Polymerization with living characteristics

A process for the synthesis of polymers selected from the group consisting of:

• 20
• comprising contacting:
• (i) a monomer having repeating units, Q, selected from the group consisting of vinyl monomers of structure CH2═CUV, maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers;
• (ii) a thiocarbonylthio compound selected from:
• 21
• having a chain transfer constant greater than about 0.1;
• and
• (iii) free radicals produced from a free radical source;
• and
• controlling the polydispersity of the polymer being formed by varying the ratio of the number of molecules of (ii) to the number of molecules of (iii);
• the polymer of Formula A being made by contacting (i), (ii) C and (iii) and the polymer of Formula B being made by contacting (i), (ii) D and (iii);
• wherein:
• Z is selected from the group consisting of hydrogen, chlorine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted alkoxycarbonyl, optionally substituted aryloxycarbonyl (—COOR″), carboxy (—COOH), optionally substituted acyloxy (—O2CR″), optionally substituted carbamoyl (—CONR″2), cyano (—CN), dialkyl- or diaryl-phosphonato [—P(═O)OR″2], dialkyl- or diaryl-phosphinato [—P(═O)R″2], and a polymer chain formed by any mechanism;
• Z′ is a m-valent moiety derived from a member of the group consisting of optionally substituted alkyl, optionally substituted aryl and a polymer chain;
• where the connecting moieties are selected from the group that consists of aliphatic carbon, aromatic carbon, and sulfur;
• Q is selected from the group consisting of
• 22
• repeating units from maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers;
• U is selected from the group consisting of hydrogen, halogen, optionally substituted C1-C4 alkyl wherein the substituents are independently selected from the group that consists of hydroxy, alkoxy, aryloxy (OR″), carboxy, acyloxy, aroyloxy (O2CR″), alkoxy-carbonyl and aryloxy-carbonyl (CO2R″);
• V is selected from the group consisting of hydrogen, R″, CO2H, CO2R″, COR″, CN, CONH2, CONHR″, CONR″2, O2CR″, OR″ and halogen;
• R is selected from a group consisting of optionally substituted alkyl;
• an optionally substituted saturated, unsaturated or aromatic carbocyclic or heterocyclic ring;
• optionally substituted alkylthio;
• optionally substituted alkoxy;
• optionally substituted dialkylamino;
• an organometallic species;
• and a polymer chain prepared by any polymerization mechanism;
• in compounds C and D, R• is a free-radical leaving group that initiates free radical polymerization;
• 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, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, isocyanato, cyano, silyl, halo, and dialkylamino;
• q is 1 or an integer greater than 1;
• p is 1 or an integer greater than 1;
• when p≧2 then R=R′;
• m is an integer≧2;
• and
• R′ is a p-valent moiety selected from a member of the group consisting of optionally substituted alkyl, optionally substituted aryl and a polymer chain;
• where the connecting moieties are selected from the group consisting of aliphatic carbon, aromatic carbon, silicon, and sulfur;
• in compounds C and D, R′• is a free radical leaving group that initiates free radical polymerization.