US4098980A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Non-aqueous dispersion polymerization of conjugated diolefins
Assignee: Goodyear Tire and Rubber Co
•
Filing: 1976-06-24
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Granted: 1978-07-04
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Expires: 1996-06-24
Abstract
Abstract A process for the non-aqueous dispersion polymerization of a conjugated diolefin monomer, for instance, butadiene or isoprene, in a liquid hydrocarbon dispersion medium, for instance, n-butane or n-pentane with a Ziegler Natta catalyst, for instance, triisobutylaluminum/titanium tetrachloride while said conjugated diolefin is in the presence of a block copolymer dispersion stabilizer. The block copolymer dispersion stabilizer is a copolymer which contains at least two blocks of polymer linked by chemical valences, at least one block (A block) is soluble in liquid organic dispersion medium and at least another block (B block) is insoluble in the dispersion medium and the stabilizer acts to disperse polymers of conjugated diolefins which are formed in the stabilizer's presence. The A block is exemplified by polyisoprene, poly(t-butyl styrene) and poly(vinyl toluene). The B block is exemplified by polystyrene, poly(α-methyl styrene), a copolymer of styrene and isoprene, poly(methyl methacrylate) and the like.
Inventors
- 👤 Richard A. Markle
- 👤 Richard G. Sinclair
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 09:48
CPC Classifications
C; C08; C08F; C08F36/00; C08F36/02; C08F36/04; C08F287/00
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
102 words
In a process for the non-aqueous dispersion polymerization of a conjugated diolefin monomer in a liquid hydrocarbon dispersion medium with a Ziegler-Natta catalyst, the improvement which comprises carrying out the polymerization of conjugated diolefins in the presence of a block copolymer dispersion stabilizer comprising at least two polymer blocks linked by chemical valences wherein at least one of said polymer blocks ("A" block) is soluble in the dispersion medium and at least another of said polymer blocks ("B" block) is insoluble in the dispersion medium and the stabilizer acts to disperse polymers of conjugated diolefins which are formed in the stabilizer's presence.
Claim 2
Dependent Claim
102 words
In a process for the non-aqueous dispersion polymerization of a conjugated diolefin monomer in a liquid hydrocarbon dispersion medium with a Ziegler-Natta catalyst, the improvement which comprises carrying out the polymerization of conjugated diolefins in the presence of a block copolymer dispersion stabilizer comprising at least two polymer blocks linked by chemical valences wherein at least one of said polymer blocks ("A" block) is soluble in the dispersion medium and at least another of said polymer blocks ("B" block) is insoluble in the dispersion medium and the stabilizer acts to disperse polymers of conjugated diolefins which are formed in the stabilizer's presence.
Claim 3
Dependent Claim
60 words
The process of claim 1 in which the soluble "A" block is selected from polyisoprene, poly(t-butylstyrene), poly(vinyl toluene), polybutadiene, polymerized higher alkyl methacrylates, polyisobutene and poly(vinyl butylether) and their copolymers, and the insoluble "B" block is selected from polystyrene, poly(alpha-methyl styrene), copolymers of styrene or alpha-methyl styrene with isoprene or butadiene, polymerized lower alkyl acrylates and methacrylates and poly(alkylene oxides).
Claim 4
Dependent Claim
24 words
The process of claim 1 in which the liquid hydrocarbon dispersion medium is selected from n-butane, neopentane, n-pentane and a mixture of isomeric pentanes.
Claim 5
Dependent Claim
13 words
The process of claim 2 in which the conjugated diolefin monomer is butadiene-1,3.
Claim 6
Dependent Claim
13 words
The process of claim 2 in which the conjugated diolefin monomer is piperylene.
Claim 7
Dependent Claim
13 words
The process of claim 2 in which the conjugated diolefin monomer is isoprene.
Claim 8
Dependent Claim
26 words
The process of claim 1 in which the weight ratio of the "A" block/"B" block of the block copolymer dispersion stabilizer ranges from 99.9/0.1 to 50/50.
Claim 9
Dependent Claim
25 words
The process of claim 7 in which the weight ratio of the "A" block to the "B" block ranges from about 99/1.0 to about 75/25.
Claim 10
Dependent Claim
25 words
The process of claim 1 in which the "A" block of the copolymer dispersion stabilizer is poly(vinyl toluene) and the "B" block is poly(methyl methacrylate).
Claim 11
Dependent Claim
19 words
The process of claim 9 in which the weight ratio of poly(vinyl tolune)poly(methyl methacrylate) ranges from 99.9/0.1 to 50/50.
