Functionalized chain extended initiators for anionic polymerization

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.

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.

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.