US4806581A
Expired / Lapsed
US
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Graft polymers of polymerizable monomers and olefin polymers
Assignee: Occidental Chemical Corp
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Filing: 1987-03-10
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Granted: 1989-02-21
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Expires: 2007-03-10
Abstract
Abstract Graft polymers are prepared by reacting an ethylenically unsaturated polymerizable monomer with a polymer of an olefin of 2 to about 8 carbon atoms in a process wherein the olefin polymer is substantially insoluble in the monomer but is capable of absorbing the monomer. In a preferred aspect, a vinyl halide polyolefin graft polymer is produced by reacting a solid polyolefin particle with a vinyl halide monomer in which the polyolefin is substantially insoluble, but is capable of absorbing the monomer. The solid particles can be contacted with the monomer in one step or in stages. When the stage-wise reaction is continued until the proportion of polyolefin in the polymer product is about 2 to about 20 weight percent, the resulting product can be formed to a transparent or translucent article. When a small proportion of solid polyolefin is employed in the polymerization process, both a graft polymer and a polymer of the unsaturated monomer are simultaneously produced in the same reactor and can be readily mechanically separated into the individual products.
Inventors
- 👤 Leigh E. Walker
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 11:26
CPC Classifications
C; C08; C08F; C08F291/00
Claims Analysis
Total Claims: 65
Claim 1
Independent Claim
120 words
A vinyl halide polyolefin graft polymer wherein the vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated compound copolymerizable therewith, and in the liquid state, is polymerized with a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms which is in the solid state in particulate form and is substantially insoluble in the monomer but absorbs a substantial amount of the monomer, and remains as a free flowing particle that does not agglomerate or fuse, wherein the proportion of monoolefin polymer in said graft polymer is about 20 to about 80 weight percent based on the weight of said monomer.
Claim 2
Dependent Claim
120 words
A vinyl halide polyolefin graft polymer wherein the vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated compound copolymerizable therewith, and in the liquid state, is polymerized with a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms which is in the solid state in particulate form and is substantially insoluble in the monomer but absorbs a substantial amount of the monomer, and remains as a free flowing particle that does not agglomerate or fuse, wherein the proportion of monoolefin polymer in said graft polymer is about 20 to about 80 weight percent based on the weight of said monomer.
Claim 3
Dependent Claim
14 words
The graft polymer of claim 1 wherein the single polymer is an ethylene-propylene copolymer.
Claim 4
Dependent Claim
17 words
The graft polymer of claim 1 wherein the single polymer is an ethylene propylene polyene modified polymer.
Claim 5
Dependent Claim
14 words
The graft polymer of claim 1 wherein the single polymer is low density polyethylene.
Claim 6
Dependent Claim
25 words
The graft polymer of claim 1 wherein the single polymer is a copolymer comprising less than about 90 weight percent of an individual 1-olefin monomer.
Claim 7
Dependent Claim
22 words
The graft polymer of claim 1 wherein the single polymer is an ethylene copolymer comprising less than about 80 weight percent ethylene.
Claim 8
Dependent Claim
31 words
The graft polymer of claim 1 wherein the single polymer is a copolymer comprising about 30 to 75 weight percent of an individual 1-olefin monomer of 2 to 8 carbon atoms.
Claim 9
Dependent Claim
24 words
The graft polymer of claim 1 wherein the single polymer is an ethylene 1-olefin copolymer comprising about 30 to 75 weight percent of ethylene.
Claim 10
Dependent Claim
24 words
The graft polymer of claim 1 wherein the single polymer is an ethylene propylene copolymer comprising about 30 to 75 weight percent of ethylene.
Claim 11
Dependent Claim
24 words
The graft polymer of claim 1 wherein the single polymer is an ethylene propylene copolymer comprising about 50 to 75 weight percent of ethylene.
Claim 12
Dependent Claim
18 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene and vinyl acetate.
Claim 13
Dependent Claim
18 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene and methyl acrylate.
Claim 14
Dependent Claim
18 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene and ethyl acrylate.
Claim 15
Dependent Claim
18 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene and vinyl chloride.
Claim 16
Dependent Claim
17 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene acrylic acid.
Claim 17
Dependent Claim
18 words
The graft polymer of claim 1 wherein the single polymer is a copolymer of ethylene and methacrylic acid.
Claim 18
Dependent Claim
35 words
The graft polymer of claim 1 wherein the single polymer is a copolymer comprising about 40 to 95 weight percent of a 1-olefin monomer and about 5 to 60 weight percent of a polar comonomer.
