Polymerization of michael-type monomers

A process for precision polymerization of Michael-type monomers comprising:

• a) contacting an α-acidic Michael-type monomer, optionally dissolved in an organic solvent, with a bridged precatalyst system comprising a Lewis acid and a Lewis base, whereby a bridged initiator and catalyst is formed, and
• b) continuing the polymerization reaction to form a polymer by reaction with at least one type of an α-acidic or non-α-acidic Michael-type monomer;
• wherein the bridged precatalyst comprises a Lewis acid part [R1R2M]+, and a Lewis base part [Z1PZ2]− or [Z1SZ]−, covalently linked via Z1;
• wherein in the Lewis acid part [R1R2M]+ M is Al, Ga, or In;
• each R1 and R2 is independently Cl, F, I, Br or linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkinyl, heterocycloalkinyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, nitro, nitroso, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkinyl, or alkoxy independently has up to 12 carbon atoms, wherein each aryl or heteroaryl independently has 5 to 10 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, alkinyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms and
• wherein in the Lewis base part [Z1PZ2]− or [Z1SZ]− each Z independently is a linear, branched, or cyclic alkyl, alkenyl, or alkinyl group, or heteroalkyl, heteroalkenyl, or heteroalkinyl, group, having up to 12 carbon atoms;
• or a donor substituted aryl or heteroaryl group having 5 to 10 ring atoms;
• wherein any hetero group comprises at least one hetero atom selected from the group consisting of O, S, and N and
• wherein Z1− is —C(R10R11)—, —S—, —O—, or —N(R12)—, wherein R10, R11, R12, independently are hydrogen or linear or branched C1-C5-alkyl.

A precatalytic bridged complex having formula R1R2MZ1PZ2 or R1R2MZ1SZ, wherein a Lewis acid part R1R2M and a Lewis base part, PZ2 or SZ, are covalently linked via a bridge Z1, wherein M is Al, Ga, or In;

• each R1 and R2 is independently Cl, F, I, Br or linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkinyl, heterocycloalkinyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, nitro, nitroso, hydroxy, or carboxyl, wherein each alkyl, alkenyl, or alkenyl group independently has up to 12 carbon atoms, wherein each aryl or heteroaryl independently has 5 to 10 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, alkinyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms and
• wherein each Z independently is a linear, branched, or cyclic alkyl, alkenyl, or alkinyl group, or heteroalkyl, heteroalkenyl, or heteroalkinyl, group, having up to 12 carbon atoms;
• or a donor substituted aryl or heteroaryl group having 5 to 10 ring atoms, wherein any hetero group comprises at least one hetero atom selected from the group consisting of O, S and N and wherein Z1− is —C(R10R11)—, —S—, —O—, or —N(R12)—, wherein R10, R11, R12, independently are hydrogen or linear or branched C1-C5-alkyl;
• with the proviso that the compound is not (dimethyl phosphinomethyl)dimethyl aluminum.

A system for precision polymerization, comprising

• a) an α-acidic Michael-type monomer,
• b) a precatalyst having formula R1R2MZ1PZ2 or R1R2MZ1SZ comprising a Lewis acid part [R1R2M]+, as catalyst, and a Lewis base part [Z1PZ2]− or [Z1SZ]− covalently combined in one molecule,
• c) optionally an organic solvent,
• wherein components a) and b) can form an active initiator and catalyst complex, wherein a Lewis acid part R1R2M and a Lewis base part, PZ2 or SZ, are covalently linked via a bridge Z1, wherein M is Al, Ga, or In;
• each R1 and R2 is independently Cl, F, I, Br or linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkinyl, heterocycloalkinyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, nitro, nitroso, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkinyl, or alkoxygroup independently has up to 12 carbon atoms, wherein each aryl independently has 5 to 10 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, alkenyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms and wherein each Z independently is a linear, branched, or cyclic alkyl, alkenyl, or alkinyl group, or heteroalkyl, heteroalkenyl, or heteroalkinyl, group, having up to 12 carbon atoms;
• or a donor substituted aryl or heteroaryl group having 5 to 10 ring atoms, wherein any hetero group comprises at least one hetero atom selected from the group consisting of O, S and N and wherein Z1− is —C(R10R11)—, —S—, —O—, or —N(R12)—, wherein R10, R11, R12, independently are hydrogen or linear or branched C1-C5-alkyl.

