# US 5,708,092 A · Functionalized chain extended initiators for anionic polymerization

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- Number: US 5,708,092 A
- Document ID: US5708092A
- Status: Granted
- Kind: A
- Application number: 08/631,524
- Filed: 1996-04-12
- Granted: 1998-01-13
- Earliest claimed: 1994-05-13
- Assignees: FMC Corporation
- Inventors: James A. Schwindeman; Conrad W. Kamienski; Robert C. Morrison
- Web page: https://patentgrep.com/patent/US5708092A

## CPC

- C08F 279/02: on to polymers of conjugated dienes
- C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton
- C08F 4/46: selected from alkali metals
- C08F 12/04: containing one ring
- C08F 12/06: Hydrocarbons
- C08F 36/04: conjugated
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS

## Abstract

A process for the preparation of hydrocarbon solutions of monofunctional ether initiators of the following general structure: M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3) wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; A is an element selected from carbon and silicon; R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and n is an integer from 1 to 5, monofunctional ethers produced by the process, use of the initiators in a polymerization process and polymers produced by the polymerization process.

## Claims

### Claim 1

A process for the preparation of hydrocarbon solutions of monofunctional ether initiators comprising reacting a monofunctional ether of the following structure:
M--Z--O--A(R.sup.1 R.sup.2 R.sup.3) (I)
wherein M is an alkali metal selected from the group consisting of lithium, sodium and potassium; Z is a branched or straight chain hydrocarbon group with contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; A is an element selected from carbon and silicon; and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; aryl, or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups, the monofunctional ether of formula (I) resulting from reacting an omega-protected-1-haloalkyl with an alkali metal having a particle size between 10 and 300 microns in size, at a temperature between 35.degree. and 130.degree. C. in an alkane or cycloalkane solvent containing 5 to 10 carbon atoms to form an intermediate alkali metal-containing monofunctional ether product of formula (I), with a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons to produce a compound having the following structure:
M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3) (II)
wherein M is a alkali metal selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group produced by the reaction of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons containing 4-25 carbon atoms with the monofunctional ether of formula (I); Z is defined as a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; A is an element selected from the group consisting of carbon and silicon; R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups, and n is an integer from 1-5.

### Claim 2 (depends on 1)

The process of claim 1 wherein the reaction temperature is the reflux temperature of the solvent.

### Claim 3 (depends on 1)

The process of claim 1 wherein the omega-protected-1-haloalkane is selected from 3-(1,1-dimethylethoxy)-1-propylhalide, 3-(1,1-dimethylpropoxy)-1-propylhalide, 4-(methoxy)-1-butylhalide, 3-(triphenylmethoxy)-1-propylhalide, 5-(triphenylmethoxy)-1-pentylhalide, 6-(triphenylmethoxy)-1-hexylhalide, 8-(triphenylmethoxy)-1-octylhalide 3-(1,1-dimethylethoxy)-2-methyl-1-propylhalide,
3-›3-(dimethylamino)-1-propyloxy!-1-propylhalide, 3-›2-(dimethylamino)-1-ethoxy!-1-propylhalide, 3-›2-(diethylamino)-1-ethoxy!-1-propylhalide, 3-›2-(diisopropyl)amino)-1-ethoxy!-1-propylhalide, 3-›2-(1-piperidino)-1-ethoxy!-1-propylhalide, 3-›2-(1-pyrrolidino)-1-ethoxy!-1-propylhalide, 4-›3-(dimethylamino)-1-propyloxy!-1-butylhalide, 6-›2-(1-piperidino)-1-ethoxy!-1-hexylhalide 3-›2-(methoxy)-1-ethoxy!-1-propylhalide, 3-›2-(ethoxy)-1-ethoxy!-1-propylhalide, 4-›2-(methoxy)-1-ethoxy!-1-butylhalide, 5-›2-(ethoxy)-1-ethoxy!-1-pentylhalide, 3-›3-(methylthio)-1-propyloxy!-1propylhalide, 3-›4-(methylthio)-1-butyloxy!-1-propylhalide, 3-(methylthiomethoxy)-1-propylhalide, 6-›3-(methylthio)-1-propyloxy!-1-hexylhalide, 3-›4-(methoxy)-benzyloxy!-1-propylhalide, 3-›4-(1,1-dimethylethoxy)-benzyloxy!-1-propylhalide, 3-›2,4-(dimethoxy)-benzyloxy!-1propylhalide, 8-›4-(methoxy)-benzyloxy!-1-octylhalide, 4-›4-(methylthio)-benzyloxy!-1-butylhalide, 3-›4-(dimethylamino)-benzyloxy!-1-propylhalide, 6-›4-(dimethylamino)-benzyloxy!-1-hexylhalide,
3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propylhalide, 6-(t-butyldimethylsilyloxy)-1-hexylhalide, 3-(t-butyldimethylsilyloxy)-2,2-dimethyl-1-propylhalide; 3-(t-butyldimethylsilyloxy)-1-propylhalide; 4-(t-butyldimethylsilyloxy)-1-butylhalide and 3-(trimethylsilyloxy)-2,2-dimethyl-1-propylhalide.