Claim 19
Dependent Claim
12 words
The graft polymer of claim 17 wherein the 1-olefin monomer is ethylene.
Claim 20
Dependent Claim
26 words
The graft polymer of claim 18 wherein the polar monomer is selected from vinyl acetate, methyl acrylate, ethyl acrylate, vinyl chloride, acrylic acid and methacrylic acid.
Claim 21
Dependent Claim
26 words
The graft polymer of claim 1 wherein the weight average molecular weight of the monoolefin polymer is in the range of about 10,000 to about 1,000,000.
Claim 22
Dependent Claim
26 words
The graft polymer of claim 1 wherein the weight average molecular weight of the monoolefin polymer is in the range of about 80,000 to about 300,000.
Claim 23
Dependent Claim
31 words
The graft polymer of claim 1 wherein the proportion of monoolefin polymer in said graft polymer is about 30 to about 50 weight percent based on the weight of said monomer.
Claim 24
Dependent Claim
12 words
The graft polymer of claim 1 prepared in a mass polymerization process.
Claim 25
Dependent Claim
18 words
The graft polymer of claim 1 prepared in a polymerization process in the presence of an inert diluent.
Claim 26
Dependent Claim
16 words
The graft polymer of claim 1 wherein in a polymerization process in the presence of water.
Claim 27
Dependent Claim
13 words
The graft polymer of claim 1 wherein the monomer is a single compound.
Claim 28
Dependent Claim
12 words
The graft polymer of claim 26 wherein the monomer is vinyl chloride.
Claim 29
Dependent Claim
14 words
The graft polymer of claim 1 wherein the monomer is two or more compounds.
Claim 30
Dependent Claim
14 words
The graft polymer of claim 28 wherein the monomer is a mixture of compounds.
Claim 31
Dependent Claim
13 words
The graft polymer of claim 29 wherein the vinyl halide is vinyl chloride.
Claim 32
Dependent Claim
16 words
The graft polymer of claim 28 wherein the monomers are reacted sequentially to the monoolefin polymer.
Claim 33
Dependent Claim
20 words
The graft polymer of claim 31 wherein vinyl chloride is first reacted with the monoolefin polymer, followed by methyl methacrylate.
Claim 34
Dependent Claim
9 words
The graft polymer of claim 1 and a stabilizer.
Claim 35
Dependent Claim
13 words
The graft polymer of claim 33 wherein the stabilizer is a dialkyltin maleate.
Claim 36
Dependent Claim
17 words
The graft polymer of claim 33 wherein the stabilizer is a dioctyltin maleate mixed with an alcohol.
Claim 37
Dependent Claim
129 words
A process for preparing a vinyl halide polyolefin graft copolymer which comprises: (1) mixing a monomer component comprising vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state, with a solid polyolefin comprising a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms, which polymer is in particulate form and substantially insoluble in the monomer or monomers, but absorbs a substantial amount of the monomer or monomers, and remains as a free flowing particle that does not agglomerate or fuse; and an initiator, and (2) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius.
Claim 38
Dependent Claim
129 words
A process for preparing a vinyl halide polyolefin graft copolymer which comprises: (1) mixing a monomer component comprising vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state, with a solid polyolefin comprising a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms, which polymer is in particulate form and substantially insoluble in the monomer or monomers, but absorbs a substantial amount of the monomer or monomers, and remains as a free flowing particle that does not agglomerate or fuse; and an initiator, and (2) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius.
Claim 39
Dependent Claim
30 words
The process of claim 36 wherein the proportion of monoolefin polymer in the graft polymer is about 20 to about 80 weight percent based on the weight of vinyl halide.
Claim 40
Dependent Claim
30 words
The process of claim 36 wherein the proportion of monoolefin polymer in the graft polymer is about 30 to about 50 weight percent based on the weight of vinyl halide.
Claim 41
Dependent Claim
11 words
The process of claim 36 conducted in a mass polymerization process.
Claim 42
Dependent Claim
13 words
The process of claim 36 conducted in the presence of an inert diluent.
Claim 43
Dependent Claim
11 words
The process of claim 36 conducted in the presence of water.
Claim 44
Dependent Claim
16 words
The process of claim 36 wherein a stabilizer is introduced at the beginning of the reaction.
Claim 45
Dependent Claim
12 words
The process of claim 42 wherein the stabilizer is a dialkyltin maleate.
