CA2088672A1 - Thermosetting compositions made of cyanate ester compounds and polyimide compounds containing organopolysiloxane groups - Google Patents

Abstract

2088672 9204395 PCTABS00110 The present invention relates to thermosetting compositions comprising (A) at least one cyanate ester compound consisting essentially of a polyfunctional aromatic cyanic ester having at least two cyanate groups (-OC = N) linked to an aromatic ring, in a prepolymer derived from said organic ester or from a co-polymer derived from said cyanic ester and from a polyamine and (B) at least one elastomer consisting essentially of an N, N'-bis-maleimide containing a diorganopolysiloxane group, in a prepolymer derived from said bis-maleimide or in a coprepolymer derived from said bis-maleimide and from a diamine. The thermosetting compositions in accordance with the present invention may also contain a suitable catalyst and one or more additional polymerizable compound (s) including in particular a conventional bis-maleimide, an optionally halogenated epoxy resin, an acrylate reagent or a alkenylphenol and they can be associated in addition with known reinforcing fillers.

Description

WO 92/0439 ~ P ~ r / FR9 1/00703 COMPOSITIONS THER ~ HARDENING A, ~ ASE D ~ COMPOS ~ S_CYANATE ESTER
AND OE POLYIHIDE COHPOSES WITH DIORGANOPO ~ YSILOXANE GROUP (S) The present invention relates to compositions 05 thermosetting compound comprising (A) at least one cyanate ester compound consisting essentially of an aromatic cyanic ester polyfunctional having at least two cyanate groups (-OCN) linked to a aromatic nucleus, in a prepolymer derived from said organic ester or in ~:
a co-polymer derived from said cyanic ester and from a polyamine and (B) at at least one elastomer consisting essentially of a polyimide compound comprising in its structure one or more group (s) diorganopolysiloxane.
It also relates to hardened resins prepared from said thermosetting compositions. The essays thermosets in accordance with the present invention may contain in addition to a suitable catalyst and one or more additional compound (s) polymerizable (s) including in particular a conventional bismaleimide, a optionally halogenated epoxy resin, an acrylate reagent or a alkenylphenol and they can be combined in addition ~ loads of known reinforcement.
Polyfunctional aromatic cyanic esters are known products which are prepared by reaction between a halide of cyanogen and a polyhydroxylated phenol (cf. US Pat. No. 3,553,244). These cyan esters can lead to hardened resins through a reaction of cyclotrimerization of cyanate groups giving rise to cycles substituted ~ is triazine which will organize themselves according to a polycyanurate network ; three-dimensional.
Such polycyanurate resins, which have found many uses in many application fields, pass properties electrical (in particular the electrical characteristics) interesting, but they have the defect of offering levels of properties still insufficient, particularly in terms of toughness (the level of shock value CHARPY1 of GlC and KlC are to be improved) and adhesion on metallic substrates.

". ~,.

2 -To obtain stubborn resins, we have ~
prior art of modifying polycyanurate resins to adding in their preparation medium: high-point plasticizers -e ~ ullition containing ester groups (cf. US-A-4,094,852);
05 an acrylonitrile-butadiene copolymer (cf. US Pat. No. 3,649,714); a elastomer such as natural rubbers, polymers derived from dienes conjugates (such as butadiene and isoprene), polychloroprenes (cf.
U.S. Patent 4,396,745); or an amorphous thermoplastic polymer such as a polysulfone, a polyarylate, a polyethersulfone (cf. request EP-AO 311 341). However such mixtures of polymers are of a nature to show a serious lack of thermostability at temperatures as high as those from 220 'C to 300' C.
It has now been found that one can get, initially polyfunctional aromatic cyanic esters, resins having the hardened state an excellent compromise of properties, particularly in terms of toughness, thermostability and adhesion, using a modification consisting essentially of a polyimide compound comprising in its structure one or more group (s) diorganopolysiloxane.
More specifically, the present invention relates to thermosetting compositions which include:
(A) - at least one cyanate ester compound chosen from the group formed by:
(1) - a polyfunctional aromatic cyanic ester, monomer, having the r formula :
R- ~ -OCN) n (I) where: n is an integer ranging from 2 to 5 and R represents an aromatic organic radical of valence n, comprising from 6 to 30 carbon atoms where the cyanate groups are linked to the nucleus (s) aromatic (s) of R;
(2) - a prepolymer of (1), and t3) - a co-polymer of (1) and an aromatic prima ~ re polyamine;
(B) - at least one elastomeric compound i and eventually :
(C) a suitable catalyst;

wo 92/04395 PCT / FR9l / 00703 said compositions being characterized in that component (B) consists of at least one compound chosen from the group formed by:
: (4) - an N, N ~ -bis-maleimide with a diorganopolysiloxane group corresponding to:.
: essentially the general formula::

3 l ~ R5 l R7 2 t ~ 4 ~ ~ l ~ ~ ~ '(CH) x '10 \ j'. '. '' NN
- CO / \ CO CO '\ CO
CH. . CH (II) CH CH
,.
in which :
- X, which is in ortho, meta or para position with respect to a.
. the carbon atom of the benzene ring linked to nitrogen, represents a link simple valential or the following atom or grouping:

o - 0 -; - S -; - S -; - S -;
OO

- Rl, R2, R3, R4, R5, R6, R ~, Rg, identical or different, each represent a hydrocarbon radical ~ monovalent cholsl parml: the alkyl radicals, linear or branched, having from 1 to 12 atoms of carbon, these radicals being able to be substituted by one or more atoms chlorine, bromine or fluorine or by a -CN group, a radical phenyle optionally substituted by one or more alkyl radicals and / or alkoxy having l ~ 4 carbon atoms or by one or more chlorine atoms;

... . . . . . . . . . .

WO 92/0439 ~ PCr / FR91 / 00703 _ '- 4 -~ -.
- the symbol x is an integer located in the interval ranging from 2 to 8; :.
- the symbols y and z represent numbers, identical or different, whole or fractional, the sum of which is in OS the range from 0 to 100;
(5) - a prepolymer of (4), and (6) - a coprepolymer of (4) and of an aromatic biprimary diamine.
Regarding the constituent (A), the symbol R of the cyanate ester of formula (I) can represent:
(i) - a radical of valence n derived from a hydrocarbon aromatic having from 6 to 16 carbon atoms such as by benzene, for example. naphthalene, anthracene or pyrene;
(2i) - a radical of valence n derived from a group comprising several aromatic nuclei linked together by a link simple valential or by an inert atom or a grouping inert divalent such as for example the group of formula:

~ O \ _R ', / ~ (III) in which R 'represents: a simple valential link or a atom or divalent inert group such as: -0-; -S-; a linear or branched alkylene radical having from 1 to 10 atoms of carbon, optionally substituted by one or more atoms of chlorine, bromine or fluorine and possibly interrupted by one or several oxygen atom (s); -C0-; -S02-; -NR ~ - where R "
represents a hydrogen atom, an alkyl radical having from 1 to 3 carbon atoms, phenyl or cyclohexyl; -C00-;

R'-C ~ ~ ~; ~; ~

.
: -, .

,. . ~

: WO 92/04395 PCl` / FR91 / 00703 - In addition, the various aromatic groups mentioned above in the paragraphs (i) and (2i) may be substituted by one or more linear or branched alkyl (s) or alkoxy (s) having 1 to

4 carbon atoms or by one or more halogen atom (s).
05 Preferably, the cyanate esters (1) of formula (1) which. ~ Nt used consist of difunctional compounds that meet the formula :
._ NC-O ~ ~ _ _R '~ OC.N (IV) () a (Rn ~) a in which :
- R '"represents a simple valential link or an atom or the.
following grouping:

-0-; -S-; -CH2-; -VS- ; -C- i -Ci -s- i \

'' HC ~ t-- ~

- the symbols R ~, identical or different, represent each a substituent chosen from a chlorine, bromine or fluorine atom or a radical m ~ ethyl, ethyl, propyl or isopropyl, two R ~ volins on the same nucleus being able to represent together an aromatic nucleus with 6 links;
- m is an integer equal to 0 or 1;
- a is an integer equal to 0, 1 or 2, the symbols a, when there are 2, which can be identical or different between them.

