GB2060490A - Composite Material and a Process for Manufacturing the Same - Google Patents

Composite Material and a Process for Manufacturing the Same Download PDF

Info

Publication number
GB2060490A
GB2060490A GB8033012A GB8033012A GB2060490A GB 2060490 A GB2060490 A GB 2060490A GB 8033012 A GB8033012 A GB 8033012A GB 8033012 A GB8033012 A GB 8033012A GB 2060490 A GB2060490 A GB 2060490A
Authority
GB
United Kingdom
Prior art keywords
fibres
composite materials
hybrid matrix
thermoplastic
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB8033012A
Other versions
GB2060490B (en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Technochemie GmbH Verfahrenstechnik
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technochemie GmbH Verfahrenstechnik filed Critical Technochemie GmbH Verfahrenstechnik
Publication of GB2060490A publication Critical patent/GB2060490A/en
Application granted granted Critical
Publication of GB2060490B publication Critical patent/GB2060490B/en
Expired legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Composite materials consisting of reinforcing fibres and a temperature- resistant flameproof binder, characterised in that the binder used is a hybrid matrix consisting of a soluble thermoplastic high polymer and thermosetting resin.

Description

SPECIFICATION Composite Materials and a Process for Manufacturing the Same The invention relates to composite materials which consist of fibres, e.g. glass fibres, carbon fibres or aromatic polyamide fibres (referred to as aramide fibres) in the form of fleeces, woven fabrics or knitted fabrics and a temperature-resistant matrix, i.e. a matrix which is non-combustible; the invention furthermore relates to a process of producing such composite materials.
The main field of application of the composite materials according to the invention resides in their use as structural components, as thermal and electrical insulators and as fireproofing materials.
It is known that high-strength and thermally stressable composite materials employing temperature-resistant resins or polymers can be produced in that the impregnating resin is dissolved in a solvent to produce an impregnating lacquer whereupon fibrous materials such as carbon fibres, glass fibres, boron fibres or organic high-module fibres consisting of aromatic polyamides (referred to as aramides) in the form of fleeces, woven fabrics or knitted fabrics, after which the solvent is evaporated off to leave a pre-impregnated fibre material (referred to as a prepreg) which can be worked under pressure and at high temperatures to produce temperature-resistant fibre laminates.
U.S. Patent No. 3,179,614 describes linear fully aromatic polyimides which, via soluble preproducts, polyamido carbonic acids, can be processed into laminates in that imidisation is carried out under high temperatures and under pressure. When the polyamido carbonic acid is transformed into the fully aromatic polyimide, this reaction takes place in the temperature range between 220 and 3000 C, water is released which leads to pores forming in the laminate. Pores in the matrix do however impair the mechanical properties of the composite fibre materials and do not permit of full utilisation of the mechanical properties inherent in the fibres. This complex of problems led to the development of thermosetting polyimide resins which are known for instance from French Patent Specifications Nos.
1,455,514 and 1,555,564 and German Offenlegungsschrifts Nos. 2,530,571,2,754,632, 2,754,631 and U.S. Patent Specifications Nos. 3,839,287, 3,689,464 and 3,562,223.
The resins of the cited patents and Offenlegungsschrifts have in common that during hardening, i.e. during the transition from the monomeric to the polymeric condition, no products of condensation are released which might lead to pore formation when the resins are used for the production of fibre laminates. Disadvantageous when the resins of the above-mentioned patents and Offenlegungsschrifts are used however is the fact that high boiling, high-polar solvents are required in order to produce the impregnating solution, due to the solubility properties of the resins. On account of their ready affinity for the resins, these solvents can only with great difficulty be completely removed from the laminates.
The residual solvent remaining in the laminates after hardening disadvantageously and particularly at high temperatures has a softening effect and in the end results in a considerable deterioration of the mechanical properties at high temperatures.
According to the state of the art, it is furthermore known that thermoplastic polymers, for example polysulphones, can be used as a matrix for fibre laminates. These fibre laminates are manufactured in that pre-impregnated fibre materials (referred to as prepregs) having a very low content of thermoplastic polymer of about 10 to 1 5% and films of thermoplastic polymers are alternately layered in a heated panel press and are moulded under pressure and at temperatures above the melting point of the thermoplastic prepreg to produce an homogeneous pore-free laminate.
Essential to the application of this technology however is the solubility of the thermoplastic resin in suitable solvents for the casting of films and the genuine fusibility of the linear polymer. Naturally, by reason of the soluble binder, such laminates are susceptible to solvents; for application at high temperatures, for example 2500C, melting points of around or above 3500C are required (literature: Phillips S Murphy, RAE Technical Report No. 76140, October 1976). However, it has been surprisingly found that mixtures of morphological thermoplastic soluble polymers and thermo-setting resins can be substantially processed to produce solvent-free films or that these films can be used for manufacturing fibre laminates in that the cited technology of the moulding of polymer films and low-resin prepregs is carried out in the press at high temperatures.
