WO1984000552A1

WO1984000552A1 - Modified thermosetting imide resins

Info

Publication number: WO1984000552A1
Application number: PCT/GB1983/000176
Authority: WO
Inventors: Horst Stenzenberger
Original assignee: Boots Co Plc
Priority date: 1982-07-21
Filing date: 1983-07-18
Publication date: 1984-02-16
Also published as: GB2125806B; GB2125806A; GB8319388D0; EP0165620B1; EP0102722A1; US4587281A; EP0102722B1; IL69221A; JPS5920323A; DE3366595D1; EP0165620A1; US4520145A

Abstract

Bisimide resins having improved fracture toughness comprises a mixture of, a) a bismide of the general formula (I), in which B represents a divalent radical containing a carbon-carbon double bond and A is a divalent radical containing at least two carbon atoms and, b) a polyisocyanate of the general formula (II): D(NCO)x , in which x has a value of between 2 and 4 and D stands for an x-valent radical. The molar ratio of a:b is in the range 2 to 100.

Description

Modified thermosetting Imide Resins

From British Patent Specification 1066390 it is known that bisimides of the general formula (A)

in which the radical B represents a divalent organic radical containing a carbon-carbon double bond, and A represents a divalent organic radical of at least two carbon atoms, can be crosslinked by simply heating them to temperatures between 100 and 400°C, providing materials with outstanding high temperature stability. Other imide resins can be obtained according to British Patent Specification 1190718 by reacting a bisimide of the general formula (A) with a diamino compound of the general formula (B)

H₂N-E-NH₂

(B) in which E represents a divalent organic radical of at least two carbon atoms.

Other examples of imide resins are obtained by reacting bisimides with dihydrazides (British Patent Application 2011920A) or amino acid hydrazides (British

Patent Application 2009767A) or azomethines (British

Patent Specification 1443067).

The so-called Bl-type resins, some of which are the subjects of the above mentioned patents, are highly crosslinked when finally cured and exhibit low tensile strength, flexural strength and a low elongation at break. When these BI-type resins are used as matrix resins in crossplied graphite laminates the above mentioned combination of mechanical properties give rise to a phenomenon called "microcracks" which have a deleterious effect on the mechanical properties of the composites.

It is an object of the present invention to provide curable bisimide resins of the Bl-type which when cured lead to heat resistant tough crosslinked polymers.

Another object of this invention is to provide

Bl-type curable bisimide resins which can be processed either from the melt or from the solution together with fibres like glass, graphite or aramides to form composites showing significantly reduced microcracking.

It is a further object of this invention to provide Bl-type laminating resins leading to composites with improved interlaminar fracture toughness.

The present invention relates to new and improved thermosetting imide resins which are obtained from curable bisimide resins which comprise a mixture of (a) at least one bisimide of formula I

in which B is a bivalent radical containing a carbon-carbon double bond and A is a bivalent radical having at least two carbon atoms and (b) a polyisocyanate of the general formula II

D(NCO)_x

II

in which x has a value in the range 2 to 4 and D stands for an x-valent organic residue. The molar ratio a:b lies in the range 2 to 100. The copolymerization of bisimides with polyisocyanates can be effected by simply heating a mixture of the two to temperatures between 100 and 350°C, long enough to finalize the reaction.

The radical designated A in general formula I may be (a) an alkylene group with up to 12 carbon atoms,

(b) a cycloalkylene group with 5 to 6 carbon atoms, (c) a heterocyclic group with 4 to 5 carbon atoms and at least one nitrogen, oxygen or sulphur atom in the ring,

(d) a mono or dicarbocyclic group or (e) at least two mono or dicarbocyclic aromatic or cycloalkylene groups which are connected to one another by a direct carbon-carbon bond or by a bivalent group chosen from oxygen, sulphur, aikylene with one to three carbon atoms, or a group of formula Ilia to IIIj

the radicals R₁, R₂, R₃ , R₄, being alkyl groups with one to five carbon atoms, R₅ being an aikylene group or an arylene group.