Claim 12
Dependent Claim
23 words
The process of claim 1 in which the "A" block of the copolymer dispersion stabilizer is polyisoprene and the "B" block is polystyrene.
Claim 13
Dependent Claim
17 words
The process of claim 11 in which the weight ratio of polyisoprene/polystyrene ranges from 99.9/0.1 to 50/50.
Claim 14
Dependent Claim
24 words
The process of claim 1 in which the "A" block of the copolymer dispersion stabilizer is polyisoprene and the "B" block is poly(methyl methacrylate).
Claim 15
Dependent Claim
18 words
The process of claim 13 in which the weight ratio of polyisoprene/poly(methyl methacrylate) ranges from 99.9/0.1 to 50/50.
Claim 16
Dependent Claim
25 words
The process of claim 1 in which the "A" block of the copolymer dispersion stabilizer is poly (vinyl toluene) and the "B" block is polystyrene.
Claim 17
Dependent Claim
18 words
The process of claim 15 in which the weight ratio of poly(vinyl toluene)/polystyrene ranges from 99.9/0.1 to 50/50.
Claim 18
Dependent Claim
30 words
The process of claim 1 in which the "A" block of the copolymer dispersion stabilizer is poly(t-butylstyrene) and the "B" block is a copolymer of methyl methacrylate and vinyl methacrylate.
Claim 19
Dependent Claim
18 words
The process of claim 17 in which the weight ratio of poly(t-butylstyrene)/methyl methacrylate/vinyl methacrylate ranges from 50-70/20-48/2-10 respectively.
Claim 20
Dependent Claim
29 words
The process of claim 7 in which the "A" block of the copolymer dispersion stabilizer is poly (t-butylstyrene) and the "B" block is a copolymer of styrene and isoprene.
Claim 21
Dependent Claim
17 words
The process of claim 19 in which the weight ratio of poly(t-butylstyrene)/styrene-co-isoprene ranges from 99.9/0.1 to 50/50.
Claim 22
Dependent Claim
53 words
The process of claim 3 in which the liquid hydrocarbon dispersion medium is n-butane and the conjugated diolefin monomer is isoprene which, upon polymerization in said process, is polymerized to poly-cis-1,4-isoprene that is a flowable dispersion of greater than 20 percent solids and does not adhere to the walls of the reaction vessel.
Claim 23
Dependent Claim
47 words
The process of claim 21 in which the butane dispersion of poly-cis-1,4-isoprene is a high conversion, high-molecular weight polymer dispersion that is flowable at greater than 20 percent solids when maintained at greater than 30° C., while, at lower temperatures, the polymer sediments substantially from the butane.
Claim 24
Dependent Claim
62 words
The process of claim 3 in which the liquid hydrocarbon dispersion medium is a mixture of isomeric pentanes and the conjugated diolefin monomer is isoprene which, upon polymerization in said process, is polymerized to poly-cis-1,4-isoprene that is flowable at greater than 20 percent solids when maintained at greater than 30° C., while, at lower temperatures, the polymer sediments substantially from the pentanes.
Claim 25
Dependent Claim
53 words
The process of claim 3 in which the liquid hydrocarbon dispersion medium is n-butane and the conjugated diolefin monomer is butadiene which, upon polymerization in said process, is polymerized to cis-1,4-polybutadiene that is a flowable dispersion of greater than 20 percent solids and does not adhere to the walls of the reaction vessel.
Claim 26
Dependent Claim
50 words
The process according to claim 22 in which the butane dispersion of the cis-1,4-polybutadiene is a high conversion, high molecular weight polymer dispersion that is flowable at greater than 20 percent solids when maintained at greater than 30° C., while, at lower temperatures, the polymer sediments substantially from the butane.
References Cited (Backward Citations)
US3728325A
Cited
GB941305A
Cited
US3218302A
Cited
US3243419A
Cited
US3400113A
Cited
US3382297A
Cited
US3499059A
Cited
US3462406A
Cited
US3707585A
Cited
US3644585A
Cited
US3906057A
Cited
US3577395A
Cited
US3954909A
Cited
US3742091A
Cited
US3770712A
Cited
US3888945A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-07-03 | 1982-01-02 | 1982-07-04 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-07-03 | 1986-01-02 | 1986-07-04 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-07-03 | 1990-01-02 | 1990-07-04 | $7700.00 | Window Closed / Lapsed |