Asymmetrically substituted bis-alkenyl diphenyl ethers, their preparation and use

Patent metadata

Field	Value
Publication number	US-11104754-B2
Application number	US-201716349399-A
Country	US
Kind code	B2
Filing date	Oct 27, 2017
Priority date	Nov 15, 2016
Publication date	Aug 31, 2021
Grant date	Aug 31, 2021

Abstract

The present invention relates to compounds according to formula (I) and to heat-curable resin compositions based on polymaleimide resin systems comprising such compounds as co-monomers: wherein R 1 signifies an 1-alkenyl- or 2-alkenyl group with 3 to 6 carbon atoms, wherein R 2 signifies hydrogen or an alkoxy group with up to 2 carbon atoms, wherein R 3 signifies hydrogen or an alkyl group with up to 4 carbon atoms, and wherein R 4 signifies hydrogen or an alkyl group with up to 4 carbon atoms. The present invention also relates to crosslinked resins obtainable by curing such compositions. Compounds of the present invention can be used amongst others in fields like structural adhesives, matrix resins for fiber prepregs, moulding compounds, as well as structural and/or electrical composites.

First claim

The invention claimed is:

1. An asymmetrically substituted bis-alkenyl diphenyl ether of formula (I):

wherein R 1 is an 1-alkenyl- or 2-alkenyl group with 3 to 6 carbon atoms,
R 2 is hydrogen or an alkoxy group with up to 2 carbon atoms,
R 3 is hydrogen or an alkyl group with up to 4 carbon atoms, and
R 4 is hydrogen or an alkyl group with up to 4 carbon atoms,
with the proviso that (I) is not a naturally occurring ottomentosa (1-methoxy-4-(1E)-1-propen-1-yl-2-[4-(1E)-1-propen-1-ylphenoxy]-benzene).

2. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 1 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is a compound of formula (Ia):

3. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 2 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is
4-vinyl-2′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-(prop-1-en-1-yl)-diphenylether,
4-(prop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylpent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-vinyl-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(prop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylpent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-vinyl-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(prop-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-2-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether, or
4-(1-ethylpent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether.

4. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 1 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is a compound of formula (Ib):

5. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 4 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is
4-vinyl-2′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-(prop-1-en-1-yl)-diphenylether,
4-(prop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether, or
4-(1-ethylpent-1-en-1-yl)-2′-(prop-1-en-1-yl)-diphenylether.

6. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 1 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is a compound of formula (Ic):

7. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 6 , wherein the asymmetrically substituted bis-alkenyl ether is
4-vinyl-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(prop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether, or
4-(1-ethylpent-1-en-1-yl)-2′-methoxy-4′-(prop-1-en-1-yl)-diphenylether.

8. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 1 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is a compound of formula (Id):

9. The asymmetrically substituted bis-alkenyl diphenyl ether according to claim 8 , wherein the asymmetrically substituted bis-alkenyl diphenyl ether is
4-vinyl-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-isopropenyl-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenyiether,
4-(prop-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(but-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(pent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylprop-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylbut-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-methylpent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylprop-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether,
4-(1-ethylbut-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether, or
4-(1-ethylpent-1-en-1-yl)-2′-ethoxy-5′-(prop-1-en-1-yl)-diphenylether.

10. A curable composition, comprising:
(a) an asymmetrically substituted bis-alkenyl diphenyl ether according to claim 1 ;
(b) a polyimide of formula (II):

wherein B is a difunctional group containing a carbon-carbon double bond,
A is a y-functional group, wherein the y-functional group denotes a group bonded to the reminder of the polyimide of formula (II) via y bonds, and
y is an integer ≥2.

11. The curable composition according to claim 10 ,
wherein B in the polyimide of formula (II) is

12. The curable composition according to claim 10 ,
wherein A in the polyimide of formula (II) is
a) an alkylene group with 2 to 12 carbon atoms;
b) a cycloalkylene group with 5 to 6 carbon atoms;
c) a heterocyclic group with 4 to 5 carbon atoms

Assignees

• Evonik Operations Gmbh

Inventors

• Evsyukov Sergey
• Pohlmann Tim
• Stenzenberger Horst
• Ter Wiel Matthijs

Classifications

• C08J5/24

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title

• C07C43/285 Primary

  having unsaturation outside the six-membered aromatic rings · CPC title

• C08F222/40 Primary

  Imides, e.g. cyclic imides · CPC title

• C08J2335/08

  Copolymers with vinyl ethers · CPC title

• C08F2810/20

  leading to a crosslinking, either explicitly or inherently · CPC title