The radical B In the general formula I represents a divalent organic radical containing a carbon-carbon double bond. The radical B may have a structure as shown in formula IV, V, VI or VII

BIsmaleimides of formula I in which the radical B is of formula IV may be used for producing the new imide resins. Examples of suitable bismaleimides are 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,12- bismaleimidododecane, 1,6-bismaleimido-(2,2,4-tri methyl)hexane, 1,3-bismaleimidobenzene, 1,4-bismale imidobenzene, 4,4 '-bismaleimidodiphenylmethane, 4,4'- bismaleimidodiphenylether, 4,4'-bismaleimidodiphenyl sulphide, 4,4'-bismaleimidodiphenylsulphone, 4,4'- bismaleimidodicyclϋαexyliαethane, 2 ,4-bismaleimido toluene, 2 ,6-bismaleimidotoluene, N,N'-m-xylylene bismaleimide, N,N'-p-xylylenebismaleimide. Examples of other suitable bisimides are N,N' -m-phenylene-bis citraconomide and N,N' -4,4'-diphenylmethane-citracon imide, in which the radical B is of formula VI and N,N'-4,4'-diphenylmethane-bis-itaconomide in which the radical B is of formula VII.

The bisimides of formula I may be modified with polyamines, polyhydrazides, amino acid hydrazides, azomethines or mixtures thereof. These modified bisimides are used in a similar manner to that described herein for bisimides of formula I to prepare curable bisimide resins of the present invention.

A wide variety of organic polyisocyanates II may be employed to react with the bisimides of the general formula I including aromatic, aliphatic and cycloaliphatic polyisocyanates. referred to here as group 1 polyisocyanates. Representative compounds include toluene-2,6-diisocyanate, toluene-2,4-di isocyanate, m-phenylenediisocyanate, 4-chloro-l,3-phenylenediisocyanate, 4,4'-biphenylenediisocyanate, 1,5-naphthylenediisocyanate, 4 ,4-bisisocyanatodiphenyl methane, 2 ,4'-bisisocyanatodiphenylmethane, 4,4'bisisocyanatodiphenyl ether, 4,4'-bisisocyanatodiphenylsulphone, 3,3-diisocyanatodiphenylsulphone, 4,4'-bisisocyanatodiphenylsulphide, and aliphatic diisocyanates such as 1,4-tetrarcethylenediisocyanate, 1,6-hexamethylenediisocyanate, 1,10-decamethylenediisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, 1,4-cyclohexylenediisocyanate, 4,4'-methylene-bis-(cyclohexyl isocyanate) , 1 , 5 -tetrahydronaphthalenediisocyanate and isophoronediisocyanate ; and polyisocyanates of formula VIII

in which a has a value between 0.1 and 2 may also be employed. Very advantageous polyisocyanates to be co-reacted with bismaleimides of formula I are those obtained by the reaction of a polyisocyanate of the aforementioned group 1 polyisocyanates with polyalkylene ether glycols, providing isocyanate- terminated macropolyisocyanates of the formula IX, referred to here as group 2 polyisocyanates,

in which R represents a divalent organic aliphatic or aromatic residue and F represents a group of formula X, XI or XII

F representing polyalkylene ether backbone, β being a number providing glycols having molecular weights of from 200 to 10,000. The group 2 polyisocyanates of formula IX are well known substances and their preparations described m detail in Kunststoffhandbuch, Band VII, p. 84-85, Carl Hanser Verlag, Munchen 1966; they may be used in quantities up to 80% of the total resin mixture.

The residue F in the general formula IX can also be a polyester backbone, and the preparation of polyisocyanates of formula IX with a polyester backbone is described in Kunststoffhandbuch, Band VII, p. 60-72, Carl Hanser Verlay, Munchen 1966.

The preparation of the new curable bisimide resins can be carried out in an inert organic solvent or diluent, for example in dimethyl formamide, dimethylacetamide, N-methyl pyrididone and tetramethyl urea, or ketone type solvents such as acetone, methyl-ethyl ketone. methyl isobutyl ketone and cyclohexanone or chlorinated solvents such as methylene chloride, ethyl chloride, 1,2-dichloroethane and ether-type solvents such as dioxane, tetrahydrofuran ethyl glycol and ester type solvents such as ethyl acetate or mixed glycol ether-esters such as ethyl glycol acetate, methyl glycol acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate etc. in such a manner that prepolymer solutions are obtained. The prepolymer can be isolated by stripping off the solvent either in vacuum or by heat or both, thus providing a solventless resin that can either be processed from the melt or as a powder.

The preparation of the new curable bisimide resins can be performed by using conventional techniques for mixing and grinding of powders or powders and liquids to intimately blend the bismaleimides with the polyisocyanates. Prepolymers are obtained by heating the homogeneous mixture at a temperature between 80 and 200 °C, for sufficient time to produce a still formable and soluble product.

