CA1052042A - Thermostable resins - Google Patents

Abstract

Thermostable polymer, characterized in that they are obtained by reaction of: a) a maleimide of average formula: (I) in which the symbol A represents an organic radical of valence n, containing up to 50 carbon atoms, the symbol Y represents H, -CH3 or Cl and n represents a number at least equal to 1.5. b) a compound containing at least one group -NH2 c) a compound containing at least one group -? R, the nature of the amino compound and of the carbonyl compound being such that the imine resulting from their reaction has the average formula: (II) in which m represents a number at least equal to 1, the symbol B represents a hydrogen atom or an organic radical of valence m, containing up to 50 carbon atoms, the symbol G represents a monovalent organic radical (G1) containing up to 35 carbon atoms or a radical of formula -G'-CR = N-B1 in which the symbol G 'represents a divalent radical containing up to 35 carbon atoms and the symbol B1 represents one of the monovalent radicals can be represented by the symbol B, or even, when m = 2, a radical of formula: -G'-CR = N-B2? N = CR-G'-CR = -N-B2) w .SIGMA. in which G 'has the meaning given above, B2 represents one of the divalent radicals which can be represented by the symbol B and the two symbols 2 representing the chain endings which can both be radicals of formula -N = CR -G'-CRO or represent one the radical -N = CR-G'-CRO and the other a group -NH2, the symbol R represents a hydrogen atom or a monovalent organic radical containing up to 35 atoms carbon, the symbols G1 and R possibly representing together a divalent radical; w represents a number between 1 and 10, the quantities of reagents used being such that there is in the presence of at least one group -? - R as well as at least one and at most ten double bonds, of maleimide ( I) by -NH2 group provided by the amino compound b).

Description

~ 5Z ~ Z
~ The invention relates to new polymers contain-mant imide groupings.
`I We know according to French patent 1,555,564 ~ ue one can obtain thermosetting polymers by reacting a ~, N'-bis-imide of unsaturated dicarboxylic acid with a biprimary diamine Furthermore, according to Swiss patent 529,152, when ~
reacts in solvent one mole of a monoimine with two moles of a mono-maleimide, obtains a product having the following configuration:

where a and ~ are the remains of the monoimne and ~ is the rest of the l monomaleimide. Depending on the type of reacti engaged and the ¦ operating editions, we thus obtain products whose point de ~ usion varies between 130 and 280C approximately. According to this same patent, products obtained after reduction of carbonyl groups can be used in the pharmaceutical industry.
It has now been found ~ ue we can get thermostable polymers P in heating ~ ant ~ at a temperature of i mo ~ ns equal to 100C, a mixture comprising:
a) a maleimide of ~ middle ormule:

("~ ~ A (I) - CO J n in which the symbol A represents an organic rad ~ cal valence n, ren ~ er ~ ant up to ~ 50 carbon atoms, the symbol ~ represents H, - ~ I3 or Cl and n represents at least an equal number ,. ~
~ 1.5, :. , '~

~ ~ Sz ~ 4 ~
b) a compound ren ~ ermant at least one gxoupemen-t - ~ 2 c) a compound containing ~ - at least one group -LR
the nature of the amino compound and of the carbonyl compound being such that the imine resulting from their reaction has the average formula:
B ~ - N = CR _ G) (II) in which m represents a number at least equal to 1, the sym-bole B represents a hydrogen atom or an orgallic radical of valence m, drifting amine ~ (ÆI2) m this radical renEermant jus-qu ~ 50 carbon atoms; the symbol G which represents one of the two radicals G1 and G 'belonging to the carbonyl compounds G1C. ~ 0 or G '~ CR0) 2 represents a monovalent organic radical (G1) ren-~ ermant up to 35 carbon atoms or a radical of ~ o ~ mule -Gl - CR. N ~ ~ 1 in which the symbol Gl represents a radi-cal divalent ren ~ erman-t ~ usqu ~ 35 a-tomes de carbon and the symbo-~ 1 represents one of the monovalent radicals which can be re-presented by the symbol ~, or even, when m = 2, a radical ; ~ de ~ ormule:
-G ~ -CR-N-: B2, ~ N-CP.-G'-CR_N-: B2) W ~
in which G 'has the meaning given above, ~ 2 represents one of the divalent radicals which can be represented by the symbol ~ and the two symbols ~ represent the termi-reasons of chain which can both be radicals of ~ ormule - M = CR - G ~ - CR0 or represent one the radical -N _ aR _ G '- C ~ 0 and the other a grouping -N ~ I2, the symbol represents a hyarogen atom or a monova- organic radical slow ren ~ ering up to 35 carbon atoms, the symbols Gl and R can together represent a divalent radical; w represents a number between 1 and 10 ~ the ~ quantities of reac-ti ~ s being implemented such that there is at least one presence - 30 a group - ~ R, as well as at least one or at most ten doubles ''',`': ~

.

- 2 -. ~, '.
... . ~.

1 ~ 35Z ~ 2 maleimide (I) bonds by -NlI2 group brought by the amino pose b.
In general, the average value of n is t in ~ érieure to 5, it is preferably between 1.7 and 4 `In a pre ~ erential way, the mean value ~ of m is between 1 and 5.
In ~ ormule I, the symbol .A can designate a radical alkylene having less than 13 carbon atoms, a phenyl radical lene, cyclohexylene, one of the radicals of ~ or ~ ules:
10 ~ C ~ [2) t ~ (CH2 ~ t ~ where t represents an integer from 1 to 3; the symbol A can also ¦ lem ~ nt represent a di ~ surrounding radical having 12 to 30 atoms de.I carbon t con ~ constituted by phenyl ~ ne or cyclohexylene radicals j; linked together by a simple essential link or by an atom ", 'i ~ OR inert group such as -0-, -S-, an alkylene group having 1 ~ 3 carbon atoms, -C0-, -S02-7 -NR ~ N = N-, -CO ~ H-, -C00- ~ -P () ~ 1-, -CONH-X-NHC0-, ~ ~ ~ ~ ~ ~ ~
~ ~ ~ v b - o ~

~ N ~ N ~ ~ - N ~ ~ / N 3 ~ 0 ~ ~ ~ S ~ ~ ~ \ SN
. ~ '''-.

. ., ~. .
'': ~ H

~ ~ N

;. .

- 3 -... .

. , 1 ~ 35209 ~ Z
where R1 represents a hydrogen atom, an ayan-t alkyl radical from 1 to 4 carbon atoms, phenyl or cyclohexyl, X represents feels an alkylene radical having less than 13 a ~ O ~ es of carbon.
In addition, the various phenylane or cyclohexylene radicals can be substituted by groups such as CH3, OCH3 or by a chlorine atom.
~ e symbol A can also represent a radical, containing up to 50 carbon atoms ~ and having from 3 to 5 free valences, said radical possibly being constituted by a no ~ naphthalene, pyridine or triazine, by a nucleus benzene can be substituted by a ~ three groups l methyl, or by several benzene nuclei linked together ¦ by an inert atom or group which may be one of those ¦ dlqucs above or -Nl-, -CH- ~ --1 () -~ nfin the symbol A can represent an alkyl radical or alkenyl, linear or branched can ren ~ ermer up to 1 ~
~ i carbon atoms, a cyc} oalkyl radical ren ~ ermant 5 or 6 a-to-. ~ my carbon in Le c ~ cle, a mono or bicyclic aryl radical, alkylaryl or aralkyl ren ~ ermant ~ usqu ~ with 18 carbon atoms, `` one of the radicals a monovalent radical consisting of a phenyl radical and a phenylane radical linked together by a simple valential bond i or by an atom or group ine ~ te such as -0- ~ -S-, a radical alkylene having 1 to 3 carbon atoms, -C0-, -S02 ~ R ~
-N = N-, CQNH-, -C00-, where R1 has the meaning indicated above-before. E ~ further ~ these various radicals can be substi-tuéspardes atoms, radicals or groups such as ~ ue ~, Cl, CI-I3, OCH3, OC2H5, .:

, '_ 4, _.
: .1 ~,.

52 ~ ~ 2 ~ CO - CH - OCOCH
OH, N02, -COOH ~ COCH3, -N \ 1 3 It follows from the foregoing that the malignant constituent imide of the process con ~ ormc ~ the inven-tion can be a polymaleimi-of dice ~ ini or a ren mixture ermanting maleimldes of ~ onctionali-tees di ~ férentes In the particular case where ~ a mixture is used comprising a monomaIéimide, the proportion of the latter in the mixture is, pre ~ erence, such that the number of functions I maleimide provided by the monomaleimide does not represent more than ; 10 30 ~ o of the total number of ~ maleimide anointings engaged in the reaction J ~ e maleimide of formula (I) can notalr ~ ent be u ~
¦ bis-imide, such as for example:
- N, N'-ethylene-bis-maleimide - N, N'-hexamethylene-bis-maleimide - N, N'-metaphenylene-bis-maleimide - N, N'-paraphenyl ~ ne ~ bis-maleimide ; - N, N'-4,4 ~, biphenylylene-bis-maleimide ~ - N, N'-4j4'-diphenylrnéthane-bis-maleimide ; 1 20 - N ~ N'-4 ~ 4'-diphenylé-ther-bis-maleimide - N ~ NI-4,4'-diphenylsul ~ ure-bis-maleimide - N ~ N'-4 ~ 4'-diphenyl ~ ul ~ one-bis-maleimide - N, N'-4,4'-dicyclohexylmethane-bis-maleimide - N ~ N'- ~ a'-4 ~ 4'-dimé-thyl ~ ne cyclohexane-bis-maleimide - N, NI-me-taxylyiene-bis-maleimide I - N ~ N'-paraxylylene-bis-maleimide ~ - N, N'-4 ~ 4'-aiphenyl-1,1 cyclohexane-bis-maleimide . ~ - N, N'- ~, 4'-diphenylmethane bis-citraconimide - N ~ NI-4,4! -diphenylmethane-bis-chloromaleimide - N, ~ '-4,4'-diphenyl-1,1 propane-bis-malé ~ nide - N ~ N'-4 ~ 4'-tripheny1-1,1,1 é-thane-bis-maleimide ......
! 5 ., I.
,.
.

~ ~ S ~ 0 4 ~
- N, N'-494'-triphenylmethane-bis-maleimide - N, ~ '-3,5-triazole ~ 1,2,4-bis-maleimide N, N 'dodecamethyl ~ ne-bis-maleimide - N, Nl-trimethyl-2,294-hexamethylene-bis-maleimide - bis (maleimido-2 é-thoxy) -192 ethane - bis (maleimido-3 propox ~) -1.3 propane - N, N'-4,4'benzophenone-bis-maleimide - N ~ NI-pyridinediyle-2 ~ 6 bis-maleimide - N, N'-naphthylene 1,5-bis-maleimide - N, N! -cyclohexylene-19 ~ -bis-maleimide - N, N'-methyl-5 phenylene-1,3 bis-maleimide - N, ~ '-me-thoxy-5-phenylene-1,3-bis maleimide These bis-irnides can be prepared by application of ~ methods described in the US patent 3,018,290 and the English patent 1,137,592 As specific examples of monomaleimides used we can indicate N-phenylmaleimideg N-phenyl-methyl-maleimide ~ N-phenylchloromalei ~ of, Np chloroph ~ nyl-maleimide, Np.methoxyphenyl-maleimide ~ Np methyIphenyl-maleimide, Np.nitrophenylmaleimide ~ Np.phenoxyphenyl-maleimide, Np.phenylaminophenylmaleimide, Np.phenoxy-carbonylphenylmaleimide, Np phenylcarbonylphenylmaleimide ~
evil ~ imido-1 acetoxysuccinimido-4 benzene, maleimido 4 acetoxysuccinimido-4 'diphenylmethane ~ maleimido-4 acetoxy-succinimido 4 'diphenyl ether, maleimido-4 acetamido-4!
diphenyl ether, maleimido-2 acetamido-6 pyridine, maleimi- -do-4 aceta ~ ido-4 'diphenylme-thane.
These mono ~ imides can be prepared by application of the method described in American patent 29444,536 for the N-arylmaleimide preparation .
',' . ,, '.

5 ~ ~ 4Z
As examples of maleimide (I), we can also cite oligomers with imide groups of ~ general formula:
~,.

CO ~ CO CO ~, CO CO ~ ~ 0 2 ~ ~

in which x represents a number ranging from approximately 0.1 to 2, the symbol R2 represents a divalent hydrocarbon radical, having from 1 to 8 carbon atoms, which is derived from an aldehyde or a ~ o ~ general ketone:
O = R2 in which the atom of ~ oxy ~ is not bonded ~ a carbon atom of the radical R2 ~ the s ~ mbole D represents a divalent organic radical having 2 c ~ 24 carbon atoms, don’t have valences ted by adjacent carbon atoms which are derived from a internal anhydride of ~ general formula:
~ CO ~
D ~ ~ o ~ a proportion of ~ at least about 60% of the D radicals represent . ~ a radical of ~ ormule:
. ~ H -- ~.
. . ~.
in which the symbol Y has the meaning given above demment ~ the radicals D é ~ entirely remaining which can in particular ~ represent an alkylene, cycloalco radical ~ l ~ ne, aromatic : i carbo- or heterocyclic. ~ a preparation of these oligomers c ~
imide groups is described dc ~ ns the German patent application n 2.2 ~ 0.874 ~ 7 -.
, 1 [) SZ
~ e compound (b) containing at least one grouping NH2 can be Arnmoniac or unemono or primary polyamine ~ (~ I2) mJ
~ e symbol ~ can represent a hydro atom ~ ene, a radical monovalent (B1), a divalent radical (~ 2) or a radical comprising l 3 to 5 free valences (~ 3) These radicals are chosen from j radlcaux mentioned above as part of the de ~ inition of I symbol A.
i ~ es compounds (C) containing at least one group - ~ - R can be mono or polyaldehydes as well as mono or polyketones such as compounds G1 CR0 ~ Gl (CR0) es G1 symbols which can be identical or di erent and the symbol R, when it does not represent an atom of hyaro gene, can represent selected monovalent radicals among:
a) aliphatic, linear or rami ~ iés radicals, l saturated or unsaturQs ren ~ e ~ mant up ~ 12 carbon atoms, ¦ b) cycloalkyl radicals containing 5, 6 or 7 carbon atoms j bone in the ring, phenyl or naphthyl radicals, c) heterocyclic mono- or polycyclic radicals, having at least one of atoms 0, N and S, such as, in particular, pyridyl, pyrimidinyl, ~ uryl, thienyl, benzo (b) radicals thienyl, indolyl, triazolyl, methylenedioxy-3, ~ phenyl, d) the radicals of ~ ormules Z ~ X1 ~ Z1 ~ and Z ~ X2 ~ Z1 ~ v in which the symbol Z represents a carbo- or hetero radical ~ 1 ' ~ monovalent rocyclic which can be chosen from the radicals ~
.! , ~ inis under b) and c) above X1 represents the valen ~ iel link or 1 an inert atom or group such as -0-, -S-, -NH-, -C00- ~
`1 ~ CONH-, -S02-, -N = N-, -N = N (~ 0) -, -C0-; X2 represents a group-ment ~ lcoylène ou alénylène, linear or rami ~ ié, ren ~ er ~ an-t jus-3o that 13 carbon atoms, Z1 represents an oarbo- or he- radical divalent terocyclic which can be chosen from radicals '''~.
l - 8 -- ~ sz ~ z divalent corresponds ~ nt to monovalent radicals de ~ inis under b) and c), and ~ is equal to 1 or 2.
e) the radicals of ~ ormules Z - X2 or X3 ~ Z1 'in the-which symbols Z ~ Z1 and X2 have the given meaning above and X3 represents an alkyl or alkenyl radical such that de ~ ini under a), ~) radicals as defined under a) ~ e) substituted by one or more atoms or groups such as ~, Cl, ~ r, OH, ~ 2 '-COOH, - ~ RO. ~ the symbols G1 and R can also form with the carbon atom linked to the nitrogen atom by the double bond its in ~ `ormule II a hydrocarbon cyclic radical ren ~ ermant

