CA2008030A1

CA2008030A1 - Nitrogen-containing polymers having terminal hydroxyl groups

Info

Publication number: CA2008030A1
Application number: CA 2008030
Authority: CA
Inventors: Sameer H. Eldin; Rolf Schmid
Original assignee: Individual
Current assignee: Novartis AG
Priority date: 1989-01-20
Filing date: 1990-01-18
Publication date: 1990-07-20
Also published as: EP0379467A3; JPH02252735A; EP0379467A2

Abstract

Nitrogen-containing polymers having terminal hydroxyl groups Abstract Nitrogen-containing polymers, having terminal hydroxyl groups, of the formula I

(I) in which X1 and X2 independently of one another are -H or , Z is OH and Y is NH or Z and Y together are N, n is an integer from 1 to 2000, R1 is, for example, a radical of the formula VIIa (VIIa) R2 consists, for example, of 95 mol % of groups of the formula II and 5 mol % of groups of the formula III

(III),

Description

2~ 30 K-17424/+

Nitrogen-containing polvmers havin~ terminal hvdroxyl groups The invention relates to nitrogen-containing polymers having terminal hydroxyl groups, ie. certain polyamides, polyamide-amic acids, polyamic acids anld the derivatives which have been cyclized to give the corresponding polyarnide-imide or polyimide, having terminal hydroxyl groups and containing, as the diamine, a phenylindanediamine anc7Jor a 2,2'-bis-(aminophenoxy)-biphenyl, to a process for the preparation of these polymers, to the use thereof, to curable epoxy resin compositions of matter containing these polymers, to the crosslinked products obtainable therefrom and to composite fibre systems containing the said polymers and a reinforcing fibre.

Polyamides, polyamide-amic acids, polyamic acids and the corresponding cyclized derivatives which have been prepared using a 2,2'-bis-(aminophenoxy)-biphenyl and which have no reactive end groups are known from US 4,196,144 and US 4,239,880.

Polyimides derived from phenylindanediamines and dianhydrides are described in US

3,856,752. These polymers do not contain any reactive end groups either.

Polyimides which are maslced by terrninal phenol groups and which contain, as the diamine, neither a phenylindanediamine nor a bis-(aminophenoxy)-biphenyl are known from US 4,026,871. In order to lengthen the chain or to increase the molecular weight, these polyimides are reacted with forrnaldehyde, with compounds which liberate formaldehyde under the reaction eonditions or with hexamethylenetetramine in thepresence of catalytic amounts of lime.

The present invention relates to nitrogen-containing polymers, having terminal hydroxyl groups, of the formula I

Xl X2 Xl ~2 .
:- .
'; ' , ' ': ~ `', ' ~

,~ . . ... . .

~0~8~)3a) in which Xl and x2 independently of one another are -H or -CZ, Z is OH and Y is NH or Z and Y together are N, n is an integer from 1 to 2000, Rl is a radical containing at least one aromatic ring, the carbonyl groups being linked to different carbon atoms in the ring, , . .
and, if at least one of Xl and X2 is the group -C-Z, this group is in each case located in the ortho-position or peri-position relative to one of the carbonyl groups so that, in a cyclization, five-membered or six-membered imide rings are formed, R2 is an aliphatic ;
radical having at least 2 C atoms, a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, at least 10 mol % of the radicals R2 being a radical of the formula II and/or III -(R ) (R5) in which R4 is H or Cl-C4alkyl, the radicals R5 independently of one another arehydrogen, halogen or Cl-C4alkyl, x is zero or an integer from 1 to 3 and y is zero or an integer from 1 to 4, and R3 is a divalent aromatic radical having 6-12 C atoms or a radical of the formula IV
~3 Tl ~ (IV) ~
in which Tl is a direct bond, methylene, isopropylidene, O, CO, NH, S or SO2.
The polymers according to the invention are suitable, for example, as matrix resins having excellent properties. Particularly when mixed with epoxy resins, they prodwce matrix resins having a very high toughness.
; .
In general, the polymers according to the invention have an intrinsic viscosity of 0.1 to 2.0, preferably 0.2 tO 1.5, and particularly 0.2 to 0.8, dl/g.

It is generally known that the intrinsic viscosity is a measure of the molecular weight of polymers. The values of intrinsic viscosi~y from û. 1 to 2.0 quoted colrespond to an average molecular weight of about 103 to 106.

. . .
~'. .

2a~

Polymers according to the invention wherein n is an integer from 2 to 200, especially from 2 to 50, are preferred.