The advantage of this procedure lies in the fact that on the one hand completely solvent-free and pore-free laminates are provided and in that the laminates obtained are after hardening resistant to solvents by reason of the proportion of thermosetting highly cross-linked imide.
A further progressive feature lies in the fact that it is possible via the content of thermosetting resin fusible at low temperatures to regulate the flow properties during moulding; i.e., the films fuse according to the melting point and content of thermosetting resin.
At the moulding stage, therefore, relatively low processing pressures are required.
The object of the present invention is to provide composite materials consisting of fibres such as for example glass fibres, carbon fibres, boron fibres or aromatic polyamide fibres in the form of fleeces, woven fabrics or knitted fabrics and a temperature flame-resistant binder, characterised in that the binder used is a hybrid matrix consisting of a soluble thermoplastic high polymer and a thermo-setting resin.
A preferred embodiment is characterised in that the ratio of thermoplastic polymer to thermosetting resin in the hybrid matrix is between 95:5 and 5:95.
The thermoplastic component of the hybrid matrix is preferably a soluble temperature-resistant high polymer chosen from polysulphone, polyhydantoin, polycarbonate, polyamide, polyimide, polyamide imide, polyphenyl quinoxalin, polybenzymidazol, polyoxadiazol or polybenzoxazol.
A further preferred embodiment is characterised in that the thermosetting component used in the hybrid matrix is a soluble temperature-resistant resin selected from polyester, epoxy resin, bismaleic imide or a prepolymer comprising terminal acetylene groups.
A further preferred embodiment is characterised in that the thermoplastic component used in the hybrid matrix is a polyamide imide obtainable from benzophenone-tetracarbonic acid dianhydride, mamino benzoic acid and diamino diphenyl methane and in that the thermosetting component employed is a bismaleicimide to the general formula
in which the radical A denotes a bivalent organic radical having at least two carbon atoms while B is a bivalent organic radical according to the following formulae
A further preferred embodiment of the composite materials according to the invention is characterised in that the thermoplastic component used is a polyether sulphone and in that the component used as a thermosetting component is a polyimide prepolymer which is obtainable by reaction of a bismaleic imide to the general formula
with a diamine to the general formula H2N-D-NH2 in which D is a bivalent organic radical with at least two carbon atoms, the molar ratio between bisimide and diamine being preferably between 1.2 and 5.
Furthermore, the present invention relates to a process for producing composite materials consisting of fibres such as for example glass fibres, carbon fibres, boron fibres, aromatic polyamide fibres, in the form of fleeces, woven fabrics or knitted fabrics and a temperature-resistant flameproof hybrid matrix consisting of a thermoplastic high polymer and a thermosetting resin which is characterised in that films of the hybrid matrix and low resin prepreg of the hybrid matrix are alternately layered and are moulded under pressure and at high temperatures.
The composite materials are preferably manufactured in that solvent-free films of the hybrid matrix system in which the thermosetting resin is contained in unhardened largely monomeric condition are alternately layered in a press with prepregs containing substantially 5 to 20% of the hybrid matrix system followed by moulding under pressure at temperatures at which the thermosetting resin is transformed into the liquid state after which cross-linking is carried out under pressure and at high temperature.
The individual steps in the process of producing composite materials from a hybrid thermoplasticthermosetting matrix are preferably as follows: a) production of hybrid films consisting of a thermoplastic high temperature polymer and a thermosetting polyimide resin in the non-hardened condition; b) production of a prepreg consisting of the pre-orientated fibres in the form of rovings, woven fabrics, knitted fabrics or fleeces and the hybrid matrix, the resin content amounting to substantially 15%, c) moulding of the films and prepregs under pressure to produce a laminate having high mechanical properties and high thermal stability.
The individual procedural steps and products which are preferably used for the new technology are described in detail hereinafter.
A condition essential to application of the new method to the production of improved high temperature laminates is the facility to produce hybrid films consisting of the thermoplastic high temperature polymer and the thermosetting high temperature resin.
It is the function of the thermoplastic polymer to impart the necessary mechanical stability to the film.
In principle, any thermoplastic film-forming polymers may be used if it is possible also to produce from them low resin prepregs, via the use of solvents.
For high temperature-resistant laminates, high temperature-resistant thermoplastic polymers are used, for example polysulphones, aromatic polyamides, polysulphones, aromatic polyamides (sic !), polyamidimides, polyimides, polyphenol quinoxalines, polyquinoxalines, polyaxadiazoles, polythiadiazoles.
Already known from U.S. Patent No. 3,708,458 are copolyimides which are readily soluble in organic solvents such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone and which can, out of these solvents, be poured to produce films.
Hybrid films are produced in that both the thermosetting and also the thermoplastic resin are dissolved in a solvent suitable for both resins and in that a film is produced on a carrier by pouring and drying.