, W o 92/04395 q ~ pcr / FK9l / oo7u3 As specific examples of cyanate esters (1) difunctionne1 of formula (IV ~ preferred, there may be mentioned in particular:
. 1,3- and 1,4-diacyanatobenzene, . 1,3-, 1,4-, 1,6-, 1.8-, 2,6- or 2.7-dicyanatonaphthalene.
05. 4,4'-dicyanatobiphenyl, . bis (4-cyanatophenyl) methane, . bis (3,5-dimethyl-4-cyanatophenyl) methane, . 2,2-bis (4-cyanatophenyl) propane, . 2,2-bis (4-cyanatophenyl) hexafluoropropane, . 1,1-bis (4-cyanatophenyl) ethane,.
. bis (4-cyanatophenyl) ether, . bis (4-cyanatophenyl) thio ~ ther, ; . bis (4-cyanatophenyl) sulfone, . bis (4-cyanatophenyl) tetrahydrodicyclopentadiene.
It is used very preferably, for the implementation work of the invention, bis (4-cyanatophenyl) methane, bis (3,5-dimethyl-4-cyanatophenyl) methane, the 2,2-bis- (4-cyanatophenyl) propane or mixtures of these cyanates.
Cyanate esters (1) can also be used in the form of a prepolymer (2), comprising symmetrical triazine rings, which is preferred by partial cyclotrimerization of cyanate groups by heating the monomeric cyanate ester (1) at a temperature ranging from 130 ° C. to 220 ° C.
for a sufficient time to cyclotimerize 5 to 75 X of the total number engaged cyanate groups, and preferably 15 ~ 50 X groups functional cyanates. Such prepolymers (2) have a mass weight average molecular ranging from 400 to 12,000; they can be prepared in the presence of an either acidic catalyst such as an acid mineral proton or an acid of LE ~ IS, either basic like for example a alkali metal hydroxide, an alkali metal alcoholate or an amine tertiary.
Cyanate esters (1) can still be used in the form a coprepolymer (3) derived from (1) and a primary polyamine aromatic preferably consists of a selected aromatic biprimary diamine in the ~ roupe formed by:

-. . ,. ~ ' WO 92/04395 PCT / FR91 / 00703.
: - 7 - ~

(3.1) - the responding species. to the general formula::
H2N - A - ~ H2 (V) in which the symbol A represents a divalent radical chosen from the : 05 group consisting of the radicals: cyclohexylenes; phenylenes; methyl-4 phenylene-1,3; 2-methyl-1,3-phenylene; 5-methyl-1,3-phenylene;
2,5-diethyl-3-methyl-1,4-phenylbne; and the radicau ~ of formula:

~ _ B ~ ~

in which B represents a simple essential link or a grouping:

'- CH 2 -; - This ; -; ~ "~

- 0 ~ 2 ~ -; ; ' ~ (3.2) - the species corresponding to the general formula Rg TT Rll .:
~ \ / ' H2N ~ E ~ --NH2 (Vl) Rlo TT R12 in which :
. the symbols Rg, Rlo, Rll and R12, identical or different, each represent a radical m ~ thyle, ~ thyle, propyl or isopropyl; , WO 92/0439

5 PCI` / FR91 / 00703 -.
. the symbols T, identical or different. each represent a hydrogen atom or a chlorine atom;
. the symbol E represents a divalent radical chosen from the group formed by radicals: ~

~ -CH2-: -c ~ C- and-c ~ O ~ C ~ 3 : CH3 '10 * and (3.3) - species corresponding to the general formula:

/ (Rl3) 3 (Vll) N ~ 2 in which :
. the amino radicals are in meta or para position one by relation to the other;
. the symbols Rl3, identical or different. represents each a methyl, ethyl, propyl or isopropyl radical.
As specific examples of dlamines (3.1) of formula (V), we can cite in particular:
- paraphenylene diamine, - methaphenylene diamine, - d ~ am ~ no-4,4 'diphenylmethane, - bis (4-amino phenyl) -2.2 propane, - benzidine, - bis- (4-aminophenyl) axiade, - dimaine-4,4 'diphenylsulfone.
Preferably used for the implementation of this invention, diamino-4,4 'diphenylmethane.

. . . . .......................... ~. . :
. , ... . , -, ~., ~ i WO 92/04395 PCI ~ FR91 / 00703 : ~ 9 ~ ,, ',,; ~ '~ J
.
As specific examples of hindered diamines (3.2) and (3.3) of formulas (VI) and (VII), there may be mentioned in particular:
- diamino-4,4 'tetramethyl-3,3', 5,5'-diphenylmethane, - diamino-4,4 'tetraethyl-3,3', 5,5'-diphenylmethane, `05 - diamino-4,4 'dimethyl-3,5 diethyl-3', 5'-diphenylmethane.
- diamino-4,4 'diethyl-3,3'dimethyl-5,5'-diphenylmethane, - diamino-4,4 'tetraisopropyl-3,3' ~ 5,5'-diphenylmethane, - diamino-4,4 'diisopropyl-3,3'dimethyl-5,5'-diphenylmethane, - bis (4-amino-3,5-dimethyl a, ~ dimethylbenzyl) -1,4 benzene.
- bis (4-amino-3,5-dimethyl ~, ~ dimethylbenzyl) -1.3 benzene, - diamino-1,3 diethyl-2,4 methyl-6 benzene, - 1,3-diamino-2-methyl-4,6-diethyl benzene.
These congested diamines can be prepared according to the processes described in the British patent GB-A-852,651 and the patent `
American US-A-3,481,900. It is preferably used for the implementation , of the present invention, 4,4 'diamino-3,3' tetramethyl, 5,5'-diphenylmethane, 4,4 'diamino-3,3' tetramethyl, 5,5'-diphenylmethane, diamino-4,4 'diethyl-3,3' dimethyl-5,5 'diphenylm ~ thane and their mixtures.
The coprepolymers (3) are obtained by r ~ action of the monomeric cyanate ester (1) and diamine by operating in a homogeneous liquid medium, possibly `
by use of an appropriate solvent such as ketones, at a temperature `~ ranging from O 'C to 100 C for a period ranging from 1 minute to 1 hour.
The proportions of cyanate ester and diamine are chosen so that that the report - `
number of qrouDes cvanate - (- OC ~ N ~
number of NH2 groups is in the range from 1.1 / 1 to 10/1 and, preferably, ' ranging from 1.5 / 1 to 5/1.
Especially preferably, for the implementation of the invention, a constituent (A) incorporated in a prepolymer (2) derived from the difunctional cyanate esters (1) of formula (IV).

`:

:.

.... .... ... .. `. :. . . `.:. . ~; . ``,,. `` ''.

r. , ~ 1` ~ 10 ~
-J
Component (B) of the curable compositions according to the present invention consists, as indicated above, in at least one compound chosen from the group formed by an N, N'-bis-maleimide if ~ oxane (4), a prepolymer (5) derived from (4) and a coprepolymer (6) derived from 05 (4) and an aromatic biprimary diamine.
With regard to the bis-maleimide siloxanes (4) of formula (II), when y and / or z are greater than 1, we are in the presence of a compound with polymer structure and we rarely have a single compound, but most often a mixture of compounds with the same chemical structure, which differ in number of recurring units of their molecule; that leads to a value mean of y and / or z which can be whole or fractional.
; When the preparation of the compositions according to the invention is carried out, as indicated below, in a diluent or any organic solvent, any of the compounds (4) of formula (II).
As suitable bis-maleimides, there may be mentioned those which correspond to formula (II) in which:
1) X - 0 -; Rl ~ R2 ~ R3 ~ R4 - Rs ~ R6 ~ R7 ~ R8 ~ alkyl radical linear having from 1 to 3 carbon atoms; x ~ 2, 3 or 4; y + z se is in the range of 0 to 100 and preferably 4 to 70.
2) X ~ - 0; Rl ~ R2 - R3 ~ R4 ~ R7 ~ R8 ~ linear alkyl radical having from 1 to 3 carbon atoms; Rs ~ R6 ~ phenyl radical; x ~ 2, 3 or 4; y + z is in the range of 0 ~ 100 and, from preferably 4 ~ 70.
3) X ~ - 0 -; Rl ~ R2 ~ R7 ~ R8 ~ linear alkyl radical having from 1 to 3 carbon atoms; R3 ~ R4 ~ Rs ~ R6 ~ phenyl radical; x ~ 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably from 4 to 70.
4) X ~ - -; Rl ~ R2 ~ R3 ~ R5 ~ R7 ~ R8 linear alkyl radical having from 1 to 3 carbon atoms; R4 ~ R6 ~ phenyl radical; x 2, 3 or 4; y + z is in the range of 0 ~ 100 and, from preferably from 4 to 70.
5) X ~ - 0; Rl ~ R3 ~ Rs ~ R7 ~ linear alkyl radical having from 1 to 3 carbon atoms; R2 ~ R4 ~ R6 ~ R8 ~ phenyl radical; x ~ 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably from 4 to 70 ~

.

