CN108546389A - A kind of modified epoxy resin system - Google Patents

A kind of modified epoxy resin system Download PDF

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Publication number
CN108546389A
CN108546389A CN201810328335.4A CN201810328335A CN108546389A CN 108546389 A CN108546389 A CN 108546389A CN 201810328335 A CN201810328335 A CN 201810328335A CN 108546389 A CN108546389 A CN 108546389A
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minutes
epoxy resin
resin system
modified epoxy
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Inventor
梁国正
韩建
王志龙
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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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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00Characterised 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
    • C08J2427/02Characterised 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
    • C08J2427/12Characterised 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
    • C08J2427/18Homopolymers or copolymers of tetrafluoroethylene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances

Abstract

The present invention relates to a kind of modified epoxy resin system, 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, obtains modified epoxy resin system, based on the plank for preparing there is excellent flame retardant property, heat resistance, especially wearability to protrude.

Description

A kind of modified epoxy resin system
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of modified epoxy resin system.
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 systems, and based on it, the plank of preparation is with excellent Wear-resisting property, excellent heat resistance, anti-flammability, processability and mechanical property;Our company has applied multiple special together simultaneously Profit illustrates central inventive point from different directions, 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 system, the modified epoxy resin system 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%;
(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, obtains modified epoxy resin system.
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), solvent is propylene glycol methyl ether acetate, passes through solid content and small molecule Adjusting can make stability of the graphene in hot-press solidifying, avoid local conductivity issues, while the compatilizer of small molecule Effect can avoid the presence of bubble, pin hole, while the wear-resisting effect provided using minute quantity nanometer polytetrafluoroethylcomposite particle, Reach good dispersion effect.For the present invention by whole compatibility and technological design, the epoxy material of obtained system preparation is heat-resisting Very well, it is fire-retardant very well, hydroscopicity it is 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.The present invention With simple function group epoxy and difunctional, conventional four-functional group epoxy is not used, it is still heat-resisting good, also improve processing Property, on the one hand due to improved silica foam the effect of, in addition the catalysis of graphene is also critically important, at the same diphenyl phosphate, 3,3 '-dithiodipropionic acids and 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 system has thus been prepared, and can prepare based on this with good mechanics Property, heat resistance material, the advantages of comprehensive polymer, two component of inorganic particulate, the shortcomings that improving two components, to improve To the comprehensive performance of material;Solidification effect is good, and cross-linked structure is uniform, and micromolecular compound can be as the phase of macromolecule organic Hold agent, on the one hand increase the compatibility of system each component, on the other hand avoids forming crosslinking uneven defect when hot-press solidifying, protect Card resin system forms stable structure, especially improves heat-resisting, the wearability of conventional epoxy, and without fire-retardant Agent is successfully avoided the hygroscopic defect of existing reactive phosphor-containing flame-proof molecule, is achieved unexpected by reasonable reaction Effect.
Specific implementation mode
With reference to embodiment, the invention will be further described:
Embodiment one
A kind of modified epoxy resin system, 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, obtains modified epoxy resin system.
Then glass cloth is immersed in modified epoxy resin system, then heated is dried to obtain prepreg, glass cloth Mass fraction be 25%, heat drying technique be 120 DEG C/30s+160 DEG C/50s+200 DEG C/30s;By 6 prepreg heaps Folded hot-press solidifying, 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.
To mechanical performance (unnotched impact strength, the Kj/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
To sum up, resin system is the basis of plate property, is played a decisive role to final products performance;It is disclosed by the invention to change Property epoxy-resin systems composition it is reasonable, compatibility is good between each component, and modified epoxy resin plate has thus been prepared, and has Good flame retardant property, excellent heat resistance especially have low hydroscopicity and good wear-resisting property.

Claims (6)

1. a kind of modified epoxy resin system, which is characterized in that the preparation method of the modified epoxy resin system includes following Step:
(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, obtains modified epoxy resin system.
2. modified epoxy resin system according to claim 1, it is characterised in that:In step (1), the nano silicon dioxide Foam, vinyl propionate, the diazoacetic acid tert-butyl ester, aryl allyl alkyl phenol, tetramethylethylenediamine, di lauric dibutyl zinc Mass ratio is 1: 1: 0.5: 1.5: 0.5: 0.008.
3. modified epoxy resin system according to claim 1, it is characterised in that:In step (2), 3,3 '-dithio dipropyls Acid, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- epoxy group cyclopenta rings The mass ratio of amyl 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 system 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 system according to claim 1, it is characterised in that:It is improved silica, double in step (4) Functional group's epoxy systems, simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle mass ratio be 0.3: 0.4: 1: 0.08.
6. modified epoxy resin system according to claim 1, it is characterised in that:In step (5), solvent is propylene glycol monomethyl ether Acetate.
CN201810328335.4A 2018-01-27 2018-04-04 A kind of modified epoxy resin system Withdrawn CN108546389A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1127284A (en) * 1993-12-21 1996-07-24 巴斯福公司 Cyclic carbonate-curable coating composition
CN102939314A (en) * 2010-06-15 2013-02-20 巴斯夫欧洲公司 Use of cyclic carbonates in epoxy resin compositions
CN105086448A (en) * 2015-08-31 2015-11-25 苏州凯欧曼新材料科技有限公司 High-dielectric constant composite material
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
CN105176081A (en) * 2015-08-31 2015-12-23 苏州凯欧曼新材料科技有限公司 Preparation method for flame-retardant heat-resistant antenna radome base material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1127284A (en) * 1993-12-21 1996-07-24 巴斯福公司 Cyclic carbonate-curable coating composition
CN102939314A (en) * 2010-06-15 2013-02-20 巴斯夫欧洲公司 Use of cyclic carbonates in epoxy resin compositions
CN105086448A (en) * 2015-08-31 2015-11-25 苏州凯欧曼新材料科技有限公司 High-dielectric constant composite material
CN105176081A (en) * 2015-08-31 2015-12-23 苏州凯欧曼新材料科技有限公司 Preparation method for flame-retardant heat-resistant antenna radome base material
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

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