The production of the new curable bisimide resins according tc this invention can also be carried out in inert diluents in which either only one of the starting materials is completely soluble or all the starting components are completely soluble. The latter procedure is preferred when the application of the resin requires a solution as is the case for the production of prepregs.

For many Industrial applications of the new curable bisimide resins of the present invention, it is advantageous to accelerate the curing process by adding catalysts. Effective curing catalysts are organic peroxides such as ditertiary butyl peroxide, diamyl peroxide, t-butyl perbenzoate in the concentration of 0.05 to 0.5% in relation to the total weight of the curable bisimide resin. Other catalysts that may be used are tertiary amines like N,N'-dimethylanilifte, N,N'-dimethyl-benzylamine, N-methylmorpholine, tri-n-butylamine, tri-methylamlne and azabicyclooctane and others.

The catalysts can be admixed with the components of the curable bisimide resins or they may be added during the production of the prepolymers either by a powder blending process or by the solvent blending process described above.

In many cases it is necessary to process the new curable bisimide resins of the present invention from the melt. To reduce the melt viscosity and to improve the pot life the resins can be blended with so-called reactive diluents, preferably those that are liquid at room temperature. The reactive diluents that may be employed carry one or more polymerizable double bonds of the general formula XIII

and may be of the vinyl-, allyl- or acryl- type. These reactive diluents can be of the ether, ester, hydrocarbon or heterocyclic type. Typical ethers that may be employed ore vinylallylether, diallylether, methallylether and vinylphenylether. Typical esters are vinyl- , allyl- , methylallyl- , 1 -chlorallyl- , crotyl-, isopropenyl esters derived from saturated or unsaturated aliphatic or aromatic mono- or polycarboxylic acids such as formic, acetic, propionic, butyric, oxalic, malonic, adipic, sebacic, acrylic, methacryvlic, phenylacrylic, crotonic, maleic, fumaric, itaconic, citraconic. tetrahyrophthalic, benzoic, phenylacetic, o-phthalic, Isophthalic or terephthalic acid and naphthalic-dicarboxylic acid or mixtures thereof. The most important hydrocarbon type reactive diluents to be used are styrene, methylstyrene, vinylhexane, vinylcyclohexane, divinylbenzene, divinyl cyclohexane, diailybenzene, vinyltoluene and 1-vinyl-4- ethyl-benzene or mixtures thereof. Examples of heterocyclic type reactive diluents are vinylpyridine and vinylpyrrolidine.

In those cases where reactive diluents are used it is possible to first blend the bisimide components with the reactive diluent and then the polyisocyanate component is added. In those cases where the polyisocyanates of the group 2 are used to modify the bisimide resins the polyisocyanate is preferably dissolved in the reactive diluent and then blended with the bismaleimide compounds. The quantity of reactive diluent that may be employed can be up to 80% by weight of the total final resin mixture.

Very advantageous reactive diluents are styrene and divinylbenzene which are used in quantities up to 30% of the total bisimide-polyisocyanate mixture. Care has to be taken with these diluents because they crosslink at very low temperatures, at around 100-11 O^C, therefore mixtures containing these diluents have to be prepared at temperatures well belox? 100°C.

The new curable bisimide resins of the present invention can be further modified with unsaturated polyester resins. Useful unsaturated polyesters are well known products which are prepared by polycondensation of polycarboxylic acid derivatives such as esters with polyglycols as described in detail in Kunststoffhandbuch, Band VII, p. 247-282, Carl Hanser Verlag, Munchen 1973.

Solutions of these polyesters in the reactive diluents described above can be used instead of the reactive diluent alone to modify the new bisimidepolyisocyanate resins.

The new curable bisimide resins of the present invention either modified or not can be thermally converted to crosslinked polyimide-isocyanate copolymers by heating them to temperatures of between

100 and 400°C, for a time sufficient to complete cure.

The new curable bisimide resins are advantageously used to produce laminated materials. In such a case the prepolymers produced from the curable bisimide resins are dissolved in suitable solvents to provide a 50-60% by weight solution, which is used to impregnate glass fibres in the form of fabrics or rovings or carbon fibres or boron fibres or organic synthetic fibres in the form of fabrics, filaments or rovings are impregnated with this solution and then stripped of the solvent by drying after which they are moulded into laminate form by the application of pressure and temperature, the crosslinked polyimide-isocyanate copolymer being the binder.