Polymers wherein at least 30 mol %, especially at least 50 mol %, of the radicals R2 are a group of the formula II and/or III are also preferred.

In ~he recurring structural elemeints of the formula Ia --~Y- ¦ Y- * (la) of the polymers according to the invention Rl, R2, Xl, x2 and Y have various meanings.
The polymers according to the invention are thus homopolymers or copolymers having a random distribution of individual structural elements having various meanings for Rl, R2, Xl,X2andY.

In the structural element of the formula Ia Xl and x2 are each preferably a jgroup -C-Z .
Cyclized derivatives in which Z and Y together are N are particularly preferred in this regard. Amongst the polymers according to the invention, polyimides having terminal hydroxyl groups of the formula V
o o o o ilO--R3 ¦ N~ ~R~ ~N --R ~ R~ ~--R3--Ob (V) O O O O
in which Rl, R2, R3 and n are as defined above are therefore preferred.

The radicals Rl of the polymers according to the invention are derived from di-, tri- or tetra-carboxylic acids. In principle, any di-, tri- or tetra-carboxylic acid which gives the radicals Rl according to the definition after removal of the carboxyl groups is suitable in this regard.
`'' 0~303~) The radical Rl can, for example, be a carbocyclic-aromatic or heterocyclic-aromatic radical or a radical which, in addition to aromatic rings, also contains a cycloaliphatic ring, for example a phenylindane radical.

As a carbocyclic-aromatic radical, Rl preferably contains at least one 6-membered ring;
in particular these are monocyclic, condensed polycyclic or polycyclic radicals having several cyclic, condensed or non-condensed systems which can be attached to one another d*ectly or via bridge members. The following may be mentionecl as exarnples of suitable bridge members -O-,-CH2CH2-,-CH2-,--f~H~ --,-S-S-,-SO-,-SO2-,-SO-,-SONH-,-CO-, Q Q :-~ CONH-,-NH-Ct)-NH-, ~j. or -O-~i O-in which Q is an alkyl group h~ving 1-6, preferably 1-4, carbon atoms or a phenyl group.

If Rl is a heterocyclic-aromatic radical, S-membered or 6-membered heterocyclic-aromatic nng systems which may be benzo-condensed and which contain O, N andlor S are particularly suitable.

Carbocyclic-aromatic or heterocyclic-aromatic radicals represented by Rl ean also be substituted, for example by nitro groups, alkyl groups having 1-4 carbon atoms, trifluoromethyl groups, halogen atoms, in particular chlorine, silyl, sulfonic acid or sulfamoyl groups.

Rl is preferably an unsubstituted, monocyclic aromatic radical, a cundensed~ bicyclic aromatic radical or a non-condensed, bicyclic aromatic radical, the aromatic nuclei in the latter case being attached to one another via the bridge member -CH2-, -O-, -CO- or -SO2, or is a tt trav~lent radical of the ~ortr ultt Vl 2~)~8~3(~

$ (vl) in which R4 is as defined above.

Examples of suitable di-, tri- and tetra-carboxylic acids or anhydrides thereof from which Rl can be derived are phthalic acid, terephthalic acid, isophthalic acid, 4,4'-dicarboxydiphenyl ether, naphthalene-2,6-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, trimellitic anhydride, pyromellitic dianhydride, 2,3,9,10-perylenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene- 1 ,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,~-tetracarboxylic dianhydride, pheanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianh~ydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-isopropylidenediphthalic dianhydride, 3,3'-isopropylidenediphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, 4,4'-methylenediphthalic dianhydride, 4,4'-thiodiphthalic dianhydride, 4,4'-ethylidenediphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 ,2,4,5-naphthalenetetracarboxylic dianhydride, 1 ,2,5,6-naphthalenetetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride or thiophene-2,3,4,5-tetracarboxylic dianhydride.
.
: Phenylindanedi-, -tri- and -~etra-carboxylic acids, in particular phenylindane dianhydrides of the forrnula VIa :, :
., .
.

~~ .

~ ;~0~8~3() . ~
~.

o (Vl~

in which R4 is hydrogen or Cl-C4alkyl are also particularly suitable.