4 to 7 carbon atoms, said radical possibly being 8tre ~ ubstituted by one or more radicals X3 die ~ inis above or by one or more atoms or groups such as dé ~ inis ~ ous ~).
~ e symbol G1 can in ~ in represent a radlcal -CRO, R being de ~
finished as before. ~ e symbol G 'represents a radical di-are worth which can be chosen from the corresponding divalent radicals corresponding to 2 monovalent radicals represented by the symbol G1.
As examples of amines, the following can in particular be mentioned:
following monoamines:
methylamine ~ ethylamine ~ n.propylamine, isoprop ~ lamin, ¦ n ~ butylamino, isobutylamine ~ tertiobutylamine, n-amylamine, n-he-xylamine, cyclopropylamine, cyclobutylamine, 1-methyl cyclopen-tylamine, cyclohexylamine, isopropyl-3 cyclopentylamine, benzyl ~
amine, aniline, isoamylaniline, n-hexylaniline, aminob ~ phenyl, -i om p.anisidine, o ~ mpphenetidine ~ o ~ mp toluidine 9 ethylaniline, p.vinylaniline, dimethyl-3,4-aniline, 2-chloro butylamine, oOm.p.
i nitroaniline, ompOchloroaniline, o ~ .p ~ aminophéno], amino_2 i ~ uranium, 2-amino thioph ~ ne, 2-amino pyridine, amino - 4 pyridine ~
aminobiphenyl, ethanolamine, amino-1 propanol-2, amino-1 chloro ~ 3 propanol-2, amino-1 cyclohexanone-2, furyl-1 amino-2 ethanol, . ! :
: 'l'. ' ... . . . . . . . . .

1 ~ 52 ~ 4Z
1-phenyl-2-amino ethanol.
~ 'amine can also be a polyamineO Pa ~ i those Ci, there may be mentioned in particular: 4,4 'diamino dicyclohexylmethane, 1,4-diamino cyclohexane, 2,6-diamino pyridine, meta-nylane diamine, paraphenylane diamine ~ diamino-4,4 'diphen-nylmethane, bis (4-amino-phenyl) 2,2 propane, benzidine, oxy-of diamino-4,41 phenyl, the sul ~ ure of diamino-4,4 'phenyl, diamino-4,4 'diphenylsul ~ one, bis (4-aminophenyl) oxide methyl phosphine, bis (4-amino phenyl) phenylphosphine oxide ~
N, ~ l bis (4-amino phenyl) methylamine ~ diamino-1 ~ 5-na ~ htalene metaxylylene diarQine, paraxylylene diamine, bis (paraamino-phenyl) 1,1 phthalane, hexamethylene diamine, diamino-6,6 ' bipyrîdyle-2,2 ', diamino-4,4' benzophenone ~ diamino-4,4 'azo-benzenep le bi ~ (4-amlno phenyl) phenylmethane ~ bis (4-amino nyl) 1.1 cyclohexane, bis (4-amino-methyl- ~ phenyl) -1.1 cyclohexa-ne, bis (~ -aminophenyl) -2.5 oxadiazole-1,3,4, bis (p ~ amino-phenyl) -2.5 oxadiaæole-1,3,4p bis (m- ~ minophenyl) -2,5 thiazolo (4,5-d) thiazole, di (m-amino-phenyl) -5,5 'bis (1,3-oxadiazolyl, 4) - (2,2 '), bis (p-aminophtnyl) 4,4' bithiazole-2,2 'J le m-bis ~ p-aminophbnyl-4) thiasolyl-2 ~ benzene, bi ~ (m-aminophenyl) -2, 2 'bibenzimidazole-5.5', diamino-4 ~ 4 'benzanilide, diamino-4p4 'phenyl benzoate, N, N'-bis (4-amino benzoyl) p-phenylene diamine, bi ~ (m-aminophenyl) - ~, 5 phenyl-4 t ~ iazole-1,2,4, N, N '~ bis (p-aminobenzoyl) diamino-494' diphenylmethane, bis . p- (4-amino phenoxycarbonyl) benzene, bis p- ~ 4-amino phenoxy) ben ~ .ene, diamino-3,5 triazole-1,2,4, bis (amino 4 phenyl) -1,1 ph ~ enyl-1 ethane, bis (4-amino phenyl) -3.5 pyridine, triamino-1,2p4 benzene, triamino-1,3 ~ 5 benzene, t.riamino-2,4p6 toluè-.. nep triamino-2,4,6 trimethyl-1,3 ~ 5 benzene, triamino-1,3,7 naphthalene, triamino-294,4 'diphenyl, triamino-2,4,6 pyri-dine, triamino-2,4p4 'phenyl ether, triamino-2,4,4' ., '': ~

'. . . .

,.

1 ~ 52 ~ 4Z
diphenylmethane, 2,4,4'-triamino diphenylsulfone, 2-triamino 4,4 ~ benzophenone, triamino-2,4,4 'methyl-3 diphenyl ~ ethane ,, N ~ N ~ N-tri (4-amino phenyl) amine, tri (4-amino phenyl) methane, triamino-4,4 ~, 4 "phenyl orthophosphate, sorting oxide (friend -no-4 phenyl) pho ~ phine, triamino-3,5,4 'benzanilide, melamine, tetraamino-3,5,3 ~, 5 'benzophenoneS tee ~ raamino-1 9 2,4,5 benzene, tetraamino-2,3,6,7 naphthalene, diamino-3,3 'benzidine9 tetraamino-3,3 ', 4,4' phenyl oxide, t-traamino-3,3 ', 4,4' diphenylmethane, tetraamino-3,3 ~, 4 ~ 4'diphenylsulIone, bis (diamino-3,4 'phenyl) -3,5 pyridine, the oligom ~ res of: Eo ~ mule average:

R2 ~

in which ~ 2 and ~ pos. have the meaning given above These oligomers containing amino groups can be obtained according to coxmus processes such as those described in the French patents 1,430,977, 1,481 ~ 935 and 1,533,696.
By way of illustration of the carbonyl compounds ~ we can in particular oiter mono and polyaldehydes and mono- Oll poly-following tones:
Aldehydes: ethanal, propanal, dimethyl-2,2 propanal, ¦ hexanal ~ 2-ethyl butanal, heptanal, 2-propyl pentanal, 2-methyl octanal ~ dimethyl-2,6 heptanal, citral, decanal, methyl-6 propyl-2 hexanal ~ 2-isobutyl-4-methyl pentanal, dodecanal, cyclopropane-carbaldehyde, cyclobutanecarbaldehyde, cyclopentanecarbaldehyde, cyclohe ~ canecarbaldéhyde, cycloheptanecarbaldéhyde ~ cyclohexyl-; i é-thanal, phenyI-2 propanal, diphenylethanal, diphenylbromoethanal ~
3 phenyl p-toluylethanal, 2,3-diphenyl propanal, triph ~ nylethanal, triphenyl-2 ~ 2 ~ 3 propanal, phenylcyclohexylethanal, cinnamalcLehyde, .1.
~ 1 ~ diphenylcyclohexylethan ~ l, a-phenylcinnamicLue aldehyde ~ aldehyde ,.

.,, -.

~ 2 ~ ~ 2 a (p chlorophenyl) cinn ~ mi ~ eu, Inaphtyl-1) ethanal, furaldehyde-2, piperonal, pyridine carbaldehyde-2, pyridine carbaldehyde-4, 3-methyl-2-furaldehyde, dimethyl ~ 3 ~ 5 f ~ 2-aldehyde ~ benzyl-5 ~ u.ral-dehyde-2, dimethyl-4,6 pyrimidinecarbaldéhyde-2, indolecarbaldéhy-de-3, a-thiophene carbaldehyde-3, triazole-1,2 ~ 3 carbaldehyde-4 ~
.: 1,5-diphenyl-1,2,3-triazole-1,2,3 carbaldehyde-4, benzaldehyae, o- etp-chlorobenzaldehyde, o- and p- ~ luorobenzaldehyde 5 O- ~ m ~ and p-tolualdehyde, p-ethylbenzaldehyde, 2,4-dimethyl benzaldehyde ,.
p-tertiobutylbenzaldehyde, cumaldehyde ~ salicylaldehyde, p-hydroxy-: 10 benzaldehyde, protocatechaldehyde, ~ -resorcilaldehyde, o-vanillin, vanillin, veratraldehyde ~ o- and p-nitrobenzaldehyde, o- and p-ani.saldehyde, 3-ethoxy-4-hydroxybenzaldehyde, -trimetho ~ y-2 ~ 4.5 benzaldehyde ~ o- and p-phenylbenzaldehyde ~ (p-nitrophenyl) benzal-dehyde ~ p- (p-tolyl) benzaldehyde, o- and p-benzylbenzaldehyde, o- and. ......
p-phenoxybenzaldehyde ~ p-thiophenoxybenzaldehyde, p-cyclohexylben-.
zaldehyde, p-cyclopentylbenzaldehyde, a-naphthaldehyde, ~ naphthal-dehyde, 1-methyl-naphthaldehyde-4, 1,6-dimethyl-naphthaldehyde-4, hydroxy-1 naphthaldehyde ~ 4, dihydro ~ y-2,3 naphthaldehyde-1, ~ o ~ yl-4 diphenylsulfone, 4-formyl azobenzene, ~ 4-ormyl azoxybenzene, ~ 4-ormyl benzophenone, glyoxal, malonaldehyde, ni-tromalonaldehyde, æucclnaldehyde ~ dibromosuccinaldehyde ~ g ~ utaraldehyde ~ adlpalda-hyde ~ pimelaldehyde, suberaldehyde, azelaldehyde, sebacaldehyae, dodecanedial, cyclohe ~ ane-1,4-dihexanal, ~ umaraldéhyae, maléal-dehyde, citraconaldehyde, pentene-2 dial, hexene-2-dial, hexene-3 .),!,, dial ~ butynedial, (butadiene-1,3 yl) -5 heptene-2 dial, phthalal-~ dehyde ~ isophthalaldehyde ~ terephthalaldehyde, naphthalene dicar-.
.
baldehyde-1,2 ~ naphthalene dicarbaldéhgde-1,3, naphthalene dicarbal-dehyde-2,5, biphenyldicarbaldehyde-4,4 ~ biphenyldicarbaldehyde-2, 6 ~. p-terphenyledicarbaldehyde-2.2 ", m-terphenyledicarbaldehyde-2 ~
6 ', p-terphenyledicarbaldehyde-4.4 ", p-terphenyledicarbaldehyde 3, 3 ", o-terphenyledicarbaldehyde-2,6, methylane-5,5 'bi - salicylal-... . .
'' . ,. , ~.

11 ~ 352C ~ 4Z
dehyde, di ~ ormyl-4,4 'diphenyl ether, diformyl-4,4l diphenylamine, diformyl ~ 4,4 'diphenylthioether, diformyl-4,4' diphenylmethane, di ~ ormyl-4, ~ 'diphenylisopropane, difo ~ myl-4,4' diphenylsulfone, diformyl-4,4 'benzophenone, diformyl-4,4' azobenzene, diformyl-474 ' phenyl benzoate, 4,4-diformylazoxybenzene, 2,6-diformyl pyridine.
Ketones: acetone, methyl ethyl ketone, methyl n-propylce-tone, diethylketone, 2-methyl butanone- ~, hexanone-2 ~ hexanone-3, 2-methyl-pentanone-3, 4-methyl-pentanone-2, 2,2-dimethyl butanone-3, heptanone-2 methyl-2 hexanone-3, methyl-2 hexanone-5, ethyl-3 pentanone-2, dimethyl-2,4 pentanone- ~, ~, octanone-3, 2-methyl heptanone-5, 1a 4,5-dimethyl hexanone- ~, ~ 1 trimethyl-2 ~ 2, ~ pen-tanone-3, tetramethyl-3.3 ~ 4, ~ pen-tanone-2, i monochloracetone, monobromaceous-tone, 1-bromo methylethyl-ketone, phenylcyclopropyl ketone, dicyclobutyl ketone, ~! ~ methylcyclopentylketone ~ cyclohexylacetone, phenylcyclohexyl-~ ketone, cyclobutanone, 2-methyl cyclopentanone, cyclohe-¦ xanone, methyl-3 isopropylid ~ ne-6 cyclohexanone, methyl-3 cyclohexanone, dimethyl 4,4 cyclohexanone, l! iæobu-tyl-3 cyclo hexanone, 2,6-dichloro cyclohexanone, phenylacetone, ~ ¦ triphenyl-1,1,1 acetone, benzylacetone, dibenzylketone, ethyl (2-phenylethyl) ketone ~ di (3-phenylpropyl) ketone, acetophenone, propiophenone, iaobutyrophenone, pivalo-l phenone ~ Yalophenone, phenylbenzyl ketone ~ benzophenone, `^ bromoacetophenone, p-chlorobenzophenone, butyro-1 'naphthone, ,. (pyridyl-2) -1 butanone-1, chalcone, di (furyl-2) ketone, ~ uryl-2I ~ pyridyl-2) ketone, bis (5-methyl-2-thienyl) ketone, m ~ diacethyl-l benzene, p-diac ~ ty ~ benzeneg m-dibenzoylbenzene, p diben2oylben-zene. -~ es proportions of the compound renfe ~ mant at least one grou-i. pement ~ I2 and the compound ren ~ ermant at least one groupeme ~ t -IX

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

~ sz ~ z are chosen so as to ~ react area preferen-tially:
a) 1 mole of ammonia or an amine of ~ or ~ ule ~ (N ~ I2) ~
with at least one or at least m moles of a compound respectively carbonyl of fol ~ ule G1 CRO.
~) 1 mole of ammonia or a primary monoamine and one m + 1 mole of a primary polyamine B (NH2) m (m ~ 2) av 2 mole of a carbonyl compound Gl (CRO) 2 ~) 1 mole of a biprimary diamine B2 (NH2) 2 with at : minus 1 mole of a dicarbonyl compound Gl (CRO) 2 ~
We can according to a varian-te of the process ~ area react pre-alably the ren compound ~ ermant at least one group ~ rI2 and the co ~ posed containing at least one group - ~ e product r ~ sultant then includes the imine of ~ medium ormule ~ -N_ ~ P.-G) m and of ~ varied proportions - that little ~ ent at zero null ~ of the compound with group ~ I2 and / or the compound with group - ~ -R.
~ According to a variant of the process, we can also replace ~ -: ~ directly cer all of the compound containing at least one group ,. pement ~ 2 and the compound containing at least one group - ~ -R
for the corresponding imine ~ ~ N = CR - G) m ~
~ es imines whose preparation is well described in literature (organic chemistry tralté by ~ rignard, ~ ulletin of the Ahimic Society of ~ rance (1956) p 710) can be by example the following imines:
'~ - benzylidene aniline . - bis (parahydroxyphenylimino) -1,2 ethane - benzylid ~ naminobenzene - bis (~ -hydro ~ yé-thyliminomét ~ yl) -1,4 benæène - bis (a-pyridyliminomethyl) ~ benzene `- p-Benzylidenaminobenzo acid ~ that ~ 0 - a- ~ ur ~ urylidènamino-2 ethanol .,;.
. ~
-.