. . ~ .. ~ .. ~:
. . ~; . -: ... .
~ -WO 92/04395 PCl '/ FR91 / 00703 As specific examples of bis-maleimide siloxanes (4) which agree, in particular:

6) O - (CH2) 3 - Si - O ---- Si - o _-- Si - (cH2) 3 - O
¦ CH3 CH3 CH3 ~ -~ ~! 4 ~ 70 ~
10 ~ ~. ~ ,. ..
rjy : NN
; ' i ~ \ // \ ':' ÇO lCO, Ç CO
lSCH - CH CH CH

.

CH3 CH3 ~ CH3: ~
sli-o- - $ io r ~ si ~ o ~ si / CH3 CH3 Y ~. CH3 \
/, O, (C ~ 2) 3 (CH ~ 2) 3 OO

(~ ~ v ~ cy ~ z ~ i70 / N \, h ~
CO CO CO CO
CH -: CH CH - CH

. - ',::. . ,. ! , ': "..',. '." ~ ,,''.':. . '''. :. . . ' ~. . .

WO 92/0439 ~ PCI / FR91 / 00703 ,,.
8) ~ ' O - (CH2) 3 - Si - Si O ---- Si - (cH2) 3 - O
05 G. CH3 ~ ¢ / `~

CO CO CO \ CO
CH CH CHCH

9 ~ CH3 CH3 CH3 O - (CHZ) 3 ~ - O Si O ~ (tH2 3 -co / \ fo co / \ co CH CH CH _ CH

;; -:,.:,.
,: `, -:.

W0 92/04395 s ~ n PCI ~ / FR91 / 00703 h When the preparation of the polymers according to the invention is , performed en masse, preferably using co ~ me bis-maleimides (4) formula (II) those where the diorganopolysiloxane group contains a ~:
plural of Si-phenyl or substituted Si-phenyl linkages. Of ;. 05 bis-maleimides of this type which ~ are particularly suitable are those '. belonging to the following groups, listed in ascending order of preference :
- bis-maleimides no 2, 3, 4 and 5, . - bis-maleimides no 7, 8 and 9.
The siloxane bis-maleimides of formula (II) are compounds which are obtained by reacting maleic anhydride in the presence of a dehydrating agent, a tertiary amine, an organic diluent and a catalyst, on a diamine containing a diorganopolysiloxane group of formula:

R1 R3 R5 ~ 7.
. X - (CH) X - Si - O - - Si - O - __ Si - O - - Si - (CH) X - X ' \ R2 R4 Y R6 R8 2 ~

: ', NH2 NH2. '.

,. . .
in which X, R1, R2, R3, R4, Rs, R6, R ~, Rg, x, y and z have the 'meanings given above for formula (II). To have more details on these bis-maleimide siloxanes and on their process preparation, we can refer in particular to the content of the request French patent FR-A-2 611 728.
The siloxane b ~ s-malélmldes (4) can also be used ~ s ~ s in the form of a prepolymer (5) which is prepared by heating the : j bis-maleimide siloxane (4) operating in bulk or in a diluent liquid, possibly a solvent. at a temperature ranging from 50 to 180 C, preferably from 80 to 170 C, for a duration ~ e ranging from S minutes to 2 hours or more, this duration being all the shorter as the adopted temperature is more ~ high ~ e ~:

., .
?: ''. ``, `` ''. ``,.:,.,. , `, ~,. . . .

WO 92/0439 ~ 14 - PCr / FR91 / 00703 The bis-maleimide siloxanes (4) can still be used in the form of a coprepolymer (6) derived from (4) and a diamine ; aromatic binary chosen from the group formed by the species (3.1), (3.2) and (3.3) discussed above with regard to the definition of oS co-polymer (3) of component (A). The co-polymer (6) can be prepared by reacting the bis-maleimide siloxane (4) and the diamine to operating in bulk or in a liquid diluent, can be a solvent, at a temperature ranging from 50 to 180 'C, preferably from 80 to 170' C.
for a period ranging from 5 minutes to 2 hours or more in a obtain a homogeneous liquid medium. The proportions of bis-imide and diamine are chosen so that the ratio number of moles of bis-imide number of moles of diamine is in the range from 1.2 / 1 to 10/1 and, preferably, ranging from 2/1 to 5/1.
We use in a very special way, for the implementation of the invention, a component (B) consisting of a bis-maleimide siloxane (4) chosen from bis-maleimides n '1 to 9.
The reactivity of the constituents of the curable compositions according to the inventian can be increased and / or regulated by addition if necessary a catalyst (C) which can be chosen from the accelerating compounds and / or regulating the reactivity of the cyanate groups both during the cyclotrimerization reaction, only during the crosslinking reaction : subsequent i as examples of compounds of this nature, mention may be made of part kulier:
- compounds with free hydrogen such as, for example, alcohols, : phenols, carboxylic acids and primary and secondary amines;
- compounds consisting of metallic carboxylates, dissolved possibly in non-volatile functional liquids such as example an alkylphenol or a monoalcohol (cf. US-A-4,604,452 and US-A-4,608,434, the substance of which is introduced here as reference);
- compounds consisting of chelates such as acetylacetonates metallic, possibly dissolved in an alkylphenol (cf.
US-A-4 7B5 075 the substance of which is also introduced here as reference), '' . ..! . . . .

WO 92/04395 PCI` / FR91 / 00703 - 15 '' ^ ~ ~

The preferred catalysts are metallic acetylacetonates and, in particular, in acety ~ acetonates zinc, copper, manganese or cobalt.
In the thermosetting compositions which have just been 05 defined, the quantities of components (A) and (B) are chosen so to have, by weight relative to the weight of the assembly (A) + (B):
- from 50 to 98% and, preferably, from 5 to 95% of constituent (A), and - from 2 to 50% and, preferably, from 5 to 25% of constituent elastomer (B).
As regards the optional catalyst (C), depending on its nature and.
depending on the crosslinking speed desired at the implementation stage, we use it when we need it at a rate in the interval ranging from 0.005 to 10% and preferably ranging from 0.01 to 5% relative to the weight of the overall composition including (AJ + (B) + possibly the: ~
lS (or the) additional polymerizable compound (s) of which we will now speak later in this memo. .
The compositions according to the invention can indeed comprise, in addition, an additive (D) consisting of one or more compound (s) additional polymerisable (s) chosen from:

(7) - an N, N'-bis maleimide of formula:

Z - C - CO ~ / CO - C - Z
ll / N - G - N ll (Ylll) Z - C - CO \ CO - C - Z
in which :
. the symbols Z, identical or different, each represent H, CH3 or Cl;
. the symbol G can represent one of the radicals represented by the symbol A in the formula (V) representing the species ~ 3.1) of aromatic biprimary diamines;

(8) - a chlorinated or brominated epoxy resin;

(9) - a non-halogenated epoxy resin;

(10) - an alkenylphenol of formula:

. :. ,, ... ,, ~,. . ... . . .......... . .