The following are examples of such dianhydrides:
1-(3',4'-dicarboxyphenyl)-1,3,3-tIimethylindane-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1 ,3,3-trimethylindane-6,7-dicarboxylic ~dianhydride, 1-t3',4'-dicarboxyphenyl)-3-methylindane-5,6-dicarboxylic dianhydride and 1-(3',4i-dicarboxyphenyl)-3-methylindane-6,7-dicarboxylic dianhydride. Phenylindane dianhydrides of this type and their preparation are described in IJS 3,577,442. ;

Polymers according to the invention wherein Rl is a raclical of the formula Vl in which R4 is methyl, or Rl is a radical of the formula VII

~ ~ (VII), in which T2 is CH2, O, SO2 or especially CO, are particularly preferred.
, The radical R2 of the polymers according to the invention is, to the extent of at least 10 mol %, a group of the formula II and/or III. This radical is derived from the corresponding diamines, from a phenylindanediamine or from a 2,2'-bis-(aminophenoxy)-biphenyl. The remaining fraction, ie. not more than 90 mol %, of the diamine component H2N-R2-NH2 can be any diamine from which the radical R3 according to the definition is derived.

Preferred polymers are those which contain, as R2, both the radical of the formula II and the radical of the formula III, in particular those wherein R2 is solely groups of the formula II and the forrnula III. In this regard, the radicals R2 preferably consist of 20-99 rnol %, in particualr 60-99 mol %, of groups of the formula II and 80-1 mol %, in particular 40-1 mol %, of groups of the formula III. Polymers which are most preferred are those wherein R2 consists of 90-99 mol % of groups of the formula II and 10-1 mol % of "
groups of the forrnula III.

:, :
.

~ 20~8~)3~

The phenylindanediamine component of the polymers according to the invention canconsist of any combination of isomers of the diamino compounds designated by theformula IIa (RS) R4 (~5) Y
H2N ~r ) ~ N~2 (rla), in which R4, Rs, x and y are as de~lned above.

The phenylindanediamine component can contain, for example, O to 100 % by weight of 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane in combination with 100 to O % by weight of 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane. Furthermore, ohe or both of these isomers can be replaced within the entire range from O to 100 % by weight by any of the substituted diamino isomers designated by the formula Ila. Examples of such substituted diamino isomers are S-amino-6-methyl- 1-(3'-amino-4'-methylphenyl)- 1,3,3-trimethylindane, S-amino-1-(4'-amino-Ar',Ar'-dichlorophenyl)-~r,Ar-dichloro-1 ,3,3-trimethylindane, 6-amino- 1 -~4'-amino-Ar' ,Ar'-dichlorophenyl)-Ar,Ar-dichloro- 1 ,3,3-trimethylindane, 4-amino-6-methyl- 1 -(3'-amino-4 '-methylphenyl)- 1 ,3,3-trimethylindane and Ar-amino-1-(Ar'-amino-2',4'-dimethylphenyl)-1,3,3,4,6-pentamethylindane. Ar and Ar' in the compounds mentioned above designate undetermined positions of the substituents concerned in the phenyl rings.

Amongst the phenylindanediamines of the formula IIa, preference attaches to those in which R4 is hydrogen or methyl and the Rss independently of one another are methyl, chlorine or bromine and the amino groups are in position 5, 6 or 7 and in position 3' or 4'.
Phenylindanediamines of the formula lla which are most preferred are $hose in which R4 is methyl, x and y are each zero and the amino groups are in position 5 or 6 and in position 4'.
: - .
Various polyimides based on phenylindanediamines and methods of synthesizing them are described in detail in US 3,856,752, which is thus a constituent of the present application.

.~
:, ' ' - .. '. . . .. , :: ,:: . , -.,. ,' ;.. :'.. : ' . , 20~86)3~

2,2'-Bis-~aminophenoxy)biphenyls of the formula IIIa o~ ':

Ia) ~0 ' ~

and their preparation are described in US 4,196,144. In accordance with the invention it is - preferable to employ, as the dia mine component, diamines of the formula IIIa in which the two amino groups are each in the ortho-position and particularly in the para-position of the benzene ring.

Aliphatic, araliphatic, cycloaliphatic, carbocyclic-aromatic or heterocyclic-aromatic radicals represented by R2 can be unsubstituted or substituted, for example by halogen atoms, such as fluorine, chlorine or bromine, or by alkyl or alkoxy groups having 1-4 ~ ~
carbon atorns in each case.

