Allyl functional urethane oligomers and related compositions for coatings and adhesives

Patent metadata

Field	Value
Publication number	US-11261288-B2
Application number	US-201716640879-A
Country	US
Kind code	B2
Filing date	Aug 22, 2017
Priority date	Aug 22, 2017
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

A urethane oligomer according to a) or b) has: a) at least two backbone residues R issued from a polyisocyanate without the NCO groups, linked between them with a diol residue RB (diol without the two OH groups) by two urethane bonds and each backbone residues R carrying (or linked to) at least two urethane segments each containing at least one terminal allyl group, b) at least one backbone residue R issued from a polyisocyanate without the NCO groups, the backbone residue R carrying (or linked to) at least two urethane segments each linked to R by one urethane bond with at least one urethane segment (arm) containing at least one terminal allyl group, and at least one urethane segment (arm) containing at least one terminal (meth)acrylate group. A curable composition containing the urethane oligomer reduces oxygen inhibition in coatings, adhesives, sealants or in resin matrix with good surface properties.

First claim

The invention claimed is:

1. A urethane oligomer according to option a) or b), wherein:
a) at least two backbone residues R issued from a polyisocyanate without the NCO groups, linked between them with a diol residue R B by two urethane bonds and each of said backbone residues R carrying or linked to at least two urethane segments each containing at least one terminal allyl group, wherein said diol residue R B is derived from a diol selected from the group consisting of alkane diols, cycloalkane diols, oligoether diols, oligoester diols, and oligourethane diols and R B as the diol residue is a moiety formed by removing two hydroxyl groups from a diol,
b) at least one backbone residue R issued from a polyisocyanate without the NCO groups, said backbone residue R carrying or linked to at least two urethane segments each linked to R by one urethane bond with:
at least one urethane segment containing at least one terminal allyl group, and
at least one urethane segment containing at least one terminal (meth)acrylate group.

2. The urethane oligomer according to claim 1 , wherein the urethane oligomer is represented by one of the following two formulae I-a or I-b, formula I-a representing option a) and formula I-b representing option b),
[(CH 2 ═CHCH 2 O) m R 1 —O—CO—NH] n′1 R—NH—CO—O—R B —O—CO—NH—R[NH—CO—O—R 1 (OCH 2 CH═CH 2 ) m ] n′2   (I-a)

wherein
m>0, independently or dependently in each occurrence,
n′1>0, n′2>0, with n′=n′1+n′2 from 2 to 10,
each of m, n′1 and n′2 is an integer, and with n′1=n′2=n1+n2-1 with n1+n2=n being the functionality of said polyisocyanate and varying from 2 to 6, each of n1 and n2 is an integer with n1 and n2 being identical or different;
or
[(CH 2 ═CHCH 2 O) m R 1 —O—CO—NH] n1 R[NH—CO—O—R′ 1 (O—CO—C(R 2 )═CH 2 ) m′ ] n2 ,  (I-b)

wherein R 2 is H or CH 3 ;
n=n1+n22 and up to 6,
n1>0, n2>0, m>0, m′>0, m′=1 to 5, n>0, each of m, m′, n, n1 and n2 is an integer with n1 and n2 being identical or different;
m is an integer of from 1 to 5;
m′ is an integer from 1 to 5 which is identical to or different from m;

wherein
the backbone residue R is a moiety formed by removing all of NCO groups from a polyisocyanate;
R 1 is independently or dependently in each occurrence a (m+1)-valent group selected from C 2 -C 12 , aliphatic group or from an (m+1)-valent oligomeric group or a combination thereof;
R′ 1 is a (m′+1)-valent group selected from C 2 -C 12 , aliphatic group or from an (m′+1)-valent oligomeric group or a combination thereof, wherein R 1 and R′ 1 can be identical or different.

3. The urethane oligomer according to claim 2 , wherein
R 1 and R′ 1 are independently an oligomeric segment selected from the group consisting of: an oligoester segment, an oligoether segment, an oligourethane segment and a combination thereof.

4. The urethane oligomer according to claim 2 , wherein R 1 is:
an oligoester segment which is a moiety consisting of the repeating units —OR′—CO— or —OR′—COO—R″—CO—; wherein said R′ and R″ are different; or which is derived by removing H and OH from an oligoester H(O—R″—O—OC—R′—CO) n —OH based on a diacid HO 2 C—R′—CO 2 H and a diol HO—R″—OH, wherein n″ is an integer of 2-10;
an oligoether segment which is a moiety consisting of the repeating units —O—R′— or —O—R′—O—R″—; or
an oligourethane segment which is a moiety consisting of the repeating units —OR′O—OC—HN—R″—NH—CO—;

wherein said R′ and R″ are identical or different, and selected from an aliphatic group containing 2 to 12 carbon atoms, a cycloaliphatic group containing 5 to 10 carbon atoms, or an aromatic group containing 8 to 10 carbon atoms.

