CN105601924A - Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof - Google Patents
Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof Download PDFInfo
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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
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- 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
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- 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
- B32B2457/00—Electrical equipment
Abstract
The invention discloses modified bismaleimide resin, a modified bismaleimide resin/carbon fiber reinforced laminated board and a preparation method thereof. The modified bismaleimide resin is prepared from bismaleimide resin by means of diamine chain extension and epoxy resin modification; and the modified bismaleimide resin serving as an adhesive and carbon fiber cloth serving as a base material are subjected to soaking and coating, adhesive drying and laminating to prepare the modified bismaleimide resin/carbon fiber reinforced laminated board. The modified bismaleimide resin provided by the invention can meet industrial production requirements. The reinforced laminated board prepared from modified bismaleimide resin and carbon fiber cloth has excellent heat resistance, remarkably improved mechanical performance and excellent comprehensive performance, and can be applied to the fields of electrical insulation, aerospace and the like.
Description
Technical field
Modified bismaleimide resin of the present invention, modified bismaleimide resin/carbon fiber enhancement layer pressing plate and preparation side thereofMethod, belongs to polymer matrix composite technical field.
Background technology
Bimaleimide resin is often used as because having excellent electrical insulation capability, resistance to elevated temperatures, chemical resistanceThe matrix resin of high-performance composite materials. But, due to BMI poor toughness, affect it and further applied.
Most study on the modification for bimaleimide resin at present, object is all in order to improve its toughness, and all obtainsCertain achievement. But the poor shortcoming of its manufacturability is still difficult to solve, in the time utilizing modified resin making layer pressing plate, configurationGlue be often difficult to be dissolved in conventional organic solvent, cause too thickness or inhomogeneous of glue, thereby affected gluing qualityAffect the performance of laminate each side.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of modified bismaleimide for the deficiency of above-mentioned prior art existencePolyimide resin, and a kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate and preparation method thereof, the modification of synthesizedResin system manufacturability is good, and the laminate properties of product that provide are good.
The present invention for the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A kind of modified bismaleimide resin, be bimaleimide resin through diamine chain extension, epoxy resin modification gained,Wherein the mol ratio of bimaleimide resin and diamine is (1.5-2): 1, and bimaleimide resin and epoxy resin qualityThan being (1-9): 1.
Press such scheme, described bimaleimide resin is 4,4 '-diphenyl methane dimaleimide (BDM).
Press such scheme, described diamine is 4,4-MDA (DDM).
Press such scheme, the model of described epoxy resin is E-44.
The preparation method of above-mentioned modified bismaleimide resin, comprises the steps:
1) accurately take bimaleimide resin, diamine, epoxy resin, wherein bimaleimide resin and diamineMol ratio be (1.5-2): 1, bimaleimide resin and epoxy resin mass ratio are (1-9): 1;
2) epoxy resin is carried out to preheating, preheat temperature 70-80 DEG C;
3) diamine is heated to 90-120 DEG C, after its complete melting, adds bimaleimide resin, at 120-140 DEG CIn temperature range, fully stir, until gained mixed liquor just changes transparent bronzing liquid into by muddy shape;
4) by step 2) preheated epoxy resin adds step 3) in the bronzing liquid of gained, remain on 130-150 DEG CIn temperature range, stir, gained mixture is modified bismaleimide resin.
Press such scheme, step 4) gained mixture slowly becomes sticky thick rear coolingly, obtains modified bismaleimide resin solidBody, can break gained modified bismaleimide resin solid sample be ground into powder into pieces, so that glue in succeeding layer pressing plateThe configuration of liquid (being maceration extract).
A kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate, its be taking above-mentioned modified bismaleimide resin asAdhesive, taking carbon cloth as base material, process dip-coating gluing, adhesive plaster are dried, lamination prepares.
The preparation method of above-mentioned modified bismaleimide resin/carbon fiber enhancement layer pressing plate, comprises the steps:
(1) preparation lotion: above-mentioned modified bismaleimide resin powder is dissolved in DMF, obtainsLotion;
(2) dipping gluing: described lotion is evenly coated on carbon cloth, and soaks into carbon cloth, be adhesive plaster;
(3) adhesive plaster is dry: step (2) gained adhesive plaster is placed in 40-50 DEG C of temperature range and is dried;
(4) lamination compacting: will suppress after the dried carcass ply of step (3) gained, press temperature is 220-235 DEG C, pressure is 1.5-2.5MPa, and temperature retention time is 1.5-2 hour, obtain after cooling modified bismaleimide resin/Carbon fiber enhancement layer pressing plate.
