CN108485200A - A kind of modified epoxy resin composite - Google Patents

A kind of modified epoxy resin composite Download PDF

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Publication number
CN108485200A
CN108485200A CN201810328483.6A CN201810328483A CN108485200A CN 108485200 A CN108485200 A CN 108485200A CN 201810328483 A CN201810328483 A CN 201810328483A CN 108485200 A CN108485200 A CN 108485200A
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epoxy resin
resin composite
added
minutes
modified epoxy
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王志龙
韩建
梁国正
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Jiaxing Li Xin New Material Co Ltd
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Jiaxing Li Xin New Material Co Ltd
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    • 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
    • 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
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
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    • 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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    • 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
    • C08G59/68—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 catalysts used
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/687—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 catalysts used containing sulfur
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/688—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 catalysts used containing phosphorus
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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Abstract

The present invention relates to a kind of modified epoxy resin composite, preparation includes that improved silica is added in difunctional epoxy systems, and simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle is added, obtains glue；It is 50% to adjust glue solid content with propylene glycol methyl ether acetate, then glass cloth is immersed in glue, then hot-press solidifying obtains modified epoxy resin composite after heated drying, is protruded with excellent flame retardant property, heat resistance, especially wearability.

Description

A kind of modified epoxy resin composite
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of modified epoxy resin composite.
Background technology
With the continuous development of science and technology, the application of polymer-based composite is more and more extensive.Meanwhile each application Also to different materials, more stringent requirements are proposed accordingly in field, such as high temperature resistant, resistance to ablation, wear-resisting etc..With fire-retardant Pay attention to, it is desirable that product has flame retardant property, fire-retardant to have class requirement, respectively UL94 V-2, UL94 V-1 and UL94 V- 0 rank, wherein UL94 V-0 ranks are the whether fire-retardant international standard of existing judgement substance.It is found between fire prevention and environmental protection Equalization point is the important node of the following flame retardant products development.The importance of fire retardant in modern society can not be ignored, but with A series of environmental protection policies in Europe are put into effect, and development and application is restricted to some extent.How to exempt from support personnel and property While by fire threat, and fire retardant can be made to be preferably minimized potential hazard existing for human body and environment, be domestic fire retardant The common focus of attention of industries such as manufacturing enterprise, research institution and downstream electronic be electrical, building materials, traffic and furniture.Simple tree Fat cannot meet the application of copper-clad plate, even if the preferable cyanate ester resin of heat resistance, with excellent dielectric properties (dielectric coefficient：2.8~3.2；Dielectric loss factor：0.002~0.003), high-fire resistance (glass transition temperature：280~ 295 DEG C), while cyanate ester resin also has low-shrinkage, excellent mechanical property and adhesive property etc., also because curing not Enough, the defects of brittleness is big fails widely applying.So using complex technique, the advantages of being not only to integrate organic-inorganic material, The organic component that compatibility is different is also wanted, is hopeful to prepare the material for meeting commercial Application.
Invention content
The object of the present invention is to provide a kind of modified epoxy resin composites, have excellent wear-resisting property, excellent Heat resistance, anti-flammability, processability and mechanical property；Our company has applied for multiple patents together simultaneously, explains from different directions Central inventive point is stated, it is especially longitudinal deep, it is expected that obtaining comprehensive protection.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
The preparation method of a kind of modified epoxy resin composite, the modified epoxy resin composite includes following step Suddenly：
(1) by nano silicon dioxide foam dispersion in toluene, then be added vinyl propionate, the diazoacetic acid tert-butyl ester and Aryl allyl alkyl phenol；It is stirred 30 minutes at 110 DEG C；Then tetramethylethylenediamine is added, February is added after being uniformly dispersed Cinnamic acid dibutyl zinc, back flow reaction 7 hours are eventually adding acetone and obtain the improved silica that solid content is 40%；
(2) at room temperature, 3,3 '-dithiodipropionic acids, dichloromethane, acetone are mixed；Then m-nitrobenzene sulfonic acid pyrrole is added Methyl butynol is added in pyridine salt and diphenyl phosphate, stirring after ten minutes, and stirring adds 2,3- epoxies basic ring penta after 35 minutes Benzylidene aniline is added after 50 minutes in cyclopentyl ether, stirring, continues stirring 5 minutes；Then N is added, N '-dicyclohexyls carbon two is sub- Amine continues stirring 30 minutes, obtains simple function group epoxy systems；
(3) graphene oxide is mixed to addition phthalic acid two after ten minutes to shrink with isomery undecyl alcohol polyoxyethylene ether In glyceride, 125 DEG C are stirred 5 minutes, and cyclic carbonate ester is then added, and are stirred 15 minutes in 110 DEG C, are obtained difunctional epoxy System；The chemical structural formula of the cyclic carbonate ester is as follows：
(4) improved silica is added in difunctional epoxy systems, 150 DEG C are stirred 20 minutes, then at 75 DEG C, Simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle is added, stirs 90 minutes, obtains glue；
(5) it is 50% to use solvent adjustment glue solid content, then reinforcing material is immersed in glue, then heated drying Afterwards, prepreg is obtained；
(6) prepreg, hot pressing is taken to obtain modified epoxy resin composite.
