Polymerisation Using Chain Transfer Agents

A method of making a functionalised polymer of Formula (1) or Formula (2).

• comprising the steps of:
• reacting a thiocarbonyl thio compound of Formula (3) or Formula (4);
• an olefinically unsaturated monomer (Q), and a first source of free radical to form a Polymer of Formula (6) or Formula (7);
• and subsequently contacting the polymer of Formula (6) or Formula (7) with a second source of free radicals, the second source of free radicals comprising a radically transferable functional moiety R1, to form a polymer of Formula (1) or Formula (2) and a compound of Formula (3) or Formula (4);
• wherein:
• R1 is moiety comprising a functional group;
• R′ is selected from the group consisting of alkyl, substituted alkyl, alkoxy, substituted alkoxy, an aromatic saturated or unsaturated carbocyclic or heterocyclic ring, optionally substituted with one or more substituents, amino alkyl, cyanoalkyl, hydroxylalkyl, saturated and unsaturated amido;
• an organometallic species, a polymer chain and any of the foregoing substituted with one or more CN or OH groups;
• Z is selected from (i) a solid support, (ii) Z comprises a linker attached to a solid support, and (iii) Z is a group selected from a straight or branched chain, substituted or non substituted C1 to C20 alkyl (especially a C1 to C4 alkyl such as methyl or ethyl);
• optionally substituted aryl, e.g. phenyl, substituted phenyl;
• phenyl covalently bonded to a polymer;
• optionally substituted heterocyclyl, substituted or non-substituted C1 to C20 (especially C1 to C4) alkoxy, optionally substituted alkyl thio, thioalkoxyl (optionally substituted with a polymer);
• substituted or non-substituted benzyl (optionally substituted with a solid support), optionally substituted aryl oxycarbonyl (—COOR″), carboxy (—COOH), optionally substituted ocyloxy (—O2CR″), optionally substituted acyloxy (—CO2CR″), optionally substituted carbomyl (—CONR″2), cyano (—CN), dialkyl- or diaryl phosphonato (—P(═OR″Z), dialkyl- or diaryl-phosphinato [—P(═O)R″Z] or SCH2CH2CO2T (where T is a solid support or a polymer);
• the linker may optionally comprise a straight or branched chain, substituted or non substituted C1 to C20 alkyl (especially a C1 to C4 alkyl such as methyl or ethyl);
• phenyl, substituted phenyl;
• phenyl covalently banded to a polymer;
• substituted or non-substituted C1 to C20 (especially C1 to C4) alkoxy, thioalkoxyl (optionally substituted with a polymer);
• substituted or non-substituted benzyl;
• most preferably Z is a solid support or a linker attached to a solid support;
• R″ is selected from the group consisting of optionally substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, alkaryl wherein the substituents are independently selected from the group that consists of epoxy, hydroxyl, alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- or aryloxycarbonyl, isocyanato, cyano, silyl. halo, and dialkylamino;
• Q is at least one olefinically unsaturated monomer, optionally two or more different olefinically unsaturated monomers;
• q=an integer of at least 2;
• p=an integer of at least 1;
• m=an integer of at least 1.