~ L ~ 52 ~
.
- bis (ben ~ ylidanamino-4 phenyl) methane ~ bis (4-benzylidenamino phenyl) -2.2 propane - bis (benzylidèna ~ ino-4 phenyl) sul ~ one - bis (4-benzylidenamino phenyl) ether - bis (benzylidenaminomethyl) -1.4 benzene - bis (salicylidènamino ~ 4 phenyl) methane - bis (salicylid ~ namino-4 phenyl) sul ~ one ~ bis (o-chlorobenzylidénino-4 phenyl) sul ~ one - bis (~ ethylene 3,4-dioxy-4-benzylidénino-phenyl) sul ~ one - bis (p-methoxybenzylidénino-4 phenyl) sul ~ one - bis (thenylidènamino- ~ phenyl) sul ~ one - bis (~ ur ~ urylidènamino-4 phenyl) methane - bis (~ u ~ furglid ~ namino-4 phenyl) sul ~ one - bls (naphthylmethylid ~ n ~ 4-nino-phenyl) methane - bis (benzylidènamino) -2,6 pyridine `11 - bis (salicyliden ~ mino) -2.6 pyridine - bis (~ ur ~ urylidènamino) -2,6 pyridine - bis (benzylidènamino) -6,6 'bipyridyle-2 ~ 2 ~ 1 - bis (heptylid ~ namino-4 phenyl) methane 1 - bis (p-phenylsulfonylben ~ ylid ~ namlno-4 phenyl) methane ; ¦ - bis (p-phenylazobenzylidanamino-4 phenyl) methane . ~ - bis ~ (pyridyl-2) m ~ thylid ~ namino-4 pheny ~ methane - bis (benzylidanamino) -1 ~ 4 ben ~ ene . ~ - bis (benzylidènamino) -1,3 benzene - '- bis (4-benzylidénino-pnényl) -3,5 pyridine j - ~ is (dimethyl-1 ~ 3 butylidanamino) -1.6 hexane - bis (dimethyl ~ butylideneamino-4 pheny) methane - bis (4-cyclohexylideneamino phenyl) ether - bis (dimethyl 1,3 butylidenaminomethyl) -1 ~ 4 benæ ~ ne - bis ~ pyridyl-2) -1 bv.tylidènamino-4 pheny ~ mé-thane . i.
. ~.

. .

. . . .

1qit5Z ~ 4Z
- bis ~ i (5-methyl-2-thienyl) 4-methylideneamino ~
methane - bis (4-methyl-benzylidenamino-4 phenyl) methane - bis (1-ethyl-benzylidenamino-4 phenyl) methane - bis (ben ~ yl-1 ethylidènamino ~ 4 phenyl ~ methane . - bis ~ dibenzylmethylidènamino-4 phenyl) methane - bis (1-methyl-phenyl-3-propylidenamino-4-phenyl) methane 1 - bis (1-benzyl-4-benzylidenamino phenyl) methane - bis (1-phenyl-4-benzylidenamino phenyl) methane - bis (1,3-diphenyl-2-propene-4-ylideno-phenyl) methane - bis ~ i (~ uryl-2) methylidene ~ mino-4 pheny ~ methane ~ - bis ~ ~ ur ~ 1-2) (2-pyridyl) methylidene mo-4 pheny ~
, .. 1 methane , l - polyimines derived from the condensation of tere-, ~ phtaldehyde with bis (amino- ~ phenyl) methane, ~ ¦ - polyimines of ~ ormule , 'i. '. '' ~ CH ~ ICH

CH2 ~} CH2--~ 'in which the value of ~ is between 0.1 and 2. ~ e la:;
`! l same way as it was specified above ~ about the male-i, imides, l! imine. engaged in the preparation of polymers : ................................................. ........................ ..
i mes to the invention may consist of a single product or dan ~ a mixture of ~ imines of mame ~ unctionnality or ~ unctionna-di erent lity. In the case of dt ~ mixture of: ~ imines, these , ^

~ ~ 52 ~ ~ Z
can, in the same way, derive from the same family of components ~
carbonylated (aldehyde or ketone) or, on the contrary, derived from compounds selected from the two aforementioned ~ amilles. We will not go out ~
no more than part of the in ~ ention using a polyimine does a derivative of a compound comprising at the time an aldehyde anointing and a ~ ketone anointing, such as for example pentanone-4 al-1 ~
In the preparation of polymers P con ~ ormes à l'inven-tion, the nature and the quantities of reaction are preferably chosen.
tifs so as to put in the presence of 1.8 to 5 double bonds maleimide for an imine double bond, present or potential.
~ es polymers according to ~ the invention can be presented ter under ~ elm of hardened resins (Rsj insoluble in solvents usual and with no no-table softening underneath from 1 ~ temperature from which they start ~ degrades der or sous ~ o ~ e of in-intermediate products, called prepolymers (P1), which generally have a softening point taken between 50 and 200 ~ and are soluble in various solvents, in particular polar solvents such as those which will be mentioned-~ és below in the presentation ~ the preparation of prepoly-mothers. These prepoly ~ eras (P1) are similar to the type A or B preconaensates well known in the chemistry of phenoplasts for example-ple Although it is possible, by bringing the reacti to Sufficiently high temperature (up to 350A) to obtain ; resins (Rs) directly it is advantageous to operate in two stages In a first stage, we can prepare the prepoly-mother (P1) which can be put into ~ elm in the state of solution, suspension, powder or even ~ the state of liquid mass.
~ es prepolymers can be prepared en masse in chauL-1 30 ~ ant until obtaining a ~ more or less homogeneous liquid i queux the mixture of reacti ~ s operating in one or two stages.
I.

... ...

~ 135204; ~ ~
When we react with rnaleimide, the derivative amine and the carbonyl compound, the reaction of llamine and COMpO-sé carbonylé cst generally su ~ fisissant exothermique, so that it there is ~ orma-tion of the prepolymer P1 without an external contribution of ¦ calories is required. Of course we can speed up the reaction tion by heating ~ age, for example up to 200C
~ A temp-rature can vary dc ~ ns d ~ fairly wide limits, in ~ anointing of the na-ture and the number of reacti ~ s present, but as a rule it is between 100 and 2003C ~ Is it advan-tageux to e ~ perform a prior homogenization of the mixture of reacti ~ s when these have a point of ~ wear relatively I high.
1, ~ A preparation of pr ~ polym ~ res can also be e ~ carried out by chau ~ age of reacti ~ s in a polar solvent such as dimethyl ~ ormamide9 N-methylpyrrolidone, dimethylacetami.de, ~ ¦ N-methylcaprolac-tame, diethyl ~ ormamide, N-acetylpyrrolidone ~
cresols at a temperature generally between 100C and `~
180C. ~ es prepol solutions ~ ners can be used such ¦ which for many jobs; we just t isolate the pre ~
polymer of its solution by precipitation ~ u using a diluent.
`! miscible with polar solvent and does not dissolve prepoly-m ~ re; as diluent, water or a organic solvent whose boiling point does not exceed no-120C table.
~ A preparation of prepolymers (P1) is not very advantageous sement be e ~ ectue in the presence of a polymeris inhibitor free radicals, such as hydroquinone or 2,4-dihydroxy azo-~ benzene. It is also possible to use other inhibitors such as `i those cited in the" ~ ncyclopedia o ~ Polymer Science and ~ echnolo-`30 gy" - Vol 7 p. 644 to 662.

.

-: I - 18 -~! . '.

52 ~ 4 ~
~ es prepolymers can be used ~ the state of mas-is fluid, a simple hot pour is sufficient for the ~ elm We can also, after re ~ stiffening and grinding, the utili-be in the form of powders which lend themselves remarkably to compression molding operations, possibly in the presence of charges in the form of powders, spheres, granules9 of . ~.
berries or glitter. In the form of suspensions or solv ~
; prepolymers can be used for the realization coatings and intermediate prepreg dlarticles whose ar-mature may consist of fibrous materials based on silicate or aluminum or zirconium oxide, carbon, graphite, boron, asbestos, or glass.
In another stage, the prepolymers can be trans ~ formed into resins (Rs) by heating ~ age up to ~ temperatures of the order of 350C, generally between 150 and 300C;
an additional elm can be done during the hardening, possibly under vacuum or superatmospheric pressure risk, these operations can also be consecutive. ~ e hardening can be done in the presence of an initiator of radical polymerization such as lauroyl peroxide, ltazobi-sisobutyronitrile, or an anionic polymerization catalyst such as diazabicyclooctane.
; ~ prepolymers (P1) and resins (Rs) can further include as adjuvants various compounds that will 8tre i specified These polymers and resins moai ~ ies also constitute 11 of the objects of the present invention. -1 ~
Pol ~ mothers modi ~ iés by inoorporation de_ om ~ osés aromati ~ es ~ Es polymers according to the invention can include, title of adju ~ ant, an aromatic compound (AR) possan-t of 2 benzene cycles, not sublimable at atmospheric pressure ~, : ~.

. . .

1 ~ 52 ~ ~
jus ~ u'à 250C and whose poin-t has ~ boiling is greater than 250C;
the addition of these aromatic compounds generally contributes to lower the softening point of the prepolymers. In these aromatic compounds, benzene rings can ~ o ~ sea des conaensé6 nuclei be connected to each other by a valential bond or by an inert atom or group such as ~ ue -0-, -C0-, -CH -, _IH_, -C (CH3) 2-? _IH ~ H2-C ~ 2 ~ ~ '~, -COO- ~ H2, -C00--CO-NH-, -S-, -S02- ~ -NH-, -N (~ H3) -, -N- ~ -N = N- 7 -N ~ -, ét ~ nt understood that in the same compound the global association of cycles can proceed from a combination of these di erent types dlassocia-tion. ~ es cycles ben ~ eni ~ ues can ~ be substi ~ ues by rad ~ inert cals such as -a ~ -aCH3 ~ Cl and -N02 ~ As examples which may be mentioned in particular isomeric terphenyls chlorinated diphenyls, phenyl oxide, naphthyl oxide ~ 2 ~ 2 ~, o-methoxyphenyl oxide, ben70phenone ~ trimethyl-2 ~ 5.4 benzophenone, p.phenylbengophenone, p- ~ luorobenzophenone, diphenylamine, diphenyl ~ e-thyla ~ ine ~ triphenylamine ~ l ~ a ~ o-benzene, 4,4-dimethyl ~ azobenzene, aæoxybenzene, diphen-nylmethane, diphenyl-1 ~ 1 ethane ~ diphenyl ~ propane ~ le triphenylmethane ~ diphenylsul ~ one, sul ~ ure de phen ~ le, le diphenyl-1 ~ 2 ethane, p-diphenoxybenzene ~ diphenyl-1,1 phthalan ~ 1,1-diphenyl cyclohexa ~ e, phenyl benzoate, ben ~ yle benzoate, p-nitrophenyl terephthalate, ; benzanilide. These aromatic adjuvants can be used up to proportions of the order of 10% by weight, reported ~ u total weight of reacti ~ s starting. ~ adjuvant (AR) can ~ be added to the prepolymer (P1), or introduced into the mixture at any time during its preparation.
tick ~
, _ 20 .,, -, .
.,.

~ 5ZC ~ Z
We can increase the mechanical properties of resins intended to undergo long-term thermal tests by the corporation of an aroic acid anhydride tri or tetracarboxy-lique It can be monoanhydrides such as ceu ~ de ~ `ormule general ~ CO ~

Z ~ \ CO /
in which the symbol Z can represent a group such as -CO ~ COOH
-COOH, ~
Among these monoanhydrides, we can mention more particularly trimellic anhydride, benzophenone acid antride -tricar-boxylic-3,4,4 '. It can also be d: ianhydrides such that pyromellic anhydride or a dianhydride of general formula the co ~ ~ ao : 'O t ~ I, - 1 ~ --o (X) , ~ co_ ~ ~ ~ o ~
; in which the symbol ~ can represent a divalent radical such as -N = ~ NN-, -CO- ~ -CO- ~ GO-. Among these ; dianhydrides, mention may more particularly be made of anhydrideazophthalic acid and the dianhydrides of m acids. or p.bis (dicar ~
boxy-3,4 benzoyl) benzene. ~ lanhydriae is a ~ antageusemen-t incorporated-; given to the prepolymer (P1) in quantities of the order of 1 to 5% by weight ~ related to the weight of the prepolyn ~ re.

! ~ 51 ~ e ~ 2LL16 ~ 3_ ~ _C ~: ~ 0: ~ tlon unsaturated monomers.
. ~. , _. . .
~ es resins according to the invention can also be modi ~ iées by the adjuctiong a ~ ant hardening, of a monomer (M) ; 30 other than a maleimide and comprising at least one ~ strongly . .
; ',, ,.,:,: ' ~ ~. . .