5. The urethane oligomer according to claim 3 , wherein said oligoester segment is derived from one or more C 4 -C 6 lactones.

6. The urethane oligomer according to claim 1 , wherein
the urethane segment containing at least one terminal allyl group comprises 1 to 5 allyl groups, which are terminal groups of said urethane oligomer; and
the urethane segment containing at least one terminal (meth)acrylate group comprises 1 to 5 (meth)acrylate groups, which are terminal groups of said urethane oligomer.

7. The urethane oligomer according to claim 2 , wherein
in the oligomer according to formula I-a
the at least one urethane arm containing at least one terminal allyl group contains from 1 to 3 allyl groups; and
in said formula I-b
the at least one urethane segment containing at least one terminal allyl group contains from 1 to 3 terminal allyl groups and the at least one urethane segment containing at least one terminal (meth)acrylate group contains from 1 to 3 terminal (meth)acrylate groups.

8. The urethane oligomer according to claim 1 , wherein
said urethane oligomer has an average in number molecular weight Mn measured by GPC in THF with polystyrene standards, from 500 to 5000 g/mol.

9. The urethane oligomer according to claim 1 , which is obtainable from the reaction of
(1) at least one polyisocyanate R(NCO)n with n=n1+n2 having at least two isocyanate groups, both of n1 and n2 are an integer>0;
(2) at least one monoalcohol having at least one allyl group as terminal group; and

one or both of the following two:
(3-b) at least one monoalcohol having at least one (meth)acrylate group as terminal group and
(3-a) at least one diol bearing no ethylenic unsaturation and selected from the group consisting of alkane diols, cycloalkane diols, oligoether diols, oligoester diols, and oligourethane diols.

10. The urethane oligomer according to claim 1 , wherein in the case of presence of both allyl and (meth)acrylate terminal groups the ratio (allyl)/(Meth)acrylate is from 0.1 to 10.

11. The urethane oligomer according to claim 1 , wherein said urethane oligomer comprises at least two allyl groups.

12. The urethane oligomer according to claim 1 , wherein it is represented by the following general formulae (I-1) or (I-2):
[(CH 2 ═CHCH 2 O) m R 1 —O—CO—NH] n1′ R—NH—CO—O—R B —O—CO—NH—R[NH—CO—O—R 1 (OCH 2 CH═CH 2 ) m ] n2′   (I-1)

[(CH 2 ═CHCH 2 O) m R 1 —O—CO—NH] n1 R[NH—CO-A-((R 3 ) y —OCOCR 2 ═CH 2 ) m′ ] n2 , wherein R 2 is H or CH 3 ;  (I-2)

wherein
n1+n2=n is an integer from 2 to and both of n1 and n2 are an integer>0;
n1′=n1+n2-1=n2′, with n1′+n2′=n′ being an integer varying from 2 to 10;
m is an integer from 1 to 5;
m′ is an integer from 1 to 5 and may be identical or different from m;
R is a residue derived by removing n=n1+n2 NCO groups from a polyisocyanate R(NCO) (n1+n2) or derived by removing all of NCO groups from an oligomer of the polyisocyanate R 0 (NCO) [(n1+n2)/n3]+1 ;
n3 is the oligomerization degree and can be an integer of 2, 3, 4, 5, 6;
R 0 is selected from an aliphatic, cycloaliphatic or aromatic [[(n1+n2)/n3]+1]-valent group, which can be substituted;
in case of being derived from the polyisocyanate R(NCO) (n1+n2) , the group R is selected from an aliphatic, cycloaliphatic or aromatic n-valent group which can be substituted;
in case of being derived from an oligomer of the polyisocyanate R 0 (NCO) [(n1+n2)/n3]+1 , the group R is an oligourethane n-valent segment;

R 1 is a (m+1)-valent group,
A is an (m+1)-valent oligomeric segment, selected from an oligoester segment resulting from an oligoester diol or from an oligolactone bearing terminal hydroxyl and carboxy terminal groups, by removing one OH and one H per each terminal group, an oligoether segment and an oligourethane segment respectively resulting by removing the two terminal groups of respectively oligoether diols or of oligourethane diols;
R 3 is oxyethylene or oxypropylene, and y is 0, 1 or 2; with the proviso that when A is an oligolactone segment then y=1

Assignees

• Arkema France

Inventors

• Fan Mingxin
• Shi Aibin
• Wei Zhenjie

Classifications

• C08G18/4825

  Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence) · CPC title

• C08G18/8166 Primary

  with unsaturated monofunctional alcohols or amines · CPC title

• C08G18/3215

  containing aromatic groups or benzoquinone groups · CPC title

• C08G18/673

  containing two or more acrylate or alkylacrylate ester groups · CPC title

• C08G18/244

  tin salts of carboxylic acids · CPC title