US 5,470,920 A · Impregnating solutions based on at least one reactive thermoplastic poly (imide-amide) oligomer and a coreactant, which can be used especially for the production of preimpregnated intermediate articles

Abstract

The present invention relates to impregnating solutions consisting: of an active principle A+B in which: A denotes at least one thermoplastic poly(imide-amide) oligomer functionalized at the chain ends with an alkenyloxy, maleimido or nadimido group, B denotes a coreactant chosen from: B1=an imide ingredient, B2=an acrylate ingredient, B3=an alkenylphenol ingredient, B4=a novolac resin, B5=a vinyl ingredient, B6=an epoxy resin, B7=an amino ingredient and B8=a mixture of a number of ingredients B1 to B7; and of one or a number of aprotic polar solvent(s), the concentration of the active principle in the solution being between 2 and 80% by weight. These solutions are employed especially for the production of preimpregnated intermediate articles.

A solution comprising an active principle containing a reactive oligomer and at least one organic solvent for the oligomer, which active principle comprises:

(A) at least one reactive thermoplastic poly(imide-amide)oligomer selected from the group consisting of:
(A1) a linear aromatic poly(imide-amide) oligomer containing alkenyloxy end groups, which oligomer is obtained by direct reaction of (i) an aromatic diisocyanate, (ii) a monoanhydride of a tricarboxylic acid, and (iii) a monocarboxylic acid substituted by an alkenyloxy group;
(A2) a linear aromatic poly(imide-amide) oligomer containing maleimido end groups optionally substituted on the maleic double bond by a methyl group, which oligomer is obtained by direct reaction of (i) an aromatic diisocyanate, (ii) a monoanhydride of a tricarboxylic acid, and (iii) a monocarboxylic acid substituted by a maleimido group which may be substituted by a methyl group;
and
(A3) a linear aromatic poly(imide-amide) oligomer containing end groups each of which includes a residue with a latent maleimide functional group, which oligomer is obtained by direct reaction of (i) an aromatic diisocyanate, (ii) a monoanhydride of a tricarboxylic acid, and (iii) a carboxylic acid containing a residue with a latent maleimide functional group;
and
(B) a coreactant comprising a compound selected from:
(B1) at least one imide selected from the group consisting of:
(B1-i) a monoimide represented by the formula:
##STR20## wherein in formula I:
each Y is identical or different and denotes H, CH.sub.3 or Cl, and R.sub.1 denotes H or an aliphatic, cycloaliphatic or aromatic monovalent hydrocarbon radical containing up to 20 carbon atoms, each hydrocarbon radical being unsubstituted or substituted by a Cl, alkoxy or alkenyloxy;
(B1-ii) an N,N'-bisimide represented by the formula:
##STR21## wherein in formula II:
Y has the meaning given in formula I;
A denotes a divalent radical selected from the group consisting of cyclohexylene, phenylene, 4-methyl-1,3-phenylene, 2-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 2,5-diethyl-3-methyl-1,4-phenylene, and a radical represented by the formula:
##STR22## in which T denotes a single valency bond or divalent radical selected from the group consisting of:
##STR23## and each X is identical or different and denotes hydrogen, methyl, ethyl or isopropyl;
(B2) at least one acrylate represented by the formula:
##STR24## wherein in formula III:
R.sub.2 denotes hydrogen or methyl;
n is a number of from 1 to 8;
B denotes an organic radical of valency n selected from the group consisting of:
(i) a saturated, linear or branched aliphatic residue containing from 1 to 30 carbon atoms optionally interrupted by one or more oxygen atoms and optionally substituted by hydroxy groups;
(ii) an aryl or araliphatic residue containing from 6 to 150 carbon atoms which is a benzene nucleus that is optionally substituted by one to three alkyl radicals containing from 1 to 5 carbon atoms or a number of benzene nuclei optionally substituted as indicated above and joined one to another by a single valency bond, an inert group or an alkylene radical containing from 1 to 3 carbon atoms, wherein the said aryl or araliphatic residue is optionally interrupted in its structure or one or more oxygen atoms and optionally substituted by one or more hydroxy groups, and wherein the free valencies of the aromatic radical B are optionally carried by a carbon atom of an aliphatic chain or by a carbon atom of a benzene nucleus;
(B3) at least one alkenylphenol represented by the formula:
##STR25## wherein in formula IV:
D denotes a single valency bond or divalent radical selected from the group consisting of:
##STR26## each R.sub.3 is identical or different and denotes hydrogen or methyl;
each R.sub.4 is identical or different and denotes hydrogen, a linear or branched alkyl radical containing from 1to 6 carbon atoms, or phenyl;
(B4) at least one thermoplastic phenol/formaldehyde polycondensate in which the molar ratio of formaldehyde to phenol is between 0.6 and 0.95 and the softening point ranges from 50.degree. to 110.degree. C.;
(B5) at least one coreactant other than an acrylate, containing a vinyl double bond which is selected from the group consisting of vinylpyridines, N-vinyl-2-pyrrolidone, vinyltetrahydrofuran, styrene, and mixtures thereof;
(B6) at least one nonhalogenated epoxy resin;
(B7) at least one amino coreactant containing one or more hindered diprimary diamines, which amino coreactant is selected from the group consisting of:
(B7-i) at least one compound represented by the formula:
##STR27## wherein in formula V:
R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are identical or different and denote methyl, ethyl, propyl or isopropyl;
Z is identical or different and denotes hydrogen or chlorine;
E denotes a divalent radical selected from the group consisting of:
##STR28## (B7-ii) at least one compound represented by the formula:
##STR29## wherein in formula VI:
the amino radicals are in meta or para position relative to one another;
each R.sub.9 is identical or different and denotes methyl, ethyl, propyl or isopropyl;
and
(B8) a mixture of two or more of the coreactants (B1) to (B7);
wherein the concentration of the active principle, expressed as a mixture of A+B relative to the entire solution, is between 2% and 80% by weight, and the proportions of the ingredients B1 to B7, when these ingredients are employed separately to devise the active principle A1+Bx (where x =1, 2, 3, 4, 5, 6 or 7), are the following:
B1:
from 2 to 50%,
B2:
from 2 to 50%,
B3:
from 1 to 30%,
B4:
from 1 to 30%,
B5:
from 2 to 50%,
B6:
from 2 to 50%,
B7:
from 1 to 30%, these proportions expressing the weight percentage of each ingredient Bx in the combination A+Bx.

56 more elements

Impregnating solutions based on at least one reactive thermoplastic poly (imide-amide) oligomer and a coreactant, which can be used especially for the production of preimpregnated intermediate articles

Life of this patent

Impregnating solutions based on at least one reactive thermoplastic poly (imide-amide) oligomer and a coreactant, which can be used especially for the production of preimpregnated intermediate articles

Life of this patent

Abstract

Claims19