GB2159165A - Curable bisimide resin-forming mixtures - Google Patents
Curable bisimide resin-forming mixtures Download PDFInfo
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- GB2159165A GB2159165A GB08502900A GB8502900A GB2159165A GB 2159165 A GB2159165 A GB 2159165A GB 08502900 A GB08502900 A GB 08502900A GB 8502900 A GB8502900 A GB 8502900A GB 2159165 A GB2159165 A GB 2159165A
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- resin
- forming mixture
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- curable bisimide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/04—Polymeric products of isocyanates or isothiocyanates with vinyl compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Bisimide resin-forming mixtures having improved fracture toughness comprise a mixture of, a) a bisimide of the general formula (I> <IMAGE> in which B represents a divalent organic radical containing a carbon-carbon double bond and A is a divalent organic radical containing at least two carbon atoms and d) a polyisocyanate of the general formula (II> D(NCO)x (II> in which x has a value of between 2 and 4 and D stands for an x-valent organic radical. The molar ratio of a:b is in the 5.25 to 100.
Description
SPECIFICATION
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 diva lent 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 resin-forming mixtures 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 resin-forming mixtures 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 curable bisimide resin-forming mixtures which comprise a mixture of (a) at least one bisimide of formula I
in which B is a bivalent organic radical containing a carbon-carbon double bond and A is a bivalent organic radical having at least two carbon atoms and (b) a polyisocyanate of the general formula II
D(NCO), II in which x has a value in the range 2 to 4 and D stands for an x-valent organic residue. The molar ration a:b lies in the range 5.25 to 100. The copolymerization of bisimides with polyisocyanates can be effected by simply heating a mixture of the two to temperatures between 80 and 400"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, alkylene with one to three carbon atoms, or a group of formula Illa to Illj
the radicals Rt, R2, q, R4, being alkyl groups with one to five carbon atoms, Rs being an alkylene 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, Vl 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,Z-bismaleimidoethane, 1,6-bismaleimidohexane, 1,1 2-bismaleimidododecane, 1 ,6-bismaleimido-(2,2,4-trimethyl)hexane, 1 ,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 4,4'-bismaleimidodiphenylmehane, 4,4'-bismaleimidodiphenylether, 4,4'-bismaleimidodi- phenylsulphide, 4,4'-bismaleimidodiphenylsulphone, 4,4'-bismaleimidodicyclohexylmethane, 2,4bismaleimidoto- luene, 2,6-bismaleimidotoluene, N,N'-m-xylylene- bismaleimide, N,N'-p-xylylenebismaleimide.Examples of other suitable bisimides are N,N-m- phenylene-biscitraconomide and N,N'4,4'-di- phenyl- methane-citraconimide, in which the radical B is of formula VI and N,N'-4,4'-diphenylmethane- bis-ita- conomide in which the radical B is of formula VII.
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-1,3- phenylenediisocyanate, 4,4'-biphenylenediisocyanate, 1,5-naphthylenediisocyanate, 4,4-bisisocyanatodiphenylmethane, 2,4'-bisisocyanatodiphenylmethane, 4,4'-bisisocyanatodiphenyl ether, 4,4'-bisisocyanatodiphenyl-sulphone, 3,3-diisocyanatodiphenylsulphone, 4,4'bis- isocyanatodiphenylsulphide, and aliphatic diisocyanates such as 1,4-tetramethylenediisocyanate, 1,6hexa- methylenediisocyanate, 1,1 0-decamethylenediisocyanate, 2,2,4,- trimethylhexamethylenediisocyanate, 1 ,4-cyclohexy- lenediisocyanate, 4,4'-methylene-bis-(cyclohexylisocyanate), 1,5-tetrahydronaphthalenediisocyanate and isophoronediiso- cyanate; 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, Xl or XII -(CH2-CH2-O),-, X
-(CH2-CH2-CH2-CH2-O)ss- XII
F representing polyalkylene ether backbone, ss being a number providing a molecular weight for the structure IX of between 200 and 10,000.The group 2 polyisocyanates of formula IX are well known substances and their preparations described in detail in Kunststoffhandbuch, Band VII, p. 84-85, Carl Hanser
Verlag, Munchen 1966, they may be used in quantities up to 80% by weight 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. 6072, Carl Hanser Verlay, Munchen 1966.
