Radical crosslinking of polyether carbonate polyols that have electron-poor and electron-rich double bonds

Patent metadata

Field	Value
Publication number	US-2016200865-A1
Application number	US-201414914308-A
Country	US
Kind code	A1
Filing date	Sep 2, 2014
Priority date	Sep 5, 2013
Publication date	Jul 14, 2016
Grant date	—

Abstract

The present invention relates to a method for producing polyether carbonate polyols, the polyether carbonate polyols having electron-poor and electron-rich double bonds, said method preferably comprising the steps of (a) providing a suspending agent and/or an H-functional starter compound and a DMC catalyst, 03) adding at least one epoxide and (y) adding carbon dioxide, an epoxide that does not contain an unsaturated group, and at least two unsaturated compounds, the unsaturated compounds in method step (y) being selected from the group comprising unsaturated epoxides and unsaturated cyclic anhydrides, and one of the unsaturated compounds having an electron-rich double bond and one of the unsaturated compounds having an electron-poor double bond. The invention also relates to the crosslinking of polyether carbonate polyols, the polyether carbonate polyols having electronpoor and electron-rich double bonds, and to the crosslinked polyether carbonates obtainable therefrom.

First claim

1 .- 15 . (canceled)

16 . A process for preparing polyethercarbonate polyols, the polyethercarbonate polyols comprising double bonds, comprising the steps of:
(α) initially introducing a catalyst and
(αα) a suspension medium which contains no H-functional groups and/or
(αβ) an H-functional starter compound
(γ) metering in carbon dioxide, an epoxide which contains no unsaturated group, and at least two unsaturated compounds,
wherein
the unsaturated compounds metered in step (γ) are selected from unsaturated epoxides and/or unsaturated cyclic anhydrides, and
(γ1) one of the unsaturated compounds comprises a double bond comprising at least one substituent selected from the group of —OX 1 , —OCOX 1 , —X 1 , —CH 2 OX 1 and/or —CH═CHX 1 , where X 1 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain;
(γ2) and another of the unsaturated compounds comprises a double bond comprising at least one substituent selected from the group of —F, —Cl, —Br, —I, —COH, COX 2 , —COOX 2 , —C≡N and/or —NO 2 or is an unsaturated, substituted or unsubstituted cyclic anhydride of an organic dicarboxylic acid, where X 2 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain;
and where additionally, if no H-functional starter compound is introduced in step (α), step (γ) comprises the metering in of an H-functional starter compound.

17 . The process as claimed in claim 16 , further comprising the following step (β) between step (α) and step (γ):
(β) metering in of at least one epoxide.

18 . The process as claimed in claim 16 , wherein the catalyst is a DMC catalyst.

19 . The process as claimed in claim 16 , wherein the unsaturated compound as per (γ2) is an unsaturated cyclic anhydride having a double bond adjacent to a carbonyl group.

20 . The process as claimed in claim 16 , wherein the unsaturated compound as per (γ2) is an unsaturated epoxide selected from the group of glycidyl esters of α,β-unsaturated acids.

21 . The process as claimed in claim 16 , wherein the temperature in step (γ) is greater than or equal to 60° C. and less than or equal to 150° C.

22 . The process as claimed in claim 16 , wherein the unsaturated compound as per (γ1) is selected from the group consisting of allyl glycidyl ether, vinylcyclohexene oxide, cyclooctadiene monoepoxide, cyclododecatriene monoepoxide, butadiene monoepoxide, isoprene monoepoxide, limonene oxide, 1,4-divinylbenzene monoepoxide, 1,3-divinylbenzene monoepoxide, glycidyl esters of unsaturated fatty acids and/or partially epoxidized fats, and oils.

23 . A polyethercarbonate polyol comprising unsaturated groups prepared by a process as claimed in claim 16 .

24 . The polyethercarbonate polyol as claimed in claim 23 , wherein the molar ratio of the double bonds with substituents as per (γ1) to double bonds with substituents as per (γ2), including the structural units in the polymer that originate from cyclic anhydrides, is less than or equal to 3:1 and greater than or equal to 1:3.

25 . The polyethercarbonate polyol as claimed in claim 23 , wherein the glass transition temperature of the polyethercarbonate polyol with unsaturated groups is greater than or equal to −60° C. and less than or equal to 80° C.

26 . A process for crosslinking polyethercarbonate polyols containing unsaturated groups, the unsaturated groups comprising:
(δ1) double bonds comprising at least one substituent selected from the group of —OX 1 , —OCOX 1 , —X 1 , —CH 2 OX 1 and/or —CH═CHX 1 where X 1 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain; and (δ2) double bonds comprising at least one substituent selected from the group of —F, —Cl, —Br, —I, —COH, —COX 2 , COOX 2 , —CN and/or —NO 2 where X 2 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain; the polyethercarbonate polyols being reacted with one another with addition of an initiator selected from the group of the photoinitiators, metal-activated peroxides and/or redox initiators.

27 . The process as claimed in claim 26 , a mixture of polyethercarbonate polyols comprising double bonds as per (δ1) and of polyethercarbonate polyols comprising double bonds as per (δ2) being crosslinked.

28 . A crosslinked polyethercarbonate prepared by the process as claimed in claim 26 .

29 . An article comprising the crosslinked polyethercarbonates as claimed in claim 28 wherein the article is a rubber, a sealant, an adhesives, a coatings or a thermoset molding.

30 . A composition, comprising:
a first polyethercarbonate polyol comprising double bonds, the double bonds comprising a substituent which is selected from the group of —OX 1 , —OCOX 1 , —X 1 , —CH 2 OX 1 and/or —CH═CHX 1 , where X 1 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain; and a second polyethercarbonate polyol containing double bonds, the double bonds comprising a substituent which is selected from the group of —F, —Cl, —Br, —I, —COH, —COX 2 , —COOX 2 , —C≡N and/or —NO 2 , where X 2 in each case is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a substituted or unsubstituted methylene chain.

Assignees

• Covestro Deutschland Ag

Inventors

• Müller Thomas E
• Gürtler Christoph
• Subhani Muhammad A
• Köhler Burkhard
• Leitner Walter

Classifications

• C09J169/00

  Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates · CPC title

• C09D169/00

  Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates · CPC title

• C08L69/00

  Compositions of polycarbonates; Compositions of derivatives of polycarbonates · CPC title

• C08G64/42

  Chemical after-treatment · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title