The curable bisimide resins according to the invention can also be processed by the known methods of the powder moulding industry in relation to curable compositions, to produce mouldings, curing out taking place with simultaneous shaping under pressure. For these applications it is possible to admix with the curable bisimide resins additives such as fillers, colourants, softeners and flameproofing agents. Ideal fillers are for example glass fibres, carbon fibres, organic high modulus fibres such as aramides, quartz flour, kaolin, silica and metals in the form of fine powders.

It is possible to modify the heat-resistance, flexibility and toughness of the resins by varying the molar proportions of the bismaleimides and the polyisocyanates over a whole range, and furthermore mixtures of two or more bismaleimides may also be used.

Accordingly, the following examples are selected to demonstrate the advantageous utility of the new resins and compositions but are not limited to them.

Example 1

100 g of 4,4'-bismaleimidodiphenylmethane, 40 g of (2,4-2,6)-bisnaleimidotoluene and 20 g of 4,4'-diisocyanatodiphenylmethane were mixed intimately by use of a ball mill. The mixture thus obtained was heated to 145°C, providing a viscous melt which was processed as follows :

(a) The molten mixture of the reactants was poured into a casting mould measuring 100 x 100 x 3 mm to form a plate which was hardened over two hours at 170°C, and for an additional 3 hours at 200°C. After removal from the mould the plate was postcured for 15 hours at 250°C. The plate was then cut into test pieces (40 x 10 x 3 mm) and tested according to DIN 53452 in a three point flexured test. The flexural strength obtained was 90 N/mm² , the flexural modulus was 4.8 KN/mm².

After 1000 hours ageing In circulating air at 220°C the remaining properties were:

flexural strength 92 N/mm² f1exural modulus 4.8 KN/mm²

indicating extremely good thermal oxidative stability.

(b) The molten mixture of the reactants was heated for 1 hour at 180°C thus providing after grinding a prepolymer powder which was cured in a cylindrical mould at a temperature of 180-220°C. The moulding pressure necessary to obtain a dense void free specimen was 300-500 N/mm². The flexural strength of the moulding measured was 120 n/mm²; the flexural modulus was found to be 4600 N/mm².

(c) The intimate mixture of 4,4'-bismaleimidodiphenylmethane, (2,4-2,6)-bismaleimidotoluene and 4,4'-diisocyanatodiphenylmethane obtained by ball milling as described above was dissolved in methylene chlorideethylglycol acetate mixture as a solvent to form a low viscosity solution containing 60% by weight of resin. This solution was used to Impregnate glass fabric type 92111/A1100 of Messrs. Interglas, thus providing after stripping off the solvent in a circulating air oven at 100°C, for ten minutes, a prepreg containing 35 to 37% by weight of resin. The prepreg pieces were stacked in a heated platen press and cured at 200°C for 4 hours, providing a laminate in which the crosslinked polyimide-isocyanate copolyirter was the binder. After postcure at 250°C, the laminate showed the following properties.

Fibre content 65% Resin content 35% by weight Density 1.95 g/cm³

Flexural Strength at room temperature 590 N/mm²

Flexural Strength at. 250ºC 410 N/mm²

Flexural Modulus at room temperature 28 KN/mm² Flexural Modulus at 250°C 24 KN/mm²

Short beam shear strength 51 N/mm²

Short beam shear strength at 250°C 38 N/mm²

Example 2

56 g of 4,4'-bismaleimidodiphenylmethane, 24 g of 2,4-bismaleimidotoluene and 20 g of 2,2,4-tri-methylhexamethylenebismaleimide were melted in a round bottomed flask at 150°C and degassed to form a clear transparent melt. The melt thus obtained was dissolved in methylene chloride at room temperature and blended with 40 g of a 50% by weight solution of 2,4-2,6-diisocyanatotoluene in methylene chloride, also containing 20 g of divinyl benzene. The mixture was heated progressively to a temperature of 75°C, finally a vacuum was used to strip off traces of solvent, thus providing a resin that could be processed according to Example 1, employing the melt casting technology.

Example 3

A resin according to British Patent Application 2009767A, Example 1 was produced by blending 1 07 .5 g (0.3 mols) of 4,4-bismaleimidodiphenylmethane and

18.12 g (0.12 mols) m-aminobenzoic acid hydrazide in a ball mill after which the mixture was prereacted for 35 minutes in a drying cabinet at a temperature of 150°C. The homogeneous melt thus obtained was dissolved in

N-methylpyrollidone to form a 50% by weight solution.

