CN118824650B - High-temperature-resistant composite insulating column and preparation method thereof - Google Patents
High-temperature-resistant composite insulating column and preparation method thereof Download PDFInfo
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- CN118824650B CN118824650B CN202411315842.6A CN202411315842A CN118824650B CN 118824650 B CN118824650 B CN 118824650B CN 202411315842 A CN202411315842 A CN 202411315842A CN 118824650 B CN118824650 B CN 118824650B
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000011810 insulating material Substances 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 33
- 239000005011 phenolic resin Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 230000000737 periodic effect Effects 0.000 claims abstract description 19
- 239000011256 inorganic filler Substances 0.000 claims abstract description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
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- 239000004332 silver Substances 0.000 claims abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 239000010931 gold Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
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- 239000000203 mixture Substances 0.000 claims description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 20
- 239000003063 flame retardant Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 18
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- 238000001816 cooling Methods 0.000 claims description 9
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims 2
- 150000002903 organophosphorus compounds Chemical group 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
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- 239000013067 intermediate product Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 229910002026 crystalline silica Inorganic materials 0.000 description 7
- 239000005350 fused silica glass Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
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- 241000863480 Vinca Species 0.000 description 6
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- 230000009477 glass transition Effects 0.000 description 6
- 239000012774 insulation material Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RGBIPJJZHWFFGE-UHFFFAOYSA-N cyclohexa-2,5-diene-1,4-dione;triphenylphosphane Chemical compound O=C1C=CC(=O)C=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RGBIPJJZHWFFGE-UHFFFAOYSA-N 0.000 description 1
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- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920006336 epoxy molding compound Polymers 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000012948 isocyanate Substances 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/60—Composite insulating bodies
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/64—Insulating bodies with conductive admixtures, inserts or layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/002—Inhomogeneous material in general
- H01B3/006—Other inhomogeneous material
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开了一种耐高温复合绝缘柱及其制备方法，包括耐高温复合绝缘材料和金属结构件，所述金属结构件被所述耐高温复合绝缘材料包覆或粘结，所述耐高温复合绝缘材料由环氧树脂、酚醛树脂、无机填料、固化促进剂、介孔纳米二氧化硅增固剂和辅助添加剂组成，所述金属结构件为金、银、铜、铝或其合金制备，所述介孔纳米二氧化硅增固剂负载特定的增固剂，在升温固化流变态时对树脂料饼或切片的特定流变阶段进行周期性加压，诱导弱粘结发生引导介孔纳米二氧化硅增固剂发挥效果，增强整体固化均匀性,最终实现高Tg、高耐热的耐高温复合绝缘柱制备。
The invention discloses a high temperature resistant composite insulating column and a preparation method thereof, comprising a high temperature resistant composite insulating material and a metal structural part, wherein the metal structural part is coated or bonded by the high temperature resistant composite insulating material, the high temperature resistant composite insulating material is composed of epoxy resin, phenolic resin, inorganic filler, curing accelerator, mesoporous nano-silica reinforcing agent and auxiliary additives, the metal structural part is prepared from gold, silver, copper, aluminum or their alloys, the mesoporous nano-silica reinforcing agent is loaded with a specific reinforcing agent, and periodic pressurization is performed on a specific rheological stage of a resin cake or slice during the temperature-raising curing rheological state, so as to induce weak bonding to guide the mesoporous nano-silica reinforcing agent to exert its effect, enhance the overall curing uniformity, and finally realize the preparation of a high Tg, high heat-resistant high temperature resistant composite insulating column.
Description
Technical Field
The invention belongs to the technical field of insulating materials, and particularly relates to a high-temperature-resistant composite insulating column and a preparation method thereof.
Background
As the charging speed requirement of the new energy automobile for charging is increasingly higher, the battery pack needs to bear larger voltage and current, the temperature of the battery is higher, and the performance requirement of the insulating column is synchronously increased. The conventional BMC plastic used at present has obviously weakened performance after being aged at 200 ℃, and torsion, tension, shearing force and the like are lower than the use standard. It is therefore desirable that the sealing material have heat conduction and flame retardant properties superior to those of conventional sealing materials. The epoxy resin is a thermosetting resin formed by curing epoxy prepolymer by a curing agent, and has excellent water resistance, heat resistance, chemical stability and electrical insulation and mechanical properties. The high-temperature resistant composite insulating material (EMC) prepared from epoxy resin, curing agent, various organic/inorganic fillers and a series of auxiliary additives is an indispensable packaging material in the electronic packaging industry, and different technological routes of the high-temperature resistant composite insulating material realize different performance requirements, so that the selectivity of downstream industrial application is enriched.
In the high-temperature-resistant composite insulating material composition provided by the invention of the patent CN 107446316B, isocyanate-modified polyether organosilicon is added to serve as a stress absorbent, and isocyanate (-NCO) groups at the tail end of the organosilicon material can react with hydroxyl (-OH) groups produced in the curing process, so that the organosilicon enters a crosslinking network, the crosslinking density is increased, the effect of improving the glass transition temperature (Tg) of the material is achieved, and meanwhile, the flexural modulus of the material can be further reduced.
