Curable resins

Claim 2

1) Curable 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) at least one alkenyl compounds of formula II D(G) m II in which m is an integer from 1 to 4, G represents a phenyl ring substituted by at least one alkenyl group and D represents (i) a group of formula IIa E-[OCH₂CH(OH)CH₂O-] n IIa in which E is a n-valent group and n is an integer from 1 to 4, (ii) a divalent group of formula IIb in which F is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO-, (iii) a group of formula IIc in which F is as defined in (ii) above, (iv) a divalent group of formula IId or (v) a divalent group of formula IIe in which J is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO- and p is 0 or 1.

Claim 3

2) Curable bisimide resins according to claim 1 in which the bisimide of the general formula I is characterized in that - A is a member selected from the groups consisting of (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 a least one nitrogen, oxygen or sulphur atom in the ring, (d) a mono or dicarbocyclic group, (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, alkylene with one to three carbon atoms, or a group of formulae IIIa to IIIj The radicals R₁, R₂, R₃, R₄, being alkyl groups with one to five carbon atoms, R₅ being an alkylene 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

Claim 4

3) Curable bisimide resins as claimed in claim 2 in which the bisimide of formula I is selected from the group consisting of 1,2-bismaleimidoethane, 1,6-bis­maleimidohexane, 1,12-bismaleimidododecane, 1,6-bis­maleimido(2,2,4-trimethyl)hexane, 1,3-bismaleimido­benzene, 1,4-bismaleimidobenzene, 4,4ʹ-bismaleimido­diphenylmethane, 4,4ʹ-bismaleimidodiphenylether, 4,4ʹ-bismaleimidodiphenylsulphide, 3,3ʹ-bis­maleimidodiphenylsulphone, 4,4ʹ-bismaleimidodiphenyl­sulphone, 4,4ʹ-bismaleimidodicyclohexylmethane, 2,4-­bismaleimidotoluene, 2,6-bismaleimidotoluene, 2,4-­bismaleimidoanisole, N , N ʹ- m -xylylenebismaleimide, N , N ʹ-p-xylylenebismaleimide and mixtures thereof.

Claim 5

4) Curable bisimide resins as claimed in claim 3 in which the bisimide of formula I comprises i) eutectic mixtures containing 4,4ʹ-bismaleimidodiphenylmethane and 2,4-bismaleimidotoluene, ii) eutectic mixtures containing 4,4ʹ-bismaleimidodiphenylmethane, 2,4-­bismaleimidotoluene and 1,6-bismaleimido(2,2,4-tri­methyl)hexane and iii) eutectic mixtures of 4,4ʹ-bis­maleimidodiphenylmethane and 2,4-bismaleimidoanisole.

Claim 6

5) Curable bisimide resins as claimed in claim 1 in which the bisimide of formula I is modified with amino acid hydrazides, polyamines, polyhydrazides, azomethines, polyisocyanates, carboxy-terminated or acrylic/vinyl-terminated polybutadiene/acrylonitrile elastomers, thermoplastic polymers or mixtures thereof.

Claim 7

6) Curable bisimide resins as claimed in claim 1 in which D represents a polyvalent group of formula IIa in which the group E is (i) an alkylene group, (ii) a cyclalkylene group containing 5 or 6 carbon atoms, (iii) phenylene, (iv) a heterocyclic group containing at least one nitrogen, oxygen or sulphur atom in the ring, (v) a mono or dicarbocyclic group, (vi) a group of formula IIf K-(L) q -K IIf in which K represents an optionally substituted mono or dicarbocyclic aromatic or cycloalkylene group, q is 0 or 1 and L is a divalent group selected from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO- or (viii) a high molecular weight epoxy compound.

Claim 8

7) Curable bisimide resins as claimed in claim 6 in which the alkenyl compound is represented by formula IIg G[OCH₂CH(OH)CH₂O]E[OCH₂CH(OH)CH₂O]G in which E is a m -phenylene group or a group of formula IIh and G represents a group of formula IIj or IIk or of formula IIm or IIn

Claim 9

8) Curable bisimide resins as claimed in claim 1 wherein D represents a divalent group of formula IIb said alkenyl compound being prepared by the reaction of an alkenylphenol and a compound of formula VIII in which F is as defined in claim 1 and X represents halo.

Claim 10

9) Curable resins as claimed in claim 8 in which the alkenylphenol is allylphenol, eugenol or diallylbisphenol A

Claim 11

10) Curable bisimide resins as claimed in claim 1 in which the alkenyl compound is represented by formula IIp in which F is -SO₂- or -CO- and G represents a group of formula IIk or IIn.

Claim 12

11) Curable bisimide resins as claimed in claim 1 wherein D is a group of formula IIc in which F is -CO- and G is a group of formula IIk or IIn.

Claim 13

12) Curable bisimide resins as claimed in claim 1 in which D represents a group of formula IId or IIe and G represents a group of formula IIj or IIm.

Claim 14

13) Curable bisimide resins as claimed in claim 1 wherein the ratio of the number of moles of bisimide present to the number of moles of alkenyl compound present lies in the range 1:1 to 50:1.