It is a further aspect of the feasibility of the new process that prepregs having a resin content of between 5% and 20% can be produced via a solution of the hybrid matrix which in the case of soluble polymers is brought about in that fibres in the form of woven fabrics, knitted fabrics, rovings or fleeces are pulled through the solution so that the fibres are impregnated, excess resin is allowed to run off and in that the impregnated fibre material is liberated from solvents by drying, for example in a circulating air cabinet.
The new composite materials are then easily produced in that alternate layers of prepregs and hybrid films are prepared and in that the stack of alternate layers is hardened in a heated panel press under pressure and at a temperature of for example between 1 70 and 2800C.
A laminate is thereby obtained, the hybrid matrix functioning as a binder. The laminates are porefree and exhibit good mechanical properties even at temperatures of around 2500C.
The following examples will serve as a further explanation of the substance of the present invention.
Example 1 The following are used as raw materials for the production of a glass fabric laminate: a) a linear morphologically thermoplastic polyamide imide (PAPI) produced from benzophenon tetracarbonic acid dianhydride, m-amino benzoic acid and 4,4-diamino diphenyl methane. The polyamide imide is soluble in dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone and has an inherent viscosity of 0.5 dl/g.
b) 4,4'-bismaleic imido diphenyl methane as a thermosetting imide resin.
c) glass fabric of the Atlas type with a weight per unit of area of 290 to 310 g/sq.m, furnished with a commercially available amino silane adhesion promoter.
6.15 g of the thermoplastic polyamide imide are dissolved in 55.35 g dimethyl formamide; furthermore, a solution of 6.1 5 g 4,4'-diamino diphenyl methane in 55.35 g dimethyl formamide is produced.
Both solutions are combined; the result is a 10% solution of the hybrid matrix in dimethyl formamide. This solution is used to produce a poured film by pouring the solution onto a crystal glass plate measuring 400x400 mm. The solvent is eliminated by drying for 3 hours at 600C and for 18 hours at 750C to the extent that the film can be pulled off the glass sheet. After drying in a circulating air drying cabinet for 19 hours at 700C, the film has a residual solvent content of 8.5%.
Furthermore, a 15% solution of the hybrid matrix in dimethyl formamide is produced, the ratio of thermoplast to duroplast being 1:1.
Prepared glass fabric blanks measuring 1 50x 1 50 mm are impregnated by being dipped in the solution of hybrid matrix, excess solution being allowed to run off and the prepregs being dried for 18 hours at 700C in a circulating air drying cabinet. After one dip, prepregs are obtained which have a resin content of hybrid matrix of 9 to 10%, while two dips result in a resin content of 16 to 1 7%. The residual solvent content of the prepregs is 0.75%.
In order to produce a glass fabric laminate, 8 glass fabric prepregs and 9 hybrid films are placed in alternate layers between two aluminium films and are hardened in a heated panel press at 2200C and under a pressure of 40 Kp/sq.cm for three hours, after which the result is cooled, removed from the mould and heat treated for 15 hours at 2500C.
The resultant laminate has the following properties at room temperature: Fibre content 45 per cent by volume Resin content 55 per cent by volume Density 1.82 g/cu.cm Bending strength 48 Kp/sq.cm (DIN53452) Bending modulus 1930 Kp/sq.cm (DIN53452) Interlaminar shearing resistance 4.5 Kp/sq.cm At 2500C, the residual strength is still 70% of the starting value.
Example 2 The procedure described in Example 1 is used in order to produce a pore-free dense temperatureresistant glass fabric laminate. Instead of the polyamidimide, a copolyether sulphone is used as the thermoplastic constituent of the hybrid matrix. By virtue of the good film forming properties of the polysulphone due to the high molecular weight, the thermoplast"durnmer ratio as 1:2.
As in Example 1, 4,4'-bismaleic imido diphenyl methane is used as the thermosetting resin.
Hardened at 2100C and 40 KpZsq.cm, the laminate exhibits the following properties: Fibre content 50 per cent by volume Density 1.0 g/cu.cm Bending strength 52 Kp/sq.cm Bending modulus 2150 Kp/sq.cm Interlaminar shearing resistance 5.8 Kp/sq.cm At 2000C, the mechanical strength properties are still 50% of the values at room temperature.
Example 3 A thermoplastic polyimide produced according to U.S. Patent No. 3,708,458, Example 1, and a thermosetting polyimide resin according to German Offenlegungsschrift No. 2,530,571, Example 1, are used in order to produce a carbon fibre fabric laminate, the said imide resins forming the hybrid matrix.
A poured film is produced via a N-methyl pyrrolidone solution of the hybrid matrix. The weight ratio of thermoplastic polyimide to duro-plastic polyimide is 2:1. Prepregs with a resin content of 10% are produced via a 15% solution of the hybrid matrix in N-methyl pyrrolidone by dipping. Excess resin is allowed to run off and the prepregs are dried for 1 5 minutes at 1 400C in a circulating air drying cabinet. The residual solvent content is 2.1%.
Films of the hybrid matrix and prepregs, produced as described, are layered alternately and hardened in a panel press at 50 Kp/sq.cm pressure and at a temperature of initially 1 900C rising to 2400 C, for a period of 4 hours.
The laminate exhibits the following properties: Density 1.50 g/cu.cm Bending strength 62 Kp/sq.cm Bending modulus 6800 Kp/sq.cm.
68% of the starting strength is still measured at 2500C.
Within the framework of this disclosure, the expression prepregs stands for "pre-impregnated fibre materials".

