CA1072242A - Crosslinkable mixtures of oligomers or polymers and diamines - Google Patents

Abstract

Abstract Crosslinkable mixtures of oligomers or polymers, containing terminal imidyl groups, and diamines are described, for example mixtures of a polyamide oligomer or polyamide-acid oligomer, or terminal polyamide polymer or polyamide-acid polymer, having maleimidylphthalic acid groups, and a diamine. These mixtures and the pre-polymers obtainable therefrom are soluble in customary organic solvents, and in general they can also be processed from the melt. The crosslinked products obtainable therefrom are distinguished in particular by their good thermo-oxidative stability.

Description

~7Z24~

The present invention relates to crosslinkable mixtures of oligorners or polymers, contalning terminal imidyl groups, and diamines, as well as to the pre-polymers and crossllnked produc-ts ob-tainable therefrom.

The crosslinkable mixtures according to -the invention conslst of at ].east one oliyomer or polymer of -the formula Ia or Ib CO-Q- Zf Q-OC ~ ~ ~ COO ) m-~ ~ Ia ) CO/ 3 -COH L~ HqOC ~ 1 C-9- z ~ Q;C {~/Co\A

or H10~0-Q-ZfQ-Oc\ /(COOHJ m-~ ~Ib) OCS/Co L(800C) n-l CO-Q-Z ~--Q-OC COR

A

or of a col~responding cycll~ed derivative,all~ o~ at least one diamine of the formula II

2 -2 (II), whereb~ the rnolar ratio of ollgomer or polym~r of the formula Ia and/or Ib, or of a corresponding cyalised d~rivative, to diamine of the formula II is between about 1.2 : 1 and 50 and whereln ;' : ; , . , :. :. ' ' . .
. . ." . . ., , , : , ..

.

' . , ' : ' , ,: .' 397~2~

the X s independently or one another represent hydrogen or, if the radical ~ \A is in the 4-position CO' of the benzene ring, also -COR2, the R s and R2 s independently of one another represent a hydroxyl group, an unsubstituted or substituted phenoxy group, an alkoxy group having 1-18 carbon atoms or an -O M~ group, the Rl s independen~ly of o~e another represent a hydroxyl group, an unsubsti~uted or substituted phenoxy group, an alkoxy group having 1~18 carbon atoms, an -O M
group~ or two adjacent Rl together represent the ~0~ grouping, the A s independently of one another represent a radical of the formula .
~3 ~4 ,G;~2 -C C C 2 X 3 ~ : ~ ~

.
or ~

R3 and R4 independently of one another represent hydrogPn, chlorine, bromine or methyl, M+ represents an alkali metal cation, a trialkylammonium . : '. ' ,:

.~ :

,. . ~ , . - ,-: , : ,' ' " ` : ' `. ~ ; . ' '` '; ' , " "` ~:' . ~' ' ' : ` " ' `'` ` .. ' .` . , -: : ` ' '` . ' ' , ' '' ' ' '. . '' " :'' ' '' ' : ~ ' ' : .' .

~ ~7 Zz 4~

cation having 3-24, especially 3-12, carbon atoms or a qua~ernary ammonium cation, a represen~s a number from 1-100, preferably a number from 1~60, and particularly a number from 1-10, m and n independently of one another represent the num~er 1 or 2, .the Z s and Z2 s independently of one another represent an aliphatic radical having at least ~ carbon atoms, a cycloaliphatic, carbocyclic-aromatLc or he~erocyclic-aromatic radical, the Q s represent NH~, or -Q-Z-Q- or -Q-Z2-Q- represent the grouping R ~

6 :
the Zl s represent an aliphatic radical having at least two ~ :
carbon atoms, or a cycloaliphatic, carbocyclic-aromatic : or heterocyclic-aromatic radical, in which the carbon-~ : amide groups and carboxyl groups are bound to dif~erent , .
: carbon atoms, and ~he carboxyl groups, if Zl re~presen~s . a cyclic radical and at least one of m and n represents .

.~ . the number 2, are each in the ortho-position with : :
:`~- ` respect to a carbonamide group~ and R~ and R6 independently of one another represent hydrogen, methyl or phenyl.
l ~ _ 4 _ :
',': ~

, .. . .

~ ~ 7 ~ ~Z

The two A s in the formula Ia and Ib represent pre~erably - identical radicals as defined, particu]arly a radical of the formula " ~r~
,1~ 11 and especially a radical of ~he formula -CH=CH-.

If Rg Rl or R2 represent substituted phenoxy groups, these are, in particular, nitro groups, alkyl or alkoxy groups having 1 or 2 carbon atoms, or phenoxy groups substituted by halo~en atoms, especially chlorine or fluorine, such as the 2-, 3- or 4-nitrophenoxy group, 2,4- or 3,5-dinitrophenoxy group, 3,5-dichlorophenoxy group, th pPnta-chlorophenoxy group, 2-methylphenoxy group or 2-methoxy-phenoxy group.

Alkoxy groups R, Rl and R2 can be straight~chai.n or branched-chain. Examples which may be mentioned are: the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, ter~
butoxy, hexyloxy, octoxy, decyloxy, dodecyloxy, ~-etradecyloxy and octadecyloxy group. The groups pre~erred are unsubstituted phenoxy group3 or alkoxy groups having 1-12 carbon atoms ~nd especially 1-4 carbon atoms.

; If R, Rl or R2 represent an -O M+ group, M+ represents, ~ ;
for example, the lithium, sodium, potassium, trimethyl-.: ammonium, triethylammonium~ methyl-diethylammonium or , ":

-..:

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

~722~Z

tri-n-octylammonium cation. Examples of quaternary ammonium cations M~ are the benzyl~rimethylal~monium and tetramethyl-ammonium cation. M~ preferably represents the sodium cation.
The R s preferably each represent a hydroxyl group and the R2 s each a hydroxyl group or an alkoxy group having - 1-4 carbon atoms. The Rl s preferably each represent an alkoxy group having 1-4 carbon atoms, particularly however a hydroxyl group; or two adjacent Rl s together form the -O- grouping.
In the formulae Ia and Ib, the individual Q~ Z~ Z
m and n can have different meanings.
.
Groups or radicals as defined which are represented by Z and Z2 can be unsubstituted or substituted, e.gO by halogen atoms such as ~luorine, chlorine or bromine, or by alkyl or alkoxy groups each having 1 to 4 carbon atoms.
Suitable aliphatic radicals Z or Z2 are, in particular, straight-chain or branched-chain alkylene groups having 2 to 12 carbon atoms, especially unsubstituted alkylene groups ha~ving 2 to 10 carbon atoms, and the al~ylene chain can also be interrupted by hetero atoms, such as 0, S or N atoms-.
Z and Z2 as a cycloaliphatic radical represent, e.g., the 1,3- or 1,4-cyclohexylene group, the 1,4-bis-~methylene)~
', :

j - 6 -~'~

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

3J,~'7224~

cyclohexane group or the dicycloh.exylmethane group.