:
WO 92/04395 ~ - ~ PCI / FR91 / 00703 l 6 ,. t CH2 - CRl4 = CH2 :. / / ~ \
R15 ~ H ~ OR15 (IX) o5 CH2 = CR14 - CH2 in which:
. the symbol H represents a simple or radical valential link divalent chosen from the group formed by radicals:

. ~ CH3 - CH2 -; - CH2 - CH2 -; - VS - ; - 0 -; - S -; - S0 -; and - S02 -;

, : IS. the symbols R14, identical or different, represent each a hydrogen atom or a methyl radical;
:. the symbols Rls, identical or different, represent each a hydrogen atom or a linear or branched alkyl radical having ; from 1 to 6 carbon atoms or a phenyl radical;

(11) - an acrylate of general formula:
(CH2 ~ CR16 - C0 - t L (X) in which :
. the symbol R16 represents a hydrogen atom or a methyl radical;
. . p represents an integer or fractional number at least equal to I and to more equal to 8;
. the symbol L represents ~ an organic radical of valenc ~ pd ~ rlvé: of saturated aliphatic residue, linéa ~ re or ramlfié, having from 1 to 30 atoms of 30 carbon and may contain one or more oxygen bridge (s) and / or one or several free hydroxyl function (s); an aromatic residue (of aryl or arylaliphatic type) having 6 3 150 carbon atoms . consisting of a benzene ring, which can be substituted by one to three . alkyl radicals having from 1 to 5 carbon atoms, or by several nuclei benzene, possibly substituted ~ s as indicated above, linked . .
'' wo 92/04395 '~ pcT / FRs1 / oo7o3 between them by a simple valential bond, an inert grouping or a radical alkylene having from 1 to 3 carbon atoms, said aromatic residue being able enclose in various places of its structure one or more bridge (s) oxygen and / or one or more free hydroxyl function (s), the (or 05 the free valence (s) of the aromatic L radical which can be worn by a carbon atom of an aliphatic chain and / or by an atom of carbon of a benzene nucleus.
When a compound ~ D) (or a mixture of compounds D) is used for the production of the compositions according to the present invention, it represents by weight from 2 to 35%, preferably from 5 to 30 X, of the overall composition (A) + (B) + (D) + possibly (C).
As specific examples of bis-maleimides (7) of formula ~ -(VIII), there may be mentioned in particular:
- N, N'-metaphenylene-bis-maleimide, - N, N'-paraphenylene-bis-maleimide, - N, N'-4,4'-diphenylmethane-bis-maleimide, - N, N'-4-4'-diphenylether-bis-maleimide, - N, N'-4,4'-diphenylsulphone-bis-maleimide, - N, N'-cyclohexylene-1,4-bis-maleimide, - N, N'-4,4'-diphenyl-1,1-cyclohexane-bis maleimide, ; - N, N'-4,4'-diphenyl-2,2-propane-bis-maleimide, - N, N'-4,4'-triph ~ nylmethane-bis-maleimide, - N, N'-methyl-2 phenylene-1,3-bis-maleimide, - H, N'-methyl-4 phenylene-1,3-bis-maleimide, - N, N'-m ~ 5-thylphenylene-1,3-bis-mal ~ imid-e, These bis-mal ~ imides can be prepared according to the methods described in the US patent US-A-3,018 2gO and the English patent GB-A-1 137 290. Preferably used for the implementation of the present invention, the N, N'-4,4'-dlphenylm ~ thane-bls maleim ~ taken alone or as a mixture with N, N'-methyl-2 ph ~ nylene-1,3-bis-maleimide, N, N'-methyl-4-phenylene-1,3 ~ bis-maleimide and / or N, N'-methyl-5 phenylene-1,3-bis-maleimide.

.

"", ~,:, "",:,,. . ",",. ~ ",.

WO 92/04395; ~ 18 - PCT / FR91 / 00703 i ... ~
It has been observed that the amount of chlo ~ e or bromine which can be added to the compositions according to the invention by the additive (8) is likely to influence certain properties of cured compositions obtained, in particular the properties in terms of thermal stability and OS those as regards adhesion of the compositions on metals such as for example copper. In this context, the best results are obtained when this amount of chlorine or bromine provided by the additive (8), expressed as the percentage by weight of elemental chlorine or bromine elementary with respect to the weight of the overall mixture (A) + (B) + compound optional (C) + optional compound (D), represents at most 8%; this amount of chlorine or bromine is preferably in the range ranging from 1 to 6%. You can easily adjust the amount of chlorine or bromine to the desired value by using for example resins epoxy (8) with more or less chlorine or bromine content or starting from mixtures of chlorinated or brominated epoxy resins (B) with non-halogenated epoxy resins (9).
By chlorinated or brominated epoxy resin (8) is meant to define a epoxy resin which has an epoxy equivalent weight of between 200 and 2,000 and which consists of a glycidic ether obtained by reacting with epichlorohydrin a chlor ~ or bromine derivative on (or them) aromatic nucleus (s) from a polyphenol selected from the group form by: the family of bis (hydroxyphenyl) alkanes such as bis (hydroxy-4 phenyl) -2.2 propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy) phenyl) methyl-phenyl-methane, bis (4-hydroxyphenyl) tolyl-methanes;
resorcinol; hydroquinone; pyrocatechol; dihydroxy-4,4 ' `diphenyl; and the condensation products of the above-mentioned phenols with a aldehyde.
The expression ~ po ~ ds of equivalent bpoxy ~ which appears cl-before, can be defined as the weight of resin (in grams) containing an epoxy function - C - / C -.

.

W o 92/04395 ~ T / FR91 / 00703 -.

We choose pr ~ ference a chlorinated or brominated epoxy resin with an epoxy equivalent weight between 25 ~ and 500. We use most preferably in the present invention an epoxy resin (8) consisting of a resin belonging to the family of glycidic ethers ~ :: 05 bis (hydroxvphenyl) alkanes. brominated on aromatic rings, of which ~ spoke above about the detailed definition of the resin (8).
By non-halogenated epoxy resin (9) is meant a resin epoxy which has an epoxy equivalent weight of between 100 and 1000:.
and which consists of a glycidic ether obtained by reacting with epichlorhyrin a non-chlorinated or non-brominated polyphenol on the (or them) ~ -: aromatic nucleus (s) chosen from the group of phenols of which we have spoken above about the detailed definition of the resin (8).
~ Preferably choose a non-halogenated epoxy resin having an epoxy equivalent weight between lSO and 300. We use most preferably an epoxy resin (9) consisting of a resin belonging to the family of glycidic ethers of bis (hydroxyphenyl) alkanes, not halogenated on the aromatic rings, of which we have spoken above about the detailed definition of the resin (8).
As specific examples of alkenylphenols (10) of formula (IX), we can quote in particular:
- 4,4-dihydroxy '3,3-diallyl' bisphenyl, - bis (4-hydroxy-3-allyl phenyl) methane, - bis (4-hydroxy-3-allyl phenyl) ether, - bis (4-hydroxy-3-allyl phenyl) -2.2 propane or O, O'-diallyl-. 25 bisphenol A, , - the methyl ether corresponding to one or other of the alkenylphenols cited above.
The alkenylphenols are pr ~ by ~ nt, alnsl that this is blen known, by thermal transpositlon (Clalsen) of the allyl ethers of phenols, which allyllic ethers are obtained in a manner known per se causing for example phenols and allyl chloride to react in the presence `of a hydroxyd ~ of m ~ alkali etal and solvents.
. ~ '.

, , .

:. ,. . ~ ,. . . : -. . . .

~, _ As suitable acrylate reagent (11), there may be mentioned:
(11.1) - the mono (meth) acrylates corresponding to formula (X) in which :
ps 1, and Oi. L represents a monovalent organic radical of formula:

- (- CH2 CH20t ~ Ll (Xl) in which: L1 represents an alkyl radical, linear or branched, having from 1 to 6 carbon atoms or a phenyl radical; and q is a integer equal to zero, 1, 2, 3, 4 or 5;
(11.2) - the di (meth) acrylates corresponding to formula (X) in which :
. p ~ 2, and . L represents a divalent organic radical of formula:
- ~ -CHzCH20) r L2 (0CH2CH2) s (XII) in which: L2 represents a divalent alkylene radical, linear or branched, having 2 to 9 carbon atoms and which may contain one or more several oxygen bridge (s) or a radical of formula:

~ U ~

in which the symbol U represents a simple value bond or a grouping:
. .

-CH2-, -CH2-CH2-, -CH (CH3) CH2-, -C-, -0-, - ~ -; the symbols r and s, WO 92/04395 PCl / FR91 / 00703 , ~.
identical or different, each represent ~ n whole number equal to . zero, 1. 2, 3, 4 or 5; - ~
(11.3) - the tri- and tetra (meth) acrylates corresponding to the formula (X) in which : . ~
05. p - 3 or 4, and:
. L represents a trivalent or tetravalent organic radical derived from a saturated, linear or branched aliphatic residue, having from 3 to 20 carbon atoms and may contain one or more bridges (s ~ oxygen `and / or one or more free hydroxyl function (s);
(11.4) - novolak epoxy (meth) acrylates which, while corresponding in formula (X), are represented here by the following formula:
;

ICO CO CO
OOO
, ~ CH2 ¢ H2 CH2 CHOH CHOH CHOH

CH2 ~ CH2 $

(XIII) ~ 30 in which . the symbol R16 has the meaning given above with respect to:, formula (X);
. the symbol R17 represents a hydrogen atom or a radical methyl;

.
.