The invention patent of the patent CN 103992641B provides a thermosetting resin composition, which is prepared by a method of co-curing an epoxy resin by an active ester resin and an allyl modified bismaleimide resin, has mild processing and curing molding conditions, has lower dielectric constant and dielectric loss, and improves the heat resistance and toughness of the resin composition after curing to a certain extent. However, the cured thermosetting resin composition has a Tg of less than 220 ℃ and a heat resistance which is not satisfactory enough to be used in a high temperature environment of 250 ℃ or more.
The epoxy 1, 2-polybutadiene provided by the invention of the patent CN 111978726A has epoxy groups and unsaturated double bonds, can react with phenolic resin and maleimide resin at the same time to participate in resin curing, so that the thermosetting resin composition has high impact strength after curing, shows good toughness, and overcomes the defects of larger brittleness and insufficient toughness of the traditional bismaleimide resin cured product. The cured resin has high glass transition temperature (Tg of 300 ℃) and thermal stability, and can be used as matrix resin to be applied to the fields of electronic packaging molding compounds, copper-clad plates, high-temperature resistant adhesives and composite materials.
Based on the background, most patents have improved heat resistance and other properties by modifying the epoxy resin or otherwise altering the matrix resin material. In practice, the failure cause of the high temperature resistant composite insulating material does not necessarily need to pursue the performance of materials such as excessively high Tg, and the like, and the aging is also important in that the malignant cycle caused by pores or cracks is convenient. In general, technical achievements improved from the aspect of preparation technology at present, in the research of preparation and performance optimization of epoxy molding compound for electronic packaging, the influence on pores or gaps is discussed in aspects of cake density, raw material carrying gas, reaction production gas, material rheological property and pore relation, silica micropowder particle size and distribution and pore relation and the like, and finally, the problem that pores become nano-scale dispersed micropores in each in-situ is solved. The problem of improvement of its principle is also lacking.
The invention aims at solving the problem of improving the application performance such as heat resistance and the like by improving the preparation process.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides a high-temperature-resistant composite insulating column and a preparation method thereof, so as to overcome the technical problems in the prior related art.
The technical scheme of the invention is realized by carrying the specific curing accelerator on mesoporous silica and reinforcing and curing the actively induced fracture or weak adhesion in the curing process, so that the overall curing effect is ensured, the overall uniformity of the high-temperature-resistant composite insulating material is realized, the internal stress is uniformly distributed, the defects and singular points are avoided under the conditions of high temperature, skin effect and the like generated when the metal structure of the insulating column bears large current, and the problem of failure expansion of the traditional device caused by the weak link of the material is solved. The specific invention comprises the following steps:
A high temperature resistant composite insulating column comprises a high temperature resistant composite insulating material and a metal structural member.
Preferably, the high-temperature-resistant composite insulating material consists of epoxy resin, phenolic resin, inorganic filler, a curing accelerator, a mesoporous nano silicon dioxide reinforcing agent and an auxiliary additive.
Preferably, the metallic structure is made of gold, silver, copper, aluminum or alloys thereof, preferably copper-containing structures.
Preferably, the metal structural member is coated or bonded with the high temperature resistant composite insulating material.
Preferably, the cyclic pressure is applied by the deformation of the high-temperature-resistant composite insulating material during cladding or bonding.
The scheme also discloses a preparation method of the high-temperature-resistant composite insulating column, which comprises the following preparation steps:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
10 to 20 parts of epoxy resin, 5 to 10 parts of phenolic resin, 80 to 50 parts of inorganic filler, 0.05 to 0.5 part of curing accelerator, 0.5 to 1.5 parts of mesoporous nano silicon dioxide reinforcing agent and 0.1 to 2 parts of auxiliary additive;
S2: mixing material
Preparing the preparation raw materials according to a preset weight ratio, and uniformly mixing at a high speed to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder at the mixing temperature of 100-110 ℃, extruding at a high speed by the extruder, cooling, and crushing to prepare cakes or slicing and discharging;
s4: heating and solidifying
Putting a material cake or a slice into a pre-heated mold cavity, arranging a metal structural member in the pre-heated mold cavity, heating and curing at a constant heating speed, starting to apply periodic pressure when the initial temperature (125-160 ℃) reaches to stop when the cut-off temperature (140-170 ℃) reaches, and then maintaining the peak pressure until the curing temperature is reached, and then completing gel curing.
Preferably, the epoxy resin is one or more of o-cresol formaldehyde epoxy resin, polyaromatic ring epoxy resin and polyfunctional epoxy resin.
Preferably, the phenolic resin is one or more of linear phenolic resin, polyaromatic phenolic resin and polyfunctional phenolic resin.
More preferably, the matching combination of the epoxy resin and the phenolic resin is one of a combination of a multifunctional epoxy resin and a phenolic novolac resin and a combination of a multifunctional epoxy resin and a multifunctional phenolic novolac resin.