In above-mentioned technical proposal, in step (1), the nanometer titanium dioxide silicon foam, vinyl propionate, the tertiary fourth of diazoacetic acid Ester, aryl allyl alkyl phenol, tetramethylethylenediamine, di lauric dibutyl zinc mass ratio be 1: 1: 0.5: 1.5: 0.5: 0.008。
In above-mentioned technical proposal, in step (2), 3,3 '-dithiodipropionic acids, dichloromethane, acetone, m-nitrobenzene sulfonic acid Pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- epoxy group cyclopenta rings amyl ether, benzylidene aniline, N, N '-dicyclohexyls The mass ratio of carbodiimide is 0.005: 0.15: 1: 0.002: 0.2: 0.02: 1: 0.3: 0.05；Be added methyl butynol when Between be 20 minutes.
In above-mentioned technical proposal, in step (3), graphene oxide, isomery undecyl alcohol polyoxyethylene ether, phthalic acid two Ethylene oxidic ester, cyclic carbonate ester mass ratio be 0.0008: 0.1: 1: 0.18.
In above-mentioned technical proposal, in step (4), improved silica, difunctional epoxy systems, simple function group epoxy body It is, the mass ratio of nanometer polytetrafluoroethylcomposite particle is 0.3: 0.4；1∶0.08.
In above-mentioned technical proposal, in step (5), in the modified epoxy resin composite, the quality point of reinforcing material Number is 25%；The reinforcing material is electronic-grade glass fiber cloth；The heat drying is 120 DEG C/30s+160 DEG C/50s+200 DEG C/30s, it is ensured that stability of the graphene in hot-press solidifying avoids local conductivity issues, at the same ladder-elevating temperature and The compatilizer of small molecule acts on, and in turn avoids the presence of bubble, pin hole, while carrying using minute quantity nanometer polytetrafluoroethylcomposite particle For good wear-resisting effect, reach good dispersion effect.
In above-mentioned technical proposal, in step (5), solvent is propylene glycol methyl ether acetate.
In above-mentioned technical proposal, in step (6), condition when hot pressing is 5kg/cm2/160℃ /20min+5kg/cm2/ 190℃/50min+8kg/cm2/ 210 DEG C/30min+ Temperature falls.This is for critically important, the solidification of thermosetting resin of the invention Process is very big on its follow-up performance influence, if curing process is improper, causes small molecule to form stress defect, is unable to reach Heat-resisting, wear-resisting demand.
In above-mentioned technical proposal, in step (6), 6 prepregs, hot pressing is taken to obtain modified epoxy resin composite.
The present invention by whole compatibility and technological design, obtained epoxy material it is heat-resisting it is fine, fire-retardant very well, hydroscopicity Low, especially wear-resisting property is good.
Inventor develops cooperatively with school, and the creative di lauric dibutyl zinc that first passes through is catalyst, in titanium dioxide The particle surface of silicon foam forms reactive organic matter, different from existing coupling agent surface treatment, nano-silica obtained by the reaction SiClx foam is directly used in resin compounded system and is conducive to participate in the solidification process of resin, lead to per se with stronger reactive group On the one hand surface nature that several organic molecular species adjust filler is crossed, preventing inorganic particulate, it is too fast to resin generation partial polymerization It influences, in addition it can adjust crosslinked polymer network so that cured product crosslinking is reasonable, and it is excessive to be unlikely to brittleness, to profit In processing, 1.5 millimeters of feed fishing sides reach 66 meters.It is pre- anti-to be mixed with several compounds before epoxy is added first by the present invention It answers, so as to access high polymer main chain with epoxy reaction, fire-retardant while will not reduce heat-resisting, can also improve wet-heat resisting；Especially The selective oxidation graphene of its invention, and first mixed with isomery undecyl alcohol polyoxyethylene ether, it adds in epoxy, it can The reactivity and dispersion degree of graphene is greatly improved so that graphene avoids gathering while playing catalytic performance, especially The design of curing process meets each elementary reaction demand, the excellent product performance of preparation.Present invention simple function group epoxy and Difunctional does not use conventional four-functional group epoxy, still heat-resisting good, processability is also improved, on the one hand due to modified two Aoxidize silicon foam the effect of, in addition the catalysis of graphene is also critically important, while diphenyl phosphate, 3,3 '-dithiodipropionic acids with Cyclic carbonate ester can all enhance amine curing effect.