52 ~ ~ Z
- ~ I = C ~ polymerizable which can be of vinylic, maleic type, allylic and acrylic. The monomers (~ I) can have more sieurs groupings -CH = C ~ provided that the double links - sounds are not in the conjugate position In a monomeric mame, these gr ~ upements can appear to be of the same type or else ~ tre of di ~ erent types. We can use a monomer of ~ ormule don-born or a mixture of monomers ~ copolymerizable res ~
~ es monomers which can be used can be esters ~, ethers, hydrocarbons, substituted heterocyclic derivatives, organometallic or organometalloid compounds.
: Among the esters, we can mention the esters of viny-allyl, methallyl, chloro-1 allyl, crotyle, iso-propenyl, cinnamyl, which are derived from mono- or polycarbo-saturated or unsaturated or aromatic aliphatic xylics such as ~ or-: mique ~ acetique, propionigue, butyrique, oxalique, malonique, succinic, adipic, sebacic ~ acrylic, m ~ thacrylic, phenyl-.
acrylic, crotonic, maleic, ~ u ~ itaconic ariquet, citraconi-that ~ tétrahgdrophtalique ~ acétglène-dicarboxylique, benzo ~ que, ¦ phenylacetic, or-thophthalic9 terephthalic, isophthalic, as well that esters of non-polymerizable alcohols such as esters - 'methyl, isopropyl, 2-ethyl hexyl, benzyl 7 which derive polymerizable acids such as those mentioned above ~ avan-t. ~ es typical examples of esters are vinyl acetate, acylate and methyl methacrylate, vinyl methacrylate, allyle7 maleate ~ allyl umarate, allyl phthalate, allyl malonate, triallylic trimellate.
As ethers which can be used, mention may be made of ether ~ -vinyl oxide and dlallyl ~ allyl oxide, methal oxide-lyle, li allyl and crotyle oxyae, vinYl oxide and phenyl i Among the substituted heterocyclic derivatives, we can !
.

, .
... .

1 ~ 52 ~ Z
mention vinylpyridines, N-vinylpyrrolidone, N-vinyl-carbazole, allyl isocyanurate, vinyltetrahydro ~ uranne, vinyldibenzofuranne9 allyloxytétrahyaro ~ uranne, N-allylcapro-lactam Hydrocarbons such as styrene can be used, alphamethylstyrene, vinylcyclohexane, vinyl ~ 4 cyclohexene, divi-nylbenzene, divinylcyclohexane, diallylbenzene, vinyltoluene.
Among the organometallic and organometallic derivatives ~ -monomers, mention should be made in particular of those which contain have one or more phosphorus, boron or silicon atoms They can be silanes or siloxanes, phosphines, oxides or sul ~ ures of phosphines, phosphates, phosphites, phosphonates, boranes, orthoborates, boronates ~ boro-~ oles ~ of borazoles, of phosphazenes As examples, we may mention vinyloxytrimed-thylsilane, 1,3-diallyl-tetra-methyldisiloxane7 o ~ yde of allyldimethylphosphine, orthophos ~
allyl phate, allyl methylphosphonate, paravinylpheny ~ -methyl boronate, triallylborazole, triallylboroxole, triallyltrichlorophosphazene, allyl phosphate, allyl-~; 20 allyl phosphonate.
~ n addition, the monomers of the di ~ erent categories envisaged above can comprise ~ er halog ~ nes atoms, mainly chlorine or ~ luor or functional groups such as an alcoholic or phenolic hydroxyl group 9 nyle, aldehyde or ketone, amido, cyano.
; As examples of monomers (M) having such substituents include allyloxyethanol, p-allylo ~ ypheno ', ; p-cyanostyrene, ac ~ ylamide, N-methylacrylamide, N ~ al-; lylacrylamide ~ N-methylolacrylamide, methylvinyl ketone, methylallyl ketone, acrylonitrile, methylacrylonitrile, ~ p-chlorostyrene, p-fluorostyrene.
..
~ '1 3 -.
'' ~ s20 ~ 2 ~ e monomer (M) can be added to the prepol ~ mother ~
or introduced into the mixture at any time during its preparation ~ a quantity used is chosen so that it ~ l represents less than 50%, preferably from 5 to 40, ~ of the weight of ¦ prepolymer (P1) or the total weight of the initial reactants ~ e hardening of the prepolymer modified by the monomer (riI) can be done under the conditions provided for hardening the unmodified prepolymer Pol ~ mothers m dl ~ iés ~ ar ad1ction of a pol ~ es-te-r unsaturé
, ~ es resins according to the invention can also be modified trusted by the addition, before Aurclssement, of an unsaturated polyester re.
~ es unsaturated polyesters are all utlisables procluits well known They are usually prepared by polycondensa-tion of polycarboxylic derivatives and polyols; by poly- derivatives carboxylic ~ means acids, esters of alcohols in ~ é-- laughers, acid chlorides and possibly anhydrides. Among the monomers subjected to polycondensation, at least one ~ contains unsaturation of olé type ~ inique. In the framework of the ; 20 present invention, on ~ ise essen-tiellemen t polye ~ ters insa-turés for which the unsaturated polycarboxylic derivatives of start are diacids or dia ~ ydrides having a double bond ! of olé type ~ inique in a ~ ~ ti-tre example, dicar derivatives-boxylics can be maleic, chloromaleic, itaconi-que, ci-traconique, aconi-tique, pyrocinchonique ~ ~ umarique, chlo-rendique ~ endométhylènetétrahydrophtalique ~ tétrahydrophtalique ~
é-th ~ lmaleique, ~ uccinique, sébacique, phtalique, isophtalique9 adi-spades, hexahydrophthalic Pa ~ mi the most popular polyols ~ nen ~
used are ethylene glycol, propylene glycol, diethyl ~ -~ 30 ne glycol ~ triethyl ~ ne glycol, neopentylglycol, tetra-! ~
,: 1.
~ ~

..

11 ~ 5Z ~:) 42 ethylane glycol, butylene glycolg dipropylane glycol9 le glycerol, trimethylol-propane, pentaerythry-tol, sorbi-tol ~ bis ~ hydroxymethyl) -3.3 cyclohexene.
~ th term "unsaturated polyester" also includes solu-tions of the polycondensates described above in a monomer (~ I ') which is able to copolymerize with them. These monomers are also well known in the polyester art and, at least There are examples of styrene, alphamethylstyrene, vinyltoluane, p (alphamethylvinyl) benzophenone, divinyl-- 10 benzene, vinyl oxide and 2-chloroethyl, the ~ -vinylpyrro-lidone ~ 2-vinyl pyridine ~ indene, a ~ methyl rylate, methyl methacrylate, acrylamide, ~ Jt.butylacrylamide, acrylonitrile, hexahydrotriacrylo-1,3 ~ 5-s-triazine, phtala-allyl te, ~ allyl umarate t allyl cyanurate, phos-dtallyle phate, diethyllcarbonate of diethyl ~ ne glycol, allyl lactate, malonate d! .allyle, tricarballylate d.'al-lyle, allyl trimesate, allyl trimellate. ~ orsqulil is used, the monomer (l ~ .It) generally represents 10 ~ to ~ o . the weight of the unsaturated polyester solution ~ A preparation of unsaturated polyesters can be ef ~ ec-. killed by application of known methods; about it, we can.
by e ~ example see the work of KI ~ KO ~ HI, ~ R:. Encyclopedia 1 of Chemical '~ echnology - 2nd edition - Volume 20 ~ es modalities concerning the introduction and the quant:
. .. ~ unsaturated polyester tees as well as hardening in resins are identical to those which were mentioned above in the part of the addition of a monom ~ re (~ iI).
~ 'Inc.orporation of a monomer (M) or a polyester insa-:
turé leads to aurcissab ~ es mixtures which can be used .1 30 as impregnation resins; after addition of fillers, one. ~ l can use them as coating masses.

. .

. I. .
. I,.
`, ''''',:.:. . . '..''': ~ '' ~ z ~ z Pol ~ mothers modi ~ iés by adding pol ~ condensa-t imines- ~ ol ~
isoc ~ anate We can also prepare the imine beforehand from the reacti ~ s (b) and (c) or directly use the imine of ~ average formula: ~ ~ N = CR - G) m and ~ area react this imine with a die ~ aut of aromatic polyisocyanate of ~ ormule ~ (~ CO) s ~
~ e mixture obtained which contains the excess cL'imine and a polycondensate iminepolyisocyanate, the nature of which will be specified below then reacted with maleimide (a) so as to ~ ¦ 10 obtain new polymers constituting an object of the present ! invention .-. ~ .imine that we ~ react with polyisocyana-te is chosen pal ~ i les ir ~ ines ~ ~ N - CR - G) m previously de ~ i-nies, the various symbols having the following meanings:
. ~ - m represents a number at least equal to 1 - B represents an organic radical of valence m, ren : closing up to 50 carbon atoms, the free valences of the radi-: ~
. cal ~ being linked through one or more atoms . of carbon belonging to an aromatic cyc} e, to groups -N = CR-G ~:
- G represents an organic radical ~ monovalent eu ~ 1 ren ~ e ~ mant up to 35 ato ~ es of carbon, the free valence of the radi-cal G1 being carried by a carbon atom belonging to a ring .- aroma.
1 ~
.G ~ epr ~ also feels a radical of ~ o ~ mule -G ~ -CR = N- ~ l I in which the symbol Gt represents a divalent radical renler-.
; mant up to 35 carbon atoms in which the two valences , 1 '.
`1 free are carried by two carbon atoms belonging ~ one ~! aromatic cycle ~ ~ 1 with the same meaning ~ ication as ~ or represents ~ 0 when m = 2 a radical of ~ or ~ ule:
~. -G ~ -CR-N- ~ 2 ~ N = CR-G'- ~ R = N-B2 ~ w .j, 1 ' ~ ', "

~ 0 5 ~ ~ ~ Z
in which G 'has the meaning given above, B2 re-has one of the divalent radicals can be represented by the symbol 3t ~, which represents a termination of string ~ does not rep ~ ^ é-one of the following two radicals:
R-G'-CX0 l - R represents a hydrogen atom or an organic radical Mon monovalent pic containing up to 35 carbon atoms ~ ~ es ; l symbols G1 and R can together represent a divalent radical.
- w represents a number between 1 and 10.
These imines which can be aromatic aldimines or aroma timines were previously from ~ inies and lists have been given.
~ es polyisocyanates that we! have to react to ~ ec l ~ s imines have isocyanate groups attached to an atom ~ ¦ of carbon belonging to an aromatic cycle. These polyisocyanates I have for ~ ormule:
E (~ 0) in which s is at least equal to 2 and o ~ ~ represent a valence radical s ren ~ ermant up to ~ 35 carbon atoms. ~ i represents ~ insi:
- a phenylene radical optionally substituted by a halogen atom or by an alkyl or alkyloxy group having 1 to 4 carbon atoms, - a radical consisting of a sequence of several phenylene radicals. Phenylane radicals which can optionally be substituted by a halogen atom, an alkyl group .
or alkyloxy having 1 to 4 carbon atoms. ~ radicals I phenylene are linked to them by the valence bond or by a , ~ 30 inert atom or grovpemellt such as:
-O- ~ -S-, a straight alkylene group or rami ~ i ~ '3 having ~ 1` ~,. . .

. ... ', , ~ L ~ 5Z ~ 3 ~ LZ

1 to 3 carbon atoms, -CO ~ 2-, -NI ~ CO ~
- POX1-, -CO ~ X NHCO-~ 1 1 - C ~
\ J ~

the radical R1 represents a hydrogen atom or u ~ alkyl radical I having from 1 to 4 carbon atoms, phenyl or cyclohexyl; X represents I feel an alkylene radical having less than 13 carbon atoms.
- an aromatic radical, consisting of a sequence of several phenylene radicals optionally substituted by a halogen atom or by an alkyl or alkyloxy group ayan- ~ from 1 to 4 carbon atoms, phenylene radicals ~ or ~ ant between them an orthocondensed or ortho and pericondensed system ¦ As a pre ~ essential polyisocyanate is a diisocya-¦ nate comprising from 1 to 2 phenylene groups e ~ entirely subs-l labeled with a chlorine atom or a methyl or methoxy group ¦ and linked according to the previous definitions. Polyarylene polyisocyanate obtained from the aniline condensation products - ~ ormaldehyde and a ~ ant is also advantageously used.
~ medium ormule NCO NCO NCO

~ H2 ~ 2 at -,. \
a being a number between 0.1 and 2.
- ~ j By ~ i polyisoc ~ usable anates include ; ''', following diisocyanates if - diisocyanato-1 t 4 benzene . ~.

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

~ ~ 52 ~ ~ Z

- 2,4 or 2,6 diisocyanato tolu ~ ne - 4,4 'diphenyl diisocyanato - diisocyanato-4,4 'dichloro-3, ~' diphenyl - diisocyana ~ o-4 ~ 4 'dimethoxy-3,3' diphenyl , - 4,4'-diisocyanato-dimethyl-3,3l diphenyl -I - diisocyanato-4, ~ 'diphenylme-thane - 4,4 'diisocyanato diphenyl ether - diisocyanato-4 ~ 4 'dimethyl-3,3' diphenylmethane - diisocyanato-1,5 naph-tal ~ ne - diisocyanato-3,3 'dimethyl-4,4' uretidine dione.
I We can also ~ ent utiiiser polyisocyana-tes of function-`tionality greater than 2. Among these compounds, mention will be made of products for adding diisocyanates to polyols having at least trols reacti ~ s groups such as glycerin, sucrose, -. . glucose, sorbitol ~ pentaerytrol ~ ma ~ nitol, dulci-~; tol, trimethylolpropane Mention will also be made of triisocyanato-2,4,4 'diphenyl-ether, triisocyanato-4,4 ', 4 "triph ~ nylmethane, and poly-aryiene polyisocyanate already mentioned ; ~ 20 As it has already been said polyisocyanate est.admis in d ~ aut compared to the imine present. For this purpose k represents-the report:.
number of imine groupings number of isocyanate groups is greater than 0.5 and pre ~ erence between 0.5 and 5. ~ a -reaction is e ~ ected by heating the reacti ~ s to a temperature-re greater than 180C and pre ~ erence between 220 and ; 2800a, jus ~ u '~ cessation of the release of carbon dioxide.
~! ~ es polymers (P1) moai ~ iés by adding polycon- ~ -densate imines-isocyanates are obtained by ~ aisant react imine i ren ~ ermant polycondensa-t i ~ ines-isocyanate ~ with maleimide.
,. , . I,.

