Curable mixtures based on xylylene bismaleimide

Patent metadata

Field	Value
Publication number	US-2016264735-A2
Application number	US-201414779189-A
Country	US
Kind code	A2
Filing date	Mar 12, 2014
Priority date	Mar 28, 2013
Publication date	Sep 15, 2016
Grant date	—

Abstract

The invention relates to a curable mixture comprising: RM % of m-xylylene bismaleimide of formula (I)

RP % of a polyimide component, and RC % of a comonomer component. Further, the invention relates to methods for the preparation of the curable mixture, methods for the preparation of a prepolymer, of a crosslinked polymer, and composite materials, in particular of fiber-reinforced composites. In addition, the present invention relates to a prepolymer, a crosslinked polymer and composite materials, in particular fiber-reinforced composites, obtainable by said methods.

First claim

1 - 19 . (canceled)

20 . Curable mixture comprising:
RM % of m-xylylene bismaleimide of formula (I)

RP % of a polyimide component, and
RC % of a comonomer component,
wherein
the polyimide component consists of at least one
polyimide of formula (II)

wherein
A is an X-functional group with at least two carbon atoms,
X is an integer ≧2, and
B is a difunctional group comprising a carbon-carbon double bond;
with the proviso that when B is

A cannot be

and X cannot be 2;
wherein the comonomer component consists of at least one comonomer selected from:
alkenylphenol, alkenylphenyl ether, alkenylphenol ether, polyamine, aminophenol, amino acid hydrazide, cyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, and divinylbenzene;
and wherein
RM % is defined as 1 wt % to 98 wt %;
RP % is defined as 1 wt % to 98 wt %;
RC % is defined as 1 wt % to 98 wt %;
and wherein the sum of RM %, RP % and RC % is less than or equal to 100 wt %.

21 . Curable mixture according to claim 20 , wherein the comonomer component consists of at least one comonomer selected from:
(a) a compound of formula (Ill)

wherein
R 1 is a difunctional group, and
R 2 and R 3 are identical or different and each is independently from the other alkenyl with 2 to 6 carbon atoms;
(b) a compound of formula (IV)

wherein
R 4 is a difunctional group, and
R 5 and R 6 are identical or different and each is independently from the other alkenyl with 2 to 6 carbon atoms;
(c) a compound of formula (V)

wherein
R 8 is a difunctional group, and
R 7 and R 9 are identical or different and each is independently from the other alkenyl with 2 to 6 carbon atoms;
(d) a compound of formula (VI)

wherein
R 11 is a difunctional group, and
R 10 and R 12 are identical or different and each is independently from the other alkenyl with 2 to 6 carbon atoms;
(e) a compound of formula (VII)

wherein
R 13 is a Y-functional group,
R 14 is alkenyl with 2 to 6 carbon atoms, and
Y is an integer 1; and
(f) a compound of formula (VIII)

wherein
R 15 is a Z-functional group,
R 16 is alkenyl with 2 to 6 carbon atoms, and
Z is an integer 1.

22 . Curable mixture according to claim 21 ,
wherein R 1 and R 4 are selected from the following groups:

and
R 2 , R 3 , R 5 and R 6 are identical and are 1-propenyl or 2-propenyl;
wherein R 8 and R 11 are selected from the following groups:

and
R 7 , R 9 , R 10 and R 12 are identical and are 1-propenyl or 2-propenyl;
wherein R 13 and R 15 are difunctional aromatic groups selected from the following groups:

and wherein R 14 and R 16 are 1-propenyl or 2-propenyl.

23 . Curable mixture according to claim 20 , wherein the comonomer component consists of at least one comonomer selected from: 3,3′-diallylbisphenol A, diallyl ether of bisphenol A, bis-(o-propenylphenoxy)benzophenone, m-aminobenzhydrazide, bisphenol A dicyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, and divinylbenzene.

24 . Curable mixture according to claim 20 , wherein the polyimide component consists of at least one polyimide of formula (II), wherein A is selected from the following difunctional groups:
a) alkylene with 2 to 12 carbon atoms; b) a mono- or dicarbocyclic aliphatic group; c) a bridged multicyclic aliphatic group; d) a heterocyclic aliphatic group; e) a mono- or dicarbocyclic aromatic group; f) a bridged multicyclic aromatic group; g) a heterocyclic aromatic group; (h) one of the following groups:

wherein R 17 , R 18 , R 19 , R 20 , R 21 and R 23 are identical or different and each is independently from the other alkyl with 1 to 6 carbon atoms,
and wherein R 22 and R 24 are identical or different and each is independently from the other alkylene with 1 to 6 carbon atoms;
(i) a group defined by formula (IX)

wherein R 25 is selected from the following groups:

25 . Curable mixture according to claim 20 , wherein B in formula (II) is selected from the following groups:

26 . Curable mixture according to claim 20 , wherein the polyimide component consists of at least one polyimide selected from 4,4′-bismaleimidodiphenylmethane, bis(3-methyl-5-ethyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, 4,4′-bismaleimidodiphenyl ether, 4,4′-bismaleimidodiphenylsulfone, 3,3′-bismaleimidodiphenylsulfone, bismaleimidodiphenylindane, 2,4-bismaleimidotoluene, 2,6-bismaleimidotoluene, 1,3-bismaleimidobenzene, 1,2-bismaleimidobenzene, 1,4-bismaleimidobenzene, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,6-bismaleimido-(2,4,4-trimethyl)hexane, 1,4-bismaleimidocyclohexane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, and 4,4′-bismaleimidodicyclohexylmethane.

27 . Curable mixture according to claim 20 , wherein
RM % is defined as 5 wt % to 70 wt %; RP % is defined as 1 wt % to 60 wt %; and RC % is defined as 20 wt % to 80 wt %.

28 . Curable mixture according to claim 20 , further comprising
a cure accelerator or a cure inhibitor.

29 . Method for the preparation of a curable mixture according to claim 20 , comprising the step of:
blending a comonomer component as defined in claim 20 , a polyimide component as defined in claim 20 and a maleimide of formula (I) as defined in claim 20 at a temperature ranging from 60° C. to 180° C. to obtain a curable mixture as a low melting low viscosity mass (resin).

30 . Method for the preparation of a curable mixture according to c

Assignees

• Evonik Degussa Gmbh

Inventors

• Evsyukov Sergey
• Pohlmann Tim
• Stenzenberger Horst

Classifications

• C08G73/10 Primary

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08L79/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08F222/404 Primary

  substituted imides comprising oxygen other than the carboxy oxygen · CPC title

• C08G73/12

  Unsaturated polyimide precursors · CPC title

• C08L79/085

  Unsaturated polyimide precursors · CPC title