CN107033328A - A kind of modified epoxy and based on the standby glass fiber reinforcement sheet material of the resin-made - Google Patents

A kind of modified epoxy and based on the standby glass fiber reinforcement sheet material of the resin-made Download PDF

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Publication number
CN107033328A
CN107033328A CN201710225286.7A CN201710225286A CN107033328A CN 107033328 A CN107033328 A CN 107033328A CN 201710225286 A CN201710225286 A CN 201710225286A CN 107033328 A CN107033328 A CN 107033328A
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modified epoxy
epoxy resin
glass
temperature
modified
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Granted
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CN107033328B (en
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曾黎明
艾吉祥
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Guangdong chuangbu Industry Co.,Ltd.
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Wuhan University of Technology WUT
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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
    • 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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • 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
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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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)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Modified epoxy/glass fiber reinforcement the sheet material prepared the present invention relates to a kind of modified epoxy and based on the resin system, preparing the raw material of the modified epoxy includes the material component of following parts by weight：100 parts of 127 epoxy resin of CYD, 4,5 18 parts of 4 ' MDAs (I), 5 15 parts of diphenyl methane dimaleimide, 4 parts of dimethyldiethoxysilane, 0.5 part of dibutyl tin laurate, 1 part of distilled water, 4,4 ' 18 28 parts of MDAs (II).The modified epoxy solidification temperature that the present invention is provided is 80 230 DEG C；Modified epoxy laminate in terms of heat resistance heat decomposition temperature up to 359 370 DEG C；Impact strength is up to 45.57 59.65KJ/m in terms of toughness2, bending strength is up to 270 295MPa, with good toughness and heat resistance.

Description

A kind of modified epoxy and based on the standby glass fiber reinforcement sheet material of the resin-made
Technical field
The invention belongs to polymer matrix composite technical field, it is related to a kind of modified epoxy and is based on
Modified epoxy/glass fiber reinforcement sheet material prepared by the resin system.
Background technology
Epoxy resin has excellent physical and mechanical properties and electric property, is widely used in insulating material, bonding The fields such as agent, anti-corrosion material.Because electronics, electrical equipment industry are developed rapidly, technology innovation is also very rapid, is that its is supporting therefore Epoxide resin material the problem of be faced with high performance.One important directions of the high performance of epoxy resin are to improve resin The heat resistance and toughness of solidfied material.Molding for epoxy resin processing performance is various, but the crosslink density after solidification is big, causes solidfied material Internal stress it is larger, obtained product fragility is big, the use of product of resistance to elevated temperatures lower limit.Epoxy resin is improved at present The method of toughness and heat resistance mainly has a various modifying agent of addition, but more single can only often to improve its tough for the specific aim of modifying agent Property or heat-resisting quantity, it is impossible to while improving its toughness and heat-resisting quantity.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of heat resistance for above shortcomings in the prior art The good modified epoxy and based on the standby glass fiber reinforcement sheet material of the resin-made with toughness.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of modified epoxy is provided, it is obtained by the solidification of modified epoxy glue, the modified epoxy glue Liquid material component and mass ratio are：
Wherein BMI and 4,4 '-MDA (I) mol ratio is 1: 2.
By such scheme, the CYD-127 epoxy resin is that hot press forming technology is resin dedicated, and viscosity is 350- at room temperature 400mPas, gel time is 20-30min.
By such scheme, the condition of cure is：2h is heated at 80 DEG C, 2h is then heated at 150 DEG C, then 180 2h is heated at DEG C, finally 1h is heated at 230 DEG C.
The present invention also provides the preparation method of above-mentioned modified epoxy, and its step is as follows：
1) dimethyldiethoxysilane and CYD-127 epoxy resin are mixed in proportion, is warming up to 80-85 DEG C, dropwise addition Dibutyl tin laurate and distilled water, then proceed to be warming up to 90-95 DEG C of reaction 5-6h, reaction solution is changed into milky, depressurized Accessory substance is distilled off and obtains organic-silicon-modified epoxy resin；
2) in proportion by diphenyl methane dimaleimide and 4,4 '-MDA (I) is placed in 135-140 DEG C of oil Melted in advance in bath, be allowed to occur Michael addition reaction, then stopped heating and be cooled to 95-100 DEG C, add step 1) gained Organic-silicon-modified epoxy resin, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled down 4 are added after to room temperature, 4 '-MDA (II) is uniformly mixing to obtain modified epoxy glue；
3) by step 2) the modified epoxy glue solidify obtaining modified epoxy.
Present invention additionally comprises the glass fibre reinforced laminate prepared according to above-mentioned modified epoxy, it is with modification Epoxy resin is matrix, using glass fibre woven roving as reinforcing material, is prepared using hot-forming.
The preparation method of above-mentioned glass fibre reinforced laminate comprises the following steps：
1) dimethyldiethoxysilane and CYD-127 epoxy resin are mixed in proportion, is warming up to 80-85 DEG C, dropwise addition Dibutyl tin laurate and distilled water, then proceed to be warming up to 90-95 DEG C of reaction 5-6h, reaction solution is changed into milky, depressurized Accessory substance is distilled off and obtains organic-silicon-modified epoxy resin；
2) in proportion by diphenyl methane dimaleimide and 4,4 '-MDA (I) is placed in 135-140 DEG C of oil Melted in advance in bath, be allowed to occur Michael addition reaction, then stopped heating and be cooled to 95-100 DEG C, add step 1) gained Organic-silicon-modified epoxy resin, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled down 4 are added after to room temperature, 4 '-MDA (II) is uniformly mixing to obtain modified epoxy glue；
3) it is laid in after 10-13 layers of glass fabric being cut out into drying on glass plate, by step 2) gained modified epoxy tree Fat glue is coated uniformly on glass fabric, modified epoxy is impregnated with glass fabric and is obtained epoxy resin/glass fibers Composite is tieed up, the progress of gained composite then is placed in into oven drying, lamination solidification obtains epoxy resin/glass fibre increasing Strong laminate.
Preferably, step 3) epoxy resin/glass fiber compound material gel content be 35-45%.
Preferably, step 3) drying condition be 100 DEG C at dry 2h.
By such scheme, the lamination curing process condition is：Epoxy resin/glass fiber compound material after drying is put In coat demoulding wax layer press upper mould, under touch between, open laminating machine, upper mould, under touch temperature and be set as 80 DEG C, and keep 1-2MPa template contacts pressure, temperature reaches after 80 DEG C is changed to 10MPa by template contacts pressure, is then warming up to 150 DEG C and keeps pressure Power is constant, is incubated 2 hours, then temperature is risen into 180 DEG C and 2 hours are incubated, and is finally incubated 1 hour at 230 DEG C, stops lamination, It is placed on after being cooled to the room temperature demoulding with mould at room temperature and obtains epoxy resin/glass fibre reinforced laminate.
The present invention uses dimethyldiethoxysilane and diphenyl methane dimaleimide modified epoxy, improves it Heat resistance and toughness.In dimethyldiethoxysilane the toughness of system, and diphenyl-methane can be not only improved containing Si-O keys The addition of the rigid radicals such as amido link and phenyl ring in bimaleimide resin is improved the heat resistance of epoxy resin.
The beneficial effects of the present invention are：The present invention is led to for the shortcoming that epoxy resin toughness is poor, heat resistance is poor Cross addition dimethyldiethoxysilane and diphenyl methane dimaleimide is modified to it, obtained one kind and disclosure satisfy that (it is required that epoxy resin heat decomposition temperature is not less than 300 DEG C, impact strength is not less than the modified epoxy of demand of industrial production 12KJ/m2, bending strength is not less than 250MPa) there is provided modified epoxy solidification temperature (epoxy resin is solid for 80-230 DEG C Change temperature at 150 DEG C, modifying epoxy resin by organosilicon solidification temperature is at 180 DEG C, and the solidification temperature of bimaleimide resin exists 230 DEG C), using the modified epoxy as adhesive, laminate is made by reinforcing material of glass fabric, the laminate has (heat decomposition temperature reaches 359-370 DEG C in terms of heat resistance, and impact strength reaches in terms of toughness for good toughness and heat resistance 45.57-59.65KJ/m2, bending strength reach 270-295MPa), also with good cementability, electrical insulating property, combination property is excellent It is good, it can be applied to the fields such as electric insulation, Aero-Space.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment It is described in further detail.
Laminating machine used in the embodiment of the present invention is the heat pressing forming machines that Wuhan Qi En developments in science and technology Co., Ltd produces, model For R-3202.
Embodiment 1
Modified epoxy is prepared, step is as follows：
1) by 4g dimethyldiethoxysilanes and 100gCYD-127 epoxy resin, (viscosity 350mPas, coagulates at room temperature The glue time is 20min) mixing, 80 DEG C are warming up to, 0.5g dibutyl tin laurates and 1g distilled water is added dropwise, heating is then proceeded to To 95 DEG C, insulation 5.5h makes dimethyldiethoxysilane fully occur chemical mixing reaction with epoxy resin, now reaction solution Milky is changed into from clarification, illustrates that reaction is complete, vacuum distillation removes accessory substance and obtains organic-silicon-modified epoxy resin；
2) 5g diphenyl methane dimaleimides and 5.53g4,4 '-MDA are placed in 135-140 DEG C of oil bath In melt in advance, be allowed to occur Michael addition reaction, stopping heating after reaction 5min is cooled to 95-100 DEG C, and adding gained has The epoxy resin of machine Si modification, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled to 28g4,4 '-MDA are added after room temperature, vacuum defoamation is uniformly mixing to obtain modified epoxy glue；
3) by step 2) gained modified epoxy glue heats 2h at 80 DEG C, then heats 2h at 150 DEG C, then 2h is heated at 180 DEG C, 1h solidifications are finally heated at 230 DEG C and obtain modified epoxy.
After tested, modified epoxy heat decomposition temperature is 370 DEG C obtained by the present embodiment, and impact strength is 20.2KJ/m2, Bending strength is 92MPa.
Embodiment 2
Glass fibre reinforced laminate is prepared, step is as follows：
1) by 4g dimethyldiethoxysilanes and 100gCYD-127 epoxy resin, (viscosity 380mPas, coagulates at room temperature The glue time is 24min) mixing, 80 DEG C are warming up to, 0.5g dibutyl tin laurates and 1g distilled water is added dropwise, heating is then proceeded to To 90 DEG C, insulation 5.5h makes dimethyldiethoxysilane fully occur chemical mixing reaction with epoxy resin, now reaction solution Milky is changed into from clarification, illustrates that reaction is complete, vacuum distillation removes accessory substance and obtains organic-silicon-modified epoxy resin；
2) by 5g diphenyl methane dimaleimides and 5.53g4,4 '-MDA is placed in 135-140 DEG C of oil bath In melt in advance, be allowed to occur Michael addition reaction, stopping heating after reaction 5min is cooled to 95-100 DEG C, adds step 1) The organic-silicon-modified epoxy resin of gained, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats it It is cooled to after room temperature and adds 28g4,4 '-MDA, vacuum defoamation is uniformly mixing to obtain modified epoxy glue；
3) glass fibre reinforced laminate is prepared:Glass fibre woven roving is cut into size big for 130mm × 130mm Small, the tiling of 12 layers of glass fibre woven roving being stacked on a glass, by step 2) gained modified epoxy glue uniformly applies Overlay on glass fabric, modified epoxy is impregnated with glass fabric and is obtained epoxy resin/glass fiber compound material and (contain Gained composite be placed in baking oven for 42%), then and dries 2h at 100 DEG C by glue amount, and by dried asphalt mixtures modified by epoxy resin Fat/glass fiber compound material be placed in coat the demoulding wax laminating machine upper mould, under touch between, open laminating machine, upper mould, under touch Temperature is set as 80 DEG C, and keeps 2MPa template contacts pressure, and temperature reaches after 80 DEG C is changed to 10MPa by template contacts pressure, Then being warming up to 150 DEG C keeps pressure constant, is incubated 2 hours, then temperature is risen into 180 DEG C and 2 hours are incubated, finally 230 DEG C insulation 1 hour, stops lamination, is placed on to be cooled to mould at room temperature and obtains epoxy resin/glass fibre after the room temperature demoulding and increase Strong laminate.
After tested, glass fiber reinforcement sheet material impact strength obtained by the present embodiment is 59.65KJ/m2, bending strength is 295MPa, heat decomposition temperature is 370 DEG C.
Embodiment 3
Glass fibre reinforced laminate is prepared, step is as follows：
1) by 4g dimethyldiethoxysilanes and 100gCYD-127 epoxy resin, (viscosity 400mPas, coagulates at room temperature The glue time is 30min) mixing, 80 DEG C are warming up to, 0.5g dibutyl tin laurates and 1g distilled water is added dropwise, heating is then proceeded to To 95 DEG C, insulation 5h makes dimethyldiethoxysilane and epoxy resin fully occur chemical mixing reaction, now reaction solution by Clarification is changed into milky, illustrates that reaction is complete, vacuum distillation removes accessory substance and obtains organic-silicon-modified epoxy resin；
2) by 10g diphenyl methane dimaleimides and 11.3g4,4 '-MDA is placed in 135-140 DEG C of oil Melted in advance in bath, be allowed to occur Michael addition reaction, stopping heating after reaction 5min is cooled to 95-100 DEG C, adds gained Organic-silicon-modified epoxy resin, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled down 23g4,4 '-MDA are added after to room temperature, vacuum defoamation is uniformly mixing to obtain modified epoxy glue；
3) glass fibre reinforced laminate is prepared:Glass fibre woven roving is cut into size big for 130mm × 130mm Small, the tiling of 12 layers of glass fibre woven roving being stacked on a glass, by step 2) gained modified epoxy glue uniformly applies Overlay on glass fabric, modified epoxy is impregnated with glass fabric and is obtained epoxy resin/glass fiber compound material and (contain Gained composite is carried out being placed in baking oven 2h at 100 DEG C and dried by glue amount for 42%), then, and by dried asphalt mixtures modified by epoxy resin Fat/glass fiber compound material be placed in coat the demoulding wax laminating machine upper mould, under touch between, open laminating machine, upper mould, under touch Temperature is set as 80 DEG C, and keeps 2MPa template contacts pressure, and temperature reaches after 80 DEG C is changed to 10MPa by template contacts pressure, Then being warming up to 150 DEG C keeps pressure constant, is incubated 2 hours, then temperature is risen into 180 DEG C and 2 hours are incubated, finally 230 DEG C insulation 1 hour, stops lamination, is placed on to be cooled to mould at room temperature and obtains epoxy resin/glass fibre after the room temperature demoulding and increase Strong laminate.
After tested, glass fiber reinforcement sheet material impact strength obtained by the present embodiment is 50.23KJ/m2, bending strength is 284MPa, heat decomposition temperature is 365 DEG C.
Embodiment 4
Glass fibre reinforced laminate is prepared, step is as follows：
1) by 4g dimethyldiethoxysilanes and 100gCYD-127 epoxy resin, (viscosity 389mPas, coagulates at room temperature The glue time is 30min) mixing, 80 DEG C are warming up to, 0.5g dibutyl tin laurates and 1g distilled water is added dropwise, heating is then proceeded to To 95 DEG C, insulation 6h makes dimethyldiethoxysilane and epoxy resin fully occur chemical mixing reaction, now reaction solution by Clarification is changed into milky, illustrates that reaction is complete, vacuum distillation removes accessory substance and obtains organic-silicon-modified epoxy resin；
2) by 15g diphenyl methane dimaleimides and 16.6g4,4 '-MDA is placed in 135-140 DEG C of oil Melted in advance in bath, be allowed to occur Michael addition reaction, stopping heating after reaction 5min is cooled to 95-100 DEG C, adds step 1) the organic-silicon-modified epoxy resin of gained, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats It, which is cooled to after room temperature, adds 18g4, and 4 '-MDA, vacuum defoamation is uniformly mixing to obtain modified epoxy glue Liquid；
3) glass fibre reinforced laminate is prepared:Glass fibre woven roving is cut into size big for 130mm × 130mm Small, the tiling of 12 layers of glass fibre woven roving being stacked on a glass, by step 2) gained modified epoxy is coated uniformly on On glass fabric, modified epoxy is impregnated with glass fabric and obtain epoxy resin/glass fiber compound material (gel content For 42%), then gained composite be placed in baking oven and dry 2h at 100 DEG C, and by dried epoxy resin/glass Glass fibrous composite be placed in coat the demoulding wax laminating machine upper mould, under touch between, open laminating machine, upper mould, under touch temperature It is set as 80 DEG C, and keeps 2MPa template contacts pressure, temperature reaches after 80 DEG C is changed to 10MPa by template contacts pressure, then Being warming up to 150 DEG C keeps pressure constant, is incubated 2 hours, then temperature is risen into 180 DEG C and 2 hours are incubated, finally in 230 DEG C of guarantors Temperature 1 hour, stops lamination, is placed on after being cooled to the room temperature demoulding with mould at room temperature and obtains epoxy resin/glass fiber reinforced layer Pressing plate.
After tested, glass fiber reinforcement sheet material impact strength obtained by the present embodiment is 45.57KJ/m2, bending strength is 270MPa, heat decomposition temperature is 359 DEG C.

Claims (8)

1. a kind of modified epoxy, it is characterised in that it is obtained by the solidification of modified epoxy glue, the modified epoxy tree Fat glue material component and mass ratio are：
Wherein BMI and 4,4 '-MDA (I) mol ratio is 1: 2.
2. modified epoxy according to claim 1, it is characterised in that the CYD-127 epoxy resin is hot-forming Technique is resin dedicated, and viscosity is 350-400mPas at room temperature, and gel time is 20-30min.
3. modified epoxy according to claim 1, it is characterised in that the condition of cure is：Heated at 80 DEG C 2h, then heats 2h at 150 DEG C, then heats 2h at 180 DEG C, finally heats 1h at 230 DEG C.
4. the preparation method of any described modified epoxies of a kind of claim 1-3, it is characterised in that step is as follows：
1) dimethyldiethoxysilane and CYD-127 epoxy resin are mixed in proportion, is warming up to 80-85 DEG C, February is added dropwise Dilaurylate and distilled water, then proceed to be warming up to 90-95 DEG C of reaction 5-6h, reaction solution is changed into milky, vacuum distillation Remove accessory substance and obtain organic-silicon-modified epoxy resin；
2) in proportion by diphenyl methane dimaleimide and 4,4 '-MDA (I) is placed in 135-140 DEG C of oil bath Melting, is allowed to occur Michael addition reaction in advance, then stops heating and is cooled to 95-100 DEG C, adds step 1) gained is organic The epoxy resin of Si modification, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled to room 4,4 '-MDA (II) is added after temperature, modified epoxy glue is uniformly mixing to obtain；
3) by step 2) the modified epoxy glue solidify obtaining modified epoxy.
5. a kind of glass fibre reinforced laminate prepared according to any described modified epoxies of claim 1-3, Characterized in that, it is using modified epoxy as matrix, using glass fibre woven roving as reinforcing material, prepared using hot-forming Obtain.
6. a kind of right 5 requires the preparation method of described glass fibre reinforced laminate, it is characterised in that including following step Suddenly：
1) dimethyldiethoxysilane and CYD-127 epoxy resin are mixed in proportion, is warming up to 80-85 DEG C, February is added dropwise Dilaurylate and distilled water, then proceed to be warming up to 90-95 DEG C of reaction 5-6h, reaction solution is changed into milky, vacuum distillation Remove accessory substance and obtain organic-silicon-modified epoxy resin；
2) in proportion by diphenyl methane dimaleimide and 4,4 '-MDA (I) is placed in 135-140 DEG C of oil bath Melting, is allowed to occur Michael addition reaction in advance, then stops heating and is cooled to 95-100 DEG C, adds step 1) gained is organic The epoxy resin of Si modification, is sufficiently mixed under the conditions of 135-140 DEG C of oil bath, stirs, and stops heating and treats that it is cooled to room 4,4 '-MDA (II) is added after temperature, modified epoxy glue is uniformly mixing to obtain；
3) it is laid in after 10-13 layers of glass fabric being cut out into drying on glass plate, by step 2) gained modified epoxy glue Liquid is coated uniformly on glass fabric, and modified epoxy is impregnated with glass fabric, to obtain epoxy resin/glass fibre multiple Condensation material, is then placed in oven drying, lamination solidification by the progress of gained composite and obtains epoxy resin/glass fiber reinforced layer Pressing plate.
7. preparation method according to claim 6, it is characterised in that step 3) epoxy resin/glass fibre composite wood Material gel content is 35-45%.
8. preparation method according to claim 6, it is characterised in that step 3) the lamination curing process condition is：Will be dry Dry rear epoxy resin/glass fiber compound material be placed in coat the demoulding wax layer press upper mould, under touch between, open laminating machine, Upper mould, under touch temperature and be set as 80 DEG C, and keep 1-2MPa template contacts pressure, temperature is reached template contacts pressure after 80 DEG C 10MPa is changed to, 150 DEG C is then warming up to and keeps pressure constant, be incubated 2 hours, then temperature is risen to 180 DEG C and 2 hours are incubated, It is last to be incubated 1 hour at 230 DEG C, stop lamination, be placed on after being cooled to the room temperature demoulding with mould at room temperature and obtain epoxy resin/glass Glass fiber-reinforced layer pressing plate.
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