If Z and %2 represent carboc.yclic-aromati.c radi.cals, these are preferably monocyclic, condensed polycyclic or condensed bicyclic aromatic radicals, and in the case of the last-mentioned the aromatic nuclei can be bound together by way o~ a bridge member.

Suitable bridge members which may be mentioned are~

for example:

Ql Ql -O - 3 -CH2CH2--9 -C~12-, -CH~ C- , -S-S~, -SO-, -S02-, ~S0 : Ql Ql Ql ~CO-, -CO-, -C C , -CO~ ~ CO-~H-, -Si~ or O--Si-O
Il 11: ~1 , , - Ql Ql wherein Ql represents an alkyl group having 1~6, preerably 1-4, ; carbon atoms, or a phenyl group.

Uncondensed bicyclic aromatic radicals Z or Z~ can also : be bound together by way of two bridge members, such as : two -S02 groups.

If Z or Z2 represent a heterocyclic-aromatic radical, : such radical.s are, in particular, heterocyclic-aromatic 5- or 6-membered rings-containing 0, N and/or S.

If Zl represen~s an alLphatic r-dical, such radicals `, , ' . ::
.. . .

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

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

~7Z~42 are preferably u.-substituted, straight-chain or branched-chain, saturated alkylene groups having 1-12 carbon atoms, especially 2-10 carbon atoms.

Cycloaliphatic radicals represented by Zl are, in particular, 5- or 6-membered cycloalkylene groups.

If Zl represents a carbocyclic-aromatic radical, this .ontains pre~erably at least one ~-membered ring; sueh radicals are, in particular, monocyclic, condensed polycyclic or polycyclic radicals with several cyclic, condensed or uncondensed systems, which can be bound together direct or by way of bridge members. Suitable bridge members are the groups mentioned in the foregoing in the discussion of ~ and Z2 If ~1 represents a heterocyclic-aromatic r~dical, possible ring systems are, in particular, 5- or 6-membered heterocyclic-aromatic, op~i.onally benzo-eondensed, ring systems containing O, N and/or S.

Carbocyclic-aromatic or heterocyclic-aromatic radicals represented by Zl can also be substituted, for example by nitro groups, alkyl groups.having 1-~ car~on a~oms, halogen atoms, especially chlorine,or silyI groups or sulphonic aeid groups or sulphamoyl groups~

:

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

The individ~lal Z 5 03- Z2 s in the case where Q ~ -NH-independen~ly of one another preferably represent an unsubstituted alkylene group having 2-12 carbon atoms, ox a monocyclic or uncondensed bicyclic aromatic radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups each having 1-4 carbon atoms, and in the case of the uncondensed bicyclic aromatic radical the aromatic nuclei can be bound together direc~ or by way of the bridge member -O-, -CH2- or~S02-. The indi.vidual Zl s independently of one another preferably represent an unsubstituted alkylene group having 2-10 carbon atoms, or an unsubstituted monocyclic aromatic radical, an unsubstituted condensed polycylic aromati~ radical or an uncondensed bicycli.c aromatic radicaL, and in the case of the last mentioned, the aromatic nuclei can be bound together by way of the bridge member -O- or -CO-.

: Of the oligomers and polymers of the formula Ia, those are preferred wherein the two radicals -N ~ \ ~ independently of one another are in the 3- or 4-position of the benzene ring, R represents a hydroxyl group, X represents hydrogen and A represents the radical -CH=CH-, as well as the corresponding cyclised derivatives.
:: :.

~: . 9 , . :
. ., . . .: . . . .. . . . . . :

. . . : . . . :
... . . . . ... . . ..

~7ZZ~iZ

~ nong the oligomers and polymers of the formula lb, those are preferred wherein ~he Rl s each represent an alkoxy group having 1-4 carbon atoms, and especially those wherein the Rl s each represent a hydroxyl group, or two adjacent Rl s together form the -O- grouping, and the corresponding cyclised derivatives.

According to a further preferred embodi.ment, there are used for the mixtures according to t'ne invention oligomers or polymers of the formula Ia or Ib wherein Q represents -NH-, Z represents an unsubstituted alkylene group having 2-10 carbon atoms, or a carbocyclic-aromatic radical, particularly the 1,3- or 1,4-phenylene group, the 4,4'-diphenyl ether group~ the 4,4'-diphenylsulphon.e group or the 4,~ diphenylmethane group, and Zl represents an unsubstituted alkylene group hav:ing 2-1.0 carbon atoms, or a carbocy~lic-aromatic radical, especially the 1,3- or 1~4-phenylene group, a benzenetriyl or benzenetetrayl group or the benzophenone ring sys~em.

~` More particularly preferred are mixtures according to the invention with oligomers or polymers of the formula Ia or Ib, wherein A, X, R and RL have the-preferred meanings mentioned in the foregoîng, a represents an integer from 1-10 and Q represents -N~-, and wherein ' ~' :

.

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

~L~72Z42 - m and n represent the number 1, Z represents the 1,3- or 1.,4-phPnylen~ group, the 4,4'-diphenylmethane group or 4,4'-diphenyl ether group, and Zl represents an alkylene group having 2-10 carbon atoms, the 1,3- or 1,4-phenylene group~ with however only one of Z and Zl representing a 1,4-phenylene group;
- m and n represents the number 2, Z represents the 4,4'-diphenylmethane or 4,4'-diphenyl ether group, and Zl represents a benzenetetrayl group or the benzophenone ring system;
- per structual element a, m represents the number 1 and n the number 2, Z represents the 4~4'-diphenylmethane group or 4,4'-diphenyl ether group, and Zl represents a benæene-; ~riyl group;
as well as the corresponding cyclised derivatives.
As diamines are preferably used compounds of the formula II wherein Q represents -NH-, and Z2 represents an unsub- . .
: stituted alkylene group having 2-10 carbon atoms, or a ~ carbocyclic-aromatic radical, particulàrly the 1,3- or 1,4- ~ :
- phenylene group, the 4,4'-diphenylsulphone group and, in particular, the 4,4'-diphenylmethane group or 4,4'-diphenyl ether group, It is also possibLe to use mixtures of different oligomers . ~ , . .
- 11 :~

,- .
.
; .' . i - . . ..

