END-FUNCTIONALIZED POLYMERS

摘要

This invention relates to end-functionalized living polymers or copolymers having a structure represented by the general formula 1 or 2, wherein R1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. R2 is a functional end group of a vinyl hetero monomer selected from the group consisting of hydroxy, epoxy, silyl, NH2, NH(C1-C6alkyl), N(C1-C6alkyl)2, —CH═CH2, —C≡CH, —C(CH3)═CH2, -0-CH═CH2, (—O—CH2—CH2)1-10—OH, —OR20, —COOR20, —CONHR20, —OCONHR20, —OCOR20 and —NH—CO—R20, wherein R20 is linear or branched C1-C20 alkyl or linear or branched C1-C20 alkyl substituted with hydroxy, epoxy, silyl, NH2 or N(C1-C6alkyl)2; or R20 is phenyl, benzyl, —CH═CH2, —C≡CH or —C(CH3)═CH2, or R2 is a residue of an acrylic acid (CH2═CH—COO—*), methacrylic acid, (CH2═C(CH3)—COO—*) or CH(CH3)═CH—COO—* or R2 is a residue of a dicarboxylic acid HOOC—Rc—COO—* or C1-C6alkyl-OOC—Rc—COO—* wherein Rc is C1-C20 alkylene, C1-C20alkenylene or phenylene; or R2 is a residue derived from the reaction of an isocyanate Ra—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being Ra—NHCOO—* or Ra—NHCO—NH—* wherein Ra is unsubstituted C1-C20alkyl, C1-C20cycloalkyl or C1-C20alkyl substituted with hydroxy, epoxy, silyl, NH2, NH(C1-C6alkyl) or N(C1-C6alkyl)2; or R2 is a residue derived from the reaction of a diisocyanate residue OCN—Rb—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *—OOC—NH—Rb—NCO or *—HNOC—NH—Rb—NCO or *—OOC—NH—Rb—NHCOR30 wherein Rb is C1-C20 alkylene or C1-C20cycloalkylene or phenylene and R30 is a residue of hydroxyethylacrylate (CH2═CH—COO—(CH2)2-0*), hydroxyethylmethacrylate (CH2═C(CH3)—COO—(CH2)2-0*), hydroxybutylacrylate (CH2═CH—COO—(CH2)4-0*) or hydroxybutylmethacrylate (CH2═C(CH3)—COO—(CH2)4-0*), A is the hetero atom of the vinyl hetero monomer selected from the group consisting of oxygen, nitrogen, sulfur and silicon; and if R2 is silyl and M is a direct bond, A is a direct bond; M is a bond or a divalent group linking the heteroatom of the vinyl hetero monomer and the functional end group of the vinyl hetero monomer said M being selected from the group consisting of C1-50 alkylene, C1-50 (hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Zn is a polymer or copolymer segment of random-, gradient- or block-type structure, which is built up from vinylic monomers selected from the group consisting of isoprene, 1,3-butadiene, α-C5-18alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH2═C(R3)—C(═R4)—R5, wherein R3 is a hydrogen atom or a methyl group, R4 is oxygen atom or sulfur atom; R5 is NH2, hydroxy, unsubstituted C1-18 alkoxy, C2-100alkoxy interrupted by at least one N and/or O atom, hydroxy-substituted C1-18alkoxy, unsubstituted C1-18alkylamino, di(C1-18alkyl)amino, hydroxy-substituted C1-18alkylamino, hydroxy-substituted di(C1-18alkyl)amino or -0-CH2—CH2—N(CH3)2; Y is the chain terminus of the polymer/copolymer Zn and Y represents the fragment of a polymerization initiator capable of initiating polymerization; Y1 represents a di-, tri- or polyvalent fragment of a di-, tri-, or polyfunctional NMP initiator; m is 2, 3 or 4, preferably 2; n is the number of monomer units Z and is between 10 and 5000.