, .. ..... ... ..... ... . . . .

wo 92/04395 ~ ~ 1 PCT / FR91 / 00703 - t is a whole or fractional number located in the range from 0.1 to 7;
(11.5) - mixtures of several acrylates and / or methacrylates of the same type 1 (11.1), (11.2). (11.3) or (11.4)) between them or mixtures of one or 05 several acylate (s) and / or methacrylate (s) of the same type with one or several acrylate (s) and / or methacrylate (s) of another type.
As specific examples of acrylate reagent (11.1) which are suitable, mention may in particular be made of: mono (meth) acrylates methyl; mono (meth) acrylates of phenol (mono-oxyethylated); the my (meth) acrylates of phenol (di-oxyethyl).
As specific examples of acrylate reagent (11.2) which suitable, there may be mentioned: ethylene glycol di (meth) acrylates;
1,4-butanediol di (meth) acrylates; the di (meth) acrylates 1,6-hexanediol; tripropylene glycol di (meth) acrylates; the di (meth) acrylates of diphenols, di (mono- or poly-oxyethylated) or not, following: dihydroxy-4,4'-diphenylmethane, bisphenol A, dihydroxy-4,4'-diphenylether and in particular the di (meth) acrylates of bisphenol A di (mono-oxyethylated) or bisphenol A di (meth) acrylates di (di-oxyethylated) (cf. formula (XII) in which L2 represents the radical :

~ ~ H

and r ~ s ~ 1 or 2).
As specific examples of acrylate reagent (11.3) which agree well, we can cite in parttculler: tri (meth) acrylates butanetriol-1,2,4; trl (m ~ th) acrylates of hexanetriol-1,2,6:
triethylethylpropane tri (meth) acrylates; the tri (meth) acrylates of pentaerythritol; pentaerythritol tetra (meth) acrylates Novolak epoxy (m ~ th) acrylates (11.4) are products known, some of which are commercially available. They can be prepared by reacting (meth) acrylic acids with a resin .

WO 92/04395 PC ~ r / FR91 / 00703 - 23 - -;

novolak type epoxy, the latter being the reaction product epichl ~ rhydrine and phenol / formaldehyde polycondensates (in the formula (XIII) given above R17 is then a hydrogen atom} or cresol / formaldehyde polycondensates in formula R17 is then a radical methyl bone). These oligomeric polyacrylates (11.4) and a process for them prepare are described for example in the US patent US-A-3,535,403.
As specific examples of acrylate reagent (11.4) which are suitable, mention may in particular be made of epoxy acrylates novolaks of formula (XIII) in which R16 and R17 represent a hydrogen atom and t is a whole or fractional number in the range of 0.1 to 5.
As specific examples of acrylate reagent (11.5) which suitable mixtures of epoxy (meth) acrylates may be mentioned novolaks (11.4) with at most 30% by weight, relative to the weight of the mixture (11.4) + (11.3), a triacrylate and / or a trimethacrylate meeting the definitions given above regarding the reagent acrylate (11.3) and in particular mixtures of epoxy acrylates suitable novolaks, just mentioned above, with at most 25 X in weight, based on the weight of the mixture, of a triacrylate and / or a suitable trimethacrylate well chosen from those just mentioned above.
The acrylate reagent (11) which is used in a very preferential is taken from the group formed by: di (meth) acrylates bisphenol A ditmono-oxyethylé3; bisphenol A di (meth) acrylates di (di-oxyethylated); novolak epoxy acrylates of formula (XIII) in which R16 and R17 represent a hydrogen atom and you are ~ a number integer or fractional lying in the range from 0.1 to 5, these compounds being taken alone or as a mixture with at most 25 X in polds, relative to the weight of the mixture, of trimethylolpropane triacrylate.
Various additions can still be incorporated into the compositions according to the invention. These adjuvants, usually used and well known to those skilled in the art, can for example be stabilizers or degradation inhibitors, lubricants, or mold release, dyes or pigments, pulverulent fillers or -., ..,; . -. , ~. . -,, ~,.,, .....:
-. . , -,, -.:. ::. ~

,. ~ ...,. , -:
.

WO 92/04395 `PCI / FR91 / 00703 particles like silicate ~ s, carbonates, kaolin, chalk, sprayed quartz, mica or glass microbeads. Can also incorporate adjuvants which modify the physical structure of the product obtained such as blowing agents or reinforcing agents 05 fibrous fibers such as carbon, polyimide, aromatic polyamides, whiskers.
The curable compositions according to the invention can be result of a simple direct mixing at room temperature (23 C) of component (A), component (B) and optionally additive (D), with the catalyst (C) if necessary.
But preferably, the curable compositions according to the invention are the result of a preliminary reaction, concerning the various constituents used, obtained by heating and leading to a homogeneous liquid material. Curable compositions `15 according to the invention thus obtained will be defined in the paragraphs following by the expression: "preferred compositions".
More specifically, said preferred compositions can be prepared by direct heating of component (A), component (B) and optionally additive (D), with catalyst (C) if necessary sufficient time to obtain a homogeneous liquid mixture; the temperature may vary depending on the physical state of ~ s compounds presence, but it is between 40 and 120 C and, preferably between 50 and 100 'C; the duration is of the order of 5 minutes to 1 hour or more.
According to an advantageous procedure, used to prepare the preferred compositions, we am ~ ne in a first step the constituent cyanate ester (A) at a temperature between 40 and 120 'C and preferably between 50 and 100' C, ~ which it is in a homogeneous liquid state, operating in the absence of the catalyst (C) eventual. Then, in a second step, we add to the liquid medium which is stirred and kept at a temperature, identical or different from that implemented in the previous step, also between 40 and 120 'C and preferably between 50 and 100' C, the polyimide component siloxane (B), stirring and temperature being maintained for one sufficient time to obtain a homogeneous liquid medium ~ ne (duration of the order WO 9 ~ / 04395 PCI / FR9 1/00703 2 5 - _; d / ~, from 5 minutes to 1 hour or more). In case we choose to do call to the optional catalyst (C), it is introduced in the second step, preferably in the form of a solution in the constituent (B) charge. In the case where one chooses to use the additi ~ (D), it 05 can be entered at any chosen time, either during the first step, or during the second step.
The viscosity in the molten state of the preferred compositions thus ~ obtained, measured at 80 C, can be easily adjusted to the value desired, between 0.1 Pa.s and 50 Pa.s, playing in particular on the nature and respective proportions of the constituents used as well only on the temperature and the duration of heating.
The operations just described can be ; not only in the melt, but also in the presence of variable quantities of a polar liquid such as for example: cresol, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methyl ethyl ketone, dioxane, cyclohexanone.
In the state of homog ~ ne liquid, the preferred compositions can be used directly for example either for the impregnation of conductors, either to make moldings by simple hot casting or by injection, or again to make adhesives We can also, after cooling and grinding, use these compositions in the form of powders for example for obtaining compression molded objects, possibly in combination with fibrous or pulverulent fillers The preferred compositions can also be used in solution for the preparation of coatings, adhesives, laminated materials the skeleton of which may be in the form of woven or non-woven sheets, unidirectional elements or fibers cut ~ es natural or synthetics such as for example filaments or glass fibers, boron, carbon, tungstbne, sillclum, da polyamide-lmide or aromatic polyamide.
The preferred compositions have a whole interest particular for obtaining intermediate articles preimpr ~ gnes without solvent. The impregnation of the fibrous material can be carried out ~ e by application of usual techniques such as immersion, coating ., . . ~ ^
..,. ~,. . .