~ ~ 2 ~ ~2 or polymers o the formula Ia or Ib, and/or mixtures of differerlt diamines of the formula II.
The molar ratio of the oligomers or polymers of the formula Ia and/or Ib, or of the corresponding cyclised derivatives, to the diamines of the formuIa II is preferably bet~een about 1.3 : 1 and 10 : 1.
: The oligomers or polymers of the formula Ia or Ib can be obtained by a process wherein (a) a compound of the formula IIIa .
. ~ CO~ ~ CORl' (IlIa) ~ CO~ 3 ~ COR
or (b) a compound of the formula IIIb ~ / ~OCl N (IIIb), /
OC~ CO

:or a mi.xture of two different compounds of the formula IIIa :
or~IIIb, wherein in respect of A and X that applies which ., ~ :
has been statecl~-mder the formulae Ia and Ib, and the Rl' s independently of one another represent a hydroxyl group~;an unsubstituted or su~stituted phenoxy group, an alkoxy group ` - 12 -, ' ,, -, , : . . ,, : . ~, .

~ . ` , i: .
- ~ .

~07Z29~2 having 1-18 carbon atoms, or ~he two ~1' s toge~.her represent the -O- grouping~ is reacted, in the molar ratio of 2:1, with an oli.gomer or polymer of the formula lV

~Z - _ ~-()C\ ~COOII)m-~.
: . ~ 1 \ (IV), . ~I-IOOC)n l CO~Q-Z - - QH

or with a corresponding cyclised derivative, wherein in respect of a, m, n, Zl~ Z and Q or -Q-Z-Q- that applies which has been stated under the formul.ae Ia and Ib; ~.
arld the resulting oligomers or polymers of the formula Ia or Ib are optionally subsequently cyclised and/or converted into another derivative as defined, i.e. into a compound o~ the formula Ia or Ib wherein the R s, ~1 s or -COR2 s have another meaning as defined. ~-In ~hP case of eventuaL cyclisation o~ the compounds of the formula Ia and Ib there OCC-ll^S the for~mation of imide, and in the case of compounds of the formula Ib optionally also of anhydrldeO Cyclisation is performed, in a manner : known per se, chemically or preferably thermally.

Chemical cyclisation is advantageously performed by ~reatment with a dehydrating agent alone or in admixture with a tertiary amine~ It is possible to use, for example, - 13 - ;-. -.

. . . . .
, , : ~ :

~07229~2 acetic acid anhydride, propionic acid anhydride and dicyclo'nexylcatbodiimide, or mix~ures of acetic acid anhydride and txiethylamine.

Thermal cyclisation is perform~d by heating at temperatures of about 50-250C, preferably about 100-150C, and optionally wi~h the addition of a solvent and/or of a water-entrainer such as xylenes or toluene. At temperatures above about 150C there generally occurs~ at least partially, also crosslinking.

The conversion into other oligomers or polymers as defined of the formuLa Ia or Ib can be performed in a manner kno~7n per se, e.g. by hydrolysation of compounds with anhydride groupings to give the correspondlng free acids, reaction of the free acids with alcohols or with salt-forming bases to yield compounds of the fonnula Ia or Ib~ wherein R, R
or R2 represent alkoxy, pheno~y or -0 M~ groups as defined or by transesterification.

The compounds of the formulae IIIa and IIIb can be obtained by a process wherein an amine of the formula V

.

;~ ~ 1 (V) ~ - 14 -:, ~ ' .

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

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

~L~337224L~2 is reacted ~ h an anhydride Or the formula ~ CO~ (~7I);
\CO
and the resulting amidocarboxyl;c aci.d of the formula VIJ
x ~f~, .C~P~"
~A~co-N~ 5 ~ (VII) .
is subsequently cyclised and optionally converted. into anot'Qer d~.ri.vative as defined of the formula IIla, or into a compound of the formula IIIb.
-In the above formulae V to VII, A has the gîven meaning and X' represents hydrogen or, if the a.mi.no group is ln the 4-posi~ion of the benzene ring, also -CO~2', Rl' and R2' represent h.ydroxyl, phenoxy, alkoxy or -O ~ groups corresponding to R or R2, wi.th however phenoxy groups ~r and R2l being free from electronegative substituents, such as nitro groups or halogen atoms, and ~' having in the case u where R'l = OH a meaning other than -O M', and in the case ..
where R'l = -O M a meaning other than -OH.
' Compounds of the formul.a IIIa wherein Rl' and/or R2 (where X -- -COR2) represent phenoxy groups having elect~o-, negative substituents are advantageously produced by ...
i reaction of t~e correspon.ding anhydrides or acid anhydrides - lS - ~

., ~

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

~ ~ 2 with suitable alcohols; or by transesterification of compound~
of the fonn~la IIIa, with Rl' and/or R2 being alkoxy or phenoxy which is free from electronegative substit~lents.