Press such scheme, modified bismaleimide resin and solvent DMF in described step (1)(DMF) preferably with 1:(1-2) volume ratio mix; The amount of solvent is with submergence modified bismaleimide resin powder justBe advisable; Organic solvent DMF can effectively dissolve bimaleimide resin.
Press such scheme, dipping gluing step is exactly the adhesion process of modified bismaleimide resin and carbon cloth. This stepIn, specifically adopt manual operation gluing, fiber cloth is laid on glass plate, with brush equably by resin-coating in fiber clothUpper, and soak into fiber cloth. The quality of dipping gluing is to ensure the important key of laminated plastic quality volume, if dipping gluing is improperWhen, will cause pressed sheet bubble, layering, flake, ixoderm, the phenomenon such as grow dim, what these all can be to laminated product is comprehensivePerformance exerts an influence.
Press such scheme, adhesive plaster drying steps generally adopts constant temperature oven dry. When the base material with resin-dipping or after applying, mustMust be dried to remove desolventizing, volatile matter and moisture, to a certain extent simultaneously, the further polymerization of this resin. Therefore,The quality of base material after glue, the uniformity of and gluing how many except gel content, other are set as volatile content, aridity, solubilityFat content etc. is just decided by dry this operation.
Press such scheme, pressing step is the master operation of laminate moulding, through compacting, makes resin solidification become cross-linked networkStructure. Lamination pressing step comprises: adhesive plaster trimming to required size, carcass ply, put into mould and (can apply in advanceReleasing agent) suppress this three key steps. Detailed process is: first by adhesive plaster trimming, required adhesive plaster size dimension is differedNot quite, then by adhesive plaster from level to level stacked put well stand-by; Then painting is put into mould after wiping releasing agent, and design temperature, adjusting are pressedAfter insulation certain hour, take out by force; Finally put at room temperature and be cooled to room temperature with mould, open mould taking-up goods and beModified bismaleimide resin/carbon fiber enhancement layer pressing plate. Preferably, temperature and pressure and insulation in described lamination compactingThe preferred control mode of time is: coat releasing agent on mould after, adhesive plaster is put into after mould, taking heating rate as 1.7-2.5 DEG C/min, mold temperature reaches 90-100 DEG C of matched moulds afterwards, at 150-160 DEG C of insulation 1-1.5 hour; Continue afterwards with sameThe heating rate of sample is warmed up to 220-235 DEG C, and pressure increases to 2.0MPa, is incubated with this understanding 1.5-2 hour, cooling de-Mould obtains modified bismaleimide resin/carbon fiber enhancement layer pressing plate.
The present invention is directed to the shortcomings such as poor, the difficult processing of bimaleimide resin toughness, by 4,4 '-MDATo its carry out chain extension, epoxy resin carries out modification to it. Bimaleimide resin good toughness after diamine chain extension, and haveGood heat resistance and mechanical property are further introduced epoxy resin in system, not only can improve the viscosity of system, andEpoxide group in epoxy resin can also and system in tertiary amine react, form crosslinked curing network, further improveBimaleimide resin toughness and its processing performance is got a promotion.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention, by Bismaleimide Resin Modified By Epoxy Resin, in improving its toughness, has improved its techniqueProperty; 2, by control loop epoxy resins, the proportioning in resin system is met the modified bismaleimide of actual needs in the present inventionPolyimide resin; 3, the present invention adopts dimethyl formamide (DMF) as solvent, and gained resin adhesive liquid viscosity appropriately and very equalEven; 4, epoxide modified bimaleimide resin/carbon-fiber-reinforcomposite composite material layer pressing plate mechanical property provided by the invention obtainsObvious lifting, bending strength can reach about 700MPa, impact strength reaches as high as 60kJ/m2Left and right.
The invention provides a kind of modified bismaleimide resin that can meet demand of industrial production; Come with this modification spanEnhancement layer pressing plate prepared by imide resin and carbon cloth, not only has good heat resistance, and its mechanical property has also obtainedSignificant raising, high comprehensive performance, can be applicable to the field such as electric insulation, Aero-Space.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but not only office of the present inventionBe limited to the following examples.