, 1 ~ 5 ~ 0 ~ 2 ~ e process is identical to that previously described and concer-~ ', nant the reaction between imines and maleimide.
~ es polymers modi ~ ies by adding the polycondensate imine- polyisocyanate compared to unmodified polymers behavior further improved in thermal behavior. This di ~ é-behavior, for example, is sensitive to the level of value of the flexural strength, Polymers of an entirely new type have been pre-prepared in the context of the present invention. These polymers res-result from the reaction at a temperature above 180 between an imine and / or a polyimine with an aromatic polyisocyanate ¦ tick of functionality equal to or greater than 2. ~ a nature of reacti ~ s is that which has been specified beforehand. ~ es poly-pools resulting from imine-polyisocyc ~ na-te condensation are completed when the dega ~ ement of carbon dioxide ceases. At this time one of the reagents has been completely transmed and the other reagent ! in e ~ cente relative to the stoichiometry of the reaction ¦ condensation - can be separated from the polymer by any known means ¦ for example by distillationO ~ es polymers resulting from the imine-polyisocyanate condensation is another object of '1 the present in ~ ention, 'A ~ in reaching ~ molecular weight polymers 'high, lor, s of imine-polyisoc condensation ~ ana-te the report , ~ k, r, represented by:

k number of imine groups -; there number of groups ~ isocyanates , is between 0.2 and 5 and from pre ~ ercnce between 0, ~ and 0.6, As a special case of the polymer which has just ~ die ~ ini ~ we will mention more particularly the reaction product '~, 30 tion between vne imine mono ~ onc-tional ~ - N - Cl ~ - ~ avac un .,.

, - ~ 0 -l ~ SZ ~ 4 ~ 2 diisocyanate E (M ~ 0) 2, It has been shown that a poly is obtained mother essentially constitutes by the repetition of moti ~ s of ~ o ~ nule: _ ~.
1 _ - ~ - N ~
l ~ - ~ - R

I. ~ G.
~ es polymers obtained by reaction between an imine and ~
or a polyimine and a polyisocyanate aror. ~ atique de ~ onctionnali-equal or greater tee ~ 2, little ~ ent-be incorporated into reacti ~ s used to pxeprepare the prepolymer ~ re P1 de ~ ini prea] .ably, These polymers can also be incorporated into prepolymer P1 ~ before hardening ~ As a general rule the quc ~ ntite of polymare imi-¦ ne-polyisocyanate introduced into the P1 polymer or polymer P is at most equal to 50 ~ of the total mass of all of the reacti ~ s and is pre ~ erential ~ ment between 10 and 30 ~ 0, ~ prepolymers (P1) and polymers P incorporated by incorporation tion before hardening of an imine-polyisocyanate polymer, cons-constitute another object of the present invention, ~ es polymers obtained by reaction between an imine and / or I 20 a polyimine and an aromatic polyisocyanate of ~ unctionnality I equal to or greater than 2 can be mixed with a maleimide ~ ~ a) -this as in ~ previously, By heating ~ age of this mixture ! above 100a we get prepolymers and polymers ~ which constitute another object of the present invention, ~ years 'l previous mixtures the proportion of the imine-isocyanate polymer '' corresponds to a maximum of 50% of all the reacti ~ s and is in I ~ generally between 5 and 30%, ~ è7 ~ e ~ ~, 1 ~ "
, ~. .
1 30 It is also possible to incorporate into the reactants:
i .
11.

~ s ~ z polymer P1 before hardening a polyurethane elastomer ; in order to con ~ er to the articles ob-held from the composition high impact resistance Ce; ~ te property called resilience is particularly desirable both ~ u level of machining articles as of their placement.
~ polyurethane elastomers thannes used as complementary constituent in the compositions co ~ elms at llin-vention are polymers ~ ormed by reaction of ~ a diisocyanate in excess with a polymer comprising hydroxyl groups at the end of the chain, then reaction of the macrodiisocyanate thus ~ or-mé with a coupling agent.
~ e hydroxylei polymer can be a polyester] inéaire or a polyether.
In the case where ~ we use a polyester-ureth ~ nne, we ; chooses pre ~ erence a starting polyester whose molar mass ; 1 cl ~ area is between 1 ~ 000 and 12 ~ 000. This polyester a, ~ -hydroxylé can be prepared from ~ a dicarboxylic aciae l and diun diol, using an amount of reai ~ s such that the oh xput ~ is greater than ~ 1 and pre ~ erence included between ~ 20 1,1 and 2.
¦ As examples of dicarboxylic acids, there may be mentioned in particular, aliphatic acids ~ such as succinic acids that ~ glutaric, adipic, pimelic, suberic, a ~ éla ~ que, séba-cique ~ malé ~ que, ~ umarique, mé ~ hyliminodi ~ c ~ -tigue ~ dim ~ hylamino-3 hexanedio ~ that ~ cyclic acids ~ alkane dicarboxylic such as cyclichexane dicarbo acid ~ lique-19 ~ dimethyl ~ mino-3 cyclopenta-do not dicarboxyli ~ ue 1,2, aromatic diacids such as phthalic acids, naphthalene dicarboxJ-lique-1,5 acid, pyrimidine or imidazole dicarboxylic acids.
As examples of diols, we can cite ethanediol-192, ,.
,, l _ 32 - ~
. .
.

~ ~ 5 ~ ~ 4Z
propanediols-19 2 and -1.3, butanediols-1,2 -2, ~ and -1, ~, pentanediol-1,5, hexanediol-1,6 ~ decanediol-1,10, dimethyl-2,2 propanediol-1,3, diethyl 2,2 propanediol-1,3, butenediol, butynediol, ltethyldiethanolamine. We can also Lement use cor ~ me diols of polyethers ~ -dihydroxylés such that the poly (oxyalkylene ~ glycols mentioned below by way of of polyethers illustration.
It is naturally possible to prepare the hydroxylated polyester at from a mixture of diacids and / or a mixture of diols. We can also use a mixture dioljpolyol ren ~ errnant 3 to 8 OH groups per molecule, the said polyol being able to provide than 10% of the total number of -OH groups. This polyol can by . example be trimethylolpropane, pentaerythritol,. saccha-. roee, sorbitol ~
; ~ n regarding the conditions in ~ the ~ luelles may:
. s.e ~ perform the diacid / diol condensation, we can re.port ~ ~:
the work of KORSS ~ L ~ K and VI ~ OG ~ ADO ~ A "Polyesters" (Pergamon Press 1965).
: ~ e polyether a, ~ -dihydroxylé can be chosen from:
. ~. . ...........
poly (oxyalkylene) glycols ~ such as poly (oxy ~ thylene) glycols, poly ~ oxypropylene) glycols, poly (oxy-) block copolymers ethylane) -poly (oxypropylene), poly (oxytetramethylene) glycols, obtained by polymerization of tetrahydro ~ urane, poly (oxybu-I tylene) ~ lycols obtained from 1,2-epoxy and / or 2,3-epoxy buta-ne, poly (o ~ yethylene) - (polyoxybutylene) block copolymers 1 and possibly poly (oxyprop ~ lene) You can also use . ~! despolyetherscontenan-t of aæote, prepared ~ from oxide ethylene, propylene oxide and / or butylene oxide and a nitrogen compound such as ethylene di ~ mine, benzene sul ~ onamide, N-methyldiethanolamine, 2-aminoethylethanol ~ mineO We use It is preferably in the invention of polyethers whose mass ,. ..

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

5 ~ ~ ~ 2 molecular is between approximately 1,000 and 12,000.
It should be understood that polyurethane can derive a single hydroxylated polymer or a rnélan ~ e comprising several dihydro ~ ylés polymers such as those described above.
In the preparation of the inte ~ medial macrodiisocyanate, NCO
we use a diisocyana-te in quantity such as the ratio ~~
is greater than 1 and pre ~ erence included between 1.1 and 6.
~ - ~ e diisocyanate can in particular be chosen from ~
I following corlpos: ts diisocyanato-1,6 hexane, diisocyana-1 10 to-2a4 toluene, 2,6-diisocyanato toluene, 1,3-diisocyanato and -1.4 benzene, bis (4-isocyanato-cyclohe ~ 2.2 propane, bis (isocyana-to-4 cyclohexyl) -methane, diisocyanato-1,5 pen; tane ~ diisocyana-to-1,4 cyclohexane, bis (isocyana-to-4 phenyl) methane, bis (isocyanato- ~ phenyl) -2 ~ 2 propane, dii.so-. cyana-to-1,5 naphthal ~ ne, dim-thyl-3,3'diisocyana-to- ~, 4 'bi-phenyl, bis (3-methyl-4-isocyanato-phenyl) methane.
¦ We can naturally use a polyurethane prapar ¦ from a single diisocyana-te or a mixture of several diiso-cyanates. In addition, a small proportion represented can be used.
for example up to 10 ~ 0 of the total number of groupings -NCO- of a compound ren ~ ermant of 3 to 8 groupemen ~ -NCO per molé
ass ~ es reaction conditions of the diisocyanate with the poly-hydroxylated mother are described for example in the work of JH
1 SAU ~ DERS and KC ~ RISCH "Polgurethanne Chemistry and '~ echnolo ~ y"
I'm leaving. 1 ~ 1962.
~! coupling agent can a ~ suitably be chosen among the following products: l! water, hydrazine9 h ~ -draziae ami-no-acetic, a diamine, a diol. ~ or ~ that we use a diol, we 1 30 can choose this pa ~ mi the diols quoted previously in the ¦ part of the preparation of the pol ~ ester. We can also use - ~ 4 ~

~ 52 ~ 9 ~ 2 a mixture ren ~ ermant a diol and a compound containing 3 ~ 8 grou-OH pements per molecule7 such as one of those described above ~ when the coupling agent is a diamine, this one can ~ be, for examplej ethylene diamine, diamino ~
propane or one of the diamines mentioned above.
~ 'use of coupling agent ~ lge in the preparation of polyester - and polyetherurethane is described in the book by SAUND ~ S preci-ty ~ ch VI section IV. In a general way, the quantity of coupling agent is chosen so as to react with all the groups - ~ CO of the macrodiisocyanate.
Generally speaking, we prefer to use in the -vention of polyurethanes derived from a polyester.
Dan ~ the co ~ positions conform ~ the inven-tion 7 and com-taking a polyurethane elastomer, we generally choose quantities of elastomer ~ of polyurethanes as they correspond-lay ~ 5 to 50, 'o and pre ~ erence to 5 and 20% of the total mass reactions.
~ es compositions according to the invention are prepared in making an intimate mixture of the compounds a, b, c (or a and produced reaction b and c) and polyurethane Depending on the physical characteristics of the ingredients, this operation can consist ~ apply the usual -tec ~ mics ¦ for the mixture of solids ~ inely diviscs, or else to ef ~ perform ? l a solution or a suspension of one of the constituents of the mixture in the other maintained ~ was the liquid, possibly in a solvent such as cresol, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, chlorobenzene.
! The mixture can then be heated for several i minutes ~ temperature of the order of 50 ~ at 180C and sufficient for the ob ~ ention of a homogeneous liquid when the mel ~ nge of depa ~ t ~ contains a stressed phase.

, 1 ~ i,.
; _ 35 _ `! '' ''',''', ~, '....

~ s ~
We can also add ~ the co ~ position co ~ bearing an elastom ~ re polyurethane, an aromatic compound possan ~
. 2 to 4 benzene rings9 not sublimable at atmospheric pressure i spherical up to 250C and with a higher boiling point at 250C These compounds are those which have been defined in advance.

i Pol ~ nères modified by adionct = ~

It can also be incorporated into reacts or prepolymers.
res P1.before curing an epoxy resin in the purpose of lowering 1 the softening point of the prepolymers P1, and of ~ aciliter . ~ 1 10 thus industrial operations such as molding by cou-I ed or by compression ., ~. the expression "epoxy resin" is currently used in its usual sense, it is dLre that it desi ~ ne a compound rcn ~ roaming more than one WC grouping ~ says it composed - which depending on the proportion and the nature of the starting reacti ~ s occurs ~ J in the form of a more or less viscous liquid or a solid of .j point of ~ usion relatively low - being likely to be irreversibly hardened into insoluble and in ~ usible solid material ~ all the usual epoxy resins can be used 1 20 in the compositions con ~ elms to the invention. We can thus use .j read polyglycid esters ~ liques that can be obtained by reaction of u ~ polycarbo ~ ylic acid on epichlorohydrin, or the ¦ glycerin dichlorohydrin in the presence of an alkali ~ e such pol ~ glycidyl esters little ~ ent derive from dicarbo acids:
! . ~ aliphatic yliques - for example oxalic acid, acid suc-kinic, glutaric acid, adipic acid, pimelic acid7 suberic acid, azé'lque acid, sebacic acid, or acid linole'lque, dimerized or trimerized - and dicarboxylic acids I aromatics such as phthalic acid, isophthalic acid ~ a-.
terephthalic acid, naphthalene acid ~ dicarboxylic-2? 6, acid :, . , Z
2,2 'diphenyldicarboxylic, bis (carboxyl ~ 4 phenyl) ethcr of ethylene glycol.
; In a more specific way such polyglycidyl esters are, for example, diglycidyl adipate and those of diglycidyl esters which correspond to the average formula:
CH ~ - ~ HC ~ 2 - (OOa ~ lt-C00- ~ X2 ~ HOH- ~ 2) q-OOa_GIl-CO0- ~ l2-C ~ - CH2 ~ in which G "represents a divalent hydrocarbon radical, such that a phenylene group, and q represents a positi ~ integer or fractional.
Other examples of epoxy resins are ~ poly- ethers glycidyls which can be obtained by the interaction of an alcohol divalent or polyvalent ~ and epichlorohydrin or a subs ~ ance unaiogue (e.g. dichlorl ~ ydrine glycerin) in . of alkaline conditions or, ~ alternatively, in the presence an acid catalyst with subsequent treatment with a ¦ alkali These compounds can be derived from diols or polyols such as ethylene glycol ~ ledié-thylène-glycol, triéthylène-glycol, propane-diol-1,2, propane-diol-1,3, butane-diol-1,4 ~ 1,5-pentane-diol, 1,6-hexane-diol, cycloalkanes polyhydroxy, hexane-triol-2,4 ~ 6 ~ glycerin or N-aryl ~ dialkanolamines ~ such as N-phenyl-diethanolamine and derivative, : 1 of pre ~ erence, of divalent or polyvalent phenols, such as resorcinol, ca-techol, hydroquinone ~ dihyarox ~ -1.4 naphthalene-i ne ~ 1,5 dihydroxy na ~ htal ~ ne, bis (hydroxy ~ 4 phenyl) methane, tetrahydroxyph ~ nyl-1,1 ~ 2,2 ethane, bis (4-hydroxyphenyl) methyl-phenylmethane ~ bis (4-hydroxyphenyl) tolyl-methanes, ~ i:
dihydroxy-4,4 'diphenyl, bis (4-hydroxyphenyl) sul ~ one and ~ in particular, bis (4-hydroxyphenyl) 2,2 propane or the products vl ~ 0 condensation dlun phenol and an aldehyde.
'1' .
,.
. ~. . . .....