WO 92/043 ~ r PCr / FR91 / 00703 r ~ ~ 26 ~
'' doctor blade or curtain or impregnation by transfer. The transferable film - and prepreg articles can be used directly or be stored for later use; they keep remarkably their properties during cold storage between O
: 05 and 10 C. The preferred compositions used for this application preferably have a viscosity in the molten state between 2 Pa.s and 50 Pa.s.
- Preimpregnated materials can be used for the realization parts with various shapes and functions in many industries such as aeronautics. These pieces that can to be pieces of revolution are obtained by plating several layers of prepregs on a form or support. We can use also prepregs as reinforcements or means of repairing parts deteriorated.
IS But it is also possible to design parts according to the technique of filament winding with or without support, intended for the production of revolution parts, a technique used in particular for make parts for the automotive and aeronautical industries. The compositions pref ~ rees used in this technique presents preferably a viscosity in the molten state between 0.1 Pa.s and 2 Pa.s.
. The curable compositions according to the invention can be hardened (or crosslinked) by heating to temperatures between . 100 and 250 C, for 10 minutes ~ 25 hours, possibly under pressure. Before cross-linking, in the case of the preparation of preferred compositions, the latter are in the form of a pr ~ polym ~ era constituted ~ of a single phase; products from constituent polyimide siloxane (B) and optionally additive (D) are in fact soluble in the product derived from the constituent cyanate ester polyfunctional (A). During reticulatlon, as and when the progress of the reactlons concerning the groups - ~ -OC ~ N) still free, a phase separation phenomenon develops and we recover finally a hardened composition with a two-phase structure consisting of a continuous phase rich in prodult from cyanate ester of start and of a discontinuous phase, formed of particles of the order of 0.01 at 1 ~ m, rich in product derived from the starting elastomer component (B) :.

WO 92/04 ~ 5 PCI / FR91 / 00703 - 2 7 - ~,?

- The following examples illustrate without limitation how the present invention can be put into practice.
. In these examples, a number of controls are . done. Likewise, various properties are measured. We indicate below 05 the operating procedures and / or the standards according to which these checks and measurements are made.

- VISCOSIT ~ IN THE FOHDU STATE ~ AT THE 9VRCISSABIF COHPOSITION:
The melt viscosity we are talking about in the present memory is the dynamic viscosity of the composition obtained at the time of pouring at the end of the preparation process conducted en masse by heating ; constituents; it is measured at 80 'C +/- 0.1' C with a viscometer RHEOMAT 30 from CONTRAVES equipped with a mobile ,! turning under a gradient of 13 s ~ l; its value is given in Pa.s.
.:
- POINT OF RAMOLLISSEMEHT ~ E LA CO ~ POSIT10 ~ W RCISSABLE:
The approximate temperature is called softening point to which a 6 mm diameter glass ring can penetrate easily a few mm in the material.
- GLASS TRANSITION TEMPERATURE OF THE W RCIE COMPOSITION:
The glass transition temperature (Tg) corresponds to the drop abrupt modulus of elasticity as a function of temperature. She can be determined on the graph representing the variations of the module elasticity (E) as a function of temperature, variations measured by dynamic mechanical analysis, using a DUPONT model 982 DMA device, at a temperature rise rate of 3 'C / minute The test pieces are conditioned ~ EHO ~ Hygrometric State Z ~ ro), i.e. they are placed in a desiccator on silica gel and dried for 24 hours at ambient temperature below 0.66-1.33.102 Pa before carrying out the measurements.

.......... ........ ...

WO 92/0439 ~, ~ PCl / FR9 1/00703 } - 28 -, - TEHACITY OF THE HARDENED COMPOSITIOW:
The CHARPY impact resistance is determined at 20 C on ~ 80 x 10 x 4 mm bar type test not having notch, conditioned to EHO, according to standard ASTM D 256. The energy of OS crack propagation GlC and the critical concentration coefficient of; KlC stress are determined on CT test pieces (CT ~ Compact Tension) according to standard ASTM E 399.

- TEST O'AGHERENCE OE THE HARDENED COMPOSITTON ON STAINLESS STEEL:
. ,.
It is carried out in simple shear according to standard ASTM D
1002. The curable composition is deposited in the form of a film of 200 µm thick on the metal substrate, then re-iculated under pressure. We measure the value of the stress at break in shear (6R).

- EXEHPL ~
1. - Example of implementation of the invention:
In a glass reactor fitted with an anchor-type stirrer, introduced at room temperature 100 9 of a prepolymer of 2,2-bis (4-cyanatophenyl) propane in which 30% of the cyanate groups functional were cyclotrimerized; this product is the one marketed by the company HI-TEK POLYMERS under the name AROCY B30.
Step 1: immerse the reactor in a preheated oil bath at 80 ° C and are contained is stirred until ~ complete melting of the constituent charged and obtaining a homogeneous liquid mass. The duration of this stage is S minutes and we proceed to a degassing under pressure scaled down.
Step 2: the liquid mass obtained is refrolded up to 60 ° C
and 18 9 of the bis ~ maleimide siloxane which is described in the paragraph 2 below and 0.025 9 of acetylacetonate of cui ~ re (Cu (CsH702) 2) previously dissolved in bis-maleimide siloxane. The mass reaction is maintained at 60 ° C with stirring until obtaining of a homogeneous liquid medium. The duration of this stage is 10 minutes ;, ~. '' - ". ''','''.""''''''''''''''' wo 92/0439 ~ PCT / F ~ 91/00703 - 29 - ~; 7 i The liquid reaction mass obtained is then poured into a mold preheated to 170 C.
The thermosetting composition thus obtained is flexible and sticky at room temperature (20 ° C). It presents a point of 05 softening close to O C. Its viscosity ~ 80 'C is 1 Pa.s and its gel time at 170 ° C is 8 minutes.
With this composition, HOT-MELT type impregnation (with solvent-free molten material) of fibrous materials, ~ base for example of woven tablecloths of carbon fibers, to make articles -; 10 prepreg intermediates, is possible in the temperature range ranging from 50 to 100 'C.
By immediately pouring the thermosetting composition into a mold as indicated above, plates can be prepared dimensions 140 x 100 x 4 mm which will undergo the following cooking cycle:
. 60 minutes i 170 C, ; . 55 minutes between 170 and 225 C, . 16 hours at 225 C, . and 2 hours between 225 and 25 C.
After demolding, the plates based on cured composition are cut to obtain specimens of appropriate dimensions on which we measure: the glass transition temperature tTg), the modulus of elasticity (E), impact resistance CHARPY (Rc) not cut and GlC and KlC values.
The values found are as follows:
. Tg: 235 C
. .
,. E: * at 20 C: 3.0 GPa . ~ at 200 C: 1.75 GPa . Rc: 22 kJ / m2 . GlC: 160 J / m2 . KlC: 0.66 Mpa Vm By way of comparison, the operations described have been reproduced above, but not using bis-maleimide siloxane. Values Rc and GlC are reduced by 50 X; the moduli of elasticity E to 20 and 200 C are increased by 10 X.

. ~
.
-. -,. . -. , .. ... .. ~

. . .
.. ~. . ,,. .
, : ~:

WO 92/04395 ~ ^ ~ PCT / FR91 / 00703 . ~ r ~, Adhesion tests on stainless steel were carried out also. The curable composition according to the example is crosslinked under a pressure of 105 Pa, according to the above-mentioned cooking cycle. Values found for the shear breaking stress (6R) are the ~.
05 following::
. 6R: ~ at 20 C: 16 Mpa -~ at 200 C: 18 MPa These values are practically not modified after having made the samples tested age 1000 hours at 180 ° C.
In the absence of bis-maleimide siloxane, the stress values at the shear failure are 10 MPa at 20 'C and 12 MPa at 200' C. :.
2. - ~ escriDtion of the DreDaratiOn Drocede of bis-maleimide to diorqanoDol qrouDements ~ siloxane used in the example!:::
This bis-maleimide has the following formula:
':.

; CH3 CH3 CH3 - (C ~ 2) 3 ~ t ~ t ~ ~ (C ~ z ~ 3 ~

lCO / `CO CO / ~ 0 CH - - CH CH - CH

.

WO 92/04395 PCI` / FR91 / 00703 ~. . ., ~ 2 2.1. - Preparation of the grouped diamine diorganopolysiloxane from which this bis-maleimide is derived:
In a glass reactor fitted with central stirring, a pouring bulb and an ascending cooler in which one establishes ~ a 05 slight overpressure of dry nitrogen, 369 9 (0.46 mole) of alpha is charged.
omega-bis (hydrogen) diorganopolysiloxane of formula:
.