### Claim 4 (depends on 3)

The process of claim 3 characterized in that the halide is selected from the group consisting of bromine and chlorine.

### Claim 5 (depends on 1)

The process of claim 1 wherein the alkali metal is lithium.

### Claim 6 (depends on 5)

The process of claim 5 wherein the lithium metal contains 0.2 to 0.8 weight percent sodium.

### Claim 7 (depends on 5)

The process of claim 5 wherein the lithium metal contains 0.3 to 0.5 weight percent sodium.

### Claim 8 (depends on 1)

The process of claim 1 wherein the conjugated diene hydrocarbon is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), 2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2,5-dimethyl-2,4-hexadiene and 1,3-octadiene.

### Claim 9 (depends on 1)

The process of claim 1 wherein the alkenylsubstituted aromatic hydrocarbon is selected from alpha-methylstyrene, styrene, vinyltoluene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methylhexene-1 and 1,1-diphenylethylene.

### Claim 10 (depends on 1)

The process of claim 1 wherein the conjugated diene hydrocarbon is butadiene and isoprene.

### Claim 11

A monofunctional ether anionic polymerization initiator comprising a compound of the formula:
M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3)
wherein M is an alkali metal, Q is an unsaturated hydrocarbyl group derived by incorporation of a conjugated diene hydrocarbon or a saturated hydrocarbyl group derived by incorporation of an alkenyl substituted aromatic hydrocarbon; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; A is an element selected from carbon and silicon; R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and n is an integer from 1 to 5.

### Claim 12 (depends on 11)

The compound of claim 11 where in the alkali metal is selected from the group consisting of lithium, sodium and potassium.

### Claim 13 (depends on 11)

The compound of claim 11 where in the alkali metal is selected from the group consisting of lithium and sodium.

### Claim 14 (depends on 11)

The compound of claim 11 where in the branched or straight chain hydrocarbon tether group contains 3 to 8 carbon atoms.

### Claim 15 (depends on 11)

The compound of claim 11 wherein the alkali metal is lithium.

### Claim 16 (depends on 15)

The compound of claim 15 wherein the lithium metal contains 0.21 to 0.8 weight percent sodium.

### Claim 17 (depends on 15)

The compound of claim 15 wherein the lithium metal contains 0.3 to 0.5 weight percent sodium.

### Claim 18

A process for the anionic polymerization of olefinic-containing monomers comprising the steps of:
a) initiating polymerization of a conjugated polyene hydrocarbon having 4 to 30 carbon atoms or a vinyl-substituted aromatic hydrocarbon in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10.degree. C. to 70.degree. C. with an initiator having the formula:
M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3)
wherein M is an alkali metal, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenyl substituted aromatic hydrocarbons; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbons atoms, optionally containing aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups; A is an element selected from carbon and silicon R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower, alkylthio, and lower dialkylamino groups, and n is an integer from 1 to 5, to produce an intermediate polymer; and
b) reacting the intermediate polymer with a functionalizing compound to produce a functionalized polymer
c) optionally hydrogenating the functionalized polymer
d) further reacting the functionalized polymer with other comonomers in the presence of a strong acid catalyst to simultaneously deprotect the polymer and polymerize the comonomers at both functional sites or
e) further reacting the functionalized polymer with comonomers in the absence of strong acid catalysts, then deprotecting the resultant copolymer, and
f) further reacting the resultant copolymer with the same or other comonomers.

### Claim 19 (depends on 18)

The process of claim 18 wherein the functionalizing compound is selected from the group consisting of oxygen, sulfur, ethylene oxide, carbon dioxide, omega-alkenylarylhalosilanes, chlorosilanes, and chlorostannanes prior to recovering the polymer.

### Claim 20 (depends on 18)

The process of claim 18 wherein the conjugated polyene hydrocarbon is a conjugated diene hydrocarbon selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), 2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2,5-dimethyl-2,4-hexadiene, and 1,3-octadiene.

### Claim 21 (depends on 18)

The process of claim 18 further comprising the step of hydrogenating the polymerized conjugated polyene hydrocarbon.