Claims (7)

Claims
1. Composite materials consisting of reinforcing fibres and a temperature-resistant flameproof binder, characterised in that the binder used is a hybrid matrix consisting of a soluble thermoplastic high polymer and a thermosetting resin.
2. Composite materials according to Claim 1, characterised in that the ratio of thermoplastic polymer to thermosetting resin in the hybrid matrix is between 95:5 and 5:95.
3. Composite materials according to Claim 1, characterised in that the thermoplastic component used in the hybrid matrix is a soluble temperature resistant high polymer chosen from polysulphone, polyhydantoin, polycarbonate, polyamide, polyimide, polyamide imide, polyphenyl quinoxalin, polybenzymidazol, polyoxadiazol or polybenzoxazol.
4. Composite materials according to claim 1, characterised in that the thermosetting component used in the hybrid matrix is a soluble temperature-resistant resin chosen from polyester, epoxy resin, bismaleic imide or a prepolymer comprising terminal acetylene groups.
5. Composite materials according to Claim 1, characterised in that the thermoplastic component used in the hybrid matrix is a polyamide imide obtainable from benzophenone-tetracarboxylic acid dianhydride, m-amino benzoic acid and diamino diphenyl methane and in that the thermosetting component employed in a bismaleic imide to the general formula
in which the radical A denotes a bivalent organic radical having at least two carbon atoms while B is a bivalent organic radical according to the following formulae
6.Composite materials according to Claim 1, characterised in that the thermoplastic component used is a polyether sulphone and in that the component used as a thermosetting component is a polyimide prepolymer which is obtainable by reaction of a bismaleic imide to the general formula
with a diamine to the general formula H2N-D-NH2 (11) in which D is a bivalent organic radical with at least two carbon atoms, the molar ratio between bisimide (I) and diamine (II) being preferably between 1.2 and 5.
7. Composite materials according to Claim 1, wherein the fibres are glass fibres, carbon fibres, boron fibres or aromatic polyamide fibres in the form of fleeces, woven fabrics or knitted fabrics characterised in that films of the hybrid matrix and low resin prepreg of the hybrid matrix are alternately layered and are moulded under pressure and at elevated temperatures.
GB8033012A 1979-10-16 1980-10-13 Composite material and a process for manufacturing the same Expired GB2060490B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2941785A DE2941785C2 (en) 1979-10-16 1979-10-16 Laminates and processes for their manufacture

Publications (2)

Publication Number Publication Date
GB2060490A true GB2060490A (en) 1981-05-07
GB2060490B GB2060490B (en) 1984-09-19

