US4409368A
Expired / Lapsed
US
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Preparation of star polymers
Assignee: Aerojet Rocketdyne Holdings Inc
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Filing: 1981-07-13
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Granted: 1983-10-11
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Expires: 2001-07-13
Abstract
Abstract Divinyl benzene and/or diisopropenyl benzene in hydrocarbon solvent is added over a period of time at low temperature to a hydrocarbon solvent containing a C 2-20 normal, secondary or tertiary alkyl or cycloalkyl lithium compound and a tertiary alkylamine having 2-4 carbon atoms prepared at low temperature to provide an initiator having an average of from 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000. These initiators are useful in polymerizing dienes and vinyl monomers to provide star polymers having an average of from about 4 to 9 arms or branches. These star polymers among other things are useful low profile or low shrink additives of FRPs, e.g., glass fiber reinforced plastics.
Inventors
- 👤 Francis J. Vitus
- 👤 Ivan G. Hargis
- 👤 Russell A. Livigni
- 👤 Sundar L. Aggarwal
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 06:44
CPC Classifications
C; C08; C08F; C08F236/00; C08F236/02; C08F236/04; C08F236/10; C08F297/00; C08F297/02; C08F297/04; C08F297/042; C08L; C08L21/00; C08L67/00; C08L67/06; Y; Y10; Y10S; Y10S525/00; Y10S525/901
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
186 words
The method which comprises polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 0° to 120° C., or from about 20° to 80° C., a polymerizable ethylenically unsaturated monomer having an activated unsaturated double bond with a hydrocarbon soluble, gel free and stable initiator in a minor amount sufficient to polymerize said monomer to obtain a polymer, said initiator being free of a solubilizing polymerizable comonomer and comprising the adduct of RLi where R is selected from the group consisting of normal, secondary and tertiary alkyl and cycloalkyl radicals of from 2 to 20 carbon atoms, or from 2 to 10 carbon atoms, and a diethylenically unsaturated aromatic compound selected from the group consisting of divinyl benzene and disopropenyl benzene and mixtures thereof, the mole ratio of RLi to said aromatic compound being about 1:0.83, said adduct having an average of from about 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000 and said polymer having an average of from about 4 to 9 arms and having Li atoms on the ends of said arms.
Claim 2
Independent Claim
186 words
The method which comprises polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 0° to 120° C., or from about 20° to 80° C., a polymerizable ethylenically unsaturated monomer having an activated unsaturated double bond with a hydrocarbon soluble, gel free and stable initiator in a minor amount sufficient to polymerize said monomer to obtain a polymer, said initiator being free of a solubilizing polymerizable comonomer and comprising the adduct of RLi where R is selected from the group consisting of normal, secondary and tertiary alkyl and cycloalkyl radicals of from 2 to 20 carbon atoms, or from 2 to 10 carbon atoms, and a diethylenically unsaturated aromatic compound selected from the group consisting of divinyl benzene and disopropenyl benzene and mixtures thereof, the mole ratio of RLi to said aromatic compound being about 1:0.83, said adduct having an average of from about 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000 and said polymer having an average of from about 4 to 9 arms and having Li atoms on the ends of said arms.
Claim 3
Dependent Claim
18 words
The method according to claim 1 where RLi is secondary butyllithium and said aromatic compound is divinyl benzene.
Claim 4
Dependent Claim
26 words
The method according to claim 1 where said monomer comprises about 10 to 40% by weight of styrene and 90 to 50% by weight of butadiene-1,3.
Claim 5
Dependent Claim
13 words
The method according to claim 3 where the butadiene-1,3 is substantially polymerized first.
Claim 6
Dependent Claim
26 words
The method according to claim 2 where said monomer comprises about 10 to 40% by weight of styrene and 90 to 60% by weight of butadiene-1,3.
Claim 7
Dependent Claim
13 words
The method according to claim 5 where the butadiene-1,3 is substantially polymerized first.
Claim 8
Dependent Claim
142 words
A rubbery star copolymer having an average of from about 4 to 9 arms, having Li atoms on the ends of the arms, having a Mn of from about 50,000 to 250,000, comprising from about 10 to 40% by weight of styrene and from 90 to 60% by weight of butadiene-1,3 and having a nucleus from an initiator (1) having a VPO Mn of from about 750 to 4,000, (2) having from 4 to 9 C-Li sites and (3) being the adduct of an aromatic compound selected from the group consisting of divinyl benzene and diisopropenyl benzene and mixtures thereof and RLi where R is from the group consisting of normal, secondary and tertiary alkyl and cycloalkyl radicals of from 2 to 20, or from 2 to 10, carbon atoms, the mole ratio of RLi to said aromatic compound being about 1:0.83.
Claim 9
Dependent Claim
142 words
A rubbery star copolymer having an average of from about 4 to 9 arms, having Li atoms on the ends of the arms, having a Mn of from about 50,000 to 250,000, comprising from about 10 to 40% by weight of styrene and from 90 to 60% by weight of butadiene-1,3 and having a nucleus from an initiator (1) having a VPO Mn of from about 750 to 4,000, (2) having from 4 to 9 C-Li sites and (3) being the adduct of an aromatic compound selected from the group consisting of divinyl benzene and diisopropenyl benzene and mixtures thereof and RLi where R is from the group consisting of normal, secondary and tertiary alkyl and cycloalkyl radicals of from 2 to 20, or from 2 to 10, carbon atoms, the mole ratio of RLi to said aromatic compound being about 1:0.83.
Claim 10
Dependent Claim
24 words
A rubbery star copolymer according to claim 7 which is a block copolymer and where the end portions of the arms comprise polystyrene blocks.
Claim 11
Dependent Claim
21 words
A rubbery star copolymer according to claim 8 in which the said Li atoms have been replaced with terminal carboxyl groups.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-10-10 | 1987-04-11 | 1987-10-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-10-10 | 1991-04-11 | 1991-10-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-10-10 | 1995-04-11 | 1995-10-11 | $7700.00 | Window Closed / Lapsed |