The reaction of t'ne amines OL the fonnula V with the anhydride of the formula VI can be perlormed in the melt, in an aqueous or aqueous-orgarLic medium ~r prefera.kly i.n an organic medium. ~ -~ For c~-clisa~ion of the amidocarbo~ylic acids o~ the : formula VII, it is possible to u3e customar-~ oat31yst~;
such as sodi~ acetat2 or triethylamine,.and/or dehyd.-a~.ing ag~nts, e.g. acetic acid anhydride. Simultalleousl~7~ h the formati~n of imide there occurs unde~ cortain circl~ms~ances, i.e. dependin~ on tha nature of the 8ubsti~u~nt R't~ â.lsO
the ormation of anhydride, e~g. if R'7 = -OH.
.
The conversion of the re~ultin~ comDounds i.nto other .
~: derivativ~s, as de~ined, of the formula IIIa or into compounds of the formula IIIb is perfo.med in a co~ventional ~
manner, for example by the ~ethods r.len~ioned in th~ fore~oing. :`
Acid chlorid2s of ~he formu~a ITIb can be ~roduced, e.g., :~ by~:reaction of compounds of tha formula IIIa, where~n X G
COR2 and R2 = -~ or -O M~, with sui~abla chlorihatin~ ~ -.agents~ sucll a3 thionyl chloride ~ : - 16 ~

' . ,: .. ' : : . , , ~ . ............................ ' ' . :
' . ,, . . . `' ` "` ' `' ~. ` ' ':

1~72Z42 --Oligomers or polymers of the formul~ IV can be obtained, .
~n a manner kno~m per se, by condensation of di~, tri-or tetracarboxyLic acid derivativ~s of the formula VIII

~1C \ / (C0~3 21 \ (VIII) C)~_l COI~
:
~her~in ~, n and ~1 have the meanings given under the :-formulae Ia and Ib, and - Ml -represen~s a chlGrine ato~, a hydroxyl group, ~n unsubstituted or su~stitut2d phenoxy group or an alkoxy group havi.ng 1-18 car~on atcms, - , : . .
or M~, if m alld/3r n -t 2, together ~?lth an M2 ~rF~ the -O- .
grouping, wherein the groups -COMl ~nd -COM~ are bound to . .
: . di~ferent ca~bon atoms, and the -COMl group or ~roups, if Zl represents a cyclised radical and m and!or n = 2, is or are n the ortho-pos.. t::~.cr ~?i~h re.~ipect i~o ~ -COM2 C,ro~p~ :
: with an excess o~ a diamine o~: the formula IX

HQ - Z - Q~ IY) wherein in respect o~ Q and ~ or -Q-Z-Q- that applies which ~:
has ~een~sta~ed under the ormulae~Ia~an~ Ib; and possible ::
subse.quent c y c l i ~q a t i oD .

~ It-is also~possible to use mix.~lres of di~Ierent co~pound.s :~ of the ~o~mu 1 a VIII and diamines o~ :~he ~orr~ula I~

.
, ~
- , .
: . :.

.,~ ~

` ~ ~ 7 ~ ~ ~Z

If ~1' s in formula IIIa or Ml s in formu].a VIII , represent unsu~s~ituted or subs~ituted phenoxy groups or . alkoxy groups having 1-18 carbon atoms, preferably 1-12 carbon a~oms and especially 1~4 carbon atoms, possible groups are, e.g., those mentioned in the foregoing in the discussion of R, Rl and R2.

, The diamines of the formula II and IX and also the compounds of the ~ormula VIII are known per se. The ~ollowing may be mentioned as examples of diamines of the forrQu]a II
or IX: o-, m- and p-phenylened;c~mine, diaminotoluenes such as 2,4-diami.notoluene, 1,4-diamino-2-methoxybenzene, 2,5-dic~minooxylol, 1,3-diamino-4-chlorobenzene, 4,4'-diamin~-diyhenyLmethane, 4,4'-diamin.odiphenyl ether, 4~4'-di2l~ino- :
~iphenylthio e~l~er, 4,4'-di.aminodiphenylsulphone, 2,2'- ..
diaminobenzophenone, 4,4'-di~minod~phenyLurea, 1,8- or 1,5-.di~minonaphthalene, ?,6-di~r.inopgridine, 2,4-dia~inopyrill~id~n~, 1,4-piperazine, ~,4-diamir~o~ ria7~ine, di-, txi~, tetra-, hexa-, hepta-, o~ta^5 deca- and dodecamothyl.en2dia~ine, 2,2-dimetllylpropylene~iamine, 2,5-dimethylhexc~methylene-diamineS 4,4-dime~hylhe~amethylenediamine, 3-methylhepta-methylenediamine, 3-methoxyhexametllylenediarnine, 2,11-diamino-dodecal~e, ~,2,4- and 2,4,4-trimethy7hexamethyl2nediamine, 192-bis-(3-amir~opropoxy)-etharle, N,N'-dimethylethylelle~iamine, :~

: - 18 - .
....

.
, ~

. .
. ~ . .-::

.
. . ''; '' %~z N,N'-dimethyl~ diaminoh2xan2, as well as ~he di~mines e H2N(~H2)30(CH2)2o(CH2)3NE~2 and H2N(CH ) -S(CH2)3NH2; and 1,4~diaminocyclohexane.

Ex~mples of suitable di-, tri- and tetracarboxylic acid derivatives of the formula VIII a e: m~lonic acid, dimethylmalonic acid, succinic acid, glutaric ~id, adipic acid, suberic aeid, sebacic acid and dodecanedicar~oxylic acid, 173-c7clopentane-dicarboxqlic acid, hexahydroiso-phthalic acid~ hexahydroterephthalic acid, ~e~ephthalic a.cid, . .... .
isophthalic acid, 4,47-dicarboxydiphenyletll2ne, naphthalene-- 2,6-dicarboxylic acid, thiophene-2,5-dicarboxyli.c acid and pyridi~e-2,3~dicarhoxylic acid, as well as thP cor~.esponding dichlor7~es ~nd di.es~ers a.s d~.f~ned; ~ri~.elli.~:t.c ac~..d-1~2--anhydride hloride (1,3-~i.G~ob2.nz3~3Gx21ane~ carboxylic acid chloride), trimellitic acid anhydr-de as we].l as esters as defined; pyromelli~ic a~id dianhydride~ 3,3',~,4'-benæophenone-tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone-tetracarboxylic acid dia~h-J~dride, ~,2',~:,3~-.
~enzophenore~tetracarboxylic acid diallhydride, 3,3?~j,4'~
diph~nyltetracarboxylic acid dianh~dride, bis-(~,3-dicar~ox7- ~
phen~l)-methanedianhydrLde, bis-(2,5,6-trifl~l~ro-3,4- . ;
dicarboxyphe~yl) -methanedi~nh~dride~ ~, 2-bis~ (2, 3-dicarbo~y : : :
phenyl)-propane-dianhydride, ~is-(3,4-dicarbo~yphenyl)-ether-. .
dianhydride~ bls-(3,4-dLcarboxyphenyl)-sulpho~e dianl~ydride - lg - . .

.
: .