The present invention does not use fire retardant, by modified filler and compound effects, is imitated in combination with polymer reaction Fruit, material can form finer and close protective layer in heated and burning, reach excellent hot oxygen screen effect, solid to assign Body adhesives excellent heat resistance and anti-flammability, while mechanical property, adhesive property are good；Overcome the resistance of prior art filler Mechanical properties decrease, the problem of heat-resisting decline that the bonding that combustion agent is brought declines and reactive flame retardant is brought.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
Compound system composition provided by the invention is reasonable, then prepares technique, inorganic nanoparticles in obtained base material There is uniform dispersion degree, preparation process to belong to chemical process in system, the inorganic matter of formation is combined with the surface of interlaminar resin Power is much stronger than the surface binding force of traditional physical mechanical blending.The material system composition that the present invention utilizes is reasonable, each to form / compatibility is good, and modified epoxy resin composite has thus been prepared, and has good mechanical property, heat resistance, The shortcomings that the advantages of comprehensive polymer, two component of inorganic particulate, two component of improvement, obtains the comprehensive performance of material to improve； Solidification effect is good, and cross-linked structure is uniform, on the one hand micromolecular compound can increase body as the compatilizer of macromolecule organic It is the compatibility of each component, on the other hand avoids forming crosslinking uneven defect when hot-press solidifying, ensure that resin system is formed surely Fixed structure, especially improves heat-resisting, the wearability of conventional epoxy, and is free of fire retardant, by reasonable reaction, at Work(avoids the hygroscopic defect of existing reactive phosphor-containing flame-proof molecule, achieves unexpected effect.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment one
A kind of modified epoxy resin composite, preparation method includes the following steps：
(1) by nano silicon dioxide foam dispersion in toluene, then be added vinyl propionate, the diazoacetic acid tert-butyl ester and Aryl allyl alkyl phenol；It is stirred 30 minutes at 110 DEG C；Then tetramethylethylenediamine is added, February is added after being uniformly dispersed Cinnamic acid dibutyl zinc, back flow reaction 7 hours are eventually adding acetone and obtain the improved silica that solid content is 40%；Nanometer two Aoxidize silicon foam, vinyl propionate, the diazoacetic acid tert-butyl ester, aryl allyl alkyl phenol, tetramethylethylenediamine, two fourth of tin dilaurate The mass ratio of base zinc is 1: 1: 0.5: 1.5: 0.5: 0.008；The present invention first uses vinyl propionate, the diazoacetic acid tert-butyl ester, allyl It is reactive while improving to reduce filler to the processing of nanometer titanium dioxide silicon foam for base aralkyl phenol, tetramethylethylenediamine monomer Dispersibility of the filler in organic matter, plays a role when hot-press solidifying；
(2) at room temperature, 3,3 '-dithiodipropionic acids, dichloromethane, acetone are mixed；Then m-nitrobenzene sulfonic acid pyrrole is added Pyridine salt and diphenyl phosphate, stirring are added methyl butynol, are added within 20 minutes and complete, stirring adds after 35 minutes after ten minutes Benzylidene aniline is added after 50 minutes in 2,3- epoxy group cyclopenta ring amyl ethers, stirring, continues stirring 5 minutes；Then N, N '-is added Dicyclohexylcarbodiimide continues stirring 30 minutes, obtains simple function group epoxy systems；3,3 '-dithiodipropionic acids, dichloro Methane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- epoxy group cyclopenta rings amyl ether, The mass ratio of benzylidene aniline, N, N '-dicyclohexylcarbodiimides are 0.005: 0.15: 1: 0.002: 0.2: 0.02: 1: 0.3: 0.05；
(3) graphene oxide is mixed to addition phthalic acid two after ten minutes to shrink with isomery undecyl alcohol polyoxyethylene ether In glyceride, 125 DEG C are stirred 5 minutes, and cyclic carbonate ester is then added, and are stirred 15 minutes in 110 DEG C, are obtained difunctional epoxy System；The chemical structural formula of the cyclic carbonate ester is as follows：
Graphene oxide, isomery undecyl alcohol polyoxyethylene ether, the quality of o-phthalic acid diglycidyl ester, cyclic carbonate ester Than being 0.0008: 0.1: 1: 0.18；
(4) improved silica is added in difunctional epoxy systems, 150 DEG C are stirred 20 minutes, then at 75 DEG C, Simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle is added, stirs 90 minutes, obtains glue；Improved silica, double officials Can roll into a ball epoxy systems, simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle mass ratio be 0.3: 0.4: 1: 0.08；
(5) it is 50% to adjust glue solid content with propylene glycol methyl ether acetate, and then glass cloth is immersed in glue, then After heated drying, prepreg is obtained, the mass fraction of reinforcing material is 25%, and heat drying technique is 120 DEG C/30s+ 160 DEG C/50s+200 DEG C/30s, solve other dryings existing surface pores, crack problem；
(6) by 6 above-mentioned modified epoxy resin composite hot-press solidifyings, you can obtain modified epoxy resin plate；Performance Test is shown in Table 1, and condition when hot pressing is 5kg/cm2/160℃/20min+5kg/cm2/190℃ /50min+8kg/cm2/210 DEG C/30min+ Temperature falls.
