End-functionalized polymers

Abstract

This invention relates to end-functionalized living polymers or copolymers having a structure represented by the general formula 1 or 2, wherein Ris a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. Ris a functional end group of a vinyl hetero monomer selected from the group consisting of hydroxy, epoxy, silyl, NH, NH(C-Calkyl), N(C-Calkyl), —CH═CH, —C≡CH, —C(CH)═CH, —O—CH═CH, (—O—CH—CH)—OH, —OR, —COOR, —CONHR, —OCONHR, —OCORand —NH—CO—R, wherein Ris linear or branched C-Calkyl or linear or branched C-Calkyl substituted with hydroxy, epoxy, silyl, NHor N(C-Calkyl); or Ris phenyl, benzyl, —CH═CH, —C≡CH or —C(CH)═CH, or Ris a residue of an acrylic acid (CH═CH—COO—*), methacrylic acid, (CH═C(CH)—COO—*) or CH(CH)═CH—COO—* or Ris a residue of a dicarboxylic acid HOOC—R—COO—* or C-Calkyl-OOC—R—COO—* wherein Ris C-Calkylene, C-Calkenylene or phenylene; or Ris a residue derived from the reaction of an isocyanate R—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being R—NHCOO—* or R—NHCO—NH—* wherein Ris unsubstituted C-Calkyl, C-Ccycloalkyl or C-Calkyl substituted with hydroxy, epoxy, silyl, NH, NH(C-Calkyl) or N(C-Calkyl); or Ris a residue derived from the reaction of a diisocyanate residue OCN—R—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *—OOC—NH—R—NCO or *—HNOC—NH—R—NCO or *—OOC—NH—R—NHCORwherein Ris C-Calkylene or C-Ccycloalkylene or phenylene and Ris a residue of hydroxyethylacrylate (CH═CH—COO—(CH)—O*), hydroxyethylmethacrylate (CH═C(CH)—COO—(CH)—O*), hydroxybutylacrylate (CH═CH—COO—(CH)—O*) or hydroxybutylmethacrylate (CH═C(CH)—COO—(CH)—O*), A is the hetero atom of the vinyl hetero monomer selected from the group consisting of oxygen, nitrogen, sulfur and silicon; and if Ris 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 Calkylene, C(hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Zis 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-Calkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH═C(R)—C(═R)—R, wherein Ris a hydrogen atom or a methyl group, Ris oxygen atom or sulfur atom; Ris NH, hydroxy, unsubstituted Calkoxy, Calkoxy interrupted by at least one N and/or O atom, hydroxy-substituted Calkoxy, unsubstituted Calkylamino, di(Calkyl)amino, hydroxy-substituted Calkylamino, hydroxy-substituted di(Calkyl)amino or —O—CH—CH—N(CH); Y is the chain terminus of the polymer/copolymer Zand 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.