~ s2i ~ 2 We can, in a similar way, also use - amino-polyepoxides such as those that o ~ ob-hold9 for example, by dehydrohalogenation of epihalohydrin reaction products i and primary or di-secondary amines, such as aniline, n-butylamine, bis (4-amino phenyl ~ methane or bis (methyl-4-aminophenyl) methane and the epoxy resins obtained by epoæy-donation of cyclic and acyclic polyolefins such as vinyl cyclohexene dioxide, limonene dioxide, dioxide dicyclopentadiene, 3,4-epoxy dihydro glycidyl ether 1 10 dicyclo-pentadienyl, epoxy-3 ', 4' cyclohexane carboxylate ! 3,4-epoxy cyclohexyl-methyl and its derivative ~ 6,6'-dimethyl, the biri (~ poxy-3,4 oyclohexane) ethyl carboxyla-ne glycol, a-acetate ~ formed between the carboxylic aldehyde of ~ poxy-3,4 cyclo-hexane and bis (hydroxymethyl) -1,1-3,4-epoxy cyclohexane and butadienes or copolymers of butadiene epoxidized with compounds ethic ~ eniques, such as styrene and vinyl acetate.
Ie epoæy- equivalent weight which represents the weight of . ~, resin (in grams) ren ~ ermant a é ~ uivalent-gram of epo ~ y can vary within very wide limits. Preferably, resins whose epoxy equivalent weight is between ~ 0 and 1 ~ 000 but these values should not be considered as limited both the scope of the invention; as for physical characteristics ~
resin, they range from liquid resins to very low ~
cosity (2 cPo at 25C) up to solids whose point of ~ u-slon little ~ reach 180C. We always give you a preference for liquid resins or solid resins with a melting point does not exceed 150C
We can use various quan-tities of res ~ ne epoxy allan ~ from 5 ~ 50%, preferably from 5 to 20 ~ o compared to the mas-0 se -total reagents ~ epo resin ~ y is generally mixed with the prepolymer. You can also add epoXy resin to the mixture of reacti ~ e con ~ constituted by 1'imine and maleimide.

- 3 ~ -~ s ~

~ es various resins according to the invention interest the areas of industry that require materials with good mechanical and electrical properties as well as great chemical inertness at temperatures of 200C 2a 300C. As ''' examples, they are well suited for the manufacture of laminates.
fiés, insulators in plates or tubular for trans ~ orrnateurs electrical, printed circuits, pinions, rings and stops u, self-lubricating s.
~ es examples which follow ~ ent illustrate in ~ en-tion.
Preparation of Polymers P.
Example 1 -I We mix with 25 ~, 125.3 g of N, N ', 4.4' diphenylmethanebis-malé-imide and 28 g of bis (4-amino-phenyl) methane then flows with stirring 29 ~ 7 g of henzaldeh ~ from ~ a -te ~ temperature in the stélève mass at 50C Apr ~ s end of exo-thermie, the product soli- '' of obtained is ground and 161.8 g of the mixture are carried for 5 h 10 min at 150a. During heating there is elimination of water. After '-' l, ¦ cooling to 2soa, 157.4 g of a prepolymer is collected which is "~" ~ softening at 1520 ° C.
~ 5 ~ of the powder obtained is placed after grinding and ta-~ bet (100 mesh, u), in a diameter cylindrical mold '' I '7 ~ 6 cm.
~ e mold is placed between the plates of a pre-press ~ ed at 250 ~ C, A pressure of 200 bars is applied . for 1 hour, then the object is removed from the mold, and annealed for 48 hours at .¦ 250C Test pieces cut from this object show the ¦ following mechanical properties: ' ¦ - 'Resistance ~ bending at break (measurement ~ 25 ~) 9 ~ ~ mm2 l - ~ qodule in bending: '280 k ~ mm2 i 30 We intimately mix:
~ 1 .1 ''.

'~ 39 -,, ~.

~ L ~ 3S2 ~ L2 - 125.3 g of N, N ', 4.4' diphenylmethane bis-maleimide - 52t3 g of bis ~ benzylid ~ namino-4 phenyl) methane.
~ e mixture is placed in an oven preheated to 1 50C.
After 4 hours, remove a prep point polymer softening 1 50C.
After cooling the prepolymer is ground ~ tarnished (100 mesh, u), then 25 g of the powder obtained are placed in a cylindrical mold with a diameter of 7.6 cm.
This mold is placed between the plates of a pre-heated to 250C. A pressure of 250 bars is applied for 1 hour, then the object is removed from the mold, and annealed for 48 hours at 250C.
- ~ Test pieces cut from this object have the properties following mechanical tees:
_ _. , Flexural strength Module ~ n flexural at break (~) at break (Mf) l ~ r ~
measured at 25C 6.5 kg / mm2 185 kg / mm2 measured at 250C 2, 3 kg / mm2 75 kg ~ mm2 I

After a stay of 2,095 hours at 250C, these values become measured at 25C: RI: 6.6 kg / mm2: Mf: 220 kg / mm2 measured at 250C: R: ~: 2.4 kg / mm2: M ~: 90 k ~; / mm2 ! ~ x ~ mple 3:
35.8 g of N, N ', 4.4' diphenylmethane bis-maleimide and ^ 1 14.16 g of bis (furfurylidene 4-amino phenyl) methane are mixed in the crusher, and brought to an oven at 145C. This mixture is left at 145C for 40 minutes after the temperature has reached 140C
- in the mass.
I, e prepolymer obtained is re ~ roidi, crushed, bro ~ re and sieved (100} 1 mesh). It has a softening point of .
.; ~.
- ~ 0 -. ~.

~ 1 ~ 5; Z ~ 091 ~ 2 145C. It is molded like darls example 1 We measure the following properties:

., _ _ _ ~
Initial After 100 h at 250C

Rf 25C 7.2.
(kg / mm2) 250C 6.5 4.2 ~ ¦ Mf 25C 290 .I. . (kg / mm2) 250C 200 180 ,. ,,,, ~ ........... . __. . '.'. ' 10 Example 4::
40.5 g of bis (salicylidene-4-amino phenyl) methane and 89.5 g of N, N ~, 4.4 ~ diphen ~ rlmethane bis-maleimide are mixed with bro ~ tor and brought to 180C for 2 h 30 min. ~ e prepolymer cooled is ground and sieved (100, u). It has a softening point 170C increment. A molded object under the conditions of example 1 present after annealing at 150C for 24 hours, the properties ~
~ i following: ~.

.; 1 _ _ _ Initlale A ~ r ~ 74 ~ hb ~ 50 E ~: E 25C -6.6 ~~ _ _ `:; (kg / mm2) 250C 2 ~ 4 4 -¦. Mf 25C 205 230.
~ k5 / Q ~ 290 ~. _ 120 , , 1, ., ~;
.1 . 125 g of N, N ', 4.4' diphé ~ ylmethane bis-maleimide and;:! .
52 g of bis (dimethyl1 ~ 1,3 butylidane-4 amino phenyl) methane are mixed with 25C until having a homogeneous p3te and brought to i60C for 30 min.
3o after cooling the prepolymer (softening oil) ,.

l ~ S2 ~ 42 160-162 It is ground and sieved (100, u). An object is molded into the conditions defined in Example 1 and reappears 20 h ~ 200C.
The following results are obtained:

~ C. ~ _!
. Initial After 1,100 h at 200C
_. _. .
. ~. X ~ 25C 13 12 : ~ k ~ mm2) 200C 220 255 M ~ 25C 6.6 6.4 : (kg / mm2) 200C ~ 100 _ _ _ _i . .
Example 6:.
. 89.5 g of N, NI, 4.4 l diphenylmethane bis-maleimide and 11 g .de bis (~ -hydroxgéthylimino ~ -1,6 benzene are mixed by grinding.
~ e mixture is brought to 150C for 27 min. ~ e product is re ~ roidi, bro ~ é and sieved (100 uj. It has a softening point 150QC. As in Example 1, a molded object is produced which is annealed 48 h at 250C
The following results are obtained:
. . . .___, . Initialj ~ After 1,000 h at 250C

. 1 20 ~ 25C. 10 10 ¦ (k ~ mm2) 250C 5 .¦ M ~ 25C 300 250 (kg / mm2) 250C ~ 20 ; ~. . . _ ~,:; , Example 7:
~ 125 g of N, ~ l, 4,4l diphenglmethane bis-maleimide and 50 g .1de bis (cyclohexylidene 4-amino phenyl) ether are mixed by grinding ~ ~ a powder is sieved (100 ~) is cnargée in a mold diameter: 7.6 cm ~ e mold is placed between the trays of a t 30 pre-press ~ fairy ~ 200Co Apply a contact presslon. ~ ~.

- ~ 2 - ~
.1.

When the te ~ perature in the r ~ a-tière reaches 180C, apply a pressure of 200 bars. After 1 hour the object is removed from the mold and annealed ~
8 p.m. at 200C.
~ he properties are as follows ~.:,. . . . . .
. Initial Apr ~ s 2,000 h at 200C
'''', ,, ..,. . ,,.
Rf 25C 3.4 5.7 (k ~ mm2) 250C 5 ~ 3 3 ~ 2:
Mf 25C 150 210 (k ~ mm2) 250C i20 125.
.` ~.
`3xera ~ 1e 8::
`89.6 g of N, N ~ 'diphenylmethane bis-maleimlde and 12 ~ 35 g of bis (p ~ hydroxyphenyl imino) -1,2 ethane are mixed in the crusher, and brought to 160C for 10 min. This prepolymer : held with a softening point of 150C is ground and:
sieved (100 ~). By proceeding as in Example 1, a molding which after annealing 48 hours at 250C has the properties : following:
::
_. - ~ After 1 tn ~ 250C.

Rf-25C 6.6 5.5.
.l (k ~ mm2) 250C 5.3 3.4 Mf 25C 310 230 (k ~ rmm2) 250C 250 180 . . . .
. . . ............................... ................. . .
~ `. xem ~ le 9:
~ 9.5 g ~ 0.25 moles) of N, N '~ 4.4l aiphenylrnéthane bis-maleimide and 18.1 ~ of benzylidanaminobenz ~ are not mixed:
grinding. This mixture is melted ~ 165C, degassed under ~ ide, pushed for 30 seconds, then poured into a pre-hot mold ~ fé at 200C

- 43 -:
, After 20 h ~ 200C, the objects obtained ~ s are annealed 29 h ~ 250C.
The properties obtained are the following:
, _ _. ~
_ Initial After 1,750 h at 250C

R ~ 25C 4 ~ 2 9.9 (k ~ mm2 ~ 250C 2.7 3.1 M ~ 25C 185 240 . (k ~ r ~ n2) 250C 80 110 Example 10:
112.5 g of N, Nl, 4.4l diph ~ n ~ lmethane bis-maleimide and 45 gd ~ benæylid ~ naminobenz ~ are not very close to the example 8 to obtain con ~ ormed objects. These have properties following::

. r ~ _ _ _. _ ~.
Initial After 1,000 hrs at 250C
_ _ . . R ~ 25 ~ 6 ~ 9 6 (k ~ mm2) M ~ 25C 195 200 ~ k ~ mm2).
'' -, t, _.

. ~ e ~
.
89.5 g of N, 1 ~ ', 4.4' diphenylmethane bis-rnaleimide and 18 ~ 7 g of bis (benzyliaene 4-amino phenyl) meth ~ are not mixed and ~ wavy at 170C. After ~ s homogenized ~ ion the liquid mass is ; degassed under a vacuum of 5 r ~ m of mercury, then poured into a mold preheat ~ é at 200C and maintained 24 h at 200C. After annealing 48 h at 250C, the following results are obtained:

; '' '' ~ - 44 -... . . .. ..

~ ~ - - - - - ~
Initial After 1,100 ha 250C
. ' , R ~ 25C 6.6 5.9 , (k ~ mm2) 250C 3.7 2 ~ 4 Mf 25C 220 160 . (k ~ mm2) 250C 135 110 i , - - '''.:
Example 12:
Example 10 is reproduced with the same amount of bis-maleimide and ~ 0.5 g of bis (salicylidene-4-amino phenyl) methane;
: after recvit of 60 h at 250C, we get the following results: ~
. ~ ~. ':
¦ ¦ ~ ¦ Ind-tial! After 1,440 hours at 25 ( : i Rf 25 ~ 9 ~ 2 12 ~ 3 : (k ~ mm2) 250C 1.3 3 ~ 8 .1 ~ ff 25C 195 230 . ~ (kg / mm2) 250C _. 120 . ~. . , ', Example ~; 1 ~:
1 20 8.78 g of N-phenyl maleimide, 81 g of N, N ~, 4.4 ′ diphole-: ¦ ~ bis-maleimide ylether and 28.8 g of bis (a-pyridylamino methyl ~
`` ¦ benzene are mixed in a grinder and then heated to 180C. 2 mins `.l after the ~ usion of the mixture the prepolym ~ re is re ~ roidi, ground and sieved (100 ~). It has a softening point of 185C.
We realize ~ e from this product a molding by com-pressure, as in Example 1, which after ~ s anneals 20 min at 250C
~ has the following properties: ~
... . .