Suitable aliphatic radicals R2 are, in particular, linear or branched alkylene groups having 2-12 carbon atoms, it being also possible for the aLlcylene chain to be interrupted by heteroatoms, such as 0, S or N atoms.
~ .
Examples of R2 when it is a cycloaliphatic radical are the 1,3-cyclohexylene, 1,4-cyclohexylene, 1,4-bis(methylene)cyclohexane or dicyclohexylmethane group, whereas suitable araliphatic radicals are, in particular, 1,3-, 1,4- or 2,4-bis(alkylene)benzene, 4,4'-bis(alkylene)diphenyl and 4,4'-bis(alkylene)diphenyl ether radicals.

As a carbocyclic-aromatic radical, R2 is preferably a monocyclic aromatic radical, a condensed, polycyclic aromatic radical or a non-condensed, bicyclic aromatic ra~ical, the aromatic nuclei being attached to one another via a bridge member in the case of the latter.
Examples of suitable bridge members are the radicals designated above as T1 in formula IV.
.
As a heterocyclic-aromatic radical, R2 is especially a heterocyclic-aromatic 5-membered ~ :

;
' ~o~

or 6-membered ring containing 0, N and/or S.

Examples of suitable diamines H2N-~2-NH2 are o-, m- and p-phenylenediamine, diaminotoluenes, such as 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene, 1 ,3-diamino-4-chlorobenzene, 4,4'-diaminodiphenylmethane, 4,~'-diarninodiphenyl ether, 4,4'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl sulfone, 2,2'-diarninobenzophenone, 1,8-diaminonaphthalene, l,S-diaminonaphthalene, 2,6-diaminopyridine, 1,4-piperazine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, di-, tri-, tetra-, hexa-, hepta-, octa- and deca-methylenediamine, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediam;ne, 4,4-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 3-methoxyhexamethyldiamine, 2,11-diaminododecane, 2,2,4-trimethylhexamethylenediamine, 2,4,4-tlimethylhexamethylenediarnine, 1,2-bis~3-aminopropoxy)ethane, N,N'-dirnethylethylenediamine, N,N'-dimethyl-1,6-diaminohexane and the diamines of the formulae H2NtCH2)30(CH2)20(CH2)3N~12 and H2N(CH2)3S(CH2)3NH2; and 1 ,4-diaminocyclohexane, 1 ,4-bis(2-methyl-4-aminopentyl)benzene and 1 ,4-bis(aminomethyl)benzene.

Carbocyclic-aromatic diamines, in particular substituted, dinuclear diamines, for example bis(4-amino-3,5-dialkylphenyl~methanes or bis(4-amino-3-chloro-5-alkylphenyl)methanes, are particularly preferred as diamine components. These compounds are described, for example, in EP-A 171,588. Examples of suitable diamines of this type are bis(3-methyl-4-arnino-5-ethylphenyl)methane, bis(3-methyl-4-amino-5-isopropylphenyl)methane, bis(3,5-diisopropyl-4-aminophenyl)methane, bis(2-chloro-3,5-diethyl-4-aminophenyl)methane, bis(3-ethyl-4-amino-5-sec-butylphenyl)methane, bis(2,6-dichloro-3,5-die~hyl-4-aminophenyl)methane and, in particular, bis(3,5-diethyl-4-arninophenyl)methane.

The radical R3 of the polymers according to the invention is derived from aminophenols of the formula XI, H2N-R3-oH. As a divalent, aromatic radical having 6-12 C atoms, R3 can be unsubstituted or can contain, as substituents, one or more Cl-C4alkyl groups or halogen atoms, in particular chlorine or bromine.

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

X(~1~8~)30 ,~.

Polymers wherein R3 is 1,2-, 1,3- or 1,4-phenylene or a radical of the formula IV in which the free bonds are in the 4,4'-position are pre~erred. It is particularly preferable for R3 to be a radical of the formula ,3 s~3 ' or, in particular, 1,4-phenylene.

.
The polymers according to the invention, the polyamides, polyamide-amic acids, polyamic acids and the derivatives cyclized to give the corresponding polyamide-imide or polyimide ~ which contain terminal hydroxyl groups can be prepared by reacting a diamine of the . formula VIII

H2N-R2-NH2 (VIII) with an amide-forming derivative of a di-, tri- or tetra-carboxylic acid of the formula IX
HOOC~ COOH
~R ~ (IX) : xl X2 .to give a polymer of the formula X
' - 1l 1l - 11 1l T oc c NH--R ~;~NH--C COH
(X) and subsequently reacting this polymer or an amide-forming derivative thereof with an aminophenol of the formula XI

H2N-R3-oH (XI) :~ .
,, . b' ' if appropriate followed by cyclizing the polymers thus obtained, if Xl andlor x2 are -C-Z
to give the corresponding imides, the compounds of the formulae VIII, IX, X and XI each being employed in an essentially stoichiometric ratio, and Rl, R2, R3, Xl, X2, Z and n .' .
,' .
, . , . .- . . , :. , .. .. -. -. : , :: .:. , .
.. . : , , : .:
.... . ....................... .