Claim 15

14) Curable resins as claimed in claim 1 containing up to 80% of the total resin mixture by weight of a reactive diluent which carries at least one polymerizable double bond and is one of the following compounds:- styrene, methylstyrene, vinyltoluene, divinylbenzene, 1-ethyl-4-vinylbenzene, vinylcyclohexane, divinylcyclohexane, vinylpyridine, vinylpyrrolidone, unsaturated polyesters or mixtures thereof.

Claim 16

15) Curable resins as claimed in claim 14 wherein the reactive diluent is styrene or divinylbenzene, the reactive diluent being present in quantities up to 30% of the total final resin mixture by weight.

Claim 17

16) Curable resins as claimed in any one of the preceding claims in which a catalyst is present in an amount of 0.01 to 10% by weight based on the total weight of the curable bisimide resins.

Claim 18

17) Prepolymers obtained by heating the curable resins as claimed in any one of claims 1 to 16 to temperatures of between 80 and 200°C for a time sufficient to obtain a still formable product.

Claim 19

18) Solutions of curable resins as claimed in any one of claims 1 to 16 in an inert organic solvent selected from dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, tetramethyl urea, acetone, methylethyl ketone, methylisobutyl ketone, cyclohexanone, methylene chloride, ethyl chloride, 1,2-dichloroethane, dioxane, tetrahydrofuran, ethyl glycol, ethyl acetate, ethyl glycol acetate, methyl glycol acetate, diethyleneglycol diethyl ether, diethyleneglycol monoethyl ether acetate and mixtures thereof in which the resin is present in a concentration of 25 to 65% of the solution by weight.

Claim 20

19) Crosslinked polymers derived by heating the curable resin mixtures of claims 1 to 16 or the prepolymers of claim 17 to temperatures of between 80 and 400°C for a time sufficient to complete cure.

Claim 21

20) Fibrous materials impregnated with curable resins as claimed in claims 1 to 16, prepolymers as claimed in claim 17 or solutions as claimed in claim 18.

Claim 22

21) Films cast from solutions of curable resins as claimed in claim 18.

Claim 23

22) Moulding compositions comprising a curable resin as claimed in any one of claims 1 to 16 or prepolymers as claimed in claim 17 and additives selected from fillers, colourants, softeners and flameproofing agents.

Claim 24

23) Laminated articles formed under heat and pressure from an alternating stack of films as claimed in claim 21 and layers of reinforcing material.

Claim 25

24) An alkenyl compound of formula II D(G) m II in which m is an integer from 1 to 4, G represents a phenyl ring substituted by at least one alkenyl group and D represents (i) a group of formula IIa E-[OCH₂CH(OH)CH₂O-] n IIa in which E is a n-valent group and n is an integer from 1 to 4, (ii) a divalent group of formula IIb in which F is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO-, (iii) a group of formula IIc in which F is as defined in (ii) above, (iv) a divalent group of formula IId or (v) a divalent group of formula IIe in which J is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO- and p is 0 or 1.

Claim 26

24) An alkenyl compound of formula II D(G) m II in which m is an integer from 1 to 4, G represents a phenyl ring substituted by at least one alkenyl group and D represents (i) a group of formula IIa E-[OCH₂CH(OH)CH₂O-] n IIa in which E is a n-valent group and n is an integer from 1 to 4, (ii) a divalent group of formula IIb in which F is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO-, (iii) a group of formula IIc in which F is as defined in (ii) above, (iv) a divalent group of formula IId or (v) a divalent group of formula IIe in which J is a divalent group chosen from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO- and p is 0 or 1.

Claim 27

25) An alkenyl compound of formula II as claimed in claim 24 in which D represents a polyvalent group of formula IIa, the group E may be (i) an alkylene group, (ii) a cycloalkylene group containing 5 or 6 carbon atoms, (iii) phenylene, (iv) a heterocyclic group containing at least one nitrogen, oxygen or sulphur atom in the ring, (v) a mono or dicarbocyclic group, (vi) a group of formula IIf K-(L) q -K IIf in which K represents an optionally substituted mono or dicarbocyclic aromatic or cycloalkylene group, q is 0 or 1 and L is a divalent group selected from -SO₂-, -SO-, -CMe₂-, -O-, -C(CF₃)₂-, -CH₂- or -CO- or (viii) a high molecular weight epoxy resin.

Claim 28

26) An alkenyl compound of formula IIg G[OCH₂CH(OH)CH₂O]E[OCH₂CH(OH)CH₂O]G IIg in which E is m -phenylene or a group of formula IIh and G is a group of formula IIj, IIk, IIm or IIn

Claim 29

26) An alkenyl compound of formula IIg G[OCH₂CH(OH)CH₂O]E[OCH₂CH(OH)CH₂O]G IIg in which E is m -phenylene or a group of formula IIh and G is a group of formula IIj, IIk, IIm or IIn

Claim 30

27) An alkenyl compound of formula II as claimed in claim 22 in which D is a divalent group of formula IIb, said alkenyl compounds being prepared by reaction of an alkenylphenol with a compound of formula VIII in which F is as defined in claim 22 and X represents halo.

Claim 31

28) An alkenyl compound of formula II as claimed in claim 25 in which the alkenylphenol is allylphenol, eugenol or diallylbisphenol A.

Claim 32

29) Compounds of formula IIp in which F is -SO₂- or -CO- and G represents a group of formula IIk or IIn

Claim 33

29) Compounds of formula IIp in which F is -SO₂- or -CO- and G represents a group of formula IIk or IIn