Embodiment 1
A kind of modified bismaleimide resin, is 4, and 4 '-diphenyl methane dimaleimide (BDM) is through being 4,4 '-diaminoBase diphenyl-methane (DDM) chain extension, epoxy resin (E-44) modification gained are wherein BDM108 according to the mass fraction12 parts of parts, DDM37 part, epoxy resin E-44.
The preparation method of above-mentioned modified bismaleimide resin, comprises the steps:
1) accurately take two BDM108g, DDM37g, epoxy resin 12g, wherein BDM and DDM mol ratio are1.6:1, BDM and E-44 mass ratio are 9:1;
2) epoxy resin after having taken is put into the baking oven preheating of 70 DEG C;
3) pour DDM into beaker, in the oil bath pan of 110 DEG C of left and right, heat; After the complete melting of DDM, pour BDM intoPowder fully stirs, until mixed liquor just changes transparent bronzing liquid into by muddy shape in 130 DEG C of left and right oil baths;
4) by step 2) preheated epoxy resin adds step 3 immediately) in the bronzing liquid of gained, keep oil bath stateStir; Gained mixture is modified bismaleimide resin;
5) slowly become sticky after thick mixture is poured out until gained mixture, after it is cooling, by gained modified bismaleimideResin solid sample is broken into pieces and is ground into powder, and is modified bismaleimide resin powder.
A kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate, its be taking above-mentioned modified bismaleimide resin asAdhesive, taking carbon cloth as base material,, lamination dry through dip-coating gluing, adhesive plaster prepares, specifically comprise asLower step:
(1) preparation lotion: above-mentioned modified bismaleimide resin powder 157g is dissolved in to DMFIn 157g, soak at room temperature, after one day, obtains the resin adhesive liquid that dip-coating is used;
(2) dipping gluing: the carbon cloth of 16 13cm × 13cm of cutting, be laid on glass plate, with brush equablyResin adhesive liquid is coated on carbon cloth, and soaks into carbon cloth, obtain adhesive plaster;
(3) adhesive plaster is dry: step (2) gained adhesive plaster is placed in to 50 DEG C of constant temperature ovens dry;
(4) lamination compacting: by the dried adhesive plaster trimming of step (3) gained, required adhesive plaster size dimension is differed notGreatly, then by adhesive plaster from level to level stacked put well stand-by; Coat releasing agent on mould after, adhesive plaster is put into mould, heating rate is2 DEG C/min, mold temperature reached 100 DEG C of matched moulds afterwards, 150 DEG C of insulations 1 hour; Continue afterwards with same heating rateBe warmed up to 230 DEG C, pressure increases to 2.0MPa, is incubated with this understanding 2 hours; Then place it under room temperature with mold coldBut to room temperature, finally open mould and take out goods, obtain modified bismaleimide resin/carbon fiber enhancement layer pressing plate.
Performance test: press dependence test standard testing modified bismaleimide resin/carbon fibre laminate composites correlationCan, its bending strength is in 500MPa left and right, and impact strength can reach 44kJ/m2。
Embodiment 2
A kind of modified bismaleimide resin, is 4, and 4 '-diphenyl methane dimaleimide (BDM) is through being 4,4 '-diaminoBase diphenyl-methane (DDM) chain extension, epoxy resin (E-44) modification gained are wherein BDM70 according to the mass fraction30 parts of parts, DDM24 part, epoxy resin E-44.
The preparation method of above-mentioned modified bismaleimide resin, comprises the steps:
1) accurately take two BDM70g, DDM24g, epoxy resin 30g, wherein BDM and DDM mol ratio are1.61:1, BDM and E-44 mass ratio are 7:3;
2) epoxy resin after having taken is put into the baking oven preheating of 70 DEG C;
3) pour DDM into beaker, in the oil bath pan of 110 DEG C of left and right, heat; After the complete melting of DDM, pour BDM intoPowder fully stirs, until mixed liquor just changes transparent bronzing liquid into by muddy shape in 130 DEG C of left and right oil baths;
4) by step 2) preheated epoxy resin adds step 3 immediately) in the bronzing liquid of gained, keep oil bath stateStir; Gained mixture is modified bismaleimide resin;
5) slowly become sticky after thick mixture is poured out until gained mixture, after it is cooling, by gained modified bismaleimideResin solid sample is broken into pieces and is ground into powder, and is modified bismaleimide resin powder.
A kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate, its be taking above-mentioned modified bismaleimide resin asAdhesive, taking carbon cloth as base material,, lamination dry through dip-coating gluing, adhesive plaster prepares, specifically comprise asLower step:
(1) preparation lotion: above-mentioned modified bismaleimide resin powder 124g is dissolved in to DMFIn 124g, soak at room temperature, after one day, obtains the resin adhesive liquid that dip-coating is used;
(2) dipping gluing: the carbon cloth of 16 13cm × 13cm of cutting, be laid on glass plate, with brush equablyResin adhesive liquid is coated on carbon cloth, and soaks into carbon cloth, obtain adhesive plaster;
(3) adhesive plaster is dry: step (2) gained adhesive plaster is placed in to 40 DEG C of constant temperature ovens dry;
(4) lamination compacting: by the dried adhesive plaster trimming of step (3) gained, required adhesive plaster size dimension is differed notGreatly, then by adhesive plaster from level to level stacked put well stand-by; Coat releasing agent on mould after, adhesive plaster is put into mould, heating rate is2.5 DEG C/min, mold temperature reached 90 DEG C of matched moulds afterwards, 160 DEG C of insulations 1 hour; Continue afterwards with same heating rateBe warmed up to 235 DEG C, pressure increases to 2.0MPa, is incubated with this understanding 1.5 hours; Then place it under room temperature with mouldBe cooled to room temperature, finally open mould and take out goods, obtain modified bismaleimide resin/carbon fiber enhancement layer pressing plate.Performance test: press dependence test standard testing modified bismaleimide resin/carbon fibre laminate composites correlated performance,Its bending strength is in 550MPa left and right, and impact strength can reach 49kJ/m2。
Embodiment 3
A kind of modified bismaleimide resin, is 4, and 4 '-diphenyl methane dimaleimide (BDM) is through being 4,4 '-diaminoBase diphenyl-methane (DDM) chain extension, epoxy resin (E-44) modification gained are wherein BDM60 according to the mass fraction60 parts of parts, DDM22 part, epoxy resin E-44.
The preparation method of above-mentioned modified bismaleimide resin, comprises the steps:
1) accurately take two BDM60g, DDM22g, epoxy resin 60g, wherein BDM and DDM mol ratio are1.5:1, BDM and E-44 mass ratio are 1:1;
2) epoxy resin after having taken is put into the baking oven preheating of 80 DEG C;
3) pour DDM into beaker, in the oil bath pan of 100 DEG C of left and right, heat; After the complete melting of DDM, pour BDM intoPowder fully stirs, until mixed liquor just changes transparent bronzing liquid into by muddy shape in 140 DEG C of left and right oil baths;
4) by step 2) preheated epoxy resin adds step 3 immediately) in the bronzing liquid of gained, keep oil bath stateStir; Gained mixture is modified bismaleimide resin;
5) slowly become sticky after thick mixture is poured out until gained mixture, after it is cooling, by gained modified bismaleimideResin solid sample is broken into pieces and is ground into powder, and is modified bismaleimide resin powder.
A kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate, its be taking above-mentioned modified bismaleimide resin asAdhesive, taking carbon cloth as base material,, lamination dry through dip-coating gluing, adhesive plaster prepares, specifically comprise asLower step:
(1) preparation lotion: above-mentioned modified bismaleimide resin powder 142g is dissolved in to DMFIn 142g, soak at room temperature, after 24 hours, obtains the resin adhesive liquid that dip-coating is used;
(2) dipping gluing: the carbon cloth of 16 13cm × 13cm of cutting, be laid on glass plate, with brush equablyResin adhesive liquid is coated on carbon cloth, and soaks into carbon cloth, obtain adhesive plaster;
(3) adhesive plaster is dry: step (2) gained adhesive plaster is placed in to constant temperature oven dry;
(4) lamination compacting: by the dried adhesive plaster trimming of step (3) gained, required adhesive plaster size dimension is differed notGreatly, then by adhesive plaster from level to level stacked put well stand-by; Coat releasing agent on mould after, adhesive plaster is put into mould, heating rate is1.7 DEG C/min, mold temperature reached 90 DEG C of matched moulds afterwards, 155 DEG C of insulations 1 hour; Continue afterwards with same heating rateBe warmed up to 235 DEG C, pressure increases to 2.0MPa, is incubated with this understanding 1.5 hours; Then place it under room temperature with mouldBe cooled to room temperature, finally open mould and take out goods, obtain modified bismaleimide resin/carbon fiber enhancement layer pressing plate.Performance test: press dependence test standard testing modified bismaleimide resin/carbon fibre laminate composites correlated performance,Its bending strength is in 620MPa left and right, and impact strength can reach 55kJ/m2。
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art,Do not depart under the prerequisite of the invention design, can also make some improvement and conversion, these all belong to protection model of the present inventionEnclose.
