CN116554441A - Tracking-resistant epoxy resin composition and application thereof - Google Patents
Tracking-resistant epoxy resin composition and application thereof Download PDFInfo
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- CN116554441A CN116554441A CN202310535102.2A CN202310535102A CN116554441A CN 116554441 A CN116554441 A CN 116554441A CN 202310535102 A CN202310535102 A CN 202310535102A CN 116554441 A CN116554441 A CN 116554441A
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- epoxy resin
- resin composition
- tracking
- anhydride
- prepreg
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 9
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005303 weighing Methods 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920002748 Basalt fiber Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- 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
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
-
- 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
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- C08K7/06—Elements
-
- 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
- C08K7/10—Silicon-containing compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to an anti-creeping epoxy resin composition and application thereof, comprising 100 parts of epoxy resin, 40-90 parts of anhydride, 0.2-10 parts of modified auxiliary agent, 0.2-1 part of coupling agent, 0.2-1 part of accelerator and 0-100 parts of solvent. The invention adopts the liquid anhydride as the curing agent of the epoxy resin, and the liquid anhydride as the curing agent can greatly reduce the viscosity of the resin system, and can select a solvent or solvent-free form to impregnate the fiber, so that the resin permeability is better, and the mechanical strength and the electrical property of the product are higher. According to the invention, the anhydride is pretreated to obtain the improved anhydride curing agent, and after the anhydride curing agent is compounded with the epoxy resin, the manufacturability of the prepreg is realized, and the surface of the prepreg is dry and sticky and is not sticky to a film. After the epoxy resin composition is cured and formed, the tracking resistance of the obtained composite material can reach 600V.
Description
Technical Field
The invention relates to an electric leakage tracking resistant epoxy resin composition and application thereof, belonging to the technical field of thermosetting resins and composite materials thereof; more particularly, it relates to an epoxy resin composition with high tracking index and preparation, forming and application of prepreg of the epoxy resin composition.
Background
With the development of electrical and electronic technology and the severe requirements of the use environment of electrical and electronic appliances, the performance requirements of insulating materials used by electrical and electronic appliances are higher and higher, and besides the basic electrical performance requirements such as insulation resistance, breakdown voltage and water immersion resistance, the electrical and electronic appliances have high requirements on tracking resistance. Tracking resistance is characterized by a tracking resistance index (in volts). The anti-tracking index of the insulation material of the general epoxy laminate is about 200V, and the anti-tracking index of the insulation material with high anti-tracking performance can reach 600V. In general, in order to improve the tracking resistance of the epoxy resin composite material, most of the epoxy resin composite material adopts forms of adding aluminum hydroxide filler and the like, and the dispersion and uniformity of the filler directly influence the final performance stability of the material although the effect of improving the tracking resistance can be achieved.
In general, in the preparation of epoxy resin prepregs, amine is mostly selected as an epoxy resin curing agent, the resin is baked and dried after being impregnated with reinforcing fibers to obtain a semi-cured product, and then the semi-cured product is subjected to high-temperature and high-pressure forming to obtain a final composite material product.
The use of liquid anhydride cured epoxy resins to make semi-cured products and their application to improve the tracking resistance of composite materials has not been found.
Based on this, the present invention has been proposed.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a tracking-resistant epoxy resin composition and application thereof, and the specific technical scheme is as follows:
the tracking-resistant epoxy resin composition comprises the following components in parts by mass:
100 parts of epoxy resin;
40-90 parts of anhydride;
0.2-10 parts of modifying auxiliary agent;
0.2-1 part of coupling agent;
0.2-1 part of accelerator;
0-100 parts of solvent.
Wherein, the solvent can be added according to the requirement.
In a further development, the epoxy resin is bisphenol A type epoxy resin, which is one or more of E51 type epoxy resin, E44 type epoxy resin and E20 type epoxy resin.
In a further improvement, the anhydride is methyl hexahydrophthalic anhydride or methyl tetrahydrophthalic anhydride.
Further improved, the modifying auxiliary agent is one or more of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000 and isopropanol.
Polyethylene glycol 200 refers to polyethylene glycol having an average molecular weight of 200.
In a further improvement, the solvent is one or more of acetone, butanone and methyl ethyl ketone.
Further improved, KH560 type silane coupling agent is selected as the coupling agent.
