Polymerization of Michael-type and heterocyclic monomers

A system for polymerization comprising a monomer component and a metal compound as sole initiator, wherein the monomer component comprises at least one heterocyclic monomer selected from the group consisting of a substituted or unsubstituted lactone having up to 9 ring atoms, a substituted or unsubstituted lactam having up to 9 ring atoms, and a substituted or unsubstituted 1,4-dioxan-2,4-dione, or a mixture thereof, wherein each substituent independently is selected from linear, branched, or cyclic alkyl, alkenyl, alkynyl groups having up to 6 carbon atoms, linear, branched, or cyclic alkoxy groups having up to 6 carbon atoms, halogen, metallocenyl, hydroxy, carboxyl, aryl, or heteroaryl;

• and wherein the metal compound is MR1R2R3, wherein M is aluminum, gallium, or indium;
• each of R1, R2, and R3 independently is CI, F, I, Br, linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkynyl, heterocycloalkynyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkynyl or alkoxy group independently has up to 12 carbon atoms, wherein each aryl or heteroaryl independently has 5 to 14 ring atoms, wherein any hetero group has at least one hetero atom selected from the group consisting of O, S, and N, wherein each alkyl, alkenyl, alkynyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms, or by at least one electron-donating or electron-withdrawing group;
• or
• wherein two of R1, R2, and R3 together with M form a substituted or unsubstituted cyclic group comprising 2 to 5 carbon atoms or 2 to 4 carbon atoms and 1 to 3 hetero atoms selected from the group consisting of O, S, and N;
• with the proviso that only up to two of groups R1, R2, and R3 can be perfluorinated aryl or heterocycle;
• alkoxy, hydroxy, or halogen.

A system for polymerization comprising a monomer component and a metal compound as sole initiator, wherein the monomer component comprises a combination of CO2 and at least one comonomer selected from the group of substituted or unsubstituted oxirane with 3 or 4 ring atoms, substituted or unsubstituted aziridine or azetidine, or a mixture thereof;

• and wherein the metal compound is MR1R2R3, wherein M is aluminum, gallium, or indium, each of R1, R2, and R3 independently is CI, F, I, Br, linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkynyl, heterocycloalkynyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkynyl or alkoxy group independently has up to 12 carbon atoms, wherein each aryl or heteroaryl independently has 5 to 14 ring atoms, wherein any hetero group has at least one hetero atom selected from the group consisting of O, S, and N, wherein each alkyl, alkenyl, alkynyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms, or by at least one electron-donating or electron-withdrawing group;
• or
• wherein two of R1, R2, and R3 together with M form a substituted or unsubstituted cyclic group comprising 2 to 5 carbon atoms or 2 to 4 carbon atoms and 1 to 3 hetero atoms selected from the group consisting of O, S, and N;
• with the proviso that only up to two of groups R1, R2, and R3 can be perfluorinated aryl or heterocycle;
• alkoxy, hydroxy, or halogen.

A process for polymerization of a monomer component using a metal compound as sole initiator, which comprises the steps:

• a) contacting a monomer component, wherein the monomer component comprises at least one of a Michael-type monomer;
• and/or at least one substituted or unsubstituted lactone having up to 9 ring atoms, substituted or unsubstituted lactam having up to 9 ring atoms, substituted or unsubstituted 1,4-dioxan-2,4-dione, or a
• mixture thereof and/or a combination of CO2 and at least one comonomer selected from the group of substituted or unsubstituted oxirane with 3 or 4 ring atoms, substituted or unsubstituted aziridine or azetidine, or a mixture thereof;
• with a metal compound MR1R2R3, optionally dissolved in an organic solvent, wherein M is aluminum, gallium, or indium, each of R1, R2, and R3 independently is CI, F, I, Br, linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkynyl, heterocycloalkynyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkynyl or alkoxy group independently has up to 12 carbon atoms, wherein each aryl or heteroaryl independently has 5 to 14 ring atoms, wherein any hetero group has at least one hetero atom selected from the group consisting of O, S, and N, wherein each alkyl, alkenyl, alkynyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, aryloxy group can be substituted by 1 up to the highest possible number of halogen atoms, or by at least one electron-donating or electron-withdrawing group, with the proviso that not all three groups R1, R2, and R3 are halogen, hydroxy, or alkoxy;
• or wherein two of R1, R2, and R3 together with M form a substituted or unsubstituted cyclic group comprising 2 to 5 carbon atoms or 2 to 4 carbon atoms and 1 to 3 hetero atoms selected from the group consisting of O, S, and N;
• and
• b) continuing the polymerization reaction with the same, additional or other monomer component to form a polymer.