Family

ID=6083571

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8033012A Expired GB2060490B (en) 1979-10-16 1980-10-13 Composite material and a process for manufacturing the same

Country Status (3)

Country Link
DE (1) DE2941785C2 (en)
FR (1) FR2467907A1 (en)
GB (1) GB2060490B (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2178364A (en) * 1985-07-31 1987-02-11 Smith H R Laminates of fibre-reinforced thermoplastics resins
US4806419A (en) * 1983-11-04 1989-02-21 The Boots Company Plc Bisimide/polyhydantoin curable resins
EP0357232A2 (en) * 1988-08-03 1990-03-07 Hoechst Celanese Corporation Composites of aromatic polybenzimidazoles and polyarylates and process for their preparation
WO1993000686A1 (en) * 1991-06-28 1993-01-07 Daimler-Benz Aktiengesellschaft Electrically insulating foil
US5434226A (en) * 1992-08-11 1995-07-18 Ciba-Geigy Corporation Epoxy resin toughened with a polyether sulfone and polyarylsulfidesulfone
EP0768334A2 (en) * 1995-10-16 1997-04-16 Sumitomo Chemical Company Limited Prepreg, process for producing the same and printed circuit substrate using the same
JP2004506799A (en) * 2000-08-22 2004-03-04 サイテク・テクノロジー・コーポレーシヨン Flexible polymer elements as toughening agents in prepregs
MY119783A (en) * 1997-03-15 2005-07-29 Sumitomo Chemical Co Prepreg, process for producing the same and printed circuit substrate/ board using the same
KR100581657B1 (en) * 1997-05-06 2006-05-23 사이텍 테크놀러지 코포레이션 Preforms for moulding process and resins therefor
GB2421953A (en) * 2004-01-09 2006-07-12 Univ Sheffield Fibre-reinforced polymer matrix
WO2008020768A1 (en) * 2006-08-15 2008-02-21 Orica New Zealand Limited Composite material manufactured from a binder system including waste powder coating powder
US8703630B2 (en) 2005-05-09 2014-04-22 Cytec Technology Corp Resin-soluble thermoplastic veil for composite materials
FR3033574A1 (en) * 2015-03-10 2016-09-16 Arkema France THERMOPLASTIC COMPOSITION AND PRE-IMPREGNE, COMPOSITE MATERIAL BASED ON SAID PRE-IMPREGN AND USES OF SAID COMPOSITE MATERIAL

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444033A (en) * 1964-06-22 1969-05-13 Aerojet General Co Lightweight armor with laminated base member resistant to delamination
GB1169613A (en) * 1967-02-21 1969-11-05 Ciba Ltd Epoxide Resin Compositions
GB1299177A (en) * 1969-01-17 1972-12-06 Ciba Geigy Uk Ltd Reinforced composites
GB1306231A (en) * 1969-10-24 1973-02-07
BE759573A (en) * 1969-11-28 1971-05-27 Ciba Geigy REINFORCED PLASTIC MATERIALS
DE2138705A1 (en) * 1971-08-03 1973-03-15 Friedrich Haarburger LIGHTWEIGHT ELEMENT, IN PARTICULAR FOR AREA STRUCTURES, LAND, AIR AND WATER VEHICLES
US3839287A (en) * 1971-09-21 1974-10-01 Union Carbide Corp Polyarylimides
BE790681A (en) * 1971-10-29 1973-04-27 Bp Chem Int Ltd FRICTION BODIES
JPS5219875B2 (en) * 1974-02-07 1977-05-31