- If - o _ - If - o _ - If - H
0 / ~

having a reaction mass of the order of 802 9.
The reactor is then introduced into a preheated oil bath at SS C, then the catalyst is added. The latter is the catalyst for KARSTED (complex based on elementary platinum and 1,3-divinyl ligands tetramethyl-1,1,3,3 disiloxane): it is in solution in toluene (concentration of 3.5% by weight) and introduced with a syringe 1.49 cm3 of this catalyst solution; the ratio (platinum weight elementary committed / pcids of the reaction mass) is equal to 91.10-5.
Then gradually poured into the reactor 137 9 (0.92 mole) of m ~ taallyloxyaniline, for a period of 60 minutes, of so as to control the exothermicity of the r ~ action. Thirty minutes after end of coul ~ e we return to room temperature. The product obtained from weight of 506 g, is a viscous oil llmplde, brown-orange color ~, presenting a proton NMR spectrum in agreement with the structure:

:
WO 92/04395, ................................. PCI / FR91 / 00703 r ~ D - 3 2 ~: ~
! :

O - ~ CH2) 3 If - O; - .. OS (CH2 ~ 3 :. NH2 H2 The molecular mass is of the order of 1,100 9. In these conditions, the conversion rate of the reagents used is 100%
(by NMR and infrared analysis, neither amine nor oligomer is detected hydrogenated siloxane) and the desired yield by weight of diamine is ., 100%.
2.2. - Preparation of bis-maleimide diorgano-polysiloxane:
- ~ 20 In a glass reactor fitted with central stirring, and a ascending refrigerant in which a slight overpressure is established dry nitrogen which is placed in a preheated oil bath ~ 55 ° C, introduced simultaneously, in 10 minutes, using 2 dropping funnels:
- 20 cm3 of a 28 9 acetone solution (0.025 mole and 25 0.02 NH 2 function) of the dimaine siloxane prepared in paragraph 2.1, - 15 cm3 of a solution in acetor.e of 6.4 9 (0.055 mole) maleic anhydride.
. ~ "., ~ ,.
When the pouring is finished ~ es, each bulb is rlncée with 5 cm3 of acetone, which are then added to the reaction mass ,; 30 kept stirring for another 15 minutes.
In the dropping funnel which contained maleic anhydride, load 6.1 9 (0.06 mole) of acetic anhydride and, in the other ampoule, load 1.67 9 (0.0165 mole) of triethylamine.

~ '.

W o 92/04395 pcT / FRsl / oo7o3 ~ ~, These two compounds are then poured into the reactor, and then add 0.3 cm3 of an aqueous solution containing 0.0528 mole of acetate nickel for 100 cm3 of solution.
The reaction mixture is kept at reflux with stirring OS for 2 hours 30 minutes. The temperature is then lowered to 20 ° C. The reaction mixture is diluted with 80 cm3 of ice water (5 C) with vigorous stirring and then extracted with 80 cm3 of ethyl acetate the oily product present. The organic phase obtained is washed with three times 80 cm3 of water to reach ~ pH 6 in the washing water, then dried for 2 hours over anhydrous sodium sulfate. After filtration, ; ethyl acetate is removed by evaporation from the organic phase in ending this operation under reduced pressure (around 70 Pa) at 60 ° C and 30.3 9 are collected (i.e. a yield by weight of 96% relative to the theory) of a viscous, orange-brown product, the NMR spectrum of which is in agreement with the structure of the desired bis-maleimide which has been defined in beginning of this example. The molecular mass is around 1,260 9.

- EXAMPLE 2:
We operate exactly as indicated in Example 1, but without charge with catalyst (copper acetylacetonate) in step 2.
At the end of step 2, the liquid reaction mass is poured into a mold preheated to 200 C.
The thermosetting composition thus obtained is flexible and sticky at room temperature (20 ° C). It presents a point of voistn softening of O C. Its viscosity at 80 C is 1 Pa.s and its freezing time at 200 C is 35 minutes.
With this composition, the HOT-MELT type impregnation (with solvent-free molten material) of fibrous materials, based for example on woven webs of carbon fibers to make articles pretmpregn ~ intermediate, is posstble in the temperature range ranging from SO to 100 C.
By immediately pouring the thermosetting composition into a mold, we can prepare plates of dimensions 140 x 100 x 4 mm which will undergo the following cooking cycle:

.

, ~ "~ '',, ' - ~, -.
-.

:
WO 92/0439 ~ PCI / FR91 / 00703 :;
. 60 minutes ~ 200 'C, . 50 minutes between 200 and 250 'C.
5 hours ~ 250 'C, . and 2 hours between 250 and 25 'C.
05 After demolding, the plates based on cured composition are cut to obtain specimens of appropriate dimensions on which we measure: the glass transition temperature (Tg ~, the : modulus of elasticity (E), the impact resistance CHARPY (Rc) not cut and GlC and KlC values.
The values found are:
. Tg: 230 'C
:. E: * ~ 20 'C: 3.0 GPa * at 200 'C: 1.75 GPa . Rc: 23 kJ / m2 lS. GlC: 165 J / m2 . KlC: 0.64 Mpa V ~

In a glass reactor fitted with an anchor-type stirrer, introduced at room temperature 75 9 of a prepolymer of 2,2-bis (4-cyanatophenyl) propane in which 30% of the cyanate groups functional were cyclotrim ~ risés; this produ ~ t is celul marketed.,: ~.
by the company HI-TEK POLYMERS under the name AROCY B30.
, Step 1: the reactor is immersed in a preheated oil bath at 80 C and are contained is acted ~ until ~ complete melting of the constituent .I charged and obtaining a homogeneous liquid mass. The duration of this stage is 5 minutes and then degassing under presslon scaled down.
~ 'Step 2: the liquid mass obtained is refrolded up to 60' C
and 18 9 of bis-maleimide s11Oxane which is described in Example 1, 0.025 9 of copper acetylacetonate previously dissolved : in bis-maleimide siloxane and 25 9 of bisph diacrylate ~ nol A
di (di-oxyethylated) ~ product available commercially under the brand registered EBECRYL 150 of the Company UCB ~. The reaction mass is '' WO 92/04395 '''' ~ Cr / FR91 / 00703 , `, _ .. ~. , maintained at 60 C with stirring until a ~ ilieu liquid is obtained - homogeneous. The duration of this stage is 10 minutes. We then sink the liquid reaction mass obtained in a mold preheated to 170 C.
The thermosetting composition thus obtained is flexible and 05 sticky at room temperature (20 C). It presents a point of softening close to -10 'C. Its viscosity at 80 C is 0.5 Pa.s and its freezing time at 170 ° C is 10 minutes.
With this composition, the HOT-MELT type impregnation (with molten material without solvent) of fibrous materials, for example based on woven carbon fiber tablecloths for making articles preimpregnated intermediates, is possible in the temperature range ranging from 50 to 100 'C.
By immediately pouring the thermosetting composition into a mold, we can prepare plates with dimensions 140 x 100 x 4 mm which They will undergo the following cooking cycle:
. 60 minutes at 170 'C, . 55 minutes between 170 and 225 C, . 16 hours 3225 'C, . and 2 hours between 225 and 25 C.
After demolding, the plates ~ base of hardened composition are cut to obtain specimens of appropriate dimensions on which we measure: the glass transition temperature (Tg), the 'modulus of elasticity ~ (E), there resistance to impact CHARPY (Rc) not notched and GlC and KlC values.
The values found are as follows:
. Tg: 210 C
. E: ~ at 20 C: 3.0 GPa at 200 'C: l, O GPa . Rc: 26 kJ / m2 . GlC: 305 J / m2 . KlC: 0.79 Mpa v ~ r .
~,. . ''. I. : ~ '

Claims (10)

1. - Thermosetting compositions which comprise:
(A) - at least one cyanate ester compound chosen from the group formed by:
(1) - a polyfunctional aromatic cyanic ester, monomer, having the formula :
R-(-OC=N)n (I) where: n is an integer ranging from 2 to 5 and R represents an aromatic organic radical of valence n, comprising from 6 to 30 carbon atoms where the cyanate groups are bonded to the ring(s) aromatic(s) of R;
(2) - a prepolymer of (1), and (3) - a coprepolymer of (1) and an aromatic primary polyamine;
(B) - at least one elastomeric compound;
and eventually :
(C) - a suitable catalyst;
said compositions being characterized in that constituent (B) consists of at least one compound selected from the group formed by:
(4) - an N,N'-bis-maleimide with a diorganopolysiloxane group corresponding essentially to the general formula:

(II) in which :
- X, which is in ortho, meta or para position with respect to the carbon atom of the benzene ring connected to nitrogen, represents a bond simple valence or an atom or a following group:

-O-; -S-; ; ;