: .,: .:
. . . . .
,............................. . : : , -- 20~8~3~) .

being as defined above.

~xamples of suitable amide-forming derivatives of the carboxylic acids of the formulae IX
or X are esters, halides, such as chlorides, or anhydrides thereof.

In general, the reaction indicated above is carried out in a customary inert organic solvent, preferably in a polar, aprotic solvent, for example dimethyl sulfoxide, N,N-dimethylforrnamide, N,N-dimethylacetamide, N,N-diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methyl-2-pyrrolidone, acetone, dioxane, ethyl acetate or tetrahydrofuran. Temperatures of about -20C to about 50C are used in this reaction.

The possible cyclization of the polyamide-amic acids or polyamic acids thus obtained is effected in a manner known per se by means of chemicals or by means of heat.

Chemical cyclization is preferably carried out by treatment with a dehydrating agent on its own or mixed with a tertiary amine. Examples of switable dehydrating agents are acetic anhy(lride, propionic anhydride and dicyclohexylcarbodiimide or a mixture of acetic anhydride and triethylamine Thermal cyclization is carried out by heating at temperatures of about 50C to 300C, preferably about 150C to 250C, if appropriate with the addition of an inert organic solvent.

The polymers, according to the invention, having terminal hydroxyl groups are suitable for the production of shaped articles of a very wide variety of types, such as fibres, films, sheeting, coating compositions, foams, laminating resins, composite materials, moulding powders, mouldings etc., in a manner known per se, if desired using customary additives, such as pigments, fillers and the like. The polymers according to the invention can also be processed readily from the melt and are distinguished by good mechanical, electrical and therrnal properties and also, in general, by a good solubility in organic solvents, for example, N,N-dimethylacetamide, N,N-dimethylforrnamide and N-methyl-2-pyrrol;done.

The polymers according to the invention, in particular the polyimides according to the invention, are particularly suitable for use in curable epoxy resin compositions of matter.
They are readily miscible with epoxy resins, the mixtures form a homogeneous rnelt 20C~ )3(1 having a }elatively low melting temperature, (for example approx. 200C) and the cured products generally have a single glass transition point. They are distinguished by high toughness together with a high heat distortion point at the same time, and are therefore particularly suitable for the formulation of matrix resins for the production of prepregs and high-toughness composite materials or for the production of adhesives or adhesive films.

The invention also relates, therefore, to curable compositions of matter containing (a) a polymer, according to the invention, of the formula I, (b) an epoxy resin and, if appropriate, (c) a curing agent and/or a curing accelerator for epoxy resins.

The invention also relates to the crosslinked products obtainable by curing these mixtures.

The invention also relates to a composite fibre system containing reinforcing fibres, for example glass fibres, carbon fibres or Aramid fibres, and a polymer of the forrnula 1.

Since the polymers according to the invention contain terminal phenolic hydroxyl groups, they can react with epoxy resins and can thus themselves be used as curing agents for epoxy resins. If suitable, further curing agents known to those skilled in the art, in particular low-molecular diphenols or polyphenols and/or curing accelerators for epoxy resins can also be added to the curable mixtures. In general, if the polymers, according to the invention, of a high molecular weight (for example over 5000) are used, it is preferable also to add an additional curing agent for epoxy resins, whereas, if relatively low-molecular compounds of the formula I are used, these compounds can be employed on their own as curing agents. The total amount of the curing agent is preferably about the amount required by stoichiometry.

In principle, any resin known to those skilled in the art can be used as the epoxy resin component (b) of the curable composition of matter according to the invention. The same applies to the curing component (c) which may be used concomitantly. Examples ofsuitable resins are described in EP-A 194,232. Examples of suitable curing agents and/or curing accelerators are disclosed in US 4,649,1~1. The curing of the mixtures according to the invention is preferably carried out within the temperature range from 50 to 300C, preferably 100 to 250C.

If suitable, the compositions of matter according to the invention can also contain .. , . . : .
~:

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

.~

high-molecular thermoplastics, in particular polyimides or polyether-imides which are readily miscible with the polymers of the formula I and have no reactive end groups. The polyimides according to US 3,856,752 derived from phenylindanediamines and dianhydrides are particularly suitable for this purpose.

