Azo compounds useful for radical polymerisation of olefinically unsaturated compounds

摘要

Azo compounds functionalized with heterocycles are useful for radical polymerisation of olefinically unsaturated compounds to give (co)polymers with heterocyclic terminal groups. Azo compounds functionalized with heterocycles are of formula (I). Y = 1-20C alkyl, 6-14C aryl, 6-14C aryl substituted with functional groups based on non-metallic elements of Groups IVA, VA, VIA or VIIA, 3-10C cycloalkyl, aralkyl with 1-10C in the alkyl portion and 6-14C in the aryl portion, 1-20C alkyl substituted with functional groups based on non-metallic elements of Groups IVA, VA, VIA or VIIA, or a group of formula (II); Ra, Ra' = H, 1-20C alkyl, 6-14C aryl, aralkyl with 1-10C in the alkyl portion and 6-14C in the aryl portion, 3-10C cycloalkyl, or (not simultaneously) functional groups based on non-metallic elements of Groups IVA, VA, VIA or VIIA; Z' = -O-, -S- or -N(R')-; X = -(C(Rb)(Rb'))l or (=N)-(C(Rb)(Rb'))m-A-(C(Rb)(Rb'))n-(E)p; Rb, Rb' = as for Ra and Ra'; A = -C(O)O-, -O-, -S-, -C(O)N(R)-, -N(R)-, -C(O)- or -C(R)=N-; E = optionally substituted 6-14C arylene; R', R = H, alkyl, aryl or aralkyl; k = 2 or 3; l = a whole number 1-24; m, n = whole numbers 0-12, and m+n /- 1; and p = 0, 1, 2 or 3, and n + p /- 1. An Independent claim is also included for the preparation of compounds (I) comprising reacting a compound of formula (IIIa) with a halogenating agent in a polar aprotic solvent at -20 to 100 deg C to form the corresponding compound (IIIb: B = Cl, Br or I), and reacting the isolated compound (IIIb) with a base in a polar protic solvent at 0-50 deg C. Y = 1-20C alkyl, 6-14C aryl, 6-14C aryl substituted with functional groups based on nonmetallic elements of Groups IVA, VA, VIA or VIIA, 3-10C cycloalkyl, aralkyl with 1-10C in the alkyl part and 6-14C in the aryl part, 1-20C alkyl substituted with functional groups based on nonmetallic elements of Groups IVA, VA, VIA or VIIA, or a residue of formula (IV); Ra, Ra' = H, 1-10C alkyl, 6-14C aryl, aralkyl with 1-10C in the alkyl part and 6-14C in the aryl part, 3-10C cycloalkyl or (not both simultaneously) functional groups based on nonmetallic elements of Groups IVA, VA, VIA or VIIA; Z' = -O-, -S- or -N(R')-; X = -(C(Rb)(Rb'))l or -(C(Rb)(Rb'))m-A-(C(Rb)(Rb'))n(E)p-; Rb, Rb' = as for Ra and Ra'; A = -C(O)O-, -O-, -S-, -C(O)N(R)-, -N(R)-, -C(O)- or -C(R)=N-; E = optionally substituted 6-14C arylene; R', R = H, alkyl, aryl or aralkyl; k = 2 or 3; l = a whole number 1-24; m, n = whole numbers 0-12, and m + n at least 1; p = 0, 1, 2 or 3, and n + p at least 1; and B = OH, mesyl, trifluoromethylsulphonyl, tosyl or brosyl.