This solution was blended with 4,4'-diisocyanatodiphenylmethane (0.1 mols) and used to produce glass fabric prepregs. Prepregs thus obtained were moulded at a pressure of 500 n/mm² at 200°C for 4 hours to produce a laminate in which the new crosslinked polyimide-isocyanate copolymer was the binder.

Example 4

A resin according to British Patent Application 2009767A was produced by blending 56 g of bismaleimidodiphenylmethane. 24 g of bismaleimidotoluene C2,4- and 2,6- isomeric mixture) and 10 g m-aminobenzoic acid hydrazide. To this resin a solution, of 5 g of the macroisocyanate (mi) in 10 g diallylphthalate was added and heated to 110°C while stirring, to form a highly viscous melt which was cast into a parallel epipedic mould and cured under a pressure of 2 bars for 12 hours at 180°C. After demoulding, the casting was postcured for 15 hours at 250°C, providing a resin sample containing no filler with the following properties:

RT 250°C

Density 1.26 g/cm³

Flexural Strength 110 N/mm² 65 N/mm²

Flexural Modulus 4.6 KN/mm² 2.9 KN/mm² Flexural Strength after 1000 hours at 200°C 115 N/mm² 58 N/mm²

Flexural Modulus after 1000 hours at 200°C 4.65 KN/mm² 3.1 KN/mm²

Preparation of the macroisocyanate (mi)

350 g of 4,4'diisocyanatodiphenylmethane and 821 g of tetramethylene glycol. (molecular weight 1000) were stirred and heated in a round bottomed flask under nitrogen gas at a temperature of 85°C for 1.5 hours, providing a macroisocyanate showing an isocyanate content of 1 x 10^-3 mols. g^{- 1} .

Example 5

A resin consisting of 60 parts of 4,4'-bismaleimidodiphenylmethane, 20 parts of toluene bismaleimide, 15 parts of 2,2,4-trimethylhexamethylene bismaleimide and 10 parts of 4,4-diisocyanatodiphenyl-methane was prepared by melt blending at a temperature of 125°C. To this melt 15 parts of the polyester sold under the trade name Dobekan FT1018 by Bech & Co., Hamburg, dissolved in 15 parts of divinylbenzene were added and intimately mixed at 70-80°C for 15 minutes providing a resin melt which was cast into a parallel epipedic form and cured under pressure for 15 hours at 200°C. After pσstcure at 250°C, for 15 hours the casting showed the following properties. RT 250°C

Density (g/cm³) 1.27 - Flexural Strength (N/mm²) 105 79 Flexural Modulus (KN/mm²) 4.1 2.7 Flexural Strength (N/mm²) after 250 hours at 300°C 80 46

Flexural Modulus (KN/mm²) after 250 hours at 300°C 4.6 3 .2

Example 6 A resin consisting of 60 parts of 4,4'-bismaleimidodiphenylmethane, 20 parts of toluenebismaleimide, 20 parts of 4,4'-dlisocyanatodlphenylmethane was prepared by melt blending at a temperature of 120°C. This melt was cooled down to a temperature of 70°C, blended with 15 parts of a solution of the macroisocyanate (mi) of Example 4 in divinylbenzene (1:2), providing a low viscosity melt at 80°C. This resin could be processed from the melt as described in Example 1, or can be dissolved in methylenechloride to form an impregnation varnish which was used to impregnate glass fabric squares (15 x 15 cm) which after drying in a circulating air oven at 40-50 °C for 20 minutes provide glass fabric prepregs which contair. 40% by weight of resin. These prepregs were stacked in a heated platen press between aluminium foils and cured at 170°C for 2 hours at a pressure of 60 N/cm². The laminate thus obtained was postcured in a circulating air oven at a temperature of 250 °C for 16 hours. The laminate obtained showed the following properties: Resin content 30% by weight Density 1.95 g/cm³