In a further improvement, the accelerator is selected from one of imidazole, boron trifluoride monoethylamine and benzylamine.
Further improvements, the use of the tracking-resistant epoxy resin composition in composite materials.
In a further development, the method for producing the composite material comprises the following steps:
step S1, adding the acid anhydride into the modified auxiliary agent, uniformly stirring at room temperature, heating to 40-100 ℃ and reacting for 60-240min to obtain a modified acid anhydride curing agent;
s2, adding the melted epoxy resin into a modified anhydride curing agent, uniformly mixing and stirring, cooling to 25-40 ℃ and dispersing for 60-120min, and selecting whether a solvent is added for dilution according to the dipping requirement;
step S3, adding a coupling agent and an accelerator, mixing and stirring for 15-20 min, and adjusting the gel time to 250-320S to obtain an epoxy resin composition;
s4, immersing the reinforcing material into a paint tank filled with the epoxy resin composition, and sending the reinforcing material into an oven for baking after dipping and gluing to obtain a semi-cured prepreg after drying;
and S5, layering the semi-cured prepreg, transferring the layered semi-cured prepreg to an oil press for hot pressing, and naturally cooling after the hot pressing is finished to obtain the composite material.
Wherein, the reinforcing material is preferably 7628 electronic grade glass cloth, the epoxy resin composition is used for dipping 7628 electronic grade glass cloth, and the prepreg is prepared by baking, and the glue content is controlled to be 30-35%.
In a further improvement, the reinforcing material can be one or more of glass fiber, carbon fiber, aramid fiber and basalt fiber.
In a further improvement, in step S5, the hot pressing process of the oil press is as follows: preheating to 110 ℃, pressurizing to 5MPa, and preserving heat for 30min; then heating to 130 ℃, starting gradient pressurization, finally pressurizing to 15MPa, heating to 150 ℃, and preserving heat for 1h; and finally naturally cooling to below 60 ℃ and unloading the plate to obtain the final composite material.
In the traditional application, the liquid anhydride cured epoxy is mainly applied to the fields of potting, pouring and the like, and the prepreg semi-solid compound which can be used for storage is difficult to manufacture. The invention prepares an epoxy resin composition for impregnation by carrying out modification pretreatment on anhydride, then compounding the anhydride with epoxy resin, adding other auxiliary materials, impregnating the composition into a reinforced substrate, and baking the reinforced substrate to obtain a smooth and dry semi-solid; and stacking or laying the obtained semi-cured products, and then laminating or molding to obtain the final thermosetting composite material product.
The invention has the beneficial effects that:
the invention adopts the liquid anhydride as the curing agent of the epoxy resin, and the liquid anhydride as the curing agent can greatly reduce the viscosity of the resin system, and can select a solvent or solvent-free form to impregnate the fiber, so that the resin permeability is better, and the mechanical strength and the electrical property of the product are higher.
Compared with the prior art, the invention has the following advantages:
1. by pre-treating the anhydride, an improved anhydride curing agent is obtained.
2. After the improved anhydride curing agent is compounded with the epoxy resin, the manufacturability of the semi-cured prepreg is realized, the surface of the semi-cured prepreg is dry and sticky, films are not adhered, and the prepreg can be normally stacked, stored and taken.
3. After the epoxy resin composition is used for impregnating glass fibers and curing and forming, the electric leakage and tracking resistance of the obtained composite material can reach 600V.
4. The epoxy resin composition can be used for preparing a composite material with glass fibers, and can also be used for preparing a prepreg with carbon fibers, aramid fibers, basalt fibers and the like.
Drawings
FIG. 1 is a graph showing the effect of the glove for prepreg in comparative example 1;
FIG. 2 is a graph showing the effect of the prepreg sandwiched between two transparent films in comparative example 1;
fig. 3 is a graph showing the effect of the prepreg of comparative example 1 after being pressed by hand;
fig. 4 is a physical view of the prepreg sheet of example 1;
FIG. 5 is a physical view of the prepreg of comparative example 1 after it is completely cured;
FIG. 6 is a graph showing the time trend of gels at different temperatures when epoxy resin is directly mixed with anhydride and the effect of accelerator.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment is a solvent group, specifically:
preparing a three-neck flask, weighing 60g of methyl hexahydrophthalic anhydride and 1.5g of polyethylene glycol 200, respectively adding the mixture into the three-neck flask, stirring and mixing uniformly, heating to 60 ℃ for reaction for 120min, adding 100g of melted E44 epoxy resin, stirring uniformly, cooling and adding 60g of acetone for dilution, stirring at 30 ℃ for 30min, and adding 0.2g of KH560 silane coupling agent; 1.0g of imidazole was weighed, dissolved in a small amount of methanol, then mixed, and the gel time was tested for 271s to obtain an epoxy resin composition.