Preferably, the inorganic filler is one or more of crystal round-angle silica, fused spherical silica, spherical boron nitride, alumina and aluminum nitride.
More preferably, the particle size of the inorganic filler is 5 to 50. Mu.m.
Preferably, the curing accelerator is an organic phosphine compound, preferably one of triphenylphosphine-p-benzoquinone, tetraphenylphosphine-dihydroxynaphthalene, and tetraphenylphosphine-dihydroxydiphenylsulfone.
Preferably, the mesoporous nano silica reinforcing agent consists of coupling agent modified mesoporous nano silica with the particle size of 100-200 nm, the mesoporous aperture is 10-30 nm, and the reinforcing agent is loaded in the mesoporous.
More preferably, the reinforcing agent is one or more of methylimidazole and aminoimidazole, preferably one of aminoimidazole and methylimidazole.
More preferably, the coupling agent is one or more of silane, titanate, aluminum chelate and zirconium aluminum oxide, preferably one of KH550, KH560 and KH 570.
More preferably, the nano silicon dioxide reinforcing agent is prepared by high-speed mixing with the reinforcing agent under the dispersion condition of the silane coupling agent and drying under the negative pressure condition of 0.8-1.2 atm.
Preferably, the preparation raw materials of the high-temperature-resistant composite insulating material further comprise one or a combination of more of 0.5-1.5 parts of coupling agent, 1-2 parts of flame retardant, 0.2-0.5 parts of colorant, 0.3-0.5 parts of release agent and 0.2-1.5 parts of stress modifier.
Preferably, the release agent is one or more of palm wax, polyethylene wax and polyamide wax, and is preferably palm wax.
Preferably, the flame retardant is one or a combination of more of phosphorus flame retardant, hydroxide flame retardant, preferably phosphate and aluminum hydroxide.
Preferably, the stress modifier is one of silicone oil, silicone resin and silicone rubber, and is preferably silicone oil.
Preferably, the colorant is one of carbon black with the particle size of 20-30 nm and black nano-silica with the particle size of 20-30 nm, and is preferably carbon black.
Preferably, the periodic pressure peak value is 12-16 Mpa, the valley value is 6-8 Mpa, and the periodic frequency is 2-8 times/min.
More preferably, the ratio of the periodic pressure peaks to the periodic pressure peaks is 2:1.
More preferably, the cycle frequency is 4 to 6 times/min.
Preferably, the initial temperature of the preheating mold cavity is 105-115 ℃, the constant temperature rising speed is 4-12 ℃/min, the initial temperature is 125-160 ℃, the cut-off temperature is 140-170 ℃, and the curing temperature is 160-200 ℃.
More preferably, the constant temperature rise rate is 6 to 10 ℃/min.
More preferably, the starting temperature and the cutoff temperature are determined according to the heat flow rate of the cake, wherein the temperature at which the heat flow rate rises to-0.1 w/g is the starting temperature, and the temperature at which the heat flow rate rises to 0.1w/g is the cutoff temperature during the heating and curing process.
More preferably, the measurement of the heat flow rate is obtained under non-periodic pressurization and at a temperature rise of 10 ℃/min.
The invention has the beneficial effects that:
Compared with the prior art, the invention improves the high-temperature-resistant composite insulating column and the preparation method thereof, and actively induces the deformation of weak bonds or weak adhesion parts through periodical pressure in a specific material gelation stage based on the use premise of normal curing accelerators, thereby releasing the special curing accelerators such as aminoimidazole loaded by mesoporous silica and the like for promoting the curing level of the weak bonds or weak adhesion parts, and realizing the homogenization of the integral performance of the high-temperature-resistant composite insulating material. Thereby solving the problem that defects of weak bonds or weak adhesion parts are easy to expand when the binding force of the material is uneven;
Furthermore, the high-temperature resistant composite insulating material of the amino imidazole loaded by the mesoporous silica can gradually release the amino imidazole when the surface of the composite insulating material is stimulated by conditions such as high current, high temperature and the like, so that the corrosion part is repaired to a certain extent, and the service life of the composite insulating material is prolonged;
Furthermore, the multifunctional epoxy resin-linear phenolic resin system selected by the invention can realize high performance such as Tg (glass transition temperature) exceeding 220 ℃ and meet the use of conditions such as heavy current, high temperature and the like through the technical scheme of the invention.
Drawings
For a clearer description of embodiments of the invention or of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are some embodiments of the invention, from which, without inventive effort, other drawings can be obtained for a person skilled in the art;
FIG. 1 is a schematic diagram of the present invention in terms of preparation pressure as a function of temperature;
FIG. 2 is a schematic representation of the production pressure of the present invention as a function of time;
FIG. 3 is a schematic diagram of the initial and cut-off temperature settings according to the present invention;
FIG. 4 is a schematic side view of a high temperature resistant composite insulating column according to the present invention;
fig. 5 is a schematic structural top view of a high temperature resistant composite insulating column according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
Examples 1 to 6 of the present invention are specifically shown in example 7 of the present invention, in order to perform material performance tests, without coating or bonding of the high temperature resistant composite material and the metal structural member.
