Telechelic polymers from mixed initiator
AssigneeFMC Corporation
InventorsJohn F. Engel, James A. Schwindeman, Roderic P. Quirk, Conrad W. Kamienski
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Abstract
This invention concerns novel, unsymmetrically protected, telechelically functionalized linear and star or multi-arm polymers, their optionally hydrogenated analogues, the polymers produced by selective removal of the protecting groups, the segmented block polymers produced by further reaction of these selectively deprotected polymers with selected comonomers, and the processes to prepare these polymers.
Claims72
A process for the preparation of linear and multi-arm polymers possessing dissimilarly protected telechelic functionalities comprising polymerizing, one or more conjugated dienes or one or more alkenylaromatic compounds or mixtures thereof, in a liquid reaction medium, at a temperature of -30.degree. C. to 150.degree. C., for a period of at least one hour, with at least two protected functionalized initiators, each of which contains a differently protected hydroxyl, amino, alkylamino, or sulfhydryl group, having the formula
- M--Q.sub.n --Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m
- wherein M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylaromatic compounds, or mixtures of one or more dienes with one or more alkenylaromatic compounds into the M--Z linkage;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen, sulfur, or nitrogen;
- (AR.sup.1 R.sup.2 R.sup.3).sub.m is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements;
- R.sup.1, R.sup.2, and R.sup.3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms;
- n is an integer from 0 to 5;
- and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen, to produce "living" polymer anions which are reacted with at least one compound selected from the group consisting of di- and polyfunctional linking agents to produce dissimilarly protected telechelically functionalized linear or multi-arm polymers, and optionally hydrogenating the resulting polymers.
The linear and multi-arm polymers possessing dissimilarly protected telechelic functionalities prepared by the process comprising polymerizing, one or more conjugated dienes or one or more alkenylaromatic compounds or mixtures thereof, in a liquid reaction medium, at a temperature of -30.degree. C. to 150.degree. C., for a period of at least one hour, with at least two protected functionalized initiators, each of which contains a differently protected hydroxyl, amino, alkylamino, or sulfhydryl group, having the formula
- M--Q.sub.n --Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m
- wherein M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylaromatic compounds, or mixtures of one or more dienes with one or more alkenylaromatic compounds into the M--Z linkage;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen, sulfur, or nitrogen;
- (AR.sup.1 R.sup.2 R.sup.3).sub.m is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements;
- R.sup.1, R.sup.2, and R.sup.3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms;
- n is an integer from 0 to 5;
- and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen, to produce "living" polymer anions which are reacted with at least one compound selected from the group consisting of di- and polyfunctional linking agents to produce dissimilarly protected telechelically functionalized linear or multi-arm polymers, and optionally hydrogenating the resulting polymers.
A process for the preparation of linear and multi-arm polymers possessing one free telechelically functional group and at least one protected telechelically functional group comprising polymerizing, one or more conjugated dienes or one or more alkenylaromatic compounds or mixtures thereof, in a liquid reaction medium, at a temperature of -30.degree. C. to 150.degree. C., for a period of at least one hour, with at least two protected functionalized initiators, each of which contains a differently protected hydroxyl, amino, alkylamino, or sulfhydryl group, having the formula
- M--Q.sub.n --Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m
- wherein M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylaromatic compounds, or mixtures of one or more dienes with one or more alkenylaromatic compounds into the M--Z linkage;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen, sulfur, or nitrogen;
- (AR.sup.1 R.sup.2 R.sup.3).sub.m is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements;
- R.sup.1, R.sup.2, and R.sup.3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms;
- n is an integer from 0 to 5;
- and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen, to produce "living" polymer anions which are reacted with at least one compound selected from the group consisting of di- and polyfunctional linking agents to produce dissimilarly protected telechelically functionalized linear or multi-arm polymers, optionally hydrogenating the resulting polymers, and selectively removing one type of protective group on the dissimilarly protected functionalities on the end(s) of the arms of the linear or multi-arm polymer chains using selective reagents specifically suited to remove the more easily removable protective group, --A--R.sup.1 R.sup.2 R.sup.3, and liberate the desired functionality, --T--H.sub.m on the end(s) of the polymer chains to produce linear or multi-arm polymers with unprotected hydroxyl, sulfhydryl, or amino groups on the ends of some of the arms of the polymer and protected hydroxyl, sulfhydryl, or amino groups on the end(s) of the other arm(s) of the linear or multi-arm polymers.