### Claim 22 (depends on 18)

The process of claim 18 wherein the intermediate polymer is reacted with isomeric divinylbenzenes and deprotected to yield star-branched polymers with hydroxy-terminated branches.

### Claim 23 (depends on 22)

The process of claim 22 wherein the star-branched polymers are hydrogenated.

### Claim 24 (depends on 23)

The process of claim 23 wherein the polymers are further reacted with ethylene oxide and potassium t-butoxide to produce hydrogels.

### Claim 25 (depends on 23)

The process of claim 23 wherein the polymers are reacted with acryloyl chloride and methacryloyl chloride.

### Claim 26 (depends on 25)

The process of claim 25 wherein the products of the reaction are further reacted with alkyl acrylates, alkyl methacrylates, and dialkyl acrylamides to produce hydrogels.

### Claim 27 (depends on 18)

The process of claim 18 wherein the functionalizing compound is ethylene oxide, the functionalized polymer is hydrogenated, and the comonomers are selected from the group of epichlorohydrin and diisocyanates to produce epoxide and isocyanate-terminated polymers.

### Claim 28 (depends on 27)

The process of claim 27 further characterized by simultaneous deprotection and polymerization of the isocyanate and epoxy-terminated polymers.

### Claim 29 (depends on 18)

The process of claim 18 wherein the functionalizing compound is ethylene oxide and the comonomers are selected from the group of dialkylterephthalates, alpha,omega-alkane diols, caprolactam and adipic acid, and the deprotection is carried out simultaneously with polymerization.

### Claim 30 (depends on 18)

The process of claim 18 wherein the functionalizing compound is ethylene oxide, the comonomer is ethylene oxide, the polymerization is carried out in the presence of potassium tert-butoxide, the resulting copolymer is deprotected and reaction with the comonomer continued.

### Claim 31 (depends on 18)

The process of claim 18 wherein the functionalizing compound is ethylene oxide, the functional polymer is hydrogenated and reacted with a diisocyanate in a 2:1 ratio, further reacted with hydroxyethylacrylate in the presence of a basic catalyst, and deprotected to yield a macromonomer.

### Claim 32 (depends on 18)

The process of claim 18 wherein the functionalizing compound is styrenyldimethylchlorosilane.

### Claim 33

A functionalized polymer produced by a process comprising the steps of:
a) initiating polymerization of a conjugated polyene hydrocarbon having 4 to 30 carbons atoms or a vinyl-substituted aromatic hydrocarbon in a hydrocarbon or mixed hydrocarbon-polar solvent medium at a temperature of 10.degree. C. to 70.degree. C. with an initiator having the formula:
M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3)
wherein M is an alkali metal, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups containing lower alkyl, lower alkylthio or lower dialkylamino groups, A is an element selected from carbon and silicon R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and n is an integer from 1 to 5;
b) reacting the intermediate polymer with a functionalizing compound,
c) optionally hydrogenating the polymer,
d) further reacting the functionalized polymer with other comonomers in the presence of a strong acid to simultaneously deprotect and polymerize the functionalized polymer at both functional sites or
e) further reacting the functionalized polymer with comonomers in the absence of a strong acid catalyst, followed by deprotection and further reaction with the same or other comonomers.

### Claim 34 (depends on 33)

The polymer of claim 33 wherein the functionalizing compound is selected from the group of ethylene oxide, oxygen, sulfur, carbon dioxide, omega-alkenylarylhalosilanes, chlorosilanes, and chlorostannanes.

### Claim 35 (depends on 33)

The process of claim 33 wherein the conjugated polyene hydrocarbon is a conjugated diene hydrocarbon selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), 2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2,5-dimethyl-2,4hexadiene, and 1,3-octadiene.

### Claim 36 (depends on 33)

The polymer of claim 33 further comprising the step of hydrogenating the polymerized conjugated polyene hydrocarbon.

### Claim 37 (depends on 22)

The polymer produced by the process of claim 22.

### Claim 38 (depends on 23)

The polymer produced by the process of claim 23.

### Claim 39 (depends on 24)

The polymer produced by the process of claim 24.

### Claim 40 (depends on 25)

The polymer produced by the process of claim 25.

### Claim 41 (depends on 26)

The polymer produced by the process of claim 26.

### Claim 42 (depends on 27)

The polymer produced by the process of claim 27.

### Claim 43 (depends on 28)

The polymer produced by the process of claim 28.

### Claim 44 (depends on 29)

The polymer produced by the process of claim 29.

### Claim 45 (depends on 30)

The polymer produced by the process of claim 30.

### Claim 46 (depends on 31)

The polymer produced by the process of claim 31.

### Claim 47 (depends on 32)

The polymer produced by the process of claim 32.