Example 1, a method for preparing a high temperature resistant composite insulation material, comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
10 parts of multifunctional epoxy resin, 5 parts of linear phenolic resin, 60 parts of crystalline silica microspheres, 15 parts of fused silica microspheres, 0.35 part of curing accelerator, 0.5 part of release agent and 0.5 part of mesoporous nano silica reinforcing agent;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
The columnar cake with the diameter of 20mm and 40mm is placed into a closed mold cavity with the temperature of 110 ℃ preheated with the diameter of 20mm and 20mm, heating is carried out at the heating speed of 6 ℃/min, periodic pressure pressurization is carried out for 6 times/min at 138 ℃, the pressure valley value is 8Mpa, the peak value is 16Mpa, and the temperature is stopped at 150 ℃. I.e. 12 pressure changes were completed. Then maintaining 16Mpa pressure until the temperature rises to 175 ℃ to finish gel curing, and after demoulding, curing for 2 hours at 175 ℃. The starting and stopping temperatures are in the interval from-0.1 to 0.1w/g of the heat flow rate of example 1 in FIG. 3.
The preparation of the mesoporous nano silicon dioxide reinforcing agent comprises the following steps:
(A) 2g of silane coupling agent is hydrolyzed for 30min under the condition of 30 ℃ with absolute ethyl alcohol (50 ml), 10g of mesoporous nano silicon dioxide is added into absolute ethyl alcohol solution (60 ml) to be mixed, and the mixture is stirred and reacted for 30min at the speed of 300r/min at the temperature of 90 ℃ to obtain an intermediate product, namely the mesoporous nano silicon dioxide modified by the silane coupling agent, and the surface amino ion property is obtained;
(B) Mixing the intermediate product obtained in the step (A) with 2g of a reinforcing agent, and stirring and reacting for 1.5 hours at 70 ℃ for 200r/min to obtain a functional mesoporous nano silicon dioxide mixed solution with a load curing accelerator;
(C) And (3) drying and separating the mixed solution obtained in the step (B) under the condition of 0.9atm negative pressure.
The multifunctional epoxy resin used in the preparation of the embodiment is Japanese chemical EPPN H, the linear phenolic resin is vinca chemical PN5080, the particle size of the inorganic filler is 15um, the curing accelerator is triphenylphosphine, the particle size of the mesoporous nano silicon dioxide is 200nm, the pore diameter is 15nm, the release agent is palm wax, the silane coupling agent is KH550, and the reinforcing agent is aminoimidazole. The amino imidazole is more suitable for being combined with mesoporous nano silicon dioxide modified by a silane coupling agent, so as to ensure the delayed expression of the thermal latent function.
Example 2a method of preparing a high temperature resistant composite insulation material comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
15 parts of multifunctional epoxy resin, 8 parts of linear phenolic resin, 70 parts of crystalline silica microspheres, 10 parts of fused silica microspheres, 0.4 part of curing accelerator, 1 part of coupling agent, 0.3 part of release agent, 1 part of flame retardant, 0.2 part of colorant, 0.5 part of stress modifier and 1.5 parts of mesoporous nano silica reinforcing agent;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
The columnar cake with the diameter of 20mm and 40mm is placed into a closed mold cavity with the temperature of 110 ℃ preheated with the diameter of 20mm and 20mm, heating is carried out at the heating speed of 5 ℃ per minute, periodic pressure pressurization is carried out for 6 times per minute at 155 ℃, the pressure valley value is 7Mpa, the peak value is 14Mpa, and the temperature is stopped at 165 ℃. I.e. 12 pressure changes were completed. Then maintaining the pressure of 14Mpa, heating to 180 ℃ for gel curing, demoulding and then post-curing at 175 ℃ for 2 hours. The starting and stopping temperatures are shown in the interval of-0.1 to 0.1w/g of the heat flow rate of example 2 in FIG. 3.
The preparation of the mesoporous nano silicon dioxide reinforcing agent comprises the following steps:
(A) 2g of silane coupling agent is hydrolyzed for 30min under the condition of 30 ℃ with absolute ethyl alcohol (50 ml), 9g of mesoporous nano silicon dioxide is added into absolute ethyl alcohol solution (60 ml) to be mixed, and the mixture is stirred and reacted for 30min at the speed of 300r/min under the temperature of 100 ℃ to obtain an intermediate product, namely the mesoporous nano silicon dioxide modified by the silane coupling agent, and the surface amino ion property is obtained;
(B) Mixing the intermediate product obtained in the step (A) with 3g of a reinforcing agent, and stirring and reacting for 1h at 80 ℃ for 200r/min to obtain a functional mesoporous nano silicon dioxide mixed solution with a load curing accelerator;
(C) And (3) drying and separating the mixed solution obtained in the step (B) under the condition of 1.0atm negative pressure.