Comparative example one
As embodiment one, wherein step (1) handles nano silicon dioxide only with 1%KH550.
Comparative example two
As embodiment one, wherein step (2) is added without diphenyl phosphate.
Comparative example three
As embodiment one, wherein step (3) is added without graphene oxide.
Comparative example four
As embodiment one, wherein step (3) is added without cyclic carbonate ester.
Comparative example five
As embodiment one, wherein step (4) is added without nanometer polytetrafluoroethylcomposite particle.
Comparative example six
As embodiment one, wherein step (6) hot pressing when condition be 5kg/cm2/150℃ /40min+8kg/em2/ 210 DEG C/60min+ Temperature falls.
To mechanical performance (unnotched impact strength, the Ki/m of the plank in above-described embodiment and comparative example2), mechanical property Can (1.5 millimeters of feeds, rice), hot property, it is wear-resisting can (decorative panel wear-resisting test), water absorption rate, it is fire-retardant be determined, as a result join It is shown in Table 1.
The performance of 1 modified epoxy resin plate of table
It is fire-retardant Oxygen index (OI) Drag for side Tear strength Td/℃ Tg/℃ Hydroscopicity Impact strength
Embodiment one V0 39 66 ＞ 600 399 208 0.018% 8.9
Comparative example one V0 36 60 ＞ 600 376 192 0.021% 8.1
Comparative example two V1 26 61 ＞ 600 390 205 0.019% 8.6
Comparative example three V1 30 42 ＞ 600 380 197 0.035% 8.3
Comparative example four V0 32 49 550 391 201 0.043% 8.0
Comparative example five V0 37 62 400 395 199 0.022% 8.2
Comparative example six V0 33 60 560 385 200 0.031% 8.0
To sum up, modified epoxy resin composite composition disclosed by the invention is reasonable, and compatibility is good between each component, by Modified epoxy resin plate has been prepared in this, has good flame retardant property, excellent heat resistance, especially has low moisture absorption Rate and good wear-resisting property.

Claims (10)

1. a kind of modified epoxy resin composite, it is characterised in that：The preparation method of the modified epoxy resin composite Include the following steps：
(1) by nano silicon dioxide foam dispersion in toluene, vinyl propionate, the diazoacetic acid tert-butyl ester and allyl is then added Base aralkyl phenol；It is stirred 30 minutes at 110 DEG C；Then tetramethylethylenediamine is added, tin dilaurate is added after being uniformly dispersed Dibutyl zinc, back flow reaction 7 hours are eventually adding acetone and obtain the improved silica that solid content is 40%；
(2) at room temperature, 3,3 '-dithiodipropionic acids, dichloromethane, acetone are mixed；Then m-nitrobenzene sulfonic acid pyridiniujm is added With diphenyl phosphate, methyl butynol is added in stirring after ten minutes, and stirring adds 2,3- epoxy group cyclopenta rings after 35 minutes Benzylidene aniline is added after 50 minutes in amyl ether, stirring, continues stirring 5 minutes；Then it is added N, N '-dicyclohexylcarbodiimides, Continue stirring 30 minutes, obtains simple function group epoxy systems；
(3) graphene oxide is mixed to addition phthalic acid 2-glycidyl after ten minutes with isomery undecyl alcohol polyoxyethylene ether In ester, 125 DEG C are stirred 5 minutes, and cyclic carbonate ester is then added, and are stirred 15 minutes in 110 DEG C, are obtained difunctional epoxy systems； The chemical structural formula of the cyclic carbonate ester is as follows：
(4) improved silica is added in difunctional epoxy systems, 150 DEG C are stirred 20 minutes, then at 75 DEG C, are added Simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle stir 90 minutes, obtain glue；
(5) it is 50% to use solvent adjustment glue solid content, then reinforcing material is immersed in glue, then after heated drying, Obtain prepreg；
(6) prepreg, hot pressing is taken to obtain modified epoxy resin composite.
