CN108485201A - A kind of preparation method of modified epoxy resin composite - Google Patents
A kind of preparation method of modified epoxy resin composite Download PDFInfo
- Publication number
- CN108485201A CN108485201A CN201810328484.0A CN201810328484A CN108485201A CN 108485201 A CN108485201 A CN 108485201A CN 201810328484 A CN201810328484 A CN 201810328484A CN 108485201 A CN108485201 A CN 108485201A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- added
- resin composite
- minutes
- modified epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of modified epoxy resin composite, including 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
Technical field
The invention belongs to electronics technical field of composite materials, and in particular to a kind of preparation of modified epoxy resin composite
Method.
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 preparation method of modified epoxy resin composite, obtained product has excellent
Different wear-resisting property, excellent heat resistance, anti-flammability, processability and mechanical property；Our company has applied multiple together simultaneously
Patent 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：
A kind of preparation method of modified epoxy resin composite, 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 body
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；The time of methyl butynol is added
It is 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 process of thermosetting resin of the invention
It is very big on its follow-up performance influence, if curing process is improper, causes small molecule to form stress defect, be unable to reach resistance to
Hot, 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：
In preparation method provided by the invention, compound system composition is reasonable, then prepares technique, nothing in obtained base material
There is machine nano particle uniform dispersion degree, preparation process to belong to chemical process, the inorganic matter and interlaminar resin of formation in system
Surface binding force be much stronger than the surface binding force of traditional physical mechanical blending.The material system composition that the present invention utilizes closes
Reason, compatibility is good between each component, and modified epoxy resin composite has thus been prepared, have good mechanical property,
The shortcomings that the advantages of heat resistance, comprehensive polymer, two component of inorganic particulate, two component of improvement, obtains material to improve
Comprehensive performance；Solidification effect is good, and cross-linked structure is uniform, micromolecular compound can as the compatilizer of macromolecule organic, one
Aspect increases the compatibility of system each component, on the other hand avoids forming crosslinking uneven defect when hot-press solidifying, ensures resin
The structure that System forming is stablized especially improves heat-resisting, the wearability of conventional epoxy, and is free of fire retardant, passes through
Reasonable reaction successfully 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 preparation method of modified epoxy resin composite, 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, dichloromethane
Alkane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- epoxy group cyclopenta rings amyl ether, benzyl
Aniline, N are pitched, the mass ratio of N '-dicyclohexylcarbodiimides is 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 body
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℃/
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/cm2/
210 DEG C/60min+ Temperature falls.
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 |
| 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 preparation method of modified epoxy resin composite, which is characterized in that 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. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (1), institute
State nanometer titanium dioxide silicon foam, vinyl propionate, the diazoacetic acid tert-butyl ester, aryl allyl alkyl phenol, tetramethylethylenediamine, February
The mass ratio of cinnamic acid dibutyl zinc is 1: 1: 0.5: 1.5: 0.5: 0.008.
3. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (2), 3,
3 '-dithiodipropionic acids, dichloromethane, acetone, m-nitrobenzene sulfonic acid pyridiniujm, diphenyl phosphate, methyl butynol, 2,3- rings
The mass ratio of oxygroup cyclopenta ring 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. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (3), oxygen
Graphite alkene, isomery undecyl alcohol polyoxyethylene ether, o-phthalic acid diglycidyl ester, cyclic carbonate ester mass ratio be 0.0008
∶0.1∶1∶0.18。
5. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (4), change
Property silica, difunctional epoxy systems, simple function group epoxy systems, nanometer polytetrafluoroethylcomposite particle mass ratio be 0.3:
0.4∶1∶0.08。
6. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (5), institute
It states in prepreg, the mass fraction of reinforcing material is 25%；The reinforcing material is electronic-grade glass fiber cloth.
7. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (5), institute
It is 120 DEG C/30s+160 DEG C/50s+200 DEG C/30s to state heat drying.
8. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：It is molten in step (5)
Agent is propylene glycol methyl ether acetate.
9. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (6), heat
Condition when pressure is 5kg/cm2/160℃/20min+5kg/cm2/190℃/50min+8kg/cm2/ 210 DEG C/30min+ drops naturally
Temperature.
10. the preparation method of modified epoxy resin composite according to claim 1, it is characterised in that：In step (6),
6 prepregs, hot pressing are taken to obtain modified epoxy resin composite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810121503 | 2018-01-27 | ||
| CN2018101215032 | 2018-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108485201A true CN108485201A (en) | 2018-09-04 |
Family
ID=63316088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810328484.0A Withdrawn CN108485201A (en) | 2018-01-27 | 2018-04-04 | A kind of preparation method of modified epoxy resin composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108485201A (en) |
Citations (5)
| 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 |
-
2018
- 2018-04-04 CN CN201810328484.0A patent/CN108485201A/en not_active Withdrawn
Patent Citations (5)
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108440907A (en) | A kind of preparation method of composite material with high dielectric property | |
| CN105694665A (en) | Flame-retardant coiled material and preparation method thereof | |
| CN113943473B (en) | High-toughness epoxy resin composition and preparation process thereof | |
| CN105367793A (en) | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof | |
| CN109504033A (en) | A kind of flexibility prepreg and preparation method thereof | |
| CN108440908A (en) | A kind of poured with epoxy resin material | |
| CN109652978A (en) | A kind of fire-retardant plant fiber and its application in reinforced polypropylene compound material | |
| CN108485201A (en) | A kind of preparation method of modified epoxy resin composite | |
| CN108485200A (en) | A kind of modified epoxy resin composite | |
| CN108485197A (en) | A kind of preparation method of modified epoxy resin system | |
| CN108424536A (en) | A kind of preparation method of modified epoxy material | |
| CN108440910A (en) | A kind of high dielectric property glue material | |
| CN108485194A (en) | A kind of modified epoxy material | |
| CN108485196A (en) | A kind of preparation method of poured with epoxy resin material | |
| CN108546389A (en) | A kind of modified epoxy resin system | |
| CN113372875B (en) | Bio-based adhesive and preparation method and application thereof | |
| CN114752334B (en) | Medium-temperature cured epoxy structural adhesive film with stable humidity and heat resistance and storage and preparation method thereof | |
| CN108485195A (en) | A kind of preparation method of high dielectric property hot-pressed material | |
| CN108440911A (en) | A kind of preparation method of high dielectric property mould material | |
| CN107759978A (en) | Copper-clad plate flame-retarded resin glue and preparation method thereof | |
| CN108440909A (en) | A kind of preparation method of high dielectric property glue material | |
| CN107759977A (en) | Copper-clad plate modified epoxy base prepreg and preparation method thereof | |
| CN113667070A (en) | Low-smoke halogen-free flame-retardant cable compatilizer, maleic anhydride grafted modified polyolefin and preparation method thereof | |
| CN114032011B (en) | High-brightness electroplating effect imitating powder coating and preparation method thereof | |
| CN108530835A (en) | A kind of high dielectric property hot-pressed material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180904 |
|
| WW01 | Invention patent application withdrawn after publication |