Polymeric cycloaliphatic epoxides

Patent metadata

Field	Value
Publication number	US-2025059317-A1
Application number	US-202218723943-A
Country	US
Kind code	A1
Filing date	Dec 23, 2022
Priority date	Dec 30, 2021
Publication date	Feb 20, 2025
Grant date	—

Abstract

The present invention relates to an alkoxylated cycloaliphatic epoxide according to the following formula (I) wherein each R 1 and R 2 is independently selected from H and Me; L is the residue of a polyol; each a is independently from 2 to 4; each b is independently 0 to 20 with the proviso that at least one b is not 0; c is at least 3. The invention also relates to compositions comprising a compound of formula (I) and a process for the preparation of a cured product. Cured products according to the invention are in particular 3D-printed articles.

First claim

1 . An alkoxylated cycloaliphatic epoxide according to the following formula (I):

wherein
each R 1 and R 2 is Independently selected from H and Me;
L is the residue of a polyol;
each a is independently from 2 to 4;
each b is independently 0 to 20 with the proviso that at least one b Is not 0;
c is at least 3.

2 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein a is 2 and the alkoxylated cycloaliphatic epoxide is according to the following formula (Ia):

wherein
L, b and c are as defined in claim 1 ;
each R 1 and R′ 1 is independently selected from H and Me.

3 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein a is 4 and R 1 and R 2 are both H.

4 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein each b is independently from 1 to 20.

5 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein the alkoxylated cycloaliphatic epoxide has an alkoxyation degree of at least 6.

6 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein c is from 3 to 10.

7 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein c is 3 and L is a trivalent linker according to the following formula (II):

wherein
R 3 is selected from H, alkyl and alkoxy;
d, d′ and d″ are independently 0 to 2 with the proviso that at least 2 among d, d′ and d″ are not 0.

8 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein c is 4 and L Is a tetravalent linker according to one of the following formulae (IIIa), (IIIb) or (IIIc):

wherein
e, e′, e″ and e′″ are Independently 0 to 2 with the proviso that at least 3 among e, e′, e″ and e′″ are not 0.

9 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein c is 5 and L is a pentavalent linker according to the following formula (IV):

10 . The alkoxylated cycloaliphatic epoxide according to claim 1 , wherein c is 6 and L is a hexavalent inker according to the following formula (Va), (Vb) or (Vc):

11 . A process for the preparation of an alkoxylated cycloaliphatic epoxide of formula (I) as defined in claim 1 , wherein the process comprises the following steps:
a) reacting a cyclohexene of formula (VI) with an alkoxylated polyol of formula (VII) to obtain an alkoxylated cyclohexene of formula (VIII); b) epoxidation of the alkoxylated cyclohexene of formula (VIII) to obtain an alkoxylated cycloaliphatic epoxide of formula (I);

wherein
L, R 1 , R 2 , a, b and c are as defined in any one of claims 1 to 10 ;
X is OH, O-Alk or Cl;
Alk Is a C1-C6 alkyl.

12 . A composition comprising a mixture of alkoxylated cycloaliphatic epoxides of formula (I):

wherein
L, R 1 , R 2 , a and b are as defined in claim 1 ;
c is at least 2; and
at least one of the alkoxylated cycloaliphatic epoxides of formula (I) in the mixture has c is at least 3.

13 . A composition comprising:
a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according to claim 1 ; and b) at least one cationically polymerizable compound other than component a).

14 . The composition of claim 13 , wherein component b) comprises at least one cationically polymerizable compound selected from the group consisting of an epoxy-functionalized compound other than component a), an oxetane, an oxolane, a cyclic acetal, a cyclic lactone, a thiirane, a thietane, a spiro orthoester, a spiro orthocarbonate, a vinyl ether, a vinyl ester, derivatives thereof and mixtures thereof.

15 . The composition of claim 13 , wherein component b) comprises at least one oxetane according to the following formula (IX):

wherein R 4 is selected from H, alkyl, aryl, alkylaryl, (meth)acryloyl, —CH 2 —CH 3 , —L 1 -O—CH 2 -oxetanyl —CH 2 —CH 3 ,
L 1 is a divalent linker, in particular-CH 2 -Ph-Ph-CH 2 or —CH 2 -Ph-CH—[O—CH 2 -Ph-CH 2 ] f —
Ph is phenylene;
f is 0 to 10.

16 . The composition according to claim 15 , wherein component b) comprises at least one oxetane according to formula (IX) wherein R 4 is H, benzyl or —CH 2 -oxetanyl-CH 2 —CH 3 .

17 . The composition according to claim 13 , wherein the weight ratio between component a) and component b) is 20:80 to 80:20.

18 . The composition according to claim 13 , wherein the composition comprises at least one cationic photoinitiator.

19 . A composition comprising:
a) at least one alkoxylated cycloaliphatic epoxide of formula (I) according to claim 1 ; and c) at least one (meth)acrylate-functionalized compound.

20 . The composition according to claim 19 , wherein the composition comprises at least one free-radical photoinitiator.

21 . The composition according to claim 13 , wherein the composition is an ink, coating, sealant, adhesive, molding, or 3D printing composition.

22 . A process for the preparation of a cured product, comprising curing the composition according to claim 19 , by exposing the composition to radiation such as UV, near-UV, visible, Infrared and/or near-infrared radiation or to an electron beam.

23 . (canceled)

24 . A cured product obtained by curing the composition according to claim.

25 . A cured product according to claim 24 , wherein the cured product is an ink, a coating, a sealant, an adhesive, a molded article or a 3D-printed article.

26 . (canceled)

Assignees

• Arkema France

Inventors

• Squires Kelly
• Sehnal Petr
• Liu Sen
• Plenderleith Richard
• Ren Kangtai

Classifications

• C09J163/00

  Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins · CPC title

• C09D163/00

  Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G65/332

  containing carboxyl groups, or halides, or esters thereof · CPC title

• C08F122/1006

  of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate · CPC title