Glycidyl ethers of limonene derivatives and oligomers thereof as curable epoxy resins

Patent metadata

Field	Value
Publication number	US-2016194297-A1
Application number	US-201414911974-A
Country	US
Kind code	A1
Filing date	Jul 30, 2014
Priority date	Aug 14, 2013
Publication date	Jul 7, 2016
Grant date	—

Abstract

Cured epoxy resins are widespread because of their excellent mechanical and chemical properties. Typically, epoxy resins based on bisphenol A diglycidyl ethers or bisphenol F diglycidyl ethers are used, but these are problematic for many sectors because of their effect on the endocrine system. The present invention relates to glycidyl ethers of limonene-based diols and/or polyols, and to curable epoxy resin compositions based thereon as alternatives to the bisphenol A diglycidyl ethers or bisphenol F diglycidyl ethers, or the epoxy resin compositions based thereon.

First claim

1 : A glycidyl ether selected from the group consisting of a glycidyl ether of formula I

and an oligomeric glycidyl ether thereof,
where
R1=H and R2=CH 2 OA and R3=H, or
R1=H and R2=CH 2 OA and R3=CR7R8OA, or
R1=CH 2 OA and R2=H and R3=H,

and where
R4=H and R5=CH 2 OA and R6=H, or
R4=H and R5=CH 2 OA and R6=CR7R8OA, or
R4=CH 2 OA and R5=H and R6=H,

and where
A is a glycidyl group or a hydrogen atom, and
R7 and R8 are each independently a hydrogen atom or a C 1 -C 4 -alkyl group,

and where
at least 2 A radicals are each a glycidyl group,

and where
when the glycidyl ether is the oligomeric glycidyl ether, the oligomeric glycidyl ether forms through an intermolecular reaction of glycidylated radicals with non-glycidylated radicals comprising a hydroxyl group in the monomeric glycidyl ether of the formula I and a partially glycidylated or non-glycidylated derivative thereof with ring opening of the oxirane ring, where the hydroxyl group which forms through the ring-opening of the oxirane ring in the oligomeric glycidyl ether is optionally in a glycidylated form, and where the oligomeric glycidyl ether has an oligomerization level of 2 to 100 and comprises, by average, at least 1.3 glycidyl groups.

2 : The glycidyl ether according to claim 1 ,
where
R1=H and R2=CH 2 OA and R3=H, or
R1=CH 2 OA and R2=H and R3=H,
and where
R4=H and R5=CH 2 OA and R6=H, or
R4=CH 2 OA and R5=H and R6=H,
and where A is a glycidyl group.

3 : The glycidyl ether according to claim 1 ,
where R3 and R6 are not both simultaneously a hydrogen atom.

4 : A process for preparing the glycidyl ether according to claim 2 , the process comprising
hydroformulating limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to give a corresponding dialdehyde, and catalytically hydrogenating the dialdehyde to give a corresponding diol, and reacting the diol with epichlorohydrin to give the glycidyl ether.

5 : A process for preparing the glycidyl ether according to claim 3 , the process comprising
hydroformylating limonene with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to give a corresponding dialdehyde, and reacting the dialdehyde with a carbonyl compound of formula R7R8C═O forming a new C—C bond in an aldol reaction to give a corresponding beta-hydroxy aldehyde, catalytically hydrogenating the beta-hydroxy aldehyde to give a corresponding tri- and tetrahydric alcohols, and reacting the tri- and tetrahydric alcohols with epichlorohydrin to give the glycidyl ether.

6 : A limonene derivative of formula II

where
R9=H and R10=CH 2 OH and R11=H, or
R9=H and R10=CH 2 OH and R11=CR7R8OH, or
R9=CH 2 OH and R10=H and R11=H,

and where
R12=H and R13=CH 2 OH and R14=H, or
R12=H and R13=CH 2 OH and R14=CR7R8OH, or
R12=CH 2 OH and R13=H and R14=H,

and where
R7 and R8 are each independently a hydrogen atom or a C 1 -C 4 -alkyl group,

and
R11 and R14 are not both simultaneously a hydrogen atom.

7 : An oligomer, obtained by a process comprising
reacting the glycidyl ether according to claim 1 with one or more diols, wherein the glycidyl ether is the glycidyl ether of the formula I.

8 : A curable epoxy resin composition, comprising
a curing agent component comprising a curing agent, and a resin component comprising at least one polyepoxide compound selected from the group consisting of the glycidyl ether according to claim 1 and an oligomer obtained by reacting the glycidyl ether of the formula I with one or more diols.

9 : The curable epoxy resin composition according to claim 8 , wherein the polyepoxide compound is the glycidyl ether according to claim 1 .

10 : The curable epoxy resin composition according to claim 8 , wherein the curing agent is at least one selected from the group consisting of an amino curing agent and a phenol resin.

11 : The curable epoxy resin composition according to claim 8 , wherein a portion of the polyepoxide of compound is at least 40% by weight, based on an overall weight of the resin component.

12 : The curable epoxy resin composition according to claim 8 , which comprises bisphenol A- or F-based compounds in a portion of less than 40% by weight, based on an overall weight of the resin component.

13 : A process for producing a cured epoxy resin, the process comprising
curing the curable epoxy resin composition according to claim 8 .

14 : A cured epoxy resin, obtained by curing the curable epoxy resin composition according to claim 8 .

15 : A process for producing an adhesive, a composite, a molding, or a coating, the process comprising:
employing the curable epoxy resin composition according to claim 8 in the process.

Assignees

• Basf Se

Inventors

• Karl Ulrich
• Charrak Monika
• Thomas Hans-Josef

Classifications

• C08G59/04

  of polyhydroxy compounds with epihalohydrins or precursors thereof · CPC title

• C07C31/133

  monocyclic · CPC title

• C08G59/50

  Amines · CPC title

• C07C31/276

  with a six-membered ring · CPC title

• C08G59/24

  carbocyclic · CPC title