CN116987271A - Epoxy resin toughening agent, epoxy resin composition, and preparation method and application thereof - Google Patents
Epoxy resin toughening agent, epoxy resin composition, and preparation method and application thereof Download PDFInfo
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- CN116987271A CN116987271A CN202310801559.3A CN202310801559A CN116987271A CN 116987271 A CN116987271 A CN 116987271A CN 202310801559 A CN202310801559 A CN 202310801559A CN 116987271 A CN116987271 A CN 116987271A
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- epoxy resin
- toughening agent
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- bisphenol
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 143
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 143
- 239000012745 toughening agent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000013530 defoamer Substances 0.000 claims description 14
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 13
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 10
- -1 alkyl glycidyl ether Chemical compound 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 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 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920006295 polythiol Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- NOYXQFBTCCSKQG-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)cyclohexyl]oxymethyl]oxirane Chemical compound C1OC1COC1CCCCC1OCC1CO1 NOYXQFBTCCSKQG-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 2
- 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004382 potting Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 description 22
- 239000010935 stainless steel Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 16
- 238000011056 performance test Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004848 polyfunctional curative Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 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 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- LDPVFXYCGMBWJO-UHFFFAOYSA-N 3a,7,7,7a-tetramethyl-5,6-dihydro-4h-2-benzofuran-1,3-dione Chemical compound C1CCC(C)(C)C2(C)C(=O)OC(=O)C21C LDPVFXYCGMBWJO-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 101100008681 Glycine max DHPS1 gene Proteins 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004017 vitrification Methods 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The application discloses an epoxy resin toughening agent, an epoxy resin composition, a preparation method and application thereof, belonging to the technical field of high polymer materials, wherein the structural formula of the epoxy resin toughening agent is shown as formula I, and R is CH 3 Phenyl, CF 3 Or C 2 H 5 The method comprises the steps of carrying out a first treatment on the surface of the m=60 to 100, n=0 to 20; the main chain of the epoxy resin toughening agent contains an organosilicon long chain, an organosilicon short chain and a benzene ring, and the side chain contains an epoxy group, so that the epoxy resin toughening agent has good compatibility with an epoxy resin system, and the organosilicon main chain has good fluidity and is easy to mix with the epoxy resin for processing; can effectively improve the impact property, shearing property and tensile property of the epoxy resin, achieves the purposes of toughening and reinforcing, and simultaneously has the thermal stability, water resistance and aging resistanceThe chemical property is not reduced, and the application range of the epoxy resin is further widened;
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to an epoxy resin toughening agent, an epoxy resin composition, a preparation method and application thereof.
Background
Epoxy resins have been widely used as thermosets, adhesives, coatings, electronic packaging, composites and other engineering materials. Because of its highly crosslinked network structure and highly rigid epoxy resin, it generally exhibits high mechanical strength, good dimensional stability, but poor crack and impact resistance. It is important for many applications, such as wind turbine blades, etc., to increase their long term reliability of epoxy resins and their composites. In order to meet the higher demands, development of high-performance epoxy resins having both excellent rigidity and good toughness is becoming a research hotspot, and a problem to be solved urgently in industrial development.
The toughening approaches of the epoxy resin mainly include one of rubber elastomer toughening, thermoplastic resin toughening and rigid particle toughening, and in recent years, the introduction of soft-segment organic silicon toughening epoxy resin becomes a research hot spot. For example, linear epoxy-functional and aminated Polydimethylsiloxane (PDMS) is commonly used for toughening epoxy resins, where toughness can be improved but other mechanical properties are greatly reduced due to phase separation caused by very poor compatibility of silicones and epoxy resins. In addition, the special structure such as cage, ladder and hyperbranched polysiloxane can be further functionalized by adding various functional organic groups, for example, epoxy functional cage polyhedral oligomeric silsesquioxane (POSS) is utilized to strengthen epoxy resin, rigid silicon cage provides strength, functional groups strengthen interaction between the silicon cage and an epoxy curing system to provide proper toughness, and heat resistance is improved. Their synthesis and isolation are rather complex, very costly, limiting their mass production and thus greatly limiting their potential of use.
In view of the above problems, how to provide a toughening agent capable of improving toughness of epoxy resins is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide an epoxy resin toughening agent, an epoxy resin composition, a preparation method and application thereof, wherein the epoxy resin toughening agent can effectively improve the impact performance, the shearing performance and the tensile performance of epoxy resin, achieves the purposes of toughening and reinforcing, and further widens the application range of the epoxy resin.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
an epoxy resin toughening agent has a structural formula shown in formula I:
wherein R is CH 3 Phenyl, CF 3 Or C 2 H 5 ；
m＝60～100，n＝0～20。
The main chain of the epoxy resin toughening agent contains an organosilicon long chain, an organosilicon short chain and a benzene ring, and the side chain contains an epoxy group, so that the epoxy resin toughening agent has good compatibility with an epoxy resin system, and the organosilicon main chain has good fluidity and is easy to mix with the epoxy resin for processing; the impact performance, the shearing performance and the tensile performance of the epoxy resin can be effectively improved, the purposes of toughening and reinforcing are achieved, meanwhile, the thermal stability, the water resistance and the ageing resistance of the material are not reduced, and the application range of the epoxy resin is further widened.
The molecular weight of the epoxy resin toughening agent is high and reaches 4-8 ten thousand, the viscosity is 3000-5000 cps, and the epoxy value is 0.2-0.35.
The epoxy resin toughening agent can solve the problems that toughening particles in physical toughening are difficult to control at a small level, the particle size is unstable, and the dispersing is difficult when the toughening particles are matched with epoxy resin for use, and the toughening agent has low viscosity although the molecular weight is high, so that the problems of high viscosity, large addition amount and environmental pollution caused by solvents in the use process are avoided.
The epoxy resin toughening agent and the epoxy component participate in the curing reaction together to form a uniformly dispersed cross-linking structure, so that the service life is longer, and the obvious reduction of the mechanical property of the system caused by adopting a method for controlling the non-uniformity of the cross-linking state of molecules to form a structure favorable for plastic deformation to realize toughening is avoided.
The application also provides a preparation method of the epoxy resin toughening agent, which comprises the following steps:
stirring diallyl bisphenol A epoxy resin, hydrogen terminated silicone oil and a catalyst uniformly in the presence of a solvent, reacting for 0.5-4 h at 60-75 ℃, adding tetramethyl dihydro disiloxane, performing chain extension reaction for 0.5-6 h at 75-85 ℃, and removing the solvent to obtain the epoxy resin toughening agent.
As a preferred embodiment of the application, the structural formula of the hydrogen-terminated silicone oil is shown as formula II:
wherein R is CH 3 Phenyl, CF 3 Or C 2 H 5 。
As a preferred embodiment of the present application, the hydrogen content of the hydrogen terminated silicone oil is 0.05% to 0.18%.
Wherein the hydrogen content of the hydrogen terminated silicone oil used in the examples is 0.18%, and R is methyl.
As a preferred embodiment of the application, the mass ratio of the diallyl bisphenol