Preparation of novel homo- and copolymers using atom transfer radical polymerization

A process for making a (co)polymer, comprising the steps of:

• (a) polymerizing an AB.sub.2 monomer of formula (V):
• ##STR9## in the presence of a catalyst system, comprising:
• (i) a transition metal compound and
• (ii) a ligand able to coordinate with said transition metal compound
• to thereby initiate polymerization of said monomer and form a branched polymer;
• wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of H, halogen, CF.sub.3, straight or branched C.sub.1 -C.sub.20 alkyl, .alpha.,.beta.-unsaturated straight or branched C.sub.2 -C.sub.10 alkenyl or alkynyl, .alpha.,.beta.-unsaturated straight or branched C.sub.2 -C.sub.6 alkenyl substituted with a halogen, C.sub.3 -C.sub.8 cycloalkyl, hetercyclyl, C(.dbd.Y)R.sup.5, C(.dbd.Y)NR.sup.6 R.sup.7 and YC(.dbd.Y)R.sup.8, where Y may be NR.sup.8 or O, R.sup.5 is C.sub.2 -C.sub.20 -alkyl, C.sub.2 -C.sub.20 alkoxy, aryloxy or heterocyclyloxy, R.sup.6 and R.sup.7 are independently H or alkyl of from 1 to 20 carbon atoms, or R.sup.6 and R.sup.7 may be joined together to form a C.sub.2 -C.sub.5 alkylene group, thus forming a 3- to 6-membered ring, and R.sup.8 is H, straight or branched C.sub.1 -C.sub.20 alkyl or aryl;
• and
• R.sup.3 is selected from the group consisting of H, halogen, C.sub.1 -C.sub.6 alkyl, COOR.sup.9, where R.sup.9 is H, an alkali metal, or a C.sub.1 -C.sub.6 alkyl group, or aryl;
• and
• R.sub.2.sup.4 is an organic spacer group and A is selected from the group consisting of R.sub.2.sup.4 '--X and X, where X is a halogen, and R.sub.2.sup.4 ' is selected from the group consisting of straight or branched C.sub.2 -C.sub.20 alkyl, .alpha.,.beta.-unsaturated straight or branched C.sub.2 -C.sub.10 alkenyl or alkynyl, .alpha.,.beta.-unsaturated straight or branched C.sub.2 -C.sub.6 -alkenyl, C.sub.3 -C.sub.8 cycloalkyl, heterocyclyl, C(.dbd.Y)R.sup.5, C(.dbd.Y)NR.sup.6 R.sup.7 and YC(.dbd.Y)R.sup.8, C(.dbd.Y)--Y--R.sup.5 --C(.dbd.Y)--R.sup.8 where Y may be NR.sup.8 or O, R.sup.5 is alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy, R.sup.6 and R.sup.7 are independently H or alkyl of from 1 to 20 carbon atoms, or R.sup.6 and R.sup.7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring, and R.sup.8 is H, straight or branched C.sub.1 -C.sub.20 alkyl and aryl;
• and
• R.sup.1 and R.sup.3 may be joined to form a group of the formula (CH.sub.2).sub.n' or C(.dbd.O)--Y--C(.dbd.O), where n' is from 2 to 6 and Y is as defined above.