..,. -~ ' '.,, ~ :: :~: ~"
. ' . , ~ .:: ` . . ., ' . ~.
' . , .:
.: :

'1~7;~;~4Z - :

N,N-~3,4-dicarbcxyphenyl3-N-methylamine diclnh~dride, bis-(3,4-dicarboxypllenyl)-diethylsilane dianhydride, 2,396,7--and 1,2,S,6~naphthalenetetracarbo~ylic acid dianhydrlde, ~.. --- .
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride and pyridine-2,3,5,6-tetracarboxylic acid d~anhydride.

.. As dicarboxylic acid derivatives are preerably used dicarboxylic acid dichlorides. `~

~ he condensation of the compoonds of the formul.ae IIIa, IIIb and VIII with the oligomers or polymers o~ the formula I~7 or the diami.nes HQ-Z-QH is perormed in 2 manrer known per se, advantageousIy at temp~ratures of about -50~C
to +300C. The condensation can be performed in the melt or preer.~1y in an ine.t.organic so].~- n~ or in a solvent mixture. Temp2rat-lres of -20C to ~50~ are preferred for -.
:the eondensation in solutions. For tl~e reaction of the : --compounds of the formulae IIIa and IIIb with the comyo~nds o f the fonmula~IV, the addition o~ known polymerisa~ion inhibitors, such as hydroquinones, brenzcatechin or cresols, e.g. di-tert.butyl cresol, can un~er cer-tain circumstances be advantageous~

As organic solvents it i.s possible to use, e.g.
20 ~

' : ' . ' . , ,' :~7;~24~ ~

-- optionally chlorinated aromatic hydrocarbons, such as . benzene, toluene, xylenes and chlorobenzene;
- chlorinated aliphatic hydrocarbons, such as methylene chloride, chloroform, tetrachloroethane and tetrachloro-ethyLene;
.- aliphatic and cycloaliphatic ketones, such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone;
- cyclic ethers, such as tetrahydrouran, tetrahydropyrane and dioxane;
- cyclic amides, such as N-methyl-2~pyrrolidone, N-acetyl-2-, pyrrolidone and N-methyl- -caprolactam;

- N,N-dialkylamides of aliphatic monocarboxylic acids ba~ring 1-3 carbon atoms in the acid moie~, such as W,~-dimethyl , . . .
formamide, N,N-dimethylacetamide, N,N-diethylace~a.nid2 :
and N,N dimethylmetho.Yyacetam de; ~
- ethylene glycol mon~allyl ether and cLhyle~e-glycol dialkyl ether each having 1 4 carbon atoms in the alkyl moieties, such as ethylene gIycol monom.Q~hyl ether, e~lylen~ glycol monoethyl ether, ethylene glycol monoisopropyl ether and et~ylene gIycol mono-n-butyl ether,:ethylene glycol dimethyl ether and ethylene glycol diethyl echer;
- alkyl esters of aliphatic monocarbo~ylic acids having a : .
total of 2 6 carbon a,oms, such as:~formic acid or acetic acid methyl ester, formic or ~cetic acid ethyl ester and . - 21 ~
~: :
` ~ :' ',~

:

: ~,~
,~ .` : .
. .
- ,:
: ' , - ~0~7ZZ4Z

formic acid or ~cetic acid n-butyl es~er;
- he~amethylphosphoric acid triamide (hexametapol);
- N2NsNl,N'-tetram~thylurea;
tetrahydrothiophene dioxide (sulpholane); and dialkyl sulphoxi~es, such as dimethyl and diethyl sulpho~ide.

It is also possible to use mixtures of such solvents~

Preferred solvents are N,~7-dialk~rlamides of aliph~tic monocarboxylic acids having 1-3 carbon atoms in the acid moiety, especially N,N-dimethylacetamide, as w211 as c-~clic ~mides, such as N-methyl-pyrrolidone. ~ ;-The hydrochloric acid forming on condensation or . .
poly~ondensation of compounds o the formula lIIb or VIII, ,;
:wherein Ml represents chlorine~ with the oligomers cr polymers of the formula IV or the d-i~oines of the ~ormula IX, can be remo~7ed by neutralisation with basic substances : :
~such as calcium hydroxide or trîethylamine, or by re~ction with an epoxide. compou~d such as ethylene o~ide or propylene oxide, and by ~.7~shing out witù suit~ble soIvents, e.g. water.
The condensa~ion reactions ~re adv~n~a~eously performed - .
with the exclusion of mois~ure, e.g. in an inert-gas atmos~
phere, such as nitrogen.

By~heating of thè crosslinkable mixtures according to - 22 ~
.

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

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

~ ~7 ~ Z ~2 the invention at temperatures of between ~bout lOO and 300C, preferably between 100 and 200C, it is possible to produced imidised or cyclised, and optionally partially crosslinked, pre-pol~ers. The pre-polymers according to the invention still contain crosslinkable groups, are soluble in the usual organic solvents, such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl~
pyrrolidone, and can also be processed in general from the melt. The pre-polymers can be produced by known methods, e.g. in the mel~, or in the presencP of an inert organic solvent 5 e.g. those of the aforementioned type or mixt~res thereof.

Preferred solven~s for the production o- the pre-polymers are: N,N-dialkylamides o~ alipha~ic monocarboxylic acids :
having 1-3 carbon atoms in the acid mciety, especially N,N~
dimethylacetamide, methylene chloride, chloroform and ~; cyclic amides, such as N-methyl-2-pyrrolidone. Depending on the purposc o~ applica'ion, it can als~ be ~dvan~ageous to per~orm th~ reacti on in the presence of catalytlc amou~ts of a st~ong acid (about 0.5 - 5 pe~ cent by ~-eight, relativ2 to he weight o~ the compo~lnd of the formula Ia and/or Ib), ~ ~
and optionally in the presence o~a ra~.ical~initia~or or o~ ~ -a radical inhibitor.

- ~ ~ 23 -:, , :
.

: .
,.

1~7;~242 Strong acids which can be used are~ for exanple, inorganic or organic acids having a pKa value in water oi below 5, such as hydroch.lorie, hydrobromic and hydro-fluoric acid, perchloric acid, s~lphuric acid, phosphoric acid, nitric acid, aro~atic or alipha~ic sulphonic acids and sa~ura~ed or urlsaturated aliphatic carboxylic acids, such as meth2nes~l1?hon~c acid; benzene.sulphonic acid~
p-toluenesulp~or.ic acid, dichloro- and trichloroacetic acid, trifluoioa~etic acid and maleic aoid.