A catalyst and initiator compound for the polymerization of Michael-type monomers, comprising a structure represented by the following formula:

• [R9]nM-[Z3-Q]3−n Formula III
• wherein M is Al, Ga, or In;
• wherein each R9 is independently Cl, F, I, or Br, linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkinyl, heterocycloalkinyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, nitro, nitroso, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkinyl, or alkoxy independently has up to 12 carbon atoms, wherein each aryl independently has 5 to 10 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, alkinyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group is optionally substituted by 1 up to the highest possible number of halogen atoms;
• wherein Z3 is a single bond, —C(R10R11)—, —S—, —O—, or —N(R12)—, wherein R10, R11, R12, independently are hydrogen or linear or branched C1-C5-alkyl;
• wherein Q is an aromatic system comprising up to 3 aromatic rings, wherein the rings can independently be condensed or covalently linked, wherein the aromatic rings are independently 5- or 6-membered carbocyclic or heteroaromatic rings, at least one of which is a 5- or 6-membered heteroaromatic ring comprising at least one and up to 3 heteroatoms selected from the group consisting of N, O, and S, wherein optionally Q has at least one unsubstituted carbon atom in a heteroaromatic ring in a position available for binding of an electrophilic substituent which is in vicinity to the heteroatom, wherein the system additionally is optionally substituted by one or more substituents selected from the group consisting of linear or branched C1-C-alkyl, C1-C5-alkoxy, amino, nitro, nitroso, cyano, halogen, C5-C10 aryl, C5-C10 heteroaryl, and C5-C10 aryloxy;
• wherein n is 0, 1, or 2
• with the proviso that the compound is not diethyl-[(4-methyl-pyridin-2-y)-methyl]aluminum, diethyl-(2-pyridinylmethyl)aluminum, or diethyl(2-quinolinyl-methyl)aluminum.

A process for polymerization of Michael-type monomers, comprising:

• a) contacting a Michael-type monomer, optionally dissolved in an organic solvent, with a bridged catalyst and initiator compound, and
• b) continuing the polymerization reaction to form a polymer by reaction with at least one type of Michael-type monomer;
• wherein the bridged catalyst and initiator compound is [R9]nM[Cp]3−n or [R9]nM[-[Z3-Q]3−n,
• wherein M is aluminum, gallium or indium, wherein Cp is cyclopentadienyl, tetramethyl cyclopentadienyl, or pentamethyl cyclopentadienyl:
• wherein each R9 is independently Cl, F, I, or Br, linear, branched or cyclic alkyl, heterocycloalkyl, linear, branched, or cyclic alkenyl, heterocycloalkenyl, linear, branched, or cyclic alkinyl, heterocycloalkinyl, linear, branched, or cyclic alkoxy, aryl, heteroaryl, aryloxy, silyl, metallocenyl, nitro, nitroso, hydroxy, or carboxyl, wherein each alkyl, alkenyl, alkinyl, or alkoxy group independently has up to 12 carbon atoms, wherein each aryl independently has 5 to 10 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, alkinyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group can be substituted by 1 up to the highest possible number of halogen atoms;
• Z3 is a single bond, —C(R10R11)—, —S—, —O—, or —N(R12)—, wherein R10, R11, R12, independently are hydrogen or linear or branched C1-C5-alkyl;
• wherein Q is an aromatic system comprising up to 3 aromatic rings, wherein the rings can independently be condensed or covalently linked, wherein the aromatic rings are independently 5- or 6-membered carbocyclic or heteroaromatic rings, at least one of which is a 5- or 6-membered heteroaromatic ring comprising at least one and up to 3 heteroatoms selected from N or S, wherein optionally Q has at least one unsubstituted carbon atom in a heteroaromatic ring in a position available for binding of an electrophilic substituent which is in vicinity to the heteroatom, wherein the system can be is optionally substituted by one or more substituents selected from the group consisting of linear or branched C1-C5-alkyl, C1-C5-alkoxy, amino, nitro, nitroso, cyano, halogen, C5-C10 aryl, C5-C10 heteroaryl, and C5-C10 aryloxy;
• wherein n is 0, 1, or 2.