The following examples illustrate the invention.

I. Preparation Examples Example 1: SYnthesis of a polYether-imide havin~ phenolic end ~oups (formula molecular wei,~ht 20,000) Ingredients taken:
4.49 g (0.0122 mol,5 mol %) of 2,2'-bis-(p-aminophenoxy)-biphenyl, ~ -II 61.49 g (0.2317 mol, 95 mol %) of 5t6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane (mixture of isomers), III 80,56 g (0.250 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride,IV 1.33 g (~.0122 mol) of 4-aminophenol, V 1300 ml of N,N-dimethylacetamide, VI 63.8 g (0.625 mol) of acetic anhydride and YII 12.65 g (0.125 mol) of triethylamine.
, I, II and V are initially placed, under nitrogen, in a 2.5 I sulfonation flask equipped with a thermometer, a glass propeller stirrer, a condenser, a cooling bath and an N2 connection, and the resulting clear, pale red-brown solution is cooled to -15C. III is then introduced into the solution and the resulting suspension is stirred for a further 2 hours while being slowly heated to 12C. A yellowish solution is formed. IV is added to this and the mixture is stirred for a further hollr. In the course of this, the temperature rises from 13 to 19C. VI
and VII are added at 19C. In the course of this, the temperature rises to 27C. The mixture is stirred at room temperature for approx. 19 hours. The polyimide is isolated by introducing the reddish-yellow solution into water (mixer) and washing the product with water and ethanol. The produet (a pale yellow, ~lne powder) is dried in vacuo at 70-80C.
Yield 138.7 g (94 % o~theory).
Characterization of the products:
r~: 0.673 dVg (0.5 % in N,N-dimethylacetamide at 25C).

., , ~

2C)~8~

Example 2: Synthesis of a polyether-imide havin~ phenolic end groups (formula -molecular wei~ht 12500!
Example 1 is repeated, using thè educts listed below. Since the amount of 4-aminophenol is somewhat greater compared with the two diamines, a polyether-imide of lower molecular weight (lower r~ ) is obtained.
In~redients taken:
4.42 g (0.0120 mol, 5 mol %) of 2,2'-bis-(p-aminophenoxy)-biphenyl II 60.60 g (0.2284 mol, 95 mol %) of 5(6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane (mixture of isomers) III 80.56 g (0.250 mol) of 3,3',4,4'-benzophenonetetracarboxylic anhydride, IV 2.10 g (0.0192 mol) of 4-aminophenol V 1300 ml of N,N-dimethylacetamide VI 63.8 g (0.625 mol) of acetic anhydride and VII 12.65 g (0.125 mol) of triethylamine Yield 139.8 g (95 % of theory) ~in: 0.426 dl/g (0.5 % in N,N-dimethylacetamide at 25C).

I~,xample 3: SYnthesis of a PolYether-imide havin~ phenolic end ~roups (formula molecular wei~ht 5000) Example 1 is repeated, using the educts listed below. A further increase in the amount of 4-aminophenol results in a polyether-imide of an even lower molecular weight.
In~redients taken:
4.14 g (0.0113 mol, 5 mol %) of 2,27-bis-(p-aminophenoxy)-biphenyl II 56.71 g (0.2138 mol,95 mol %) of S(6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane (mixture of isomers) III 80.56 g (0.250 mol) of 3,3',4,4'-benzophenonetetracarboxylic anhydride, IV 5.46 g (0.050 mol) of 4-aminophenol V 1300 ml of N,N-dimethylacetamide VI 63.8 g (0.625 mol) of acetic anhydride and VII 12.65 g (0.125 mol) of triethylamine Yield 133.2 g (91 % of theory) rlin: 0.223 dl/g (0.5 % in N,N-dimethylacetamide at 25C).
.

Example 4: Synthesis of a polvether-imide havin~ phenolic end ~roups (forrnula molecular wei~ht 12,500~
Example 1 is repeated, using the educts listed below. The diamines I and II are employed ' ':
.~ .
.

zoos~3~
:

- l S -in equimolar amounts.
Ingredients taken: -43.80 g (0.119 mol, 50 mol %) of 2,2'-bis-(p-aminophenoxy)-biphenyl II 31.58 g (0.119 mol, 50 mol %) of 5~6)-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane (mixture of isomers) III 80.56 g (0.250 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride,IV 2.60 g (0.0238 mol) of 4-aminophenol V 1300 ml of N,N-dimethylacetamide VI 63.8 g (0.625 mol) of acetic anhydride and ~ ;
VII 12.65 g (0.125 mol) of triethylamine Yield 151.2 g (95 % of theory) 0.383 dl/g (0.5 % in N,N-dimethylacetamide at 25C).