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806419A (en) * 1983-11-04 1989-02-21 The Boots Company Plc Bisimide/polyhydantoin curable resins
GB2178364B (en) * 1985-07-31 1990-01-04 H R Smith Production of laminates
GB2178364A (en) * 1985-07-31 1987-02-11 Smith H R Laminates of fibre-reinforced thermoplastics resins
EP0357232A2 (en) * 1988-08-03 1990-03-07 Hoechst Celanese Corporation Composites of aromatic polybenzimidazoles and polyarylates and process for their preparation
EP0357232A3 (en) * 1988-08-03 1991-07-10 Hoechst Celanese Corporation Composites of aromatic polybenzimidazoles and polyarylates and process for their preparation
WO1993000686A1 (en) * 1991-06-28 1993-01-07 Daimler-Benz Aktiengesellschaft Electrically insulating foil
US5434226A (en) * 1992-08-11 1995-07-18 Ciba-Geigy Corporation Epoxy resin toughened with a polyether sulfone and polyarylsulfidesulfone
EP0768334A2 (en) * 1995-10-16 1997-04-16 Sumitomo Chemical Company Limited Prepreg, process for producing the same and printed circuit substrate using the same
EP0768334A3 (en) * 1995-10-16 1997-06-04 Sumitomo Chemical Company Limited Prepreg, process for producing the same and printed circuit substrate using the same
US5851646A (en) * 1995-10-16 1998-12-22 Sumitomo Chemical Company, Limited Prepreg, process for producing the same and printed circuit substrate/board using the same
MY119783A (en) * 1997-03-15 2005-07-29 Sumitomo Chemical Co Prepreg, process for producing the same and printed circuit substrate/ board using the same
KR100581657B1 (en) * 1997-05-06 2006-05-23 사이텍 테크놀러지 코포레이션 Preforms for moulding process and resins therefor
JP2004506799A (en) * 2000-08-22 2004-03-04 サイテク・テクノロジー・コーポレーシヨン Flexible polymer elements as toughening agents in prepregs
EP1754743A1 (en) 2000-08-22 2007-02-21 Cytec Technology Corp. Flexible polymer element as toughening agent in prepregs
GB2421953A (en) * 2004-01-09 2006-07-12 Univ Sheffield Fibre-reinforced polymer matrix
GB2421953B (en) * 2004-01-09 2008-06-18 Univ Sheffield Self-healing composite material
US8703630B2 (en) 2005-05-09 2014-04-22 Cytec Technology Corp Resin-soluble thermoplastic veil for composite materials
US9566762B2 (en) 2005-05-09 2017-02-14 Cytec Technology Corp. Resin-soluble thermoplastic veil for composite materials
WO2008020768A1 (en) * 2006-08-15 2008-02-21 Orica New Zealand Limited Composite material manufactured from a binder system including waste powder coating powder
FR3033574A1 (en) * 2015-03-10 2016-09-16 Arkema France THERMOPLASTIC COMPOSITION AND PRE-IMPREGNE, COMPOSITE MATERIAL BASED ON SAID PRE-IMPREGN AND USES OF SAID COMPOSITE MATERIAL

Also Published As

Publication number Publication date
DE2941785A1 (en) 1981-04-30
FR2467907B1 (en) 1985-03-29
GB2060490B (en) 1984-09-19
DE2941785C2 (en) 1991-07-04
FR2467907A1 (en) 1981-04-30

Similar Documents

Publication Publication Date Title
GB2060490A (en) Composite Material and a Process for Manufacturing the Same
CA2187857A1 (en) Prepreg, process for producing the same and printed circuit substrate/board using the same
US4649080A (en) Fiber-reinforced materials
NO301020B1 (en) Precursor for a composite material and process for making a composite
EP1553125B1 (en) Fibre reinforced resin assembly
US6222007B1 (en) Films, preimpregnated tapes and composites made from polyimide “Salt-like” Solutions
US4996267A (en) Heat-curable resin mixture of monocyanate, polycyanate and reactive thermoplastic
US3930097A (en) Novel compositions and process
KR100189169B1 (en) Carbon fiber reinforced composite material having a morphology gradient
US5460746A (en) Terminal-modified imide oligomer composition
US5196259A (en) Matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole
US5260412A (en) Terminal-modified imide oligomer composition
US4880584A (en) Fiber reinforced thermoplastic resin matrix composites
CN1155646C (en) Modified dimaleimide resin capable of being used to transfer molding and its prepn
EP0371154A1 (en) Prepreg of reinforced imide oligomer
JPH03124731A (en) Fiber-reinforced poly(biphenylene sulfide) composite material and its manufacture
US5077363A (en) Heat-curable bismaleidmide/alkenyl phenol/n-vinyl pyrrolidone resin
US5248721A (en) Prepregs containing a fiber and a thermoplastic polybenzazole copolymer matrix
US4999419A (en) Polyimide resins from bis-imide, monomer having two methylene groups activated by adjacent carbonyls, and polyamine
CN1033647C (en) Preparation method of high-toughness polyimide composite material
KR100186813B1 (en) High performance aramid matrix composites
Stenzenberger Bismaleimide resins for flame resistant honeycomb sandwich panels
Rakoutz et al. Siloxane modification of bismaleimide resins
JP3232647B2 (en) Method for producing thermosetting resin prepreg
JP2882044B2 (en) Thermosetting resin prepreg

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19971013