Flexural Strength at RT 640 N/mm²

Flexural Strength at 250ºC 380 N/mm² Flexural Modulus at RT 29.5 KN/mm²

Flexural Modulus at 250°C 21.0 KN/mm²

Short beam shear strength at RT 58 N/mm²

Short: beam shear strength at 250°C 41 N/mm²

Example 7 A resin consisting of 56 parts of 4,4'-bismale imidodiphenylmethane, 24 parts of 2,4-bismaleimido toluene and 40 parts of a styrene solution of the unsaturated polyester sold under the trade name Dobekan FT 1018 (1:1) was prepared by melting the components at 70-80°C. After cooling the resin was dissolved in 120 parts of methylene chloride to which a solution of 5 parts of the macroisocyanate (mi) of Example 4 dissolved in 10 parts of methylene chloride was added under stirring to provide a homogeneous resin solution. Methylene chloride was stripped off in vacuum by use of a rotary evaporator and the final melt thus obtained was degassed in vacuum of 70-75°C. The resin melt could be further processed as described in Example 1.

Example 8 A resin consisting of 56 parts 4,4'-bismaleimidodiphenylmethane, 24 parts of 2,4-bismaleimidotoluene, 20 parts of 4,4'-diisocyanatodiphenylmethane, and 30 parts of the unsaturated polyester sold under the trade name Dobekan FT 1018 were melt blended at 110°C for 15 minutes, said melt being mixed with a solution of 0.7 parts of azobicyclooctane dissolved in 30 parts of diallylphthalate at a temperature of 70-100°C. The resin thus obtained was processed as follows: (a) The molten mixture prepared as described above was poured into a mould as described in Example 1 and cured for 2 hours at 170°C, and 2 hours at 200°C. After demoulding the plate is postcured at 210°C for 15 hours. The following properties were obtained

Flexural strength at 25°C 05 N/mm² Flexural strength at 250°C 49 N/mm²

(b) The molten mixture of the reactants was heated for 1 hour at 165°C thus providing after grinding, a prepolymer which was cured in a cylindrical mould at temperatures of between 170-210°C, and at pressures of 250-400 N/cm².

(c) 100 parts of the resin mixture prepared as described above was dissolved in 60 parts of acetone to form a low viscosity resin solution which was used to impregnate carbon fibre rovings (type Celion 6000) and carbon fibre unidirectional tapes were prepared by a filament winding operation. The tapes were dried at 30°C in circulating air and moulded in an autoclave at a pressure of 6 bars for 3 hours at 170°C. The unidirectional laminate obtained was postcured for 15 hours at 210°C and showed the following properties:

Density 1.50 g/cm³

Flexural Strength at 25°C 2050 N/mm² Flexural Strength at 250°C 1350 N/mm² Flexural Modulus at 25°C 128 KK/mm² Flexural Modulus at 250 °C 124 KN/mm² Interlaminar shear strength at 25°C 95 N/mm² Interlaminar shear strength at 250°C 52 N/mm²

Claims

1) Curable bisimide resins comprising a mixture of a) at least one bisimide of the general formula I

in which B represents a divalent radical containing a carbon-carbon double bond and A is a divalent radical containing at least two carbon atoms and

b) a polyisocyanate of the general formula (II)

D(NCO)_x

(II)

in which x has a value in the range 2 to 4 and D stands for an x-valent radical, in which the molar ratio a:b is in the range 2 to 100.

2) Curable bisimide resins according to claim 1 in which the bisimide of the general formula I is characterised in that

- A being a member selected from the groups consisting of (a) an aikylene group with up to 12 carbon atoms, (b) a cycloalkylene group with 5 to 6 carbon atoms, (c) a heterocyclic group with 4 to 5 carbon atoms and at least one nitrogen, oxygen or sulphur atom in the ring, (d) a mono or dicarbocyclic group or (e) at least two mono or dicarbocyrclic aromatic or cycloalkylene groups which are connected to one another by a direct carbon-carbon bond or by a bivalent group chosen from oxygen, sulphur, aikylene with one to three carbon atoms, or a group of formulae Ilia to IIIj

the radicals R₁ , R₂, R₃. R₄ , being alkyl groups with one to five carbon atoms, R₄ being an aikylene group or an arylene group and

B is a group which is capable of addition polymerization selected from a group of formula IV, V, VI or VII

3) Curable bisimide resins as claimed in claim 1 or claim 2 in which the polyisocyanate of the general formula II is selected from one of the following compounds: toluene 2,6-diisocyanate, toluene 2,4-diisocyanate, m-phenylenediisocyanate,

