Polymerization of Michael-type and heterocyclic monomers

Patent metadata

Field	Value
Publication number	US-10894845-B2
Application number	US-201716087278-A
Country	US
Kind code	B2
Filing date	Mar 22, 2017
Priority date	Mar 22, 2016
Publication date	Jan 19, 2021
Grant date	Jan 19, 2021

Abstract

A system for precision polymerization is disclosed comprising at least one Michael-type monomer and a metal compound MR1R2R3 as sole catalyst and initiator, 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 alkenyl, 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 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, alkinyl or alkoxy, heterocycloalkyl, heterocycloalkenyl, heterocycloalkinyl, aryl, heteroaryl, aryloxy group can be substituted by 1 up to the highest possible number of halogen atoms, or 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 or heterocyclic group having 3 to 6 atoms, wherein a heterocyclic group has at least one hetero atom selected from the group consisting of O, S, and N; as well as processes for preparing polymers and the polymers obtained therewith.

First claim

The invention claimed is:

1. A system for polymerization comprising a monomer component, and a metal compound as sole initiator, wherein the monomer component comprises at least one Michael-type monomer, and wherein the metal compound is MR 1 R 2 R 3 , wherein M is aluminum, gallium, or indium, each of R 1 , R 2 , and R 3 independently is 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; with the proviso that not all three groups R 1 , R 2 , and R 3 are halogen, hydroxy, or alkoxy; or
wherein two of R 1 , R 2 , and R 3 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.

2. The system for polymerization according to claim 1 , comprising
a) at least one Michael-type monomer,
b) a compound MR 1 R 2 R 3 , wherein M, R 1 , R 2 , and R 3 are as defined in claim 1 , as sole initiator;
c) optionally an organic solvent,
wherein the initiator is adapted to the monomer such that for an electron deficient monomer the initiator is MR 1 R 2 R 3 with a FIA of about 530 or less; for a monomer having medium electrophilicity the initiator is MR 1 R 2 R 3 with a medium FIA of less than 530 and more than 393; and for an electron donating or electron-rich monomer the initiator is MR 1 R 2 R 3 with a low FIA of 393 or more.

3. The system for polymerization according to claim 1 wherein the Michael-type monomer is a vinylphosphonate or mono- or dialkyllvinylphosphonate; a vinylsulfonate or mono- or dialkylsulfonate, a substituted or unsubstituted acrylate or methacrylate, a substituted or unsubstituted acrylamide or methacrylamide, acrylonitrile, a substituted or unsubstituted heteroaromatic vinyl compound, a substituted or unsubstituted vinyl ketone, acrolein, or an acrolein derivate, or a mixture of two or more thereof; or wherein the Michael-type monomer is butyl acrylate, isobutyl acrylate, tert. -butyl acrylate, isobornyl acrylate, furfuryl acrylate, glydidyl acrylate, butyl methacrylate, isobutyl methacrylate, tert. -butyl methacrylate, isobornyl methacrylate, furfuryl methacrylate, or glycidyl methacrylate, or a mixture thereof.

4. 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 MR 1 R 2 R 3 , wherein M is aluminum, gallium, or indium; each of R 1 , R 2 , and R 3 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 R 1 , R 2 , and R 3 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 R 1 , R 2 , and R 3 can be perfluorinated aryl or heterocycle; alkoxy, hydroxy, or halogen.

5. A system for polymerization comprising a monomer component and a metal compound as sole initiator, wherein the monomer component comprises a combination of CO 2 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 MR 1 R 2 R 3 , wherein M is aluminum, gallium, or indium, each of R 1 , R 2 , and R 3 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 R 1 , R 2 , and R 3 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 R 1 , R 2 , and R 3 can be perfluorinated aryl or heterocycle; alkoxy, hydroxy, or halogen.

6. The system for polymerization according to claim 1 , wherein the monomer component comprises at least one Michael-type monomer and/or at least one heterocyclic monomer and/or a combination of CO 2 and at least one comonomer selected from the group consisting of substituted or unsubstituted oxirane with 3 or 4 ring atoms, substituted or unsubstituted aziridine or azetidine, substituted or unsubstituted lactone having up to 9 ring atoms, substituted or unsubstituted lactam having up to 9 ring atoms, and substituted or unsubstituted 1,4-dioxan-2,4-dione, or a mixture thereof.

7. 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 CO 2 and at least

Assignees

• Univ Muenchen Tech

Inventors

• Knaus Maximilian
• Giuman Marco
• Rieger Bernhard

Classifications

• C08F28/02

  by a bond to sulfur · CPC title

• C08F4/005 Primary

  Friedel-Crafts catalysts in general · CPC title

• C08F30/02

  containing phosphorus · CPC title

• C08F20/54

  Amides {, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide} · CPC title

• C08F20/18

  with acrylic or methacrylic acids · CPC title