Cutting 7628 electronic grade glass cloth into 200 mm-sized cloth pieces, soaking each cloth piece by using 7.5g of the epoxy resin composition, suspending in a 130 ℃ oven, baking for 240-300s, taking out, flattening, cooling to obtain a semi-cured prepreg, wherein the prepreg is dry and sticky on the touch surface, is not sticky to films, and can be normally stacked, stored and taken out.
The semi-cured prepreg is put into a 160 ℃ oven to be baked for 10min to detect the volatile content:
13.20g of the mixture before baking, 13.05g of the mixture after baking and 1.14 percent of volatile matter.
24 pieces of prepreg were produced in total, the above 24 pieces of prepreg were stacked, and then fed into an oil press which had been heated to 120℃until the pressure was increased to 5MPa, and after 25 minutes, the temperature was increased to 140℃and 15MPa at a rate of 1MPa/3 minutes, and the temperature was increased to 150℃and maintained for 1 hour, and then cooled to obtain a laminate sheet of 3.5mm (one type of composite material).
The laminate was sampled and the samples obtained by sampling were tested after standard processing, the properties of which are shown in table 1:
TABLE 1
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 600 |
| 2 | Vertical layer flexural Strength | MPa | 562 |
| 3 | Parallel layer impact strength | kJ/m 2 | 76 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 80 |
Example 2
The embodiment is a solvent group, specifically:
preparing a three-neck flask, weighing 60g of methyl hexahydrophthalic anhydride and 1.5g of polyethylene glycol 200, respectively adding the three-neck flask and 1g of isopropanol for compound modification, stirring and mixing uniformly, heating to 60 ℃ for reaction for 120min, adding 100g of melted E44 type epoxy resin, stirring uniformly, cooling and adding 60g of acetone for dilution, stirring at 30 ℃ for 30min, adding 0.2g of KH560 silane coupling agent, weighing 1.0g of imidazole, dissolving with a small amount of methanol (2 times of the dosage of the imidazole), adding and mixing, and testing gel time for 254s to obtain the epoxy resin composition.
Cutting 7628 electronic grade glass cloth into 200 mm-sized cloth pieces, soaking each cloth piece by using 7.5g of epoxy resin composition, hanging the cloth pieces in a 130 ℃ oven, baking for 240-300s, taking out and flattening, cooling to obtain a semi-cured prepreg, and enabling the surface to be dry and sticky and free of films, wherein compared with the single polyethylene glycol 200 modified prepreg, the surface of the semi-cured prepreg is smoother, the stiffness is better after shaping, and the stacking effect is better, and the semi-cured prepreg is stored and taken.
24 pieces of prepreg were produced in total, the above 24 pieces of prepreg were stacked, and then fed into an oil press which had been heated to 120℃until the pressure was increased to 5MPa, and after 25 minutes, the temperature was increased to 140℃and 15MPa at a rate of 1MPa/3 minutes, and the temperature was increased to 150℃and maintained for 1 hour, and then cooled to obtain a laminate sheet of 3.5mm (one type of composite material).
The laminate was sampled and the samples obtained from the sampling were tested after standard processing and the properties are shown in table 2:
TABLE 2
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 600 |
| 2 | Vertical layer flexural Strength | MPa | 570 |
| 3 | Parallel layer impact strength | kJ/m 2 | 79 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 75 |
Example 3
The embodiment is a solvent group, specifically:
preparing a three-neck flask, weighing 60g of methyl hexahydrophthalic anhydride and 1.5g of polyethylene glycol 200, respectively adding the mixture into the three-neck flask, stirring and mixing uniformly, heating to 60 ℃ for reaction for 120min, adding 100g of melted E51 type epoxy resin, stirring uniformly, cooling and adding 60g of acetone for dilution, stirring at 30 ℃ for 30min, adding 0.2g of KH560 silane coupling agent, weighing 1.0g of imidazole, dissolving with a small amount of methanol, adding and mixing, and testing the gel time for 300s to obtain the epoxy resin composition.
