogen atom, an alkyl or alkoxy group having from 1 to about 24 carbon atoms, R" represents R or a hydrogen atom; D represents the group ##STR23## D' represents the group ##STR24## T represents the group ##STR25## Q represents the group ##STR26## x is an integer having a value ranging from about 2 to about 12; y is an integer having a value ranging from about 2 to about 12; the z in T z is an integer having a value ranging from 0 to about 6; and the z of Q z is an integer having a value ranging from 1 to about 6.
Claim 51
Dependent Claim
39 words
The polyorganosiloxane of claim 47 wherein x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 47.
Claim 52
Dependent Claim
65 words
The polyorganosiloxane of claim 47 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having from about 8 to about 16 carbon atoms, R" represents a methyl group, x has a value of from about 4 to about 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 47.
Claim 53
Dependent Claim
60 words
The polyorganosiloxane of claim 47 wherein R represents a methyl group, R' represents an alkyl or alkoxy group having about 12 carbon atoms, R" represents a methyl group, x has a value of from about 4 to 8, y has a value of from about 4 to about 8, and each z has a value as defined in claim 47.
Claim 54
Dependent Claim
31 words
The polyorganosiloxane of claim 47 wherein R represents a methyl group, R' represents an alkoxy group having from about 8 to about 16 carbon atoms, and R" represents a methyl group.
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) | 1992-05-15 | 1992-11-14 | 1993-05-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-15 | 1996-11-14 | 1997-05-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-15 | 2000-11-14 | 2001-05-16 | $7700.00 | Window Closed / Lapsed |