. ' ~.
, ~ 5 . i,. . . . . . . . .

l ~ S ~ Z
_. . _ _ _.
Initial Apras 500 h at 250C
_ _. . __ _ _ l R ~ 25C 7.2 10 (kg / mm2) 250C 2 2.3 M ~ 25C 255 250 ~ k ~ mm2) 250C 110 , _ _ _ _ _. .

xample 14:
125.3 g of N, ~ 1 ', 4.4' diphenylmethane bis are mixed.
maleimide with 52.3 g of a polyimine of ~ ox ~ ule 2 ~ CH2 ~
0.28:
':
. After ~ use of the mixture (165C) and degassing under vacuum9 the liquid mass is co ~ ee in a mold pxéchau ~ é ~ 200C ~
~ ensernble is maintained 20 h at 200C ~
: ~ article obtained has the following properties:
- -. __. . '' . . . . Initi ~ ie Apr ~ s 450 h at 250C
~ ~,,, _ 25C 4 ~ 6 4.5 1; (k ~ m ~ 2) 250C 2 ~ 3 ~ 2.2 i ~ Mf 25C 205 185 . ~ ~ kg / mm2) 250C 75 110: ~:

; l _ ~ 6 -ll ~ S2 ~ 9 ~ Z

Example 15:
We prepare a polyimine whose moti ~ recurrent has for ~ o ~ rnule:
-CH = N ~ CH2 ~ = C ~
from u ~ 1st methanolic solution of terephthaldehyde and a bis (4-amino-phenyl) methane methanolic solution, the ratio dialdehyde molar diamine being 1.
~ a polyimine does not present a point of: ~ usion up to `ll 260C, and is insoluble in usual solventsO
29.6 g of this polyimine and 89.5 g of N, N ', 4.4 t diphole-bis-maleimide nylmethane are mixed by grinding and kept at 160C for 30 rnn. ~ e polym ~ re obtained is ground, sieved (100 ~) and molded by pressure at 300C, according to. the procedure described in example 1.
~ article obtained has the following properties:
R: E at 25C 5 5 6 kg / mm2 at 250C 4 kg / mm2 `1,.
'M ~ at 25C 290 kg / mm2 at 250C 220 k ~; / rnm2 xample 16 2022.5 g of p-benzylideneaminobenzoic acid and 89.5 g ae N, ~ diphenylmethane bis-maleimide are mixed by grinding,: welded at 175C, and poured into a preheated mold at 200C We leave 20 hours c ~ this temperature. ~ unmolded object is annealed 72 hours at 200C. It exhibits resistance to "
Ilexion 3. ' the initial rupture, measured at 25 ~ C ambient of ' 3 kg / mrn2 and a 140 kg / mm2 module E ~ cernple 17: '' ~ ' 134 ~ 5 g of N, Nt, 4.4! diphenylmethc ~ ne bis-rnaleimide and ~ ' i! 61 g of bis (salicylid ~ 4-amino phenyl) methane are loaded, with ~ '3o 130 g of cresol5, in a cylindrical reactor equipped with agitated dlune-central ~ ~ ~ a ~ mother ~ and ~ a condenser. '' ~ 7 l ~ SZq [D ~ 2 ~ e mixture is brought to 150C and maintained 6 hours at this temperature.
After dilution with 130 g of cresol, the solution is covered lée in 1 li-tre of ether where the poly ~ Qère precipitates. After ~ tra-~ "tion, the precipitate is resuspended in 1 liter of cyclo-; hexane and ground using a turbine. ' ~ e polymer is then ¦ filtered and washed with cyclohexane.
After vacuum drying of 2 mm of mercury for 24 hours ~ 50 ~, then 24 hours at 150C, the isolated polymer (196 g) ~ i 10 has a softening point of 180C. I, e polymer is molded in '' the conditions described in example 1 ~ After annealing ~ 8 hours ; ~ 250 ~ C, the shaped object has the mechanical properties 'following, measured ~ 25C:' `RE: 8 ~ 8 kg / mm2 M: e: 280 kg / rnm2 '' After 1,000 hours at 250C, these values are respected 8.7 kg / mm2 and 290 kg ~ mm2.
1 Preparation of_Pol ~, rrneres imines-isoc rana-tes and llincor ~ oration 'i of these ~ ol: yraères_ aux olYmères 3 ?.
xample 18 '1 132 g of benzalaniline are introduced into a flask ¦ (1 mole) and 125 g of diisocyanato-4? ~ Diphenylmbthane (0.5 mole), ohau ~: ~ e hang 11 h at 220-2 ~ 0C under nitrogen and collects during the ' ~ ¦ heating period ~ Iage 17.4 g of carbon dioxide. ~!
~ e solid (~) ob-kept is ground e ~} powder. We determine by imra-red analysis the presence of imine groups resi-'~' duels. 10 g of son-G powder mixed with 90 g of bis-maleimi-do- ~ diphenylmethane and the mixture is heated ~ e for 15 min at 150-165C. ~ e resulting prepolymer ~ Iondu ce-te tempéra ~ ure, is rei ~ roidi then: Einement crushed. 27.5 g of the powder obtained are placed in a cylindrical soft ~ e 75 mm in diameter. ~ e .
... . .
", _ ~

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

1 ~ 5 ~ ~ ~ 2 i ~ mold is kept in press under 200 bar ct for 1 hour at ~ l 250C After demoulding, test pieces of 7.5 x 5 x 30 mm and measures the flexural strength. ~ the value found is 1 9.1 k ~ mm. ~ e flexural modulus is 228 k ~ mm2O ~ are tested ! ve-ttes are then maintained at 250C ~ es resistance values tance to the ~ lexion and bending module is the following:
. 1, I Heating rate ~ Age Resistance ~ 21a bending Module de2 ~ 1exion 250C k ~ ~ nk ~ mm . I _ _ _. ,.
I 10 1,000 h. 7,240 . ,.
1,500 h 6.3 220 .. _ _ _ _.
2,000 h 6 ~ 4,225 . ___ I. . ~ -.
~ xample 19:
¦ 30 g of the solid (S) resulting from the previous example, :. are mixed with 120 g of bis-mal ~ imido- ~, 4 'diphenylmethane . and the mixture is heated for 15 min at 150-165C. Cornme in the previous example, a molded object and tests ~ are on ~ uelles we determine, after varying periods . of heating ~ age at 250C the values of resistance ~ bending, and the ~ lexion module. ~ the results are recorded in the ta-. following stain:

. Heating duration Resistance ~ 21a ~ lexlon ~. ~ Odule de2 ~ 1exion, ; l ~ 250 k ~ mm k ~ mm ,. ,, __ _._. _. _ i. 0 h 8.7 ~ ~ 227 . ~. ., _ _ _ _ 1,000 h 9.1 ~ 226 ; ~ ~ _, ~
30 1,500 h 9, ~ 2,254 ~ _. _ _ ~,. ~.
: .1 2,000 h 8.08 .
4`9-:

l ~) S ~ 2 Example 20:
Heated for 7 h at 230-240C 286 g of benzalaniline and 195 g of diisocyana-to-4,4 'diphenylmethaner It emerges duran ~
the heating period 28.6 g of carbon dioxideO
~ A reaction mass is then subject to a distill lation under a pressure of Q, 5 mm of mercury. We collect the excess benzalaniline, i.e. 128 g. : I; e polymer - imine -polyisocyanate has a softening point between 116 -¦ and 120C and, has an inherent viscosity measured in the I ~ -methyl ¦ 10 pyrrolidone equal to 0.2.
It is shown by inIra-red analysis that this polymer is made up of groups:
~ C112 ~

I: xem ~ on the 21st:
We heat 2 hours at 250C 112.5 g of bis (ben ~ ylidene-arnino) -4.4 'diphenylmethane and 37.5 g of diisocyanato-4.4' diphen-20 nylmethane. ~ e release of carbon dioxide having ceased, onre ~ roidi t, grinds the solid and extracts the residual bis-irnine by ex-traction ~ using a benzene-cyclohexane mixture (33% - 66%).
44 g of de-bis-imine are thus collected.
~ e imine polymer ~ polyisocyanate has a point of ramol-smoothing of 127-130C.
24 g of the preceding polymer are mixed with ~ ec 96 g of bis-maleimido-4,4 'diphelylme-thane and chauI: Ee 15 min at 155-165C.
There is thus obtained a prepolymer P1 having a softening point men ~ from 145-1 ~ 7C. 30 g of prepolymer P1 are placed in a 30 cylindrical mold 7.5 cm in diameter. ~ e mold is maintained 1 h ~ 250C under a 200 bar press-ion. ~ 'molded object has a .1 ~

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

~ ~ 5Z ~ ~ 2 flexural strength of 6.3 k, ~ mm2 and a modulus of ~ lexion of 232 k ~ mm2. After heating the ~ ant 2,030 hours at 250C these va-their respectively 7944 k ~ mm2 and 235 k ~ mm2.
Example 22:
I

It is heated for 2 h 15 min at 260C 75.8 g of bis (benzylideneamino) -4.4 'diphenylmethane and 50 g of 4-diisocyanato, 4 'diphenylmethane. 5.8 g of carbon dioxide are released.
After grinding the reaction mass and washing with ben ~ ene and acetone a ~ in to remove excess bis-imine, an imine-diisocyanate polymare having a ramol point is obtained smoothing of 176 - 180C.
A well hornogenic mixture of 50 g of the previous polymer with 150 g of bis maleimido-4,4 'diphenylmethane is heated ~
rant 30 min at 165 - 170C so as to obtain a prepolymer having a softening point of 148 - 150C. From this prepoly-mother we carry out molding in the manner described in the examples previous ples. ~ es the values of the resistances in ~ lexion and the ~ lexion module are as follows:
., . ...,. _ ~ _ I 20 Heating duration ~ Resistance to ~ lexion ~ Lexion module at 250C in k ~ mm kg / mm2 . . .
O 5 ~ 1,232 . _. . . . -1 ~ 160 h 6.8 266 , ~ _,, _ ~
2,230 h 6 ~ 5,257 ~,. , _ .- -.
; ~ 3,250 h6 ~ 7,226 , 1. - -. ...... .. - _ _ ~
~ XEMP ~ 2 ~:
On chau ~ e under nitrogen duran-t 3 h ~ 245 ~ 2500a mixture consisting of:
- ~ `1 250 g of diisocyt ~ nato - 4,4 ~ diphenylmethane, 187 g of bis (benzylid ~ eamino) 4,4 ~ diphenylmethane.

., ~ 5Z ~ ~
It emerges during the heating period ~ 30.50 g carbon dioxide ~ ue.
~ the ground reaction mass is hot ~ ée again 3:30 a.m. ~ 275C. ~ 10 g of carbon dioxide is released again than.
~ The powder obtained is molded directly in the condi-- usual matters. ~ molded lobàet has resistance ~ the ~ 6.75 k ~ mm2 lexion and a ~ lexion of 2 ~ 8 k ~ mm2 module.
~ X ~ ~ 24:
'' 10We warm for 2 h 40 min at 240 - 250C 217 g of bis (benzylideneamino) -4.4 ~ diphenylmethane and 155 g of diisocyanato-4.4 ~ diphenylmethane. 21.65 g of carbon dioxide is released.
than. After re ~ roidis ~ ement the powder is ground and chau ~ fairy new ~ 250C.
50 g of the polymer imine - diisocy ~ ate are heated ~ fairy for 50 min ~ 155C with 150 g of bis- ~ randomimido - 4.4 ~ diph-nylmethane. A prepolymer is obtained having a point of ramol-smoothing of 152 - 153C.
We e ~ fectue ~ from this prepolymer a molding in the usual conditions. ~ es ~ aleurs resistances in ~ the ~ ion and the ~ lexion module are determined as above-; ment (flexural strength after ~ 3 ~ 000 h: 4.1 k ~ mm2) ~

,. . . _ _. !
Heating time Resistance to fleece Flexural modulus at 250C in k ~ mm k ~ mm2 ~ ', ~. - ~ - -, '. . .
2,000 h 4.3 238 _ ~ _ '' 2,500 h 4.1 245 3.00G ~ i 246 .'`, -. . . . . . . ,. . ~ ~ ..
.
''.

,, ',.

l ~ SZ ~ 9LZ

Preparation of pol; ymers P r..odi: ~ iés by pol ~ ureth nnes.
Example 25:
At ambient temperature, 42 g of N are intimately mixed, Nl, 4.41 diphenyl ~ é-thane bis-maleimide9 9.3 g of bis ~ 4-amino phenyl) methane and 6 g of an elastom ~ re polyurethane prepared from an ethylene glycol adipate of hexamethylene diisocyanate and ethylenediamine. Then added with stirring 9.6 g benzaldehyde. ~ at temperature s then rises to 48C.
~ when the temperature has dropped to 25 (~, the pro-10 duit obtained is ground and placed in the oven at 150C for 5 h. The softening point of the polymer obtained is 147.5 C.
We then efIectue grinding ~ in and the powder obtained l is put in a cylindrical mold, This mold is placed between the plates of a pre-press chau: E ~ ée at 250C and subjected to a pressure of 200 kg / cm2 for 1 hour. ~ object is then removed from the mold and annealed for 24 hours. at 2500a.
~ The mechanical properties are as follows:
resistance to bending ~ rup-ture at 25C: 9.0 kg / mm2 - resistance to. shock: 33 kgcm / cm3 (Standard DIN 51 230) - Ilexion module: 210 kg / mm2.
¦ Example 26:
.1. Dissolve 8.5 g of a prepared polyne thanne tornere elas -I by reaction of ~ one mole of ethyl adipate ~ ne ~ Lycol, of 3 moles of.
bis (4-isocyanato-phenyl) methane and 2 moles of-butanediol 1-4, i. in a mixture of 7.1 g of bis (4-amino phenyl) methane eb 3.2 g `~
~: of benæylidénaminobenz ~ not brought to 15CC.
. ~ We ~ a ~ wave at 170 ~ 65 g of N, N ~, 4,4 'diphenyl-. ' bis-maleimide methane, then add the poly-. 30 uretha ~ not prepared above .,.
i ~ ~

.i '.

52 ~ 4 ~
~ ~ a liquid composition obtained is degassed and poured I in a mold preheated ~ é at 200C
The whole is left at 200C for 24 h., Then unmolded I ~ 25C. ~ A plate obtained is then annealed 24 h ~ 250C.
¦ We measure on this plate: The resistance, ance to shock (Rc) 'as well as the resistance to ~ breakage at break (R ~) and the modu-: ¦ le de ~ lexion (M ~). .
We note:
-. . . . =.
; 1. . at 25 ~ at 250C
~ ~ ~ _ R ~ (~ c ~ mm2). 12.3 6.6 . ,,,. . . . ~ -. . Xc (l ~ gcm / cm ~) 38 ,. .` - ~. .
. Mf (k ~ mm2) 243 158 ,. . . . .,. _. ~ ~.