Cutting 7628 electronic grade glass cloth into 200 mm-sized cloth pieces, soaking each cloth piece by using 7.5g of epoxy resin composition, suspending in a 130 ℃ oven, baking for 240-300s, taking out, flattening, cooling to obtain a semi-cured prepreg, and enabling the surface to be dry and free of sticking, film sticking and normal stacking, storage and taking.
24 pieces of prepreg were produced in total, the above 24 pieces of prepreg were stacked, and then fed into an oil press which had been heated to 120℃until the pressure was increased to 5MPa, and after 25 minutes, the temperature was increased to 140℃and 15MPa at a rate of 1MPa/3 minutes, and the temperature was increased to 150℃and maintained for 1 hour, and then cooled to obtain a laminate sheet of 3.5mm (one type of composite material).
The laminate was sampled and the samples obtained from the sampling were tested after standard processing and the properties are shown in table 3:
TABLE 3 Table 3
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 600 |
| 2 | Vertical layer flexural Strength | MPa | 555 |
| 3 | Parallel layer impact strength | kJ/m 2 | 88 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 80 |
Example 4
The embodiment is a solvent group, specifically:
preparing a three-neck flask, weighing 60g of methyl hexahydrophthalic anhydride and 1.5g of polyethylene glycol 200, respectively adding the mixture into the three-neck flask, stirring and mixing uniformly, heating to 60 ℃ for reaction for 120min, adding 100g of melted epoxy resin E44, stirring uniformly, cooling and adding 60g of acetone for dilution, stirring at 30 ℃ for 30min, adding 0.2g of coupling agent KH560, weighing 0.8g of boron trifluoride monoethylamine, dissolving with a small amount of methanol, adding into the resin for mixing, and testing the gel time for 260s to obtain the epoxy resin composition.
Cutting 7628 electronic grade glass cloth into 200 mm-sized cloth pieces, soaking each cloth piece by using 7.5g of epoxy resin composition, suspending in a 130 ℃ oven, baking for 240-300s, taking out, flattening, cooling to obtain a semi-cured prepreg, and enabling the surface to be dry and free of sticking, film sticking and normal stacking, storage and taking.
24 pieces of prepreg were produced in total, the above 24 pieces of prepreg were stacked, and then fed into a press machine which had been heated to 120℃until the pressure was 5MPa, and after 25 minutes, the temperature was started to rise to 140℃and 15MPa was added at a rate of 1MPa/3 minutes, and the temperature was raised to 150℃and kept for 1 hour, and then cooled to obtain a laminate (one of composite materials) of 3.5 mm.
The laminate was sampled and the samples obtained from the sampling were tested after standard processing and the properties are shown in table 4:
TABLE 4 Table 4
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 600 |
| 2 | Vertical layer flexural Strength | MPa | 562 |
| 3 | Parallel layer impact strength | kJ/m 2 | 72 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 65 |
Example 5
The present example is a solvent-free group, specifically:
preparing a three-neck flask, weighing 60g of methyl hexahydrophthalic anhydride and 1.5g of polyethylene glycol 200, respectively adding the mixture into the three-neck flask, stirring and mixing uniformly, heating to 60 ℃ for reaction for 120min, adding 100g of melted E44 epoxy resin, stirring uniformly, cooling to 40 ℃ for stirring for 30min, adding 0.2g of KH560 silane coupling agent, weighing 1.0g of imidazole, dissolving with twice of methanol, adding and mixing, and testing the gel time for 285s to obtain the epoxy resin composition.
Cutting 7628 electronic grade glass cloth into 200 mm-sized cloth pieces, soaking each cloth piece by using 5g of epoxy resin composition, suspending in a 130 ℃ oven, baking for 240-300s, taking out, flattening, cooling to obtain a semi-cured prepreg, and enabling the surface to be dry and smooth, not sticky to hands and films, and normally stacking, storing and taking.
24 pieces of prepreg were produced in total, the above 24 pieces of prepreg were stacked, and then fed into an oil press which had been heated to 120℃until the pressure was increased to 5MPa, and after 25 minutes, the temperature was increased to 140℃and 15MPa at a rate of 1MPa/3 minutes, and the temperature was increased to 150℃and maintained for 1 hour, and then cooled to obtain a laminate sheet of 3.5mm (one type of composite material).