Claim 46
Dependent Claim
16 words
The process of claim 43 wherein the stabilizer is a dioctyltin maleate mixed with an alcohol.
Claim 47
Dependent Claim
100 words
A process for producing a vinyl halide polyolefin graft copolymer which comprises reacting vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state with a solid polyolefin of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms in particulate form, that is substantially insoluble in the monomer but absorbs a substantial amount of the monomer, and remains as a free flowing particle that does not agglomerate or fuse, in the presence of an initiator for the reaction.
Claim 48
Dependent Claim
100 words
A process for producing a vinyl halide polyolefin graft copolymer which comprises reacting vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state with a solid polyolefin of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms in particulate form, that is substantially insoluble in the monomer but absorbs a substantial amount of the monomer, and remains as a free flowing particle that does not agglomerate or fuse, in the presence of an initiator for the reaction.
Claim 49
Dependent Claim
11 words
The process of claim 45 wherein the monomer is vinyl chloride.
Claim 50
Dependent Claim
30 words
The process of claim 45 wherein the proportion of monoolefin polymer in the polymer product is about 20 to about 80 weight percent based on the weight of said monomer.
Claim 51
Dependent Claim
30 words
The process of claim 45 wherein the proportion of monoolefin polymer in the polymer product is about 30 to about 50 weight percent based on the weight of said monomer.
Claim 52
Dependent Claim
11 words
The process of claim 45 conducted in a mass polymerization process.
Claim 53
Dependent Claim
13 words
The process of claim 45 conducted in the presence of an inert diluent.
Claim 54
Dependent Claim
11 words
The process of claim 45 conducted in the presence of water.
Claim 55
Dependent Claim
16 words
The process of claim 45 wherein a stabilizer is introduced at the beginning of the reaction.
Claim 56
Dependent Claim
12 words
The process of claim 52 wherein the stabilizer is a dialkyltin maleate.
Claim 57
Dependent Claim
16 words
The process of claim 52 wherein the stabilizer is a dioctyltin maleate mixed with an alcohol.
Claim 58
Dependent Claim
161 words
A process for preparing a vinyl halide polyolefin graft copolymer which comprises: (1) mixing a monomer component comprising vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state, with a solid polyolefin comprising a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms, wherein the polyolefin is in particulate form and substantially insoluble in the monomer or monomers, but absorbs a substantial amount of the monomer or monomers, and remains as a free flowing particle that does not agglomerate or fuse; and an initiator, and (2) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius, (3) mixing additional monomer component with the product of step (2), and (4) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius.
Claim 59
Dependent Claim
161 words
A process for preparing a vinyl halide polyolefin graft copolymer which comprises: (1) mixing a monomer component comprising vinyl halide alone or in combination with up to 50 percent by weight based on the total weight of monomer of an ethylenically unsaturated monomer copolymerizable therewith, in the liquid state, with a solid polyolefin comprising a single polymer of an aliphatic hydrocarbon monoolefin of 2 to about 8 carbon atoms, wherein the polyolefin is in particulate form and substantially insoluble in the monomer or monomers, but absorbs a substantial amount of the monomer or monomers, and remains as a free flowing particle that does not agglomerate or fuse; and an initiator, and (2) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius, (3) mixing additional monomer component with the product of step (2), and (4) heating the resulting mixture at a temperature in the range of about 30 to about 90 degrees Celsius.
Claim 60
Dependent Claim
36 words
The process of claim 55 wherein the proportion of polyolefin in the polymer product of the process is in the range of about 20 to about 80 weight percent based on the weight of vinyl halide.
Claim 61
Dependent Claim
19 words
The process of claim 55 wherein the monomer of step (2) is different than the monomer of step (4).
Claim 62
Dependent Claim
23 words
The process of claim 57 wherein the polymer product of step (4) has a lighter color than the polymer product of step (2).
Claim 63
Dependent Claim
19 words
The process of claim 55 wherein the monomer of step (3) is different than the monomer of step (1).
Claim 64
Dependent Claim
23 words
The process of claim 55 wherein the polymer product of step (4) has a lighter color than the polymer product of step (2).
Claim 65
Dependent Claim
17 words
The process of claim 55 wherein steps (3) and (4) are repeated sequentially one or more times.
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) | 1992-02-21 | 1992-08-22 | 1993-02-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-02-21 | 1996-08-22 | 1997-02-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-02-21 | 2000-08-22 | 2001-02-21 | $7700.00 | Window Closed / Lapsed |