The multifunctional epoxy resin used in the preparation of the embodiment is Japanese chemical EPPN H, the linear phenolic resin is vinca chemical PN5080, the particle size of the inorganic filler is 15um, the curing accelerator is tetraphenylphosphine-dihydroxynaphthalene, the particle size of the mesoporous nano silicon dioxide is 150nm, the pore diameter is 10nm, the release agent is palm wax, the silane coupling agent is KH570, the reinforcing agent is methylimidazole, the colorant is Mitsubishi chemical MA600, the flame retardant is phosphate, and the stress modifier is silicone oil. This example adds additives to improve the stress, flame retardant properties of conventional systems. Wherein the coupling agent in the raw material for preparing the high-temperature resistant composite insulating material is KH570.
Example 3 a method of preparing a high temperature resistant composite insulation material comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
15 parts of multifunctional epoxy resin, 8 parts of multifunctional phenolic resin, 70 parts of crystalline silica microspheres, 10 parts of fused silica microspheres, 0.4 part of curing accelerator, 0.5 part of coupling agent, 0.3 part of release agent, 1 part of flame retardant, 0.2 part of colorant, 0.5 part of stress modifier and 1.5 parts of mesoporous nano silica reinforcing agent;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
The columnar cake with the diameter of 20mm and 40mm is placed into a closed mold cavity with the temperature of 110 ℃ preheated with the diameter of 20mm and 20mm, heating is carried out at the heating speed of 10 ℃/min, periodic pressure pressurization is carried out for 8 times/min at 160 ℃, the pressure valley value is 7Mpa, the peak value is 14Mpa, and the temperature is stopped at 170 ℃. I.e. 8 pressure changes were completed. Then maintaining the pressure of 14Mpa, heating to 180 ℃ for gel curing, demoulding and then post-curing at 175 ℃ for 2 hours. The starting and stopping temperatures are shown in the interval of-0.1 to 0.1w/g of the heat flow rate of example 3 in FIG. 3.
The preparation of the mesoporous nano silicon dioxide reinforcing agent comprises the following steps:
(A) 2g of silane coupling agent is hydrolyzed for 30min under the condition of 30 ℃ with absolute ethyl alcohol (50 ml), 9g of mesoporous nano silicon dioxide is added into absolute ethyl alcohol solution (60 ml) to be mixed, and the mixture is stirred and reacted for 30min at the speed of 300r/min under the temperature of 100 ℃ to obtain an intermediate product, namely the mesoporous nano silicon dioxide modified by the silane coupling agent, and the surface amino ion property is obtained;
(B) Mixing the intermediate product obtained in the step (A) with 3g of a reinforcing agent, and stirring and reacting for 1h at 80 ℃ for 200r/min to obtain a functional mesoporous nano silicon dioxide mixed solution with a load curing accelerator;
(C) And (3) drying and separating the mixed solution obtained in the step (B) under the condition of 1.0atm negative pressure.
The multifunctional epoxy resin used in the preparation of the embodiment is Japanese chemical EPPN H, the multifunctional phenolic resin is Ming He chemical MEH7500, the particle size of the inorganic filler D50 is 15um, the curing accelerator is tetraphenylphosphine-dihydroxynaphthalene, the particle size of the mesoporous nano silicon dioxide D50 is 150nm, the pore diameter is 10nm, the release agent is palm wax, the silane coupling agent is KH550, the reinforcing agent is methylimidazole, the colorant is Mitsubishi chemical MA600, the flame retardant is phosphate, and the stress modifier is silicone oil. Wherein the coupling agent in the raw material for preparing the high-temperature resistant composite insulating material is KH550.
Example 4a method of preparing a high temperature resistant composite insulation material comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
10 parts of multifunctional epoxy resin, 5 parts of linear phenolic resin, 60 parts of crystalline silica microspheres, 15 parts of fused silica microspheres, 0.35 part of curing accelerator, 1 part of coupling agent, 0.5 part of release agent, 1 part of flame retardant, 0.2 part of colorant, 0.5 part of stress modifier and 0.5 part of modified mesoporous nano silica;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: stepped temperature rise complete solidification
And (3) placing the columnar cake with the diameter of phi of 20mm and 40mm into a closed mold cavity with the diameter of phi of 20mm and 20mm preheated at 110 ℃, keeping the pressure of 16Mpa, and curing for 40s after the temperature is raised to 175 ℃, so as to finish initial curing, and curing for 2h after demolding and the temperature is 175 ℃. The starting and stopping temperatures are shown in FIG. 3 in the interval of-0.1 to 0.1w/g of the heat flow rate of example 4, in particular at 140℃and 160 ℃.
The preparation of the mesoporous nano silicon dioxide reinforcing agent comprises the following steps:
(A) 2g of silane coupling agent is hydrolyzed for 30min under the condition of 30 ℃ with absolute ethyl alcohol (50 ml), 10g of mesoporous nano silicon dioxide is added into absolute ethyl alcohol solution (60 ml) to be mixed, and the mixture is stirred and reacted for 30min at the speed of 300r/min at the temperature of 90 ℃ to obtain an intermediate product, namely the mesoporous nano silicon dioxide modified by the silane coupling agent, and the surface amino ion property is obtained;
(B) And (3) drying and separating the mixed solution obtained in the step (A) under the condition of 0.9atm negative pressure.