II. Use Examp1es Example Al: 165 g of the polyether-imide according to Example 1, 50 g of a tetraglycidyl derivative of 4,4'-diaminodiphenylmethane having an epoxide content of 7.8 equivalents/kg and an average functionality of 3.2 epoxide groups per molecule, 50 g of an epoxyphenol novolak which is liquid at room temperature and has a functionality of 2.2 and an epoxide content of 5.7 equivalents/kg and 65 g of 4,4'-dihydroxydiphenyl ether are dissolved in 765 g of methylene chloride. A film of the solution is drawn on silicone paper by means of a doctor blade. A homogeneous, tough film is forrned after drying (12 hours at 50C and 30 minutes at 90C in vacuo). Several layers of the film are compressed for 10 minutes at 20C and approx. 300 kPA and the product is then cured in an oven for 3 hours at 210C. The cured moulding (30 x 30 x 1 mm) has a well-defined Tg (measured by means of thermomechanical analysis) of 193C tsoftening starts at 169C).
. ~ , - , Example A2: 50 g of the tetraglycidyl derivative of 4,4'-diaminodi.phenylmethane used in Example Al and 50 g of the epoxyphenol novolak are added to a solution in methylene chloride of 82 g of the polyether-imide according to Example 1 and 82 g of a polyimide having phenylindane units, a glass transition temperature of 305C and an average molecular weight of approx. 65,000 (Matrimid(g) 5218, Ciba-Geigy), and the mixture is thoroughly stirred. The solution is concentrated to a resin content of approx. 40 % by weight. A solution of 65 g of 4,4'-dihydroxydiphenyl ether in methyl ethyl ketone is then added, with stirring. After the solvent has been removed by evaporation to give a solids content of approx. 70 % by weight1 a film is drawn and processed as in Example Al. A Tg ~, :
:. .
. , , - Z0~803~

of 225C (glass transition begins at 199C) is measured on the resulting mouldings.

Example A3: 25 g of polyether-imide according to Example 3 are dissolved in 200 g of CH2CI2, and 40 g of the tetraglycidyl ether of 2,2,6,6-tetramethylolcyclohexanol (prepared in accordance with Example 2 of US 4,549,008) having an epoxide equivalent weight of 129 and 60 g of the epoxyphenol novolak used in Example A1 are added. The solvent is evaporated off by heating and the remaining mixture is then processed as in Example A4, after 58 g of 4,4'-dihydroxydiphenyl ether and 0.1 g of 2-phenylimidazole have been added. The shaped articles obtained have the following properties:
Tg= 115C
Flexural strength (ISO 178) = 122 MPa Flexural elongation (ISO 178) = >13.5 % (without fracture).

Example A4: 82 g of polyether-imide according to Example 2 and 82 g of a polyimide having phenylindane units, a glass transition temperature of 305C and an average molecular weight of approx. 65,000 (Matrimid(3~) 5218, Ciba-Geigy) are dissolved in 200 g of mcthylene chloride.50 g of the tetraglycidyl derivative of 4,4'-diaminodiphenylmethane used in E~xample Al and 50 g of the epoxyphenol novolak used in Example A1 are then added and are thoroughly mixed with the solution of therrnoplastic. After the solvent has been evaporated off to give an approx. 60 % by weight solution, a second solution of 65 g of 4,4'-dihydroxydiphenyl ether and 0.1 g of 2-ethyl-4-methylimidazole in 40.3 g of methyl ethyl ketone is added dropwise, with stirring. Further solvent is removed by evaporation, with stirring, until a clear solution is formed. A film is drawn on silicone paper by means of a doctor blade. A homogeneous, tough film is fonned after drying (12 hours at 50C and 30 minutes at 90C in vacuo).
Several layers of the film are compressed for 10 minutes at 200C ~md the product is then cured in an oven for 2 hours at 200C. The cured moulding (30 x 30 x 1 mm) has a Tg of 155C. (Softening begins at 141C).