The laminate was sampled and the samples obtained from the sampling were tested after standard processing and the properties are shown in table 5:
TABLE 5
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 600 |
| 2 | Vertical layer flexural Strength | MPa | 593 |
| 3 | Parallel layer impact strength | kJ/m 2 | 73 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 80 |
Test example 1
Comparative example of conventional epoxy composition:
preparing a three-neck flask, weighing 100g of E20 type epoxy resin, adding the E20 type epoxy resin into the three-neck flask, heating to 100 ℃ for melting for 30-60min, after the E20 type epoxy resin is completely melted, adding 40g of formamide in steps, starting stirring, cooling to 60 ℃ after uniformly mixing, adding 4g of dicyandiamide, stirring for 60-120min until the dicyandiamide is completely dissolved, weighing imidazo, dissolving with a small amount of solvent (2 times of the dosage of imidazole), adding and mixing, and adjusting the gel time to 250-300s to obtain the common epoxy composition.
Cutting 7628 electronic grade glass cloth into 200 x 400mm size pieces, soaking each piece of cloth piece by using 15g of common epoxy composition, suspending in a 160 ℃ oven, baking for 180-210s, taking out, and cutting into 200 x 200mm size sizing material.
The above 24 pieces of sizing material are stacked, fed into a press which has been heated to 120 ℃, the pressure is increased to 5MPa, the temperature is increased to 140 ℃ after 25min, the pressure is increased to 15MPa at a speed of 1MPa/3min, the temperature is increased to 160 ℃, and the temperature is reduced after the temperature is maintained for 1h, so that a laminated board (one of composite materials) with the thickness of 3.5mm is obtained.
The laminate was sampled and the samples obtained from the sampling were tested after standard processing and the properties are shown in table 6:
TABLE 6
| Sequence number | Inspection item | Unit (B) | Actual measurement result |
| 1 | Tracking index | V | 200 |
| 2 | Vertical layer flexural Strength | MPa | 517 |
| 3 | Parallel layer impact strength | kJ/m 2 | 61 |
| 4 | Parallel layer breakdown voltage (90 ℃ oil) | KV | 80 |
In the above examples, if the conventional liquid acid anhydride is directly compounded with the epoxy resin and the reinforcing base material is directly impregnated, the prepared prepreg sheet is baked at a temperature ranging from 110 ℃ to 140 ℃, and before solidification, the prepreg sheet always presents a non-dry and greasy state (wet pyridazine), and gloves, films, skins and the like can be adhered to the surface of the prepreg sheet by touching, so that the prepreg sheet is not suitable for being carried, stored and used (the form is shown in fig. 1-3).
Comparative example 1
The epoxy resin composition was formulated as follows:
60g of methyl hexahydrophthalic anhydride is weighed in a three-neck flask, 100g of melted E44 type epoxy resin is added, the mixture is stirred uniformly at 60 ℃, the temperature is reduced to 40 ℃, 0.2g of KH560 type silane coupling agent is added, and 0.5-1.0g of benzylamine is used for regulating the gel time to 300s, so that the epoxy resin composition is obtained.
7628 cutting electronic grade glass cloth into 200 x 200mm (9 g/piece) size cloth pieces, soaking each piece of cloth piece with 5g epoxy resin composition, suspending in 130 deg.C oven, baking for 240-300s, and taking out to obtain prepreg, the state of which is as shown in figure 1, and the surface of which is wet-sticky, hand-sticky and film-sticky. FIG. 1 shows a glove for baked prepreg stuck on the glove and standing upright, the glove not falling off; FIG. 2 shows a baked prepreg sandwiched together with two transparent films, standing upright with the outer film removed from a corner; fig. 3 shows that the baked prepreg is lifted and suspended in the half space after being pressed by hand, and the prepreg does not fall off. FIGS. 1 to 3 are all intended to illustrate the effect of wet pyridazine and not dry even after baking before unmodified.
Putting the prepreg into a 160 ℃ oven for baking for 10min to detect the volatile content:
13.22g of the material before baking, 13.08g of the material after baking and 1.06 percent of volatile matters.
If the anhydride is not modified, the epoxy resin is compounded by using the common anhydride, and the intermediate process window for transition from a greasy state to solidification only takes about 10s, and the window period can not be enlarged only by increasing the baking temperature or prolonging the baking time, so that the prepreg/prepreg is in a solidified state when the prepreg/prepreg is changed into a dry state, and the subsequent hot press molding manufacturing can not be carried out any more.