The multifunctional epoxy resin used in the preparation of the embodiment is Japanese chemical EPPN H, the linear phenolic resin is vinca chemical PN5080, the particle size of the inorganic filler D50 is 15um, the curing accelerator is triphenylphosphine, the particle size of the mesoporous nano silicon dioxide D50 is 200nm, the pore diameter is 15nm, the release agent is palm wax, and the silane coupling agent is KH560. The mesoporous nano silicon dioxide modified by the silane coupling agent has amino function, is also suitable for being combined with epoxy resin, and increases the interfacial binding force of organic matters and inorganic matters, wherein the coupling agent in the raw material for preparing the high-temperature resistant composite insulating material is KH560.
Example 5 a method of preparing a high temperature resistant composite insulation material comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
16 parts of multifunctional epoxy resin, 8 parts of linear phenolic resin, 65 parts of crystalline silica microspheres, 10 parts of fused silica microspheres, 0.35 part of curing accelerator, 0.5 part of coupling agent, 0.5 part of release agent, 1 part of flame retardant, 0.2 part of colorant and 0.5 part of stress modifier;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
And (3) placing the columnar cake with the diameter of phi of 20mm and 40mm into a closed mold cavity with the diameter of phi of 20mm and 20mm preheated at 110 ℃, keeping the pressure of 16Mpa, and curing for 40s after the temperature is raised to 175 ℃, so as to finish initial curing, and curing for 2h after demolding and the temperature is 175 ℃. The starting and stopping temperatures are shown in FIG. 3 in the range of-0.1 to 0.1w/g for the heat flow rate of example 5, specifically 125℃and 145 ℃.
The multifunctional epoxy resin used in the preparation of this example was Japanese chemical EPPN H, the phenolic novolac resin was vinca chemical PN5080, the inorganic filler D50 particle size was 15um, the curing accelerator was triphenylphosphine, the release agent was palm wax, the colorant was Mitsubishi chemical MA600, the flame retardant was phosphate, the stress modifier was silicone oil, and the coupling agent was KH550.
Example 6 a method of preparing a high temperature resistant composite insulation material comprising the steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
16 parts of polyaromatic epoxy resin, 8 parts of polyaromatic phenolic resin, 65 parts of crystalline silica microspheres, 10 parts of fused silica microspheres, 0.35 part of curing accelerator, 0.5 part of coupling agent, 0.5 part of release agent, 1 part of flame retardant, 0.2 part of colorant and 0.5 part of stress modifier;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
And (3) placing the columnar cake with the diameter of phi of 20mm and 40mm into a closed mold cavity with the diameter of phi of 20mm and 20mm preheated at 110 ℃, keeping the pressure of 16Mpa, and curing for 40s after the temperature is raised to 175 ℃, so as to finish initial curing, and curing for 2h after demolding and the temperature is 175 ℃. The starting and stopping temperatures are shown in FIG. 3 in the interval of-0.1 to 0.1w/g of the heat flow rate of example 5, specifically 125℃and 155 ℃.
The polyaromatic epoxy resin used in the preparation of this example was Japanese chemical EPPN H, the polyaromatic phenolic resin was vinca chemical PN5080, the particle size of the inorganic filler D50 was 15um, the curing accelerator was triphenylphosphine, the mold release agent was palm wax, the colorant was Mitsubishi chemical MA600, the flame retardant was phosphate, the stress modifier was silicone oil, and the coupling agent was KH550.
The starting and stopping temperatures of 125℃and 155℃were defined by the heat flow rate of the resin material of example 6, the temperature difference was 30℃and the periodic pressurization was carried out 3 times per minute at a temperature rise rate of 12℃per minute, as shown in FIG. 1, which is a schematic diagram showing the change of the production pressure with temperature according to the present invention, and since the temperature difference range of other examples was small, this example was used as an illustration, irrespective of other results. FIG. 2 is a schematic representation of the process pressure of the present invention over time, and it can be seen that a rheologically periodic pressurization run of about 2 minutes is provided.
Examples 1 to 6 are not provided with metal supports or connectors for performance measurement, so that high temperature resistant composite insulating materials for more application fields are not completely prepared. However, one of copper, silver, aluminum and alloys thereof can be placed in the preheating mould cavity as a support or a connecting piece, preferably a copper-containing support or connecting piece.