The preparation of the new curable bisimide resin-forming mixtures can be carried out in an inert organic solvent or diluent, for example in dimethyl formamide, dimethylacetamide, N-methyl pyrrolidone 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 resin-forming mixtures can be performed by using conventional techniques for mixing and grinding of powders or powders and liquids to intimately blend the bisimides 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 resin-forming mixtures according to 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- forming mixtures requires a solution as is the case for the production of prepregs.
For many industrial applications of the new curable bisimide resin-forming mixtures 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-forming mixtures.
Other catalysts that may be used are tertiary amines like N,N'-dimethylaniline, N,N'-dimethyl-benzylamine, N-methylmorpholine, tri-n-butylamine, tri-methylamine and azabicyclooctane and others.
The catalysts can be admixed with the components of the curable bisimide resin-forming mixtures 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 resin-forming mixtures of the present invention from the melt. To reduce the melt viscosity and to improve the pot life the resin-forming mixtures 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
CH2 = C, Xlil 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 are 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, methacrylic, phenylacrylic, crotonic, maleic, fumaric, itaconic, citraconic, tetrahydrophthalic, 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, diallybenzene, 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 po lyisocyanates 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 110-110 C, therefore mixtures containing these diluents have to be prepared at temperatures well below 100 C.
The new curable bisimide resin-forming mixtures of the present invention can be thermally converted to crosslinked polyimide-isocyanate copolymers by heating them to temperatures of between 80 and 400"C, for a time sufficient to complete cure.
The new curable bisimide resin-forming mixtures are advantageously used to produce laminated materials. In such a case the prepolymers produced from the curable bisimide resin-forming mixtures 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-isocyanace copolymer being the binder.
The curable bisimide resin-forming mixtures 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 appiications it is possible to admix with the curable bisimide resin-formign mixtures 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)-bismaleimidotoluene and 20 g of 4,4'-diisocyanato- diphenylmethane 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 220KdgC the remaining properties were:
flexural strength 92 N/mm2
flexural modulus 4.8 KN/mm2 indicating extremely good thermal oxidative stability.
(b) The molten mixture of the reactants was heated for 1 hour at 1800C 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'-bismaieimidodiphenyl- methane, (2,4-2,6)-bismaleimidotoluene and 4,4'di- isocyanatodiphenylmethane obtained by ball milling as described above was dissolved in methylene chloride- ethylglycol acetate mixture as a solvent to form a low viscosity solution containing 60% by weight of resin- forming mixture. 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 polyimideisocyanate copolymer 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/cm2
Flexural Strength at 250"C 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
Claims (22)
1. A curable bisimide resin-forming mixture comprising a mixture of
a) at least one bisimide of the general formula I
in which B represents a divalent organic radical containing a carbon-carbon double bond and A is a
divalent organic radical containing at least two carbon atoms and
b) a polyisocyanate of the general formula (II) D(NCO) (II) in which x has a value in the range 2 to 4 and D stands for an x-valent organic radical, in which the molar ratio a:b is in the range 5.25 to 100.
2. A curable bisimide resin-forming mixture 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 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 and (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 Illa to Illj
the radicals R1, R2, R2, R4, being alkyl groups with one to five carbon atoms, Rs 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
3. A curable bisimide resin-forming mixture 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-ch loro 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,
1,1 0-decamethylenediisocyanate, 2,2,4-trimethylhexamethylenediisocyanate 1 ,4-cyclohexylenediisocyanate, 4,4'-methylene-bis-(cyclohexyl isocya ndte), 1,5-tetrahydronaphthalenediisocyanate,
isophorone diisocyanate,
or a polyisocyanate of formula Vlil
in which a has a value of between 0.1 and 2.
4. A curable bisimide resin-forming mixture 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 R represents a divalent, aliphatic or aromatic organic residue and F stands for a divalent polyalkylene ether glycol residue of formula X, Xl or XII -(CH2-CH2-O),-, X
-(CH2-CH2-CH2-CH2-O)- XII ss being a number providing a molecular weight for the structure (IX) of between 200 and 10,000.