The prepreg in this example was again put into an oven and baked at 160 ℃ for a minimum of 8min until the cured discoloration was complete to a yellowish brown state, as shown in fig. 5. It is known that when the modified anhydride curing agent is not impregnated, the baking is carried out to a state in which the discoloration is completely cured as in fig. 5, and the dry and non-tacky state is not achieved, but it is known to those skilled in the art that it cannot be continued for the hot press molding of the layup.
Comparative example 2
The epoxy resin is directly mixed with the anhydride, and the aging time and window can be rapidly shortened at the treatment temperature exceeding 140 ℃ in the presence of the accelerator; as shown in fig. 6, fig. 6 is a graph of gel time variation trend at different temperatures by directly mixing epoxy resin with anhydride and under the action of an accelerator; in FIG. 6, the abscissa indicates temperature (in degrees Celsius) and the ordinate indicates time (in s).
The epoxy resin is directly mixed with the anhydride and the usable prepreg cannot be obtained by increasing the temperature or extending the baking time in the presence of the accelerator. And after the reinforcing material is impregnated with the epoxy resin composition prepared from the modified anhydride curing agent and the epoxy resin, the prepreg with dry and comfortable surface can be prepared by baking at the same temperature.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The tracking-resistant epoxy resin composition is characterized by comprising the following components in parts by mass:
100 parts of epoxy resin;
40-90 parts of anhydride;
0.2-10 parts of modifying auxiliary agent;
0.2-1 part of coupling agent;
0.2-1 part of accelerator;
0-100 parts of solvent.
2. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the epoxy resin uses bisphenol A type epoxy resin, which is one or more of E51 type epoxy resin, E44 type epoxy resin and E20 type epoxy resin.
3. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the anhydride is methyl hexahydrophthalic anhydride or methyl tetrahydrophthalic anhydride.
4. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the modifying auxiliary agent is one or more of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000 and isopropanol.
5. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the solvent is one or more of acetone, butanone and methyl ethyl ketone.
6. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the coupling agent is KH560 type silane coupling agent.
7. The tracking-resistant epoxy resin composition according to claim 1, characterized in that: the accelerator is one of imidazole, boron trifluoride monoethylamine and benzylamine.
8. Use of the tracking-resistant epoxy resin composition according to any one of claims 1 to 7 in composite materials.
9. Use of the tracking-resistant epoxy resin composition according to claim 8 in a composite material, wherein the preparation method of the composite material comprises the following steps:
step S1, adding the acid anhydride into the modified auxiliary agent, uniformly stirring at room temperature, heating to 40-100 ℃ and reacting for 60-240min to obtain a modified acid anhydride curing agent;
s2, adding the melted epoxy resin into a modified anhydride curing agent, uniformly mixing and stirring, cooling to 25-40 ℃ and dispersing for 60-120min, and selecting whether a solvent is added for dilution according to the dipping requirement;
step S3, adding a coupling agent and an accelerator, mixing and stirring for 15-20 min, and adjusting the gel time to 250-320S to obtain an epoxy resin composition;
s4, immersing the reinforcing material into a paint tank filled with the epoxy resin composition, and sending the reinforcing material into an oven for baking after dipping and gluing to obtain a semi-cured prepreg after drying;
and S5, layering the semi-cured prepreg, transferring the layered semi-cured prepreg to an oil press for hot pressing, and naturally cooling after the hot pressing is finished to obtain the composite material.
10. The use of the tracking-resistant epoxy resin composition according to claim 9 in a composite material, wherein in step S5, the hot pressing process of the oil press is as follows: preheating to 110 ℃, pressurizing to 5MPa, and preserving heat for 30min; then heating to 130 ℃, starting gradient pressurization, finally pressurizing to 15MPa, heating to 150 ℃, and preserving heat for 1h; and finally naturally cooling to below 60 ℃ and unloading the plate to obtain the final composite material.
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| CN202310535102.2A CN116554441A (en) | 2023-05-12 | 2023-05-12 | Tracking-resistant epoxy resin composition and application thereof |
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| CN202310535102.2A CN116554441A (en) | 2023-05-12 | 2023-05-12 | Tracking-resistant epoxy resin composition and application thereof |
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