Example 7, a mesoporous nanosilica reinforcing agent was prepared comprising the steps of:
(A) 2g of silane coupling agent is hydrolyzed for 30min under the condition of 30 ℃ with absolute ethyl alcohol (50 ml), 9g of mesoporous nano silicon dioxide is added into absolute ethyl alcohol solution (60 ml) to be mixed, and the mixture is stirred and reacted for 30min at the speed of 300r/min under the temperature of 100 ℃ to obtain an intermediate product, namely the mesoporous nano silicon dioxide modified by the silane coupling agent, and the surface amino ion property is obtained;
Mixing the intermediate product obtained in the step (A) with 3g of a reinforcing agent, and stirring and reacting for 1h at 80 ℃ for 200r/min to obtain a functional mesoporous nano silicon dioxide mixed solution with a load curing accelerator;
(C) And (3) drying and separating the mixed solution obtained in the step (B) under the condition of 1.0atm negative pressure.
Preparing a high-temperature-resistant composite insulating column, which comprises the following steps of:
s1: the high-temperature-resistant composite insulating material comprises the following preparation raw materials in parts by weight:
12 parts of multifunctional epoxy resin, 6 parts of linear phenolic resin, 70 parts of crystalline silica microspheres, 10 parts of fused silica microspheres, 0.4 part of curing accelerator, 0.8 part of coupling agent, 0.3 part of release agent, 1 part of flame retardant, 0.2 part of colorant, 0.5 part of stress modifier and 1.5 parts of mesoporous nano silica reinforcing agent;
S2: mixing material
Preparing the preparation raw materials according to preset weight parts, and mixing at a high speed of 800r/min for 10min to obtain a pre-mixture;
s3: rubber mixing
Mixing the pre-mixture in an extruder, extruding at the mixing temperature of 105 ℃ and the rotating speed of 750r/min, cooling and crushing to prepare a cake;
s4: heating and solidifying
The method comprises the steps of placing a columnar material cake with the diameter of phi 17 mm and the diameter of 50mm into a closed mold cavity with the temperature of phi 18 mm and the diameter of 25mm, which is preheated at 110 ℃, wherein an internal thread copper structural member with the length of 15mm is arranged in the mold cavity, and the external diameter structural member phi 10mm and the internal diameter phi 8 mm of the structural member are arranged, and the internal thread depth is 10mm. Heating at a heating rate of 5 deg.C/min, and periodically pressurizing at 155 deg.C for 8 times/min with a pressure valley of 7Mpa and a peak of 14Mpa to 165 deg.C. I.e. 16 pressure changes are completed. Then maintaining the pressure of 14Mpa, heating to 180 ℃ for gel curing, demoulding and then post-curing at 175 ℃ for 2 hours. The starting and stopping temperatures are shown in the interval of-0.1 to 0.1w/g of the heat flow rate of example 2 in FIG. 3.
The multifunctional epoxy resin used in the preparation of the embodiment is Japanese chemical EPPN H, the linear phenolic resin is vinca chemical PN5080, the particle size of the inorganic filler is 15um, the curing accelerator is tetraphenylphosphine-dihydroxynaphthalene, the particle size of the mesoporous nano silicon dioxide is 150nm, the pore diameter is 10nm, the release agent is palm wax, the silane coupling agent is KH550, the reinforcing agent is methylimidazole, the colorant is Mitsubishi chemical MA600, the flame retardant is phosphate, and the stress modifier is silicone oil. This example adds additives to improve the stress, flame retardant properties of conventional systems. Wherein the coupling agent in the raw material for preparing the high-temperature resistant composite insulating material is KH550.
The structure of the prepared high-temperature resistant composite insulating column is shown in fig. 4 and 5. The surface of the copper structural member (the insert 1 and the insert 2 are formed together in the side view schematic diagram of fig. 4) is also provided with protrusions, so that the binding force between the high-temperature-resistant insulating material and the copper structural member is increased. The high temperature resistant composite insulating material coats part of the copper structural member, and the reserved internal thread (shown by the smallest inner diameter circle and the second smallest inner diameter semicircle in the top view schematic diagram of fig. 5) provides an external current connection port. When in use, the interface between the high-temperature resistant composite insulating material and the copper structural member is under the high-current working condition, is influenced by skin effect, has high heat aggregation degree, and has higher requirement on heat resistance. The Tg of the high temperature resistant composite insulating material adopted in the embodiment exceeds 220 ℃, td exceeds 340 ℃, bending strength exceeds 180MPa, and the difference of torsion, tensile force and shearing force of the material in different axial directions is less than 3%. And thus more suitable for extreme condition applications.
Comparative example 1 BMC bulk molding compound was prepared in a conventional manner.