- R1, R2, R3, R4, R5, R6, R7, R8, identical or different, each represent a monovalent hydrocarbon radical chosen from:
alkyl radicals, linear or branched, having from 1 to 12 carbon atoms carbon, these radicals possibly being substituted by one or more atoms chlorine, bromine or fluorine or by a -CN group; a radical phenyl optionally substituted by one or more alkyl radicals and/or alkoxy having from 1 to 4 carbon atoms or by one or more chlorine atoms;
- the symbol x is an integer located in the interval ranging from 2 to 8;
- the symbols y and z represent numbers, identical or different, whole or fractional, the sum of which lies in the range from 0 to 100;
(5) - a prepolymer of (4), and (6) - a coprepolymer of (4) and an aromatic biprimary diamine 2. - Thermosetting compositions according to claim 1, characterized in that with regard to the component (A), the symbol R of the cyanate ester of formula (I) can represent:
(i) - a radical of valence n derived from a hydrocarbon aromatic containing from 6 to 16 carbon atoms such as by for example benzene, naphthalene, anthracene or pyrene;
(2i) - a radical of valence n derived from a group comprising several aromatic nuclei linked together by a link simple valence or by an inert atom or a group inert divalent such as for example the group of formula:

in which R' represents: a simple valence bond or a divalent inert atom or group such as: -O-; -S-; a linear or branched alkylene radical having from 1 to 10 carbon atoms carbon, optionally substituted by one or more carbon atoms chlorine, bromine or fluorine and optionally interrupted by one or several oxygen atoms; -CO-; -SO2-; -NR"- where R"
represents a hydrogen atom, an alkyl radical having from 1 to 3 carbon atoms, phenyl or cyclohexyl; -COO-;

; ; the various aromatic groups mentioned in paragraphs (i) and (2i) which may be substituted by one or more alkyl(s) or alkoxy radicals, linear or branched, having 1 to 4 carbon atoms or by one or several halogen atoms. 3. - Thermosetting compositions according to claim 2, characterized in that the cyanate esters (1) of formula (1) which are used consist of difunctional compounds that meet the formula :

(IV) in which :

- R''' represents a single valence bond or an atom or the following group:

-O-; -S-; -CH2-; ; ; ; ; ;

; ;

- the symbols R'''', identical or different, represent each a substituent selected from a chlorine, bromine or fluorine atom or a methyl, ethyl, propyl or isopropyl radical, two neighboring R'''' on the same nucleus being able together to represent an aromatic nucleus 6 links;
- m is an integer equal to 0 or 1;
- a is an integer equal to 0, 1 or 2, the symbols a, when there are 2 of them, which can be identical or different from each other. 4. - Thermosetting compositions according to any one of claims 1 to 3, characterized in that, with regard to the constituent (3), bis-maleimide siloxane (4) is taken from the group formed by bis-maleimide siloxane of formula (II) in which:
1) X = -O-; R1 = R2 = R3 = R4 = R5 = R6 = R7 = R8 = alkyl radical linear having from 1 to 3 carbon atoms; x = 2, 3 or 4; y + z se ranges from 0 to 100 and preferably from 4 to 70.
2) X = -O-; R1 = R2 = R3 = R4 = R7 = R8 = linear alkyl radical having from 1 to 3 carbon atoms; R5=R6=phenyl radical; x = 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably, from 4 to 70.

3) X = -O-; R1 = R2 = R7 = R8 = linear alkyl radical having from 1 to 3 carbon atoms; R3=R4=R5=R6=phenyl radical; x = 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably, from 4 to 70.
4) X = -O-; R1 = R2 = R3 = R5 = R7 = R8 = linear alkyl radical having from 1 to 3 carbon atoms; R4=R6=phenyl radical; x = 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably, from 4 to 70.
5) X = -O-; R1 = R3 = R5 = R7 = linear alkyl radical having from 1 to 3 carbon atoms; R2=R4=R6=R8=phenyl radical; x = 2, 3 or 4; y + z is in the range from 0 to 100 and, from preferably, from 4 to 70. 5. - Thermosetting compositions according to any one of claims 1 to 4, characterized in that the catalyst (C), when uses one, is taken from the group formed by:
- labile hydrogen compounds consisting of alcohols, phenols, carboxylic acids and primary or secondary amines, - compounds consisting of metal carboxylates, dissolved optionally in an alkylphenol or a monoalcohol, - compounds consisting of metal acetylacetonates, dissolved optionally in an alkylphenol. 6. - Thermosetting compositions according to any one of claims 1 to 5, characterized in that the quantities of the constituents (A) and (B) so as to have, by weight relative to the weight of the set (A) + (B):
- from 50 to 98% and preferably from 75 to 95% of constituent (A), and - from 2 to 50% and preferably from 5 to 25% of constituent elastomer (B). 7. - Thermosetting compositions according to one of claims 1 to 6, characterized in that they additionally comprise a additive (D) consisting of one or more additional compound(s) polymerizable product(s) chosen from:
(7) - an N,N'-bis maleimide of formula:

(VIII) in which :
. the symbols Z, identical or different, each represent H, CH3 or Cl;
. the symbol G represents a divalent radical chosen from the group consisting of the radicals: cyclohexylenes; phenylenes; methyl-4 1,3-phenylene; 2-methyl-1,3-phenylene; 5-methyl-1,3-phenylene;
2,5-diethyl-3-methyl-1,4-phenylene; and the radicals of formula:

in which B represents a single valence bond or a group:

- CH2 -; ; -O-; ; ; ;

(8) - a chlorinated or brominated epoxy resin;
(9) - a non-halogenated epoxy resin;
(10) - an alkenylphenol of formula:
(IX) in which :
. the symbol H represents a single or radical valence bond divalent chosen from the group formed by the radicals:
- CH2 -; - CH2 - CH2 -; ; -O-; -S-; -SO-; and -SO2-;
. the R14 symbols, identical or different, represent each a hydrogen atom or a methyl radical;
. the identical or different R15 symbols represent each a hydrogen atom or a linear or branched alkyl radical having from 1 to 6 carbon atoms or a phenyl radical;
(11) - an acrylate of general formula:
(X) in which :
. the symbol R16 represents a hydrogen atom or a methyl radical;
. p represents an integer or fractional number at least equal to 1 and at plus equal to 8;

the symbol L represents an organic radical of valence p derived: from a saturated aliphatic residue, linear or branched, having from 1 to 30 carbon atoms carbon and possibly containing one or more oxygen bridge(s) and/or one or several function(s) free hydroxyl(s); of an aromatic residue (of aryl or arylaliphatic type) having 6 to 150 carbon atoms consisting of a benzene ring, which may be substituted by one to three alkyl radicals having 1 to 5 carbon atoms, or by several rings benzene, optionally substituted as indicated above, linked between them by a simple valence bond, an inert group or a radical alkylene having from 1 to 3 carbon atoms, said aromatic residue possibly contain at various points of its structure one or more bridge(s) oxygen and/or one or more free hydroxyl function(s), the (or the) free valence(s) of the aromatic L radical that can be carried by a carbon atom of an aliphatic chain and/or by an atom of carbon of a benzene ring. 8. - Thermosetting compositions according to any one of claims 1 to 7, characterized in that the catalyst (C), when uses one, is employed at a rate within the range of from 0.005 to 10% and, preferably, ranging from 0.01 to 5% with respect to the weight of the overall composition including (A) + (8) + optionally the (or the) additional polymerizable compound(s) (D). 9. - Process for preparing thermosetting compositions according to any one of claims 1 to 8, characterized in that:
- in a first step, the cyanate ester constituent (A) is brought to a temperature, between 40 and 120 ° C and, preferably between 50 and 100° C., at which it is in a homogeneous liquid state, operating in the absence of any catalyst (C);
- then, in a second step, we add in the liquid medium which is agitated and maintained at a temperature, identical or different from that set used in the previous step, also between 40 and 120 °C
and preferably between 50 and 100°C, the polyimide component siloxane (B), the agitation and the temperature being maintained for a sufficient time to obtain a homogeneous liquid medium;
- by ensuring that in the event that one chooses to call on the optional catalyst (C), the latter is introduced in the second stage, preferably in the form of a solution in the component (B) charged. 10. - Application of thermosetting compositions according to any one of claims 1 to 8, in the manufacture:
- adhesives;
- structural parts using the technique of simple molding hot casting or injection, or filament winding;
- intermediate articles preimpregnated using the technique of solvent-free impregnation of various fibrous materials