. Example 27:
; ¦ Dissolve 8 g of the polyurethane elastomer used 1 in Example 26, in 26 g of bi ~ (4-benzylideneamino-phenyl) . ~ 1 methane at 150C, .l On ~ ond at 170C 65 g of N, N ~, 4.4. ~. di.phenylmethane bis-¦ 20 maleimide ~ then incorporates the solution into the bis-imide ~ wavy polyurethane in diimine.
.Place the assembly in a mold, as in example-. .....
! ple 26, and maintains it at 200C for 2 ~ h then, after ~ demoulding, anneals for 2 ~ h at 250C. -.
We note: ~.
~ 25C to 250C
...,. ... . -. , ~ .... ... . _. .
R ~ ~ k ~ mm2) 9.7 4.8 ., i.
. Rc (kgcm / cm3) 36 ~ 9 , j ._ _, _ ~ _,, ~
M ~ (k ~ mm2) 184 _ -.-.
`I _ .1.
~ _ 5 ~

~ ~ ~ 2 ~ ~ Z
xernple 28:
j We repeat the test of exernple 27 using 9 g of the polyurethane-thanne elastomer, 28 g of bis (furfuryli-dene 4-amino phenyl) methane and 70 g of N, N ', 494' diphenylmethane ¦ bis-maleimide. ~ e rewinding is e ~ carried out under the conditions ~ written ~ example 26.
-¦ We note:

- ~ ~ 25C to 250C
: 1,. _. . . _ i 10 Rf (k ~ r ~ m2) 9 ~ 6 6.2 .1 _. , _ Rc (kgcrn / cm3) 3 ~, 7 ,. . . _-. , M ~ (k ~ mm2) 230 120 . ``.
Preparation_of ~ ol ~ m ~ res ~ _rnodi ~ -lés by epox resins ~
, I ExeAmple 23:
¦ In a container r. ~ Aintenu in a hot fluid ~ é à
160C ~ we introduce:
- 41, ~ gd ~ an epoxy-no ~ olaque resin which can ~ be represented by the average madness:
C - CH2 - CII _ CH2 ~ CE2 C \ ~ 2 2 ~ CH2 not - - 17.2 g of bis ~ benzylideneamino) 4.47 diphenylmethane - 41, ~ g of N, N '- ~, 4' diphenylmethane bis-maleimide.
! ~ when the mixture comes into use, we submit it to agitation and the dissolved air is eliminated by reducing the pressure sion ~ up to ~ 5 mm of mercury. We then keep the mixture - for 5 minutes ~ the ~ wavy state.
; the '1:

5 ~ 0 ~ Z
~ e liquid mixture is then poured into a paral mold-lélepipèdique (125 x 75 x 6 mm) whose internal wall poss ~
a silicone coating, previously heated to 200C
I We leave the unit for 24 hours at this time.
1 scratch and then demolded hot and we have to undergo the mold object a complementary heat treatment ~ area for 24 hours at 250C.
It then has a resistance to ~ lexion at break s 11.7 kg / mm2 measured at 25C. ~ near a thermal test of 2,000 hours at 250C this resistance is still 9.1 k ~ m ~ l2.
On the other hand, the molded object ~ initially has a resistance to breakage of 4.2 kg / mm2 measured at ¦ 200C After a technical test of 1 ~ 000 hours ~ 200C this resistance is still 3.5 k ~ mm2 and weight loss is key O, 5 ~ o only.
. ' ~::
1 A molding is prepared by casting in the same condi- -I tions as above from the following mixture ~ nt:
- 30 g of the epox resin ~ used in example 29 - 12 g of ~ is (benzylideneamino) 4,4 'diphenylmethane - 58 g of N, N ~ diphenylmethane bis-maleimide.
~ molded object has resistance ~ la ~ lexion ~ la rupture of 11.2 kg / mm2 measured at 25C After a test the ~ mi-¦ that of 2,000 hours at 250C this resistance is 11.8 k ~ m ~ 2 1 On the other hand, the molded object initially has a ; 1 resistance to ~ lexion ~ rupture of 4.9 k ~ m ~ 2 measured at 1,200 ~ C. After a thermal test of 1,000 hours at 200C this time resistance is still 4.3 k ~ m2 and the weight loss is l ~% only Example 31:
We mix at 160C:
~ - 20 g of the epoxy resin used in Example 29 ;, ~
!
- 56 -;

.

~ 2 - 33 g of Bi ~ (b ~ nzylid ~ neamino) 4, ~ 'diphenylmethane - 47 g of N, N '- 4.4 ~ diphenylmé-tlnane bis-maleimide.
This molding is carried out by casting in ¦ the conditions described in example 29, ~ 'molded object has a resilience to the ~ lexion to the failure of 14.9 k ~ mm2 measured ~ 25C, After a thermal test than 2,000 hours at 250C this resistance is 8.6 k ~ mm2, On the other hand, the molded object initially has a resistance to rupture ~ 2.8 k ~ ~ n2 measured at 200C, After a technical test of 1,000 hours at 200 ~ this ; The resistance is 2.4 k ~ mm2 and the weight loss is 0.2 ~ only lement, Example 32:
.
In a 250 cm3 container hand-held in a mixed bath tallique chau ~ fé at 125C, we cha-rge:
Epoxy resin used in Example 29 = 66.2 g ¦ - ~ ismaleimido ~, 4 'diphenylmethane - 66.2 g - ~ is (benzylideneamino) 4.4 'diphenylmethane = 27.5 ~, and stir until the mixture is known ~ isammen-t fluid for atre poured on a pyrex plate. Then, the tray is carried in ! oven at 165C and abandoned 3 h 50, 1 ~ th product is then re ~ roidi and finely ground - the ¦ prepolymer thus obtained has a softening point of 95C, 1 30 g of prepolymer are loaded into a cyiind mold i that 75 mm diameter that was placed between press plates chau ~ és ~ 200C; a pressure of 1 hour is maintained 250 k ~ cm2, ; l After a ~ 2 ~ h thermal treatment at 200C, the object molded has a resistance in ~ -The ~ ion of 1 ~ 7 ~ k ~ mm2 measured at 25C ~
, After v ~ e thermal test of 2,000 hours at 250C, I this resistance is 11 ~ 6 k ~ m ~ l2, "

Claims (19)

The embodiments of the invention, about which an exclusive right of property or privilege is claimed, are defined as follows: 1 thermostable polymers, characterized in that they are obtained by reaction of:
a) a maleimide of average formula:

(I) in which the symbol A represents an organic radical of valence n, containing up to 50 carbon atoms, the symbol Y
represents H, -CH3 or Cl and n represents at least an equal number at 1.5.
b) a compound containing at least one -NH2 group c) a compound containing at least one group -? R, the nature of the amino compound and of the carbonyl compound being such that the imine resulting from their reaction has the average formula:
(II) in which m represents a number at least equal to 1, the sym-bole B represents a hydrogen atom or an organic radical of valence m, containing up to 50 carbon atoms, the symbol G represents a monovalent organic radical (G1) containing up to 35 carbon atoms or a radical of formula -G'-CR = N-B1 in which the symbol G1 represents a divalent radical closing up to 35 carbon atoms and the symbol B1 represents one of the monovalent radicals which can be represented by the symbol B, or even, when m = 2, a radical of formula:
-G'-CR = N-B2? N = CR-G'-CR = N-B2) w .SIGMA.
in which G 'has the meaning given above, B2 represents one of the divalent radicals which can be represented with the symbol B and the two symbols .SIGMA. representing the chain endings which can both be radicals of formula -N = CR-G'-CRO or represent one the radical -N = CR-G'-CRO and the other a group -NH2, the symbol R represents-te a hydrogen atom or a monovalent organic radical containing-mant up to 35 carbon atoms, the symbols G1 and R can represent present together a divalent radical; w represents an inclusive number between 1 and 10, the quantities of reagents used being such that there is at least one group -? - R as well as minus one and at most ten double bonds, of maleimide (I) by -NH2 group provided by the amino compound b). 2. Polymers according to claim 1, obtained from a maleimide a), a compound containing at least one group -NH2 b), and of a compound containing at least one group -? - R
c), characterized in that one reacts beforehand partially-completely or completely the compounds b) and c), then reacts the resulting product comprising the imine of medium formula , with maleimide a). 3. Polymers according to claims 1 or 2, in which we replace the compounds b) and c) by the corresponding imine dante . 4. Polymers according to claims 1 or 2, character-that the nature and the proportions of the reagents are -such that there are 1.8 to 5 maleimide double bonds per group-ment -NH2 originating from the amino compound or by imine group. 5. Polymers according to claim 1, and having a softening point between 50 and 200 ° C, obtained by heating between 100 and 200 ° C in one stage or in two stages, reagents a), b), c). 6. Polymers according to claim 1, insoluble and showing no softening below the temperature at from which they begin to degrade, obtained by heating between 150 and 350 ° C, in one stage or two stages, reactions a), b), c). 7. Polymers according to claim 6, characterized in what it consists of heating between 150 and 350 ° C a polymer depending claim 5. 8. Polymers according to claim 1, modified by incorporation into the reagents or prepolymer of an aromatic compound tick with 2 to 4 benzene rings which cannot be sublimated atmospheric pressure up to 250 ° C and whose boiling point is higher than 250 ° C. 9. Polymers according to claim 1, and modified by the addition before hardening of a monomer other than a maleimide a) and comprising at least one group polymerizable and / or unsaturated polyester. 10. Polymers according to claims 1 or 8, and mo-defined by the addition before hardening of an acid anhydride aromatic tri- or tetracarboxylic. 11 Polymers according to claim 1, modified before hardening characterized in that:
1. - compounds b) and c) are reacted beforehand so as to form the imine of average formula:
B? N = CR-G) m the various symbols having the following meaning:
- m represents a number at least equal to 1 - B represents an organic radical of valence m, containing up to 50 carbon atoms, the free valences of the radical B being linked through one or more carbon atoms resulting in an aromatic cycle, in groups -N = CR-G.
- G represents a monovalent organic radical G1 containing up to 35 carbon atoms, the free valency of the radical G1 being carried by a carbon atom belonging to an aromatic cycle.
- G also represents a radical of formula -G'-CR-N-B1 in which -the the symbol G 'represents a divalent radical containing up to 35 carbon atoms in which the two free valences are carried by two carbon atoms belonging to an aromatic ring tick. B1 has the same meaning as B, or represents when m = 2 a radical of formula:
-G'-CR = N-B2? N = CR-G'-CR = N-B2? W .SIGMA.
in which G 'has the meaning given above; B2 re-has one of the divalent radicals which can be represented by the symbol B..SIGMA. which represents a chain termination represents one of the following two radicals:
-N = CR-G'-CRO

- n represents a hydrogen atom or a monova- organic radical slow containing up to 35 carbon atoms. The symbols G1 and R
can together represent a divalent radical.
- w represents a number between 1 and 10.
2. - Then the imine is reacted with a defect in aromatic polyisocyanate of formula:
E (NCO) s in which s is at least equal to 2 and where E represents a valence radical s containing up to 35 carbon atoms, the free valences with the radical E being carried by carbon atoms not belonging to aromatic rings.
The following report:
being greater than 0.5.
3. In a third step, the mixture is reacted ge resulting from stage n ° 2 constituted by imine and by the imine-polyisocyanate condensation product with malei-mide a), 12. Polymers according to claim 11, obtained in causing the imine of formula to react in a first step mean B- (N = CR-G) m with a defect in polyisocyanate then Pairing the resulting mixture with maleimide a), 13. Polymers characterized in that they are reagents obtained by heating above 180 ° C
following:
1. an imine or polyimine of formula:
B? N = CR-G) m the various symbols having the following meaning:
- m represents a number at least equal to 1, - B represents an organic radical of valence m, containing up to 50 carbon atoms, the free valences of the radical 3 being linked through one or more carbon atoms belonging to an aromatic cycle with -N = CR-G groups, - G represents a monovalent organic radical G1 containing up to 35 carbon atoms 9 the free valence of the radical G being carried by a carbon atom belonging to a aromatic cycle.
- G also represents a radical of formula -G'-CR = N-B1 in which the symbol G 'represents a divalent radical containing up to 35 carbon atoms in which both free valences are carried by two carbon atoms belonging to an aromatic cycle, B1 with the same meaning that B, or represents when m = 2 a radical of formula:
-G'-CR = N-B2? N = CR = G'-CR-N-B2? W .SIGMA.
in which G 'has the meaning given above, B2 represents one of the divalent radicals which can be represented by the symbol B..SIGMA., which represents a chain termination represents one of two radicals following:
-N = CR-G'-CRO

- R represents a hydrogen atom or an organic radical monovalent containing up to 35 carbon atoms. The symbols G1 and R can together represent a radical divalent.
- w represents a number between 1 and 10.
2. a polyisocyanate of formula:
E (NCO) s where s is at least 2 and where é represents feels a valence radical s containing up to 35 atoms of carbon, the free valences of the radical E being carried by carbon atoms belonging to aromatic rings ques, this radical E being:
- a phenylene radical optionally substituted by a halogen atom or by an alkyl group or alkyloxyl having from 1 to 4 carbon atoms, - a radical consisting of a sequence of several phenylene radicals these phenylene radicals possibly being be substituted by a halogen atom, a group alkyl or alkyloxy having 1 to 4 carbon atoms. The phenylene radicals are linked together by the valence bond or by an inert atom or group such as: -O-, -S-, a straight or branched alkylene group having 1 to 3 atoms carbon, -CO-, -SO2-, -NR1-, -N = N-, CONH-, -POR1-, -CONH-X-NHCO-, the radical R1 represents a hydrogen atom or a radical alkyl having from 1 to 4 phenyl or cyclo carbon atoms hexyl. X represents an alkylene radical having less than 13 carbon atoms.
- an aromatic radical formed by a chain of several optionally substituted phenylene radicals by a halogen atom, or by an alkyl group or alkyloxy having 1 to 4 carbon atoms, the radicals phenylene forming between them an orthocondensed system or ortho and precondensed.
- a radical originating from a polyarylene polyisocyanate of medium formula:
.alpha. being a number between 0, 1 and 2. 14. Polymer according to claim 13 essential-Lement constituted by the repetition of patterns of formula:
obtained by reaction between a monofunctional imine BN = CR-G and a diisocyanate E (NCO) 2. 15. Polymers according to claim 14 in which K report:
is between 0, 2 and 5. 16. Polymers modified by the addition before curing of a polymer according to claims 12, 13 or 14, the latter being used in an amount such as this corresponds to less than 50% of the total mass of the reagents. 17. Polymers characterized in that they are obtained by heating to a temperature at least equal at 100 ° C of a mixture comprising:
- an imine-polyisocyanate polymer as defined in claims 13, 14 or 14.
- a maleimide in which the symbol A represents an organic radical of valence n, containing up to 50 carbon atoms, the symbol Y represents H, -CH3 or Cl and n represents a number at least equal to 1.5 and the proportion of the polymer imine-isocyanate corresponding to a maximum of 50% of all reagents. 18. Polymers according to claim 1, modified by adding a polyurethane elastomer before hardening rethann used in quantity such as this corresponds 5 to 50% of the total mass of the reactants. 19. Polymers according to claim 1, modified by adding an epoxy resin before hardening used in a quantity such as this corresponds to 5 at 50% on the total mass of the reagents,