Claims (9)
1. a modified bismaleimide resin, is characterized in that it is that bimaleimide resin is through diamine chain extension, ringEpoxy resins modification gained, wherein the mol ratio of bimaleimide resin and diamine is (1.5-2): 1, BMI treeFat and epoxy resin mass ratio are (1-9): 1.
2. a kind of modified bismaleimide resin according to claim 1, is characterized in that described BMIResin is 4,4 '-diphenyl methane dimaleimide.
3. a kind of modified bismaleimide resin according to claim 1, is characterized in that described diamine is 4,4-MDA.
4. a kind of modified bismaleimide resin according to claim 1, is characterized in that the type of described epoxy resinNumber be E-44.
5. a preparation method for modified bismaleimide resin, is characterized in that comprising the steps:
1) accurately take bimaleimide resin, diamine, epoxy resin, wherein bimaleimide resin and diamineMol ratio be (1.5-2): 1, bimaleimide resin and epoxy resin mass ratio are (1-9): 1;
2) epoxy resin is carried out to preheating, preheat temperature 70-80 DEG C;
3) diamine is heated to 90-120 DEG C, after its complete melting, adds bimaleimide resin, at 120-140 DEG CIn temperature range, fully stir, until gained mixed liquor just changes transparent bronzing liquid into by muddy shape;
4) by step 2) preheated epoxy resin adds step 3) in the bronzing liquid of gained, remain on 130-150 DEG CIn temperature range, stir, gained mixture is modified bismaleimide resin.
6. modified bismaleimide resin/carbon fiber enhancement layer pressing plate, is characterized in that it is with modified bismaleimidePolyimide resin is adhesive, and taking carbon cloth as base material, process dip-coating gluing, adhesive plaster are dried, lamination prepares.
7. the preparation method of a kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate according to claim 6,It is characterized in that comprising the steps:
(1) preparation lotion: modified bismaleimide resin powder is dissolved in DMF, obtains dip-coatingLiquid;
(2) dipping gluing: described lotion is evenly coated on carbon cloth, and soaks into carbon cloth, be adhesive plaster;
(3) adhesive plaster is dry: step (2) gained adhesive plaster is placed in 40-50 DEG C of temperature range and is dried;
(4) lamination compacting: will suppress after the dried carcass ply of step (3) gained, press temperature is 230-235 DEG C, pressure is 1.5-2.5MPa, and temperature retention time is 1.5-2 hour, obtain after cooling modified bismaleimide resin/Carbon fiber enhancement layer pressing plate.
8. the preparation method of a kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate according to claim 7,It is characterized in that in described step (1) modified bismaleimide resin and solvent DMF (DMF) withVolume ratio 1:(1-2) is mixed.
9. the preparation method of a kind of modified bismaleimide resin/carbon fiber enhancement layer pressing plate according to claim 7,It is characterized in that in the compacting of described lamination, the control mode of temperature and pressure and temperature retention time is: on mould, coat releasing agent itAfter adhesive plaster is put into after mould, taking heating rate as 1.7-2.5 DEG C/min, mold temperature reach 90-100 DEG C after matched moulds,150-160 DEG C of insulation 1-1.5 hour; Continue to be afterwards warmed up to 220-235 DEG C with same heating rate, pressure increases to2.0MPa, is incubated 1.5-2 hour with this understanding.
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| CN111334184A (en) * | 2020-04-21 | 2020-06-26 | 西安高缘立达电气有限公司 | Heat-resistant 220-grade sulfur hexafluoride-resistant organic insulating coating and preparation method thereof |
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