Example3 of suitahle radical initiaLors are inor$anic and organic peroxLdes or azo compounds, e .g. hydrogen pexoxide5 tert.butylhydroxy peroxide, peracetic aci~
benæoyl peLo~:~de, tert.butylperDenzoate, cumolh~Tdroperoxide, dicumyl peroxide and a,a~-azo-isob~1t~7ronitrile~ : :

Suitable radical inhibitors are, e.g., hydroquinone, brenzcatechin, di-ter.. butyl cresol, picric acid and :
diphenylpicryl hydrazine.
.
The pre-polymers according to the -lnven~i~n can be converted in a second stage, by known methods, into fully crosslinked products, which are insoluble în the customary ;~ . :
organic solvents.~Alternative1y, it~is also possible to~
process and to crosslink directly the mi~tures,~accordlng ~ ; ~
to the invention9 of co~pound:s of the formula Ia andlor ~ :

- 24 ~
,: ~ : .
: ~ . . : . : : : . .
, , . ~ ' . . . . . . . . .. .. .

:L~7Z;~Z

Ib and diamines. The crosslinking can be performed, in a kllOWn manner, chemically or thermally, or under the influence of elec~romagnetic waves9 especially light.

Chemical crosslinking is generally performed a~
temperatures of about S0 to 250C, in the presence of radical initiators of the aorementioned t~pe. The~mal crosslin~ing is performed advantageously ~y hea~in~ a~
temperatures of about 350C, preferably 1~0-250C, and also radical initiators may be concomitantly used. Cross- -linking under the influence of electromagnetic waves can . .
b~ perormed, e.g.` by irradiation with X rays or ~ith W li&ht, and optior.ally in tlle presence of sensit;sers, .
such as benzene, 1,4-diacetyl~en~ene, phenol, ben~onitrile~
acetophenone, ben~ophenone, ben2aldehy~e~ d--isopropyl ketone and fluorene.
-The mîxtures and pre-polymers according ~o the invention are suitable for the production of industrial prod~cts s-lch , ~ ~
~s fi~res, ~ilms (sheets), coating cor.pounds, lacquers, foam plasti.cs, adhesives, laminating resins, c.omposi~e materials, mouldin~ powders, moulded articles and 90 forth?
in a manner known per se and optionally~with th use of customary additives, such as~pig~ents,~fillers,~etc. The~

, ~ ~
pre-polymers according to the invention can also be processed ~ -25 ~

- - ~: :

:~ ;
,, , , ~ . .

~7224Z

:
from the melt. The products ~btained on crossiir~king have good mech~nlcal~ ~iec~ical at~d/or therma1 properl:ies.
They are d_sJ;in~uished in par~:icuiar by their high thermooxide.tl.~e stability.

, ' ~

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

. . . .
.

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

. : : . . ~

26~

- ; . .~:

.. . , , , ., ", . .

~'722~Z . :

' . - :
In a nitrogen atmosphere ill a ~ulphonating fl~sk, 15.~6 g (0008 mole) of 4,4'-diam-Lnodiphenylmethane is dissolved in 180 ml of anhydrous ~imethylacetamide (DMA), and '.h~ solution is cooled to -15 to -20C. With stirring, 12.63 ~ (O.OG mole) of trimellitic acid anhydride chloride in solid orm i5 added portionwise in such a manner that the temperature of the reaction soluti.on does 110t exceed -15C. The solution is then stirred 2t -15C for 30 minute.s and af ~0-25~C ~or ~ : :
.
one hour. 6.07 g (0.06 mole~ of ~rie~ 71a,.li~e in 50 mL of ~ `~
DMA is then ~dded dropwise, wh~reupon a fine precipltaLe is formed. The reactioll mi~:tur~ ;.s stirred or a f~rther hour at 20-25~, and an 2ddi ion is su~seq~lell~Ly ~ade po-.~ionwi~e &t 15-20C o~ 9.72 ~ (Q.04 mole) of a 1~
:
mix~ure of 3- and ~_malel.~idylph~ 1Lc ac~d a~ ydride. .

~ After one hour's stirring ~t 70-25C, Lhe precipitate~

:; ~ triethylaminie hydrochLorid~ is separated by filtration. To the filtered reac~.ion so~ution is then ~.dded dropwise, with :~

~stirring, 160 ml of ace~ic acid anhydride and stirrillg is ~ continued at 20-25C for 1~6~hours. Th~; r2action soluti~ ~i.s -~ : subsequntly poured onto water~ the precipitated~product . ~
_ is separated, ~iashed several times with water and dr~ed in:
a vacuum drying cham~er for 16 hours at ~0C/lCO~torr and~

~ 27 ~
~ : : ':: ~':

.

:

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

2~
for 16 ~lours at 80C/10 2 ~orr. 32 g-of a crosslinkable oligo~mide-imide in the forrL~ of a yellow powder is obtain2d.

12.84 g (0.0075 mole) of the above oligoarnide-i~ide and 0.89 g (0.0045 ~ole) of 4~4'-diaminodiphenylmethane are dissolved in 85 ml of anhydrous DM~, and the solution is heated in a nitrogen atmosphere, with stirri.ng, at 130C for 2 hours 30 minutes. The solution obtained, after cooling to about 25C, i5 poured into ice water; the precipitated product is filtered off~ washed with ~7ater and dried for 20 hours at 80G/IOO torr and 80C/10 1 torr~
respectively.

