NITROXYL DERIVATIVES WITH GLYCIDYL OR ALKYLCARBONYL GROUPS AS INITIATORS FOR RADICAL POLYMERISATION

摘要

The present invention relates to a compound of formula (Ia) or (Ib), wherein the R1, are each independently of one another hydrogen, halogen, NO2, cyano, -CONR5R6, -(R9)COOR4, -C(O)-R7, -OR8, -SR8, NHR8, -N(R8)2, carbamoyl, di(C1-C18alkyl)carbamoyl, -C(=NR5)(NHR6); unsubstituted C1-C18alkyl, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C2-C12heterocycloalkyl; or C1-C18alkyl, C2-C18alkenyl, C2-C18alkynyl, C7-C9phenylalkyl, C3-C12cycloalkyl or C2-C12heterocycloalkyl, which are substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; or phenyl, naphthyl, which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen, cyano, hydroxy, carboxy, C1-C4alkylamino or di(C1-C4alkyl)amino; R4 is hydrogen, C1-C18alkyl, phenyl, an alkali metal cation or a tetraalkylammonium cation; R5 and R6 are hydrogen, C1-C18alkyl, C2-C18alkyl which is substituted by at least one hydroxy group or, taken together, form a C2-C12alkylene bridge or a C2-C12alkylene bridge interrupted by at least one O or/and NR8 atom; R7 is hydrogen, C1-C18alkyl or phenyl; R8 is hydrogen, C1-C18alkyl or C2-C18alkyl which is substituted by at least one hydroxy group; R9 is C1-C12alkylene or a direct bond; or all R1 form together the residue of a polycyclic cycloaliphatic ring system or a polycyclic heterocycloaliphatic ring system with at least one di- or trivalent nitrogen atom; the R2 are independently of each other phenyl or C1-C6alkyl or two together with the linking carbon atom form a C5-C6cycloalkyl group; A is a divalent group required to form a cyclic 5-, 6- or 7-membered ring and R3 is a radical of formula (II), wherein X is phenyl, naphthyl or biphenyl, which are unsubstituted or substituted by NO2, halogen, amino, hydroxy, cyano, carboxy, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or di(C1-C4alkyl)amino; the R12 are independently of each other H or CH3; D is a group (A), a group C(O)-R13 or a group C(O)-R9-C(O)-R13; R13 is C1-C18alkyl and m is a number from 1 to 4. Further subjects of the invention are a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) a glycidyl or alkylcarbonyl functional nitroxide initiator compound of formula (Ia) or (Ib), a process for polymerizing ethylenically unsaturated monomers, and the use of glycidyl and alkylcarbonyl functional nitroxide initiators for radical polymerization.