Part of the solution is used to impregnate a fabric composed of longitudinally arranged carbon fibres (T 300) which are held together with a few thermoplastic fibres as a web ("Quasi~ Gewebe" G 87 of Brochier SA). Laminated sheets ha~ing the following properties are obtained after drying and compression:
Flexural strength transversely to the fibre (ISO 178) = 76 MPa Flexural strength in the principal direction of the fibres = 1204 MPa Tg = 225C.

: . . -.. ~

` 20 Example A5: Using 82 g of a polyether-imide having recurring units of the formula :

~n\ ~Lo~30¢~

O CH3 0 n and a glass transition temperature of 219C (Ultem(~) 1000 made by General Electric) instead of the polyimide according to Example A4, and with composition and processing otherwise identical to that of Example A4 gives a laminate having the following properties:
Tg = 207C . ~ :
Flexural strength in the principal direction of the fibres = 1395 MPa Flexural strength transversely to the principal direction of the fibres = 65 MPa ; ~ . ,.

, ;~

,

Claims

1. A nitrogen-containing polymer, having terminal hydroxyl groups, of the formula I

(I), in which X1 and x2 independently of one another are -H or , Z is OH and Y is NH or Z and Y together are N, n is an integer from 1 to 2000, R1 is a radical containing at least one aromatic ring, the carbonyl groups being linked to different carbon atoms in the ring, and, if at least one of X1 and X2 is the group , this group is in each case located in the ortho-position or peri-position relative to one of the carbonyl groups so that, in a cyclization, five-membered or six-membered imide rings are formed, R2 is an aliphatic radical having at least 2 C atoms, a cycloaliphatic, araliphatic, carbocyclic-aromatic or heterocyclic-aromatic radical, at least 10 mol % of the radicals R2 being a radical of the formula II and/or III

(II), (III), in which R4 is H or C1-C4alkyl, the radicals R5 independently of one another arehydrogen, halogen or C1-C4alkyl, x is zero or an integer from 1 to 3 and y is zero or an integer from 1 to 4, and R3 is a divalent aromatic radical having 6-12 C atoms or a radical of the formula IV
(IV), in which T1 is a direct bond, methylene, isopropylidene, O, CO, NH, S or SO2.

2. A polymer according to claim 1, wherein X1 and X2 are each .

3. A polyimide having terminal hydroxyl groups according to claim 2 of the formula V

(V) in which R1, R2, R3 and n are as defined in claim 1.

4. A polymer according to claim 1, wherein n is an integer from 2 to 200.

5. A polymer according to claim 1, wherein at least 30 mol % of the radicals R2 are a group of the formula II and/or III.

6. A polymer according to claim 1, wherein the radicals R2 consist of 20-99 mol % of groups of the formula II and 80-1 mol % of groups of the formula III.

7. A polymer according to claim 1, wherein R1 is an unsubstituted, monocyclic aromatic radical, a condensed, bicyclic aromatic radical or a non-condensed, bicyclic aromatic radical, the aromatic nuclei in the latter case being attached to one another via the bridge member -CH2-, -O-, -CO- or -SO2, or is a tetravalent radical of the formula VI

(VI), in which R4 is as defined in claim 1.

8. A polymer according to claim 7, wherein R1 is a radical of the formula VI in which R4 is methyl or a radical of the formula VII

(VII) in which T2 is CH2, O, SO2 or CO.

9. A polymer according to claim 1, wherein R3 is 1,2-, 1,3- or 1 ,4-phenylene or a radical of the formula IV in which the free bonds are in the 4,4'-position.

10. A polymer according to claim 9, wherein R3 is a radical of the formula or is 1,4-phenylene.

11. A process for the preparation of a polymer according to claim 1 by reacting a diamine of the formula VIII

H2N-R2-NH2 (VIII) with an amide-forming derivative of a di-, tri- or tetra-carboxylic acid of the formula IX

(IX) to give a polymer of the formula X

(X) and subsequently reacting this polymer or an amide-forming derivative thereof with an aminophenol of the formula H2N-R3-OH (XI) if appropriate followed by cyclizing the polymers thus obtained, if X1 and/or X2 are , to give the corresponding imides, the compounds of the formulae VIII, IX, X and XI each being employed in an essentially stoichiometric ratio, and R1, R2, R3, X1, X2, Z and n are as defined in claim 1.

12. A curable composition of matter containing (a) a polymer according to claim 1, (b) an epoxy resin and, if appropriate, (c) a curing agent and/or a curing accelerator for epoxy resins.

13. A crosslinked product obtainable by curing the composition of matter according to claim 12.

14. A composite fibre system containing reinforcing fibres and a polymer according to claim 1.