.
F~r processing by the compression process, the pre-polymer obtained is introduced into a compression mould, prehea~.ed - to 240C, for circular discs, ~nd moulded at this temperature for 35 minuts under a pressure of 450 kp/cm . Annealing for 16 hours a~ 2~0C yields solid moulded specimens h~ving good e].ectrical properties.
!

ln a nitrogen atmosphere in a sulphonating flask, 4032 g (0.04 mole) of m-phenylenediamine is dissolved in 100 rnl of anhydrous DMA, and the solution is~coole~ to -15 to 20C.
With stirring, 8 37 g (0.035 mole) ~f sebacic acid dichloride , .
.. .
'i ' ' -.
:

~, . . ~
. :

~7Z;~

is added dropwise in su~h a manner that th- temperature of the reactioll mixtur2 does not exeeed -15C. The reaotion mixture is then stirred at 20-25C for a further hour.
With renewed cooling to -15C, 7.08 g (0.07 mole) of triethylamine in 1~ ml of DMA is added dropwise, whereupo a white precipitate is formed. The reaction mixture is stirred at 20-25C for a further hour~ and the precipitated triethylamine hydrochloride is separated by filtration.
The precipitate is washed with 30 ml of DMA7 and to the ~iltrate is added at 0C 2.43 g ~0.01 mole) o~ 3-male~
imidyl-phthalic acid anhydride. The resulting reaction solution is stirred for 2 hours at 20-25C. S0 ~1 of acetic acid anhydridP is then added; the reactîon soluticn ls stirred for 16 hours at 20-25C, and is finally poured into water. The precipita~ed product is iltered off~
washed several times ~ith water and dried in a vacuum dryinO
chamber for 16 hours at 80C/20 torr ~nd for 16 hours at 80C/10 torr. There is obtained 11. g of a crosslinkable oligo~mide.

3.0 g (~bout 1.5 mMol) of this oligo~mide is mixed wLth 0.178 g (0,9 m~Iol) of 4,4'-diaminodiphery]irethane a~ 20GCC in the melt. The ?~ ture is maintained for 10 minutes at this temperature and, after ~ooling, ground ~o - 29 - ~

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

~ : . .

~7ZZ~

a fine powder. This is moulded, by the compression process analogous to Lhat in Example 1, at 225-230C for 30 minutes under a pressure of 325 kp/cm into the form of transparent discs having a good mechanical strength.
The 3_maleimidylphthalic acid anhydride used in the foregoing Examples can be produced~ in a manner kno~m per se, by reaction o 3-aminophthalic acid with maleic aci~
anh~dride and cyclisation of the resulting amide acid with anhydrous sodium acetate and acetie anhydride (see DOS 2,459,673). -~

Example 3 . .
By the procedure described in Example 1, 1.62 g(0.015 mole) o~ m-phenylenediamine, 2.03 g (0.01 Lr.o3ej of isophthalic aeid dichlorlde,~ 2.02 g (0.02 mole) o~ triethyl-- amine and 2.43 g (0.01 mole) of 3_maleimidylphthalic acid ~ -.
-anhydride are reacted in 40 ml OL anhydroùs D~A. To the formed reactiori mixture is added 0~59 g (0.003 mole) of-

4,4'-diaminodiph~nylmethane, and ~he mix~ure is stirred for one hour at 20-25C. After removal by filtrat-~on of the~
resultin2 precipitate ~triethylamine hydroc~.loride3~ t~-Le reaction ~olution is poured onto al~mini~r. pl~tes. The coatings are dried for 16 hours at 80C/20-torr, 1 hour 30 ~
. . .. ..
~, . . . . .
:
: - . , ~ :

. .
' ..

.

~ ~ 7'~ Z 4Z

respectively at lOO~C/20 torr, 120C/20 ~orr and 14QC/20 ~orr, 2 hours at 150C/20 torr and for 16 hours ~t 200C/10 1. Transp~rent, slightly brittle coa~ings ar~
obtained.

Exc~m2~e 4 2.48 g (0.0125 mole) of 4,4'-diaminodiphenylmethane is dissolved in 27 ml of anhydrous DMA in a nitrcgen atmosphere i~ a sulphonating flask, and the solution is cooled to -15C. With stirring, 2.03 g (0.01 mole) of : isophthalic acid dichloride is added portionwise in such a manner that the temperaeure does not exceed -15C.
Stirring is continued for 30 minutes at -15C and or one ~ .
hour at 20-25C~ The rc~c ction mixtvre is then cooled a~ain . . .
-to -15C, and 2.02 g (0.02 mole) of triethylar~line iQ 2 ml :
of Dl~ is added dropwise. The mixture is s tirred ror 1 hovr at 20-25C and ~llen cooled again to -15C, whe-eupo~ 2091 g ~ O.Ol mole) of 4_m~1eLmidyl~rimellitlc aci~ anhydride chlori~e is added. After a further l hour's sti.rring at 20-25C and sv.~scq~len~ cooling to -15~C, -~n addi~ion is made dropwise of 0.5Q g {G.005~moie) of triethylamine in : 2 ml o~ DMA. Stirring is a~ain performed for one ho~lr at ; 20-25C, and 0.2~ g (O.OOl mole)~of 4,4'-diaminodiph2ny].
ether is added. After a further one hour's stirring at 20-25'C, 31 - :
, F

: L
"~ ~' ~G~722~2 the precipitated triethylamine hydrochloride is filtered o~f and the reac~ion solutior~ is pou~ed onto alu~inium - plates.
Curing is performed for 6 hours at 100C/20 torr, 1 hour at 120C/20 torr, one hour at 150C/~0 ~orr and 16 hours at 200C/10 1 torr. Transparent flexible coatings are o~tained~

. The 4_maleimidyltrimellitic acid anhydride chlo~id2 ~ :
- :
used in the above Example can be:produced as follo~Js: ~ :

~ 102 g (0.4 mole) of 4-nitrotrimellitic acid (obtained by : nitration of trimellitic acid anh-~dride with H2S0~/H~03) ~ .
ls hydrogenated in the presence of 10 g of a palla~ilL~ ;
: ~ charco21 catalyst, containing 5~%~b~J weight of ~d, at 30C
in lO00 ml of dioxane. The: reaction solution is filtered ~ ~ .
. .
~ ~nd 46.8 g (0.48 mole) of maleic acicl anhyd~ide is then ~ :
., added. The reaction mixture is allowed to stand~for l2 hou-s-~at 20-~25~C and is subæequently concentrated to dr~le.ss at~
60C in a rota~y e.v6p~rator. The resic;ue:is heated t~ice~
to boiling? with stirt i~ wl.th ~CO ml of~acetic acid ethyl ~: . :
ester each time, and dried at~80C/100 torr l.vr 24 hours.to~
obtain lOS 8 f 4-maleamidyltrimellitic ~c d.~ 32.2 g 0.1 mole) of the 4-maleamidyltrimellltic acid is mixed with:1.6 g of anhydl~ous sodi-un acetate and 83 ml~of acetic : . . . .: ~ : : .