In examples 1 to 6, a high-temperature resistant composite insulating material is prepared by adopting a 110 ℃ preheating closed type mold cavity with a cylindrical cavity of phi 20mm x 20mm, and the preheating temperature can be selected to be 105-115 ℃. Relevant tests were carried out on the high temperature resistant composite insulating material and the intermediate prepared in the above examples. The test criteria are as follows:
(1) Spiral flow length: taking 15g of a resin composition sample to be tested according to the method shown in SJ/T11197-2013 high-temperature resistant composite insulating material, injecting the resin composition sample into a spiral flow metal mold of EMMI-1-66 on a transfer molding press to measure the spiral flow length of the sample, setting the temperature of the upper mold and the lower mold to be 175+/-3 ℃, the transfer pressure to be (125 kg+/-5 kg) cm -2, the transfer speed to be (6.0 cm+/-0.1 cm) s -1, curing for 120s, taking out the sample from the metal mold, reading the spiral flow length, testing the same sample for three times, taking the average value of the sample, and dividing the transfer pressure by the injection molding head area;
(2) Gel time: according to the method shown in SJ/T11197-2013 high temperature resistant composite insulating material, an electric heating plate is heated to 175+/-2 ℃, 0.5g of a resin composition sample is placed on the electric heating plate, the flattening area of the sample is about 5cm 2, melting starts to time, a needle stirring tip or a flat shovel is used for stirring, powder gradually becomes gel (the sample cannot be pulled into filaments) as an end point, the required time is read out, the operation is repeated twice, and the average value is obtained;
(3) Glass transition temperature Tg: the resin composition was molded using an injection molding machine at 175 ℃ and then post-cured, provided that: 2 hours at 175℃and 2 hours at 200 ℃; then using a differential scanning calorimeter to measure according to the national standard of the people's republic of China GB/T19466.2-2004 section 2 of the Plastic Differential Scanning Calorimeter (DSC): measurement of glass transition temperature Tg;
(4) Flexural strength, flexural modulus: the resin composition was molded using an injection molding machine at 175 ℃ and then post-cured, provided that: 2 hours at 175℃and 2 hours at 200 ℃; then testing according to national standard GB/T9341-2008 "determination of Plastic bending Property" of the people's republic of China;
(5) Initial thermal decomposition temperature (Td): the resin composition was molded using an injection molding machine at 175 ℃ and then post-cured, provided that: 2 hours at 175℃and 2 hours at 200 ℃; then taking about 5mg of sample, using a thermal weight loss analyzer, heating from room temperature to 800 ℃ at a heating rate of 10 ℃/min under nitrogen atmosphere, and taking the corresponding temperature (Td) when the sample weight loss is 1wt% as an initial thermal decomposition temperature to evaluate the thermal stability of the resin composition after curing;
(6) Coefficient of thermal expansion: the resin composition was molded using an injection molding machine at 175 ℃ and then post-cured, provided that: 175 ℃ for 2 hours and 220 ℃ for 2 hours; then according to the national standard of the people's republic of China GB/T36800.2-2018 section 2 of the Plastic thermo-mechanical analysis method (TMA): measurement of linear thermal expansion coefficient and glass transition temperature;
(7) DSC profile: and (3) carrying out rubber mixing 4 min on an open mill at 105 ℃, then crushing and sieving to obtain the refined high-temperature-resistant composite insulating material. Placing about 10 mg samples in a sample tray, protecting the samples by nitrogen, and obtaining a curing curve through a differential thermal scanner at a heating rate of 10 ℃/min;
(8) And testing torsion, tensile force and shearing force after ageing the high-temperature-resistant composite insulating material for 4 hours at 200 ℃. The test points are 2 points in the same axial direction at the same position.
The results of the performance tests of examples 1 to 6 and comparative example 1 are shown in Table 1 below, and the results of the performance tests after aging at 200℃for 4 hours are shown in Table 2 below.
TABLE 1
As can be seen from table 1, the curing time of the EMC plastic is slightly longer than that of the BMC plastic. However, due to the combination of epoxy resin and phenolic resin and the combined action of accelerator, inorganic filler and the like, the prepared high-temperature-resistant composite insulating material has higher bending strength and breaking deflection and shows good toughness. The mesoporous nano silicon dioxide reinforcing agent introduced in the preparation process and the technology for eliminating weak adhesion by periodic pressure active induction in the melting process show obvious strength increasing tendency. The combination of the multifunctional epoxy resin and the phenolic novolac resin is the best combination of the multifunctional epoxy resin and the phenolic novolac resin in example 2, but the pyrolysis temperature and the flexural strength are compared with those of the multifunctional epoxy resin and the phenolic novolac resin in example 3. Compared with the technical process of removing mesoporous nano silicon dioxide reinforcing agent and actively inducing periodic pressure in the melting process in the embodiment 5, the performance is reduced by 15-25%, and the difference is obvious.
TABLE 2
As can be seen from Table 2, after aging, the test differences in different axial directions of torsion, tension and shear force of comparative examples 1, 5 and 6 are significantly discrete and nonuniform compared with examples 1-4, the degree of larger discrete exceeds 15%, and the degree of discrete optimal material properties of the invention is lower than 3%. The preparation method provided by the invention has the advantages that the consistency of the overall performance of the product is obviously improved, and the plastic package material provided by the invention is more suitable for weakening the reliability defect caused by extreme conditions.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
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| CN105968808A (en) * | 2016-07-05 | 2016-09-28 | 苏州大学 | Self-repair resin-based composite material and preparation method thereof |
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| CN107629411A (en) * | 2017-09-27 | 2018-01-26 | 桂林理工大学 | The preparation method of hollow mesoporous silica microsphere reinforced epoxy composite |
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