Linear and multi-arm polymers possessing one free telechelically functional group and at least one protected telechelically functional group prepared by the process comprising polymerizing, one or more conjugated dienes or one or more alkenylaromatic compounds or mixtures thereof, in a liquid reaction medium, at a temperature of -30.degree. C. to 150.degree. C., for a period of at least one hour, with at least two protected functionalized initiators, each of which contains a differently protected hydroxyl, amino, alkylamino, or sulfhydryl group, having the formula
- M--Q.sub.n --Z--T--(A--R.sup.1 R.sup.2 R.sup.3).sub.m
- wherein M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of one or more conjugated diene hydrocarbons, one or more alkenylaromatic compounds, or mixtures of one or more dienes with one or more alkenylaromatic compounds into the M--Z linkage;
- Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen, sulfur, or nitrogen;
- (AR.sup.1 R.sup.2 R.sup.3).sub.m is a protecting group, in which A is an element selected from Group IVa of the Periodic Table of the Elements;
- R.sup.1, R.sup.2, and R.sup.3 are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms;
- n is an integer from 0 to 5;
- and m is 1 when T is oxygen or sulfur, and 2 when T is nitrogen,. to produce "living" polymer anions which are reacted with at least one compound selected from the group consisting of di- and polyfunctional linking agents to produce dissimilarly protected telechelically functionalized linear or multi-arm polymers, optionally hydrogenating the resulting polymers, and selectively removing one type of protective group on the dissimilarly protected functionalities on the end(s) of the arms of the linear or multi-arm polymer chains using selective reagents specifically suited to remove the more easily removable protective group, --A--R.sup.1 R.sup.2 R.sup.3, and liberate the desired functionality, --T--H.sub.m on the end(s) of the polymer chains to produce linear or multi-arm polymers with unprotected hydroxyl, sulfhydryl, or amino groups on the ends of some of the arms of the polymer and protected hydroxyl, sulfhydryl, or amino groups on the end(s) of the other arm(s) of the linear or multi-arm polymers.
A process for the preparation of polymers possessing dissimilarly protected telechelic functionalities, comprising:
- polymerizing at least one monomer selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic compounds, and mixtures thereof, with at least two dissimilarly protected functionalized initiators of the formula
- M--Q.sub.n --Z--T--(AR.sup.1 R.sup.2 R.sup.3).sub.m
- wherein:
- M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of at least one compound selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic compounds, and mixtures thereof;
- n is an integer from 0 to 5;
- z is a straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen;
- and
- AR.sup.1 R.sup.2 R.sup.3 is a protecting group in which A is an element selected from Group IVa of the Periodic Table of Elements;
- and R.sup.1, R.sup.2, and R.sup.3 are alkyl, with the proviso that one of the at least two dissimilarly protected functionalized initiators is a compound in which A is carbon and the other of the at least two dissimilarly protected functionalized initiators is a compound in which A is silicon, to produce living polymer anions;
- and
- reacting the living polymer anions with linking agents to produce dissimilarly protected telechelically functionalized polymers.
Polymers possessing dissimilarly protected telechelic functionalities prepared by the process comprising:
- polymerizing at least one monomer selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic compounds, and mixtures thereof, with at least two dissimilarly protected functionalized initiators of the formula
- M--Q.sub.n --Z--T--(AR.sup.1 R.sup.2 R.sup.3)
- wherein:
- M is an alkali metal;
- Q is an unsaturated hydrocarbyl group derived by incorporation of at least one compound selected from the group consisting of conjugated dienes, alkenylsubstituted aromatic compounds, and mixtures thereof;
- Z is a straight chain hydrocarbon connecting group which contains 3-25 carbon atoms;
- T is oxygen;
- AR.sup.1 R.sup.2 R.sup.3 is a protecting group in which A is an element selected from Group IVa of the Periodic Table of Elements;
- and R.sup.1, R.sup.2, and R.sup.3 are alkyl, with the proviso that one of the at least two dissimilarly protected functionalized initiators is a compound in which A is carbon and the other of the at least two dissimilarly protected functionalized initiators is a compound in which A is silicon, to produce living polymer anions;
- and
- reacting the living polymer anions with linking agents to produce dissimilarly protected telechelically functionalized polymers.
Dependencies are inferred from the claim text.