4-chloro 1,3-phenylenediisocyanate,

4,4'-biphenylenediisocyanate,

1,5-naphthylenediisocyanate,

4,4'-bisisocyanatodiphenylmethane,

2,4'-bisisocyanatodiphenylmethane,

4,4'-bisisocyanatodiphenyl ether,

4,4'-bisisocyanatodiphenylsulphone,

3,3'-diisocyanatodiphenylsulphone,

4,4'-bisisocyanatodiphenylsulphide,

1,4-tetramethylenedIisocyanate,

1,6-hexamethyIenediisocyanate,

1,10-decamethylenediisocyanate,

2,2,4-trimethylhexamethylenediisocyanate

1,4-cyclohexylenediisocyanate,

4,4'-methylene-bis-(cyclohexylisocyanate),

1,5-tetrahydronaρhthalenediisocyanate, isophorone diisocyanate, or a polyisocyanate of formula VIII

in which α has a value of between 0.1 and 2.

4) Curable bisimide resins as claimed in claim 1 or claim 2 in which the polyisocyanate of the general formula II is a diisocyanate of the formula IX

in which P represents a divalent organic residue and F stands for a divalent polyalkylene ether glycol of formula X, XI or XII

β being a number providing a molecular weight for the structure IX of between 200 and 10,000.

5) Curable bisimide resins as claimed In claim 4 wherein the diisocyanate IX is present in quantities up to 80% of the total final resin mixture by weight.

6) Curable bisimide resins as claimed in any one of claims 1 to 5 containing a reactive diluent which carries at least one polymerizable double bond of the general formula XIII

which may be of the vinyl-, allyl- or acryl- type.

7) Curable bisimide resins as claimed in claim 6 in which the reactive diluent is one of the following compounds or mixtures thereof: styrene, methylstyrene, vinyltoluene, divinylbenzene, vinylcyclohexane, divinylcyclohexane, vinylpyridine, vinylpyrrolidone.

8) Curable bisimide resins as claimed in claim 7 wherein the reactive diluent is present in quantities up to 80% of the total final resin mixture by weight.

9) Curable bisimide resins as claimed in claim 8 wherein the reactive diluent is styrene or divinylbenzene, the reactive diluent being present in quantities tip to 30% of the total final resin mixture by weight.

10) Curable bisimide resins as claimed in any one of claims 1 to 9 characterized by containing an unsaturated polyester, the said unsaturated polyester being obtained by the polyecndensation of polycarboxylic acids with polyglycols.

11) Curable bisimide resins as claimed in any one of claims 1 to 10 in which the bisimide of the general formula (I) is modified with compounds selected from one of the following groups:

polyamines, polyhydrazides, amino acid hydrazides, azomethines, or mixtures thereof.

12) Curable bisimide resins as claimed in any one of claims 1 to 11 containing curing catalyst selected from one of the following compounds:

ditertiary butyl peroxide, diamyl peroxide, t-butyl perbenzoate, N,N' dimethylbenzylamine, N,N' dimethyl aniline,

N-methylmorpholine, tri-n-butylamine, tri-methylamine and azabicyclooctane.

13) Curable bisimide resins as claimed in claim 12 wherein a peroxide catalyst is present in the concentration of 0.05 to 0.5% of the total final resin mixture by weight.

14) Prepolymers obtained by heating the curable bisimide resins as claimed in any one of claims 1 to 13 to temperatures of between 80 and 200°C for a time sufficient to obtain a still formable product.

15) Prepolymers as claimed in claim 14 wherein a catalyst is used and the resin mixture is in the melt form or In solution.

16) Solutions of curable bisimide resins as claimed in any one of claims 1 to 15 in an inert organic solvent selected from dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, tetramethyl urea, acetone, methyl-ethyl ketone, methyl-isobutyl ketone, cyclohexanone, methylene chloride, ethyl chloride, 1,2-dichIcroethane, dioxane, tetrahydrofuran, ethyl glycol, ethyl acetate, ethyl glycol acetate, methyl glycol acetate, diethvleneglycol diethyl ether, diethyleneglycol monoethyl ether acetate and mixtures thereof.

17) Solutions according to claim 16 suitable for producing laminates in which the resin is present in a concentration of 50 to 60% of the solution by weight.

18) Crosslinked polyimide-isocyanate copolymers derived by heating the curable bisimide resins mixtures of claims 1 to 12 to temperatures of between 80 and 400°C for a time sufficient to complete cure.

19) Crosslinked polyimide-isocyanate copolymers derived by heating the prepolymers of claims 14 and 15 to temperatures of between 80 and 400°C for a time sufficient to complete cure.