1~7;~242 .

anhydride and heated for 30 min~tes at 80C. The r~sulting solution is concen~rated by evaporation to dryness and subsequently dried at 50C/O.OS torr. To the residue is added 200 ml of thionyl chloride, and the reaction ~ixture is heated at 80C for 2.5 hours. It is then concentrated to dryness; 150 ml of benzene is added, filtration is performed and ~he filtrate is concentrated by evaporation and finally dri~d at ~0C/O.l torr. On washing with cyclohexane and bellzene a-.d drying, there is obtained . .
18.31 g of crystal]~'ne 4 maleimidyltrimellitic acid anhydride chloride, m.p. 143-14~C.

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

' `:
.

:, :.
-~ _ ~3~ ~
.. . ., . . ~ .

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

Claims (9)

WHAT WE CLAIM IS:

1. A crosslinkable mixture which consists of at least one oligomer or polymer of the formula Ia or Ib (Ia) or (Ib) or of a corresponding cyclised derivative, and of at least one diamine of the formula II
HQ - Z2 -QH (II), whereby the molar ratio of oligomer or polymer of the formula Ia or Ib, or of a corresponding cyclised derivative, to diamine of the formula II is between about 1.2 : 1 and 50 : 1, and wherein the X is independently of one another represent hydrogen or, if the radical is in the 4-position of the benzene ring, also -COR2, the R s and R2 s independently of one another are a member of the group selected from a hydroxyl group, an unsub-stituted or substituted phenoxy group, an alkoxy group having 1-18 carbon atoms and an -O-M+ group, the R1 s independently of one another are a member of the group selected from a hydroxyl group, an unsubstituted or substituted phenoxy group, an alkoxy group having 1-18 carbon atoms, and an -O-M+ group, or two adjacent R1 s together represent the -O- grouping, the A s independently of one another are a member of the group selected from a radical of the formula , , , , and , R3 and R4 independently of one another are a member of the group selected from hydrogen, chlorine, bromine and methyl, M+ is a member of the group selected from an alkali metal cation, a trialkylammonlim cation having 3-24 carbon atoms, and a quaternary ammonium cation, a represents a number from 1-100, m and n independently of one another represent the number 1 or 2, the Z s and Z2 s independently of one another are a member of the group selected from an aliphatic radical having at least 2 carbon atoms, a cycloaliphatic, a carbocyclic aromatic and a heterocyclic-aromatic radical, the Q s represent -NH-, or -Q-Z-Q- or -Q-Z2-Q- represent the grouping the Z1 s are a member of the group selected from an aliphatic radical having at least two carbon atoms, a cycloaliphatic, a carbocyclic-aromatic and a heterocyclic-aromatic radical, in which the carbon-amide groups and carboxyl groups are bound to different carbon atoms, and the carboxyl groups if Z1 represents a cyclic radical and at least one of m and n represents the number 2, are each in the ortho-position with respect to a carbonamide group, and R5 and R6 independently of one another are a member of the group selected from hydrogen, methyl and phenyl.

2. A crosslinkable mixture according to claim 1, which contains at least one oligomer or polymer of the formula Ia, or a corresponding cyclised derivative, wherein the two radicals independently of one another are each in the 3- or 4-position of the benzene ring, R represents a hydroxyl group, X represents hydrogen, and A represents a radical -CH=CH-.

3. A crosslinkable mixture according to claim 1, which contains at least one oligomer or polymer of the formula Ib, or a corresponding cyclised derivative, wherein A represents the radical -CH=CH-, and the R1 s each represent a hydroxyl group, or two adjacent R1 s together represent the -O-grouping.

4. A crosslinkable mixture according to claim 1, which contains at least one oligomer or polymer of the formula Ia or Ib, or a corresponding cyclised derivative, and at least one diamine of the formula II, wherein Q represents -NH-, the Z s and Z2 s independently of one another are a member of the group selected from an unsubstituted alkylene group having 2-10 carbon atoms, the 1,3- or 1,4-phenylene group, the 4,4'-diphenyl ether group, 4,4'-diphenylsulphone group and the 4,4'-diphenylmethane group, and Z1 is a member of the group selected from an unsubstituted alkylene group having 2-10 carbon atoms, the 1,3-phenylene group, the 1,4-phenylene group, a benzenetriyl group, a benzenetetrayl group and the benzophenone ring system.

5. A crosslinkable mixture according to claim 1, which contains at least one oligomer or polymer of the formula Ia or Ib, or a corresponding cyclised derivative, wherein A
represents a radical -CH=CH-, X represents hydrogen, R represents a hydroxyl group, R1 s each represent a hydroxyl group, or two adjacent R1 s together represent the -O-grouping, a represents an integer from 1-10, Q represents -NH-, where m and n = 1, Z is a member of the group selected from the 1,3-phenylene group, the 1,4-phenylene,group, the 4,4'-diphenylmethane group and the 4,4'-diphenyl ether group, and Z1 is a member of the group selected from an alkylene group having 2-10 carbon atoms, the 1,3-phenylene group and the 1,4-phenylene group, with only one of Z and Z1 represen-ting a 1,4-phenylene group" or, if m and n = 2, Z is a member of the group selected from the 4,4'-diphenylmethane group and the 4,4'-diphenyl ether group, and Z1 is a member of the group selected from a benzenetetrayl group and the benzo-phenone ring system, and, where m = 1 and n = 2, Z is a member of the group selected from the 4,4'-diphenylmethane group and the 4,4'-diphenyl ether group, and Z1 represents a benzenetriyl group.

6. A crosslinkable mixture according to claim 1 having a molar ratio of oligomer or polymer of the formula Ia or Ib or of a corresponding cyclised derivative, to diamine of the formula II of about 1.3 : 1 to 10 : 1.

7. A crosslinkable mixture according to claim 1, which contains as diamine of the formula II 4,4'-diaminodiphenyl-methane or 4,4'-diaminodiphenyl ether.

8. A pre-polymer which is obtained by heating a mixture of at least one oligomer or polymer of the formula Ia or Ib, or a corresponding cyclised derivative, and at least one diamine of the formula II according to claim 1 at temperatures of between about 100 and 300°C.

9. A crosslinkable product which is obtained by cross-linking a mixture according to claim 1, or a pre-polymer according to claim 8, thermally or chemically or under the influence of electromagnetic waves.