Curable mixtures based on xylylene bismaleimide

Patent metadata

Field	Value
Publication number	US-9828468-B2
Application number	US-201414779189-A
Country	US
Kind code	B2
Filing date	Mar 12, 2014
Priority date	Mar 28, 2013
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

The inventionrelates 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

The invention claimed is:

1. A 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 selected from

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 the group consisting of 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 %.

2. The curable mixture of claim 1 , wherein the comonomer component consists of at least one comonomer selected from the group consisting of:
(a) a compound of formula (III)

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.

3. The curable mixture of claim 2 ,
wherein R l and R 4 are selected from the group consisting of:

 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 groups consisting of:

 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 group consisting of:

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

4. The curable mixture of claim 1 , wherein the comonomer component consists of at least one comonomer selected from the group consisting of: 3,3′-diallylbisphenol A, diallyl ether of bisphenol A, bis-(o-propenylphenoxy)benzophenone, m-minobenzhydrazide, bisphenol A dicyanate ester, diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, styrene, and divinylbenzene.

5. The curable mixture of claim 1 , wherein the polyimide component consists of at least one polyimide of formula (II), wherein A is a difunctional group selected from the group consisting of:
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 an alkyl with 1 to 6 carbon atoms,
and wherein R 22 and R 24 are identical or different and each is independently an alkylene with 1 to 6 carbon atoms; and

(i) a group defined by formula (IX)

wherein R 25 is selected from the following groups:

6. The curable mixture of claim 1 , wherein the polyimide component consists of at least one polyimide selected from the group consisting of 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.

7. The curable mixture of claim 1 , 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 %.

8. The curable mixture of claim 1 , further comprising
a cure accelerator or
a cure inhibitor.

9. A method for the preparation of a curable mixture according to claim 1 , comprising the step of:
blending the comonomer component as defined in claim 1 , the polyimide component as defined in claim 1 and the m-xylylene bismaleimide of formula (I) as defined in claim 1 at a temperature ranging from 60° C. to 180° C. to obtain a curable mixture as a low melting, low viscosity mass.

10. A method for the preparation of a curable mixture according to claim 1 , comprising the steps of:
dissolving the comonome

Assignees

• Evsyukov Sergey
• Pohlmann Tim
• Stenzenberger Horst
• Evonik Degussa Gmbh

Inventors

• Evsyukov Sergey
• Pohlmann Tim
• Stenzenberger Horst

Classifications

• C08F222/40

  Imides, e.g. cyclic imides · CPC title

• C08L79/08

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

• C08G73/12

  Unsaturated polyimide precursors · CPC title

• C08G73/10 Primary

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

• C08K5/13

  Phenols; Phenolates · CPC title