20) Fibrous materials impregnated with curable bisimide resins as claimed in claims 1 to 13, prepolymers as claimed in claim 14 or 15 or solutions as claimed in claims 16 or 17.

21 ) Impregnated materials as claimed in claim 20 in which the fibrous materials are rovings, fabrics, mats or felts.

22) Articles formed under heat and pressure from the curable bisimide resins claimed in claims 1 to 13.

23) Articles formed under heat and pressure from the prepolymers claimed in claims 14 and 15.

24) Articles formed under heat and pressure from the impregnated fibrous materials as claimed in claim 20 or

21.

25) A process lor the manufacture of curable bisimide resins comprising mixing a) at least one bisimide of the general formula I

in which B represents a divalent radical containing a carbon-carbon double bond and A is a divalent radical containing at least two carbon atoms and b) a polyisocyanate of the general formula (II)

in which x has a value in the range 2 to 4 and D stands for an x-valent radical,

In such proportions that the molar ratio a:b is in the range 2 to 100.

26) A process for the manufacture of curable bisimide resins according to claim 25 in which the bisimide of the general formula I is characterised in that

A being a member selected from the groups consisting of (a) an aikylene group with up to 12 carbon atoms, (b) a cycloalkylene group with 5 to 6 carbon atoms, (c) a heterocyclic grotip with 4 to 5 carbon atoms and at least one nitrogen, oxygen or sulphur atom in the ring, (d) a mono or dicarbocyclic group or (e) at least two mono or dicarbocyclic aromatic or cycloalkylene groups which are connected to one auother by a direct carbon-carbon bond or by a bivalent group chosen from oxygen, sulphur, aikylene with one to three carbon atoms, or a group of formulae IlIa to IIIj

the radicals R alkyl groups 1 , R₂ , R₃ , R_{4 ,} wita one to five carbon atoms, R₅ being an aikylene group or an arylene group and

- B is a group which is capable of addition polymerization selected from a group of formula IV, V, VI or VII

27) A process for the manufacture of curable bisimide resins as claimed In claim 25 or claim 26 in which the polyisocyanate of the general formula II is selected from one of the following compounds:

toluene 2,6-diisocyanate, toluene 2,4-diisocyanate, m-phenylenediisocyanate, 4-chloro 1,3-phenylenediisocyanate, 4,4'-biphenylenediisocyanate, 1,5-naphthylenediisocyanate, 4,4'-bisisocyanatodiphenylmethane, 2,4'-bisisocyanatodiphenylmethane, 4,4'-bisisocyanatodiphenyl ether, 4,4'-bisisocyanatodiphenylsulphone, 3,3'-diisocyanatodiphenylsulphone, 4,4'-bisisocyanatodiphenylsulphide, 1,4-tetramethylenediisocyanate, 1,6-hexamethylenediisocyanate, 1,10-decamethylenediisocyanate, 2,2,4-trimetnylhexamethylenediisocyanate

1,4-cyclohexylenediisocyanate,

4,4'-methylene-bis-(cyclohexylisocyanate),

1,5-tetrahydronaphthalenediisocyanate,

Isophorone diisocyanate, or a polyisocyanate of formula VIII

in which α has a value of between 0.1 and 2.

28) Curable bisimide resins as claimed in claim 25 or claim 26 in which, the polyisocyanate of the general formula II Is a diisocyanate of the formula IX

in which R represents a divalent organic residue and F stands for a divalent polyalkylene ether glycol of formula X, XI or XII

29) A process for the manufacture of curable bisimide resins according to claim 25, 26 or 27 in which a reactive diluent having at least one polymerisable double bond of general formula is included in the mixture.

30) A process for the manufacture of curable bisimide resins according to any one of claims 25 to 28 in which the bisimide of formula I is modified with compounds selected from polyamines, polyhydrazides, amino acid hydrazides, azomethines and mixtures thereof.

31) A process for producing cross-linked polyimide- isocyanate copolymers comprising heating a curable bisimide resin prepared by a process as claimed in anyone of claims 25 to 29 to a temperature of between 80° and 400°C for sufficient time to complete the curing of the curable resin.

32) A process for producing fibrous materials impregnated with cross-linked polyimide-isocyanate copolymers comprising impregnating fibrous materials with a curable bisimide resin prepared by a process as claimed in any one of claims 25 to 29 by the application of heat and pressure.