Alkenyl ether polyols

Patent metadata

Field	Value
Publication number	US-10316134-B2
Application number	US-201715451729-A
Country	US
Kind code	B2
Filing date	Mar 7, 2017
Priority date	Sep 9, 2014
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

The invention relates to a method for producing radiation-curable alkenyl ether polyols, to radiation-curable alkenyl ether polyols produced using the method according to the invention, and to the use thereof for the synthesis of radiation-interlinkable oligomers or polymers by means of polyaddition reactions or polycondensation reactions, in particular for the synthesis of radiation-curable polyesters, polyethers, polyurethanes and polyureas, particularly preferably UV-curable polyurethanes. The invention also relates to radiation-curable polyurethane polymers that are obtained by reacting at least one alkenyl ether polyol according to the invention with a polyisocyanate.

First claim

The invention claimed is:

1. A method for manufacturing an alkenyl ether polyol containing at least one alkenyl ether group and at least two hydroxyl groups (—OH), comprising:
A) conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from —OH, —COOH, —SH, −NH 2 and derivatives thereof,

with (i) an epoxide or (ii) a cyclic carbonate or derivative thereof; or
B) conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from (i) epoxide groups and (ii) cyclic carbonate groups or derivatives thereof, with a thiol, a carboxylic acid, or an amine or derivative thereof; or
C) conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from cyclic carbonate groups or derivatives thereof, with an alcohol.

2. The method as set forth in claim 1 , wherein the alkenyl ether polyol is manufactured through conversion of an alkenyl ether containing at least one alkenyl ether group and at least one functional group selected from —OH, —COOH, —SH, −NH 2 and derivatives thereof with (i) an epoxide or (ii) a cyclic carbonate or derivative thereof, wherein:
the alkenyl ether polyol is an alkenyl ether polyol of formula (I)

where
R 1 is selected from a divalent organic residue; a divalent linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom,
R 2 is selected from an organic residue; an organic residue with at least one —OH group and/or 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom,
X is O, S, C(═O)O, OC(═O)O, C(═O)OC(═O)O, NR x , NR x C(═O)O, NR x C(═O)NR x , or OC(═O)NR x ,
each R and R′ is selected independently from H, C 1-20 alkyl, and C 2-20 alkenyl; or one of R and R′ is H and the other is C 1-4 alkyl; or both R and R′ are H,
each A, B, and C is independently selected from among CR″R′″,
R″ and R′″ are selected independently from H, a functional group, an organic residue, C 1-20 alkyl; or R″ and R′″ together or with the carbon atom to which they are bonded are an organic residue; or two of R″ and R′″ that are bonded to neighboring carbon atoms form a bond together in order to form a double bond between the neighboring carbon atoms,
is a single or double bond, and if it is a double bond, the carbon atom that is bonded to R 2 bears only one substituent R″ or R′″,

m is an integer from 1 to 10, preferably 1,
n, p, and o are each 0 or an integer from 1 to 10, and
R x is H, an organic residue, or

and if X is not NR x where

R 2 has at least one substituent that is
selected from among —OH and

3. The method as set forth in claim 2 wherein n+p+o=1 or 2.

4. The method as set forth in claim 2 , wherein the alkenyl ether, which contains at least one alkenyl ether group and at least one functional group selected from among —OH, —COOH, —SH, NH 2 and derivatives thereof, is an alkenyl ether of formula (II)

where
R 1 is selected from a divalent organic residue; a divalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom,
X 1 is a functional group selected from among OH, —COOH, —SH, —NHR y and derivatives thereof,
R y is H or an organic residue,
each R and R′ is selected independently from among H, C 1-20 alkyl, and C 2-20 alkenyl; or one of R and R′ is H and the other is C 1-4 alkyl; or both R and R′ are H, and
m is an integer from 1 to 10.

5. The method as set forth in claim 4 , wherein in the alkenyl ether of formula (II),
m is 1,
X 1 is —OH or —NH 2 ,
R 1 is selected from a divalent, linear or branched C 1-10 alkyl residue, ethyl, propyl, butyl, pentyl, or hexyl, and
one of R and R′ is H and the other is H or —CH 3 .

6. The method as set forth in claim 1 , wherein the epoxide is an epoxide of formula (III)

where R 2 is selected from an organic residue; an organic residue with at least one —OH group; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom, and
q is an integer from 1 to 10.

7. The method as set forth in claim 6 , wherein:
q is 1 or 2, and
if q is 2, R 2 is —CH 2 —O—C 1-10 -alkylenyl-O—CH 2 —; and if q is 1, R 2 is —CH 2 —O—C 1-10 -alkyl.

8. The method as set forth in claim 1 , wherein the cyclic carbonate is an ethylene carbonate of formula (IV)

where R 2 is selected from an organic residue; an organic residue with at least one —OH group; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom; or a C 1-10 hydroxyalkyl,
is a single or double bond,
d is 0 or 1, and
r is an integer from 1 to 10.

9. The method as set forth in claim 4 , wherein:
(i) X 1 is —NH 2 or a derivative thereof, and
q or r is 1; or

(ii) X 1 is —OH or a derivative thereof, and
q or r is 2.

10. The method as set forth in claim 1 , wherein the alkenyl ether polyol is an alkenyl ether polyol of formula (V)

where
R 1 is selected from a divalent organic residue; a divalent linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; or a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom,
R 3 is selected from an organic residue; an organic residue with 1 to 1000 carbon atoms; an optionally divalent or polyvalent, linear or branched, substituted or unsubstituted, alkyl with 1 to 20 carbon atoms; a linear or branched, substituted or unsubstituted, heteroalkyl with 1 to 20 carbon atoms and at least one oxygen or nitrogen atom; a (poly)alkylene glycol of the formula —O—[CHR a CH 2 O] b —R b , where b is 1 to 100, R a is H or a C 1-4 alkyl residue, R b is H; or

X is O, S, OC(═O), OC(═O)O, OC(═O)OC(═O), NR z , NR z C(═O)O, NR z C(═O)NR z , or OC(═O)NR z ,
each R and R′ is selected independently from H, C 1-20 alkyl, C 2-20 alkenyl; or one of R and R′

Assignees

• Henkel Ag & Co Kgaa
• Max Planck Gesellschaft

Inventors

• Taden Andreas
• Landfester Katharina
• Kirschbaum Stefan

Classifications

• C08G18/4825

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

• C07C41/03

  by reaction of oxirane rings with hydroxy groups · CPC title

• C07C217/28

  having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines · CPC title

• C08G18/2835

  having less than 5 ether groups · CPC title

• C08G18/6715 Primary

  Unsaturated monofunctional alcohols or amines · CPC title