5. A curable bisimide resin-forming mixture 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. A curable bisimide resin-forming mixture 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
CH2 = C= XIII of the vinyl-, allyl- or acryl- type.
7. A curable bisimide resin-forming mixture 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. A curable bisimide resin-forming mixture 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. A curable bisimide resin-forming mixture as claimed in claim 8 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.
10. A curable bisimide resin-forming mixture as claimed in any one of claims 1 to 9 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.
11. A curable bisimide resin-forming mixture as claimed in claim 10 wherein a peroxide catalyst is present in the concentration of 0.05 to 0.5% of the total final resin mixture by weight.
12. A prepolymer obtained by heating the curable bisimide resin-forming mixture as claimed in any one of claims 1 to 11 to temperatures of between 80 and 200"C for a time sufficient to obtain a still formable product.
13. A prepolymer as claimed in claim 12 wherein a catalyst is used and the resin mixture is in the melt form or in solution.
14. A solutions of a curable bisimide resin-forming mixture as claimed in any one of claims 1 to 11 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-dichloroethane, dioxane, tetrahydrofuran, ethyl glycol, ethyl acetate, ethyl glycol acetate, methyl glycol acetate, diethyleneglycol diethyl ether, diethyleneglycol monoethyl ether acetate and mixtures thereof.
15. A solutions according to claim 14 suitable for producing laminates in which the resin-forming mixture is present in a concentration of 50 to 60% of the solution by weight.
16. A crosslinked polyimide-isocyanate copolymer derived by heating the curable bisimide resin-forming mixture of claims 1 to 11 to temperatures of between 80 and 400"C for a time sufficient to complete cure.
17. A crosslinked polyimide-isocyanate copolymer derived by heating the prepolymer of claims 12 and 13 to temperatures of between 80 and 400"C for a time sufficient to complete cure.
18. A fibrous material impregnated with a curable bisimide resin-forming mixture as claimed in claims 1 to 11, a prepolymer as claimed in claim 12 or 13 or a solution as claimed in claims 14 or 15.
19. An impregnated material as claimed in claim 18 in which the fibrous material is roving, fabric, mat or felt.
20. An article formed under heat and pressure from a curable bisimide resin-forming mixture claimed in claims 1 to 11.
21. An article formed under heat and pressure from a prepolymer claimed in claims 12 and 13.
22. An article formed under heat and pressure from an impregnated fibrous material as claimed in claim 18 or 19.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB08502900A GB2159165B (en) | 1982-07-21 | 1985-02-05 | Curable bisimide resin-forming mixtures |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8221116 | 1982-07-21 | ||
GB8319388A GB2125806B (en) | 1982-07-21 | 1983-07-18 | Modified thermosetting imide resins |
GB08502900A GB2159165B (en) | 1982-07-21 | 1985-02-05 | Curable bisimide resin-forming mixtures |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8502900D0 GB8502900D0 (en) | 1985-03-06 |
GB2159165A true GB2159165A (en) | 1985-11-27 |
GB2159165B GB2159165B (en) | 1986-04-23 |
Family
ID=27261673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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GB08502900A Expired GB2159165B (en) | 1982-07-21 | 1985-02-05 | Curable bisimide resin-forming mixtures |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0230741A2 (en) * | 1986-01-18 | 1987-08-05 | Technochemie GmbH - Verfahrenstechnik | Curable resins |
-
1985
- 1985-02-05 GB GB08502900A patent/GB2159165B/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0230741A2 (en) * | 1986-01-18 | 1987-08-05 | Technochemie GmbH - Verfahrenstechnik | Curable resins |
EP0230741B1 (en) * | 1986-01-18 | 1993-08-11 | Technochemie GmbH - Verfahrenstechnik | Curable resins |
Also Published As
Publication number | Publication date |
---|---|
GB8502900D0 (en) | 1985-03-06 |
GB2159165B (en) | 1986-04-23 |
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Legal Events
Date | Code | Title | Description |
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732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970718 |