2. modified epoxy resin composite according to claim 1, it is characterised in that：In step (1), the nano-silica SiClx foam, vinyl propionate, the diazoacetic acid tert-butyl ester, aryl allyl alkyl phenol, tetramethylethylenediamine, di lauric dibutyl The mass ratio of zinc is 1: 1: 0.5: 1.5: 0.5: 0.008.
3. modified epoxy resin composite according to claim 1, it is characterised in that：In step (2), 3,3 '-two is thio Dipropionic acid, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- epoxies basic ring penta The mass ratio of cyclopentyl ether, benzylidene aniline, N, N '-dicyclohexylcarbodiimides are 0.005: 0.15: 1: 0.002: 0.2: 0.02∶1∶0.3∶0.05；The time that methyl butynol is added is 20 minutes.
4. modified epoxy resin composite according to claim 1, it is characterised in that：In step (3), graphene oxide, Isomery undecyl alcohol polyoxyethylene ether, o-phthalic acid diglycidyl ester, cyclic carbonate ester mass ratio be 0.0008: 0.1: 1: 0.18。
5. modified epoxy resin composite according to claim 1, it is characterised in that：In step (4), modified titanium dioxide Silicon, difunctional epoxy systems, simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle mass ratio be 0.3: 0.4: 1: 0.08。
6. modified epoxy resin composite according to claim 1, it is characterised in that：In step (5), the prepreg In, the mass fraction of reinforcing material is 25%；The reinforcing material is electronic-grade glass fiber cloth.
7. modified epoxy resin composite according to claim 1, it is characterised in that：In step (5), the heat drying For 120 DEG C/30s+160 DEG C/50s+200 DEG C/30s.
8. modified epoxy resin composite according to claim 1, it is characterised in that：In step (5), solvent is propylene glycol Methyl ether acetate.
9. modified epoxy resin composite according to claim 1, it is characterised in that：In step (6), condition when hot pressing For 5kg/cm2/160℃/20min+5kg/cm2/190℃/50min+8kg/cm2/ 210 DEG C/30min+ Temperature falls.
10. modified epoxy resin composite according to claim 1, it is characterised in that：In step (6), 6 semi-solid preparations are taken Piece, hot pressing obtain modified epoxy resin composite.
CN201810328483.6A 2018-01-27 2018-04-04 A kind of modified epoxy resin composite Withdrawn CN108485200A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182831A (en) * 2013-04-02 2013-07-03 陕西生益科技有限公司 Preparation technology of copper-clad laminate based on halogen-free flame-retardant resin compositions
CN104987665A (en) * 2015-06-29 2015-10-21 安徽育安实验室装备有限公司 High-temperature resisting corrosion-resistant modified epoxy resin pad for laboratory table board
CN105172297A (en) * 2015-09-02 2015-12-23 苏州益可泰电子材料有限公司 Flame-resistant and heat-resistant copper clad laminate preparation method
CN107418490A (en) * 2017-09-26 2017-12-01 安徽大松树脂有限公司 A kind of epoxy resin adhesive containing graphene oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103182831A (en) * 2013-04-02 2013-07-03 陕西生益科技有限公司 Preparation technology of copper-clad laminate based on halogen-free flame-retardant resin compositions
CN104987665A (en) * 2015-06-29 2015-10-21 安徽育安实验室装备有限公司 High-temperature resisting corrosion-resistant modified epoxy resin pad for laboratory table board
CN105172297A (en) * 2015-09-02 2015-12-23 苏州益可泰电子材料有限公司 Flame-resistant and heat-resistant copper clad laminate preparation method
CN107418490A (en) * 2017-09-26 2017-12-01 安徽大松树脂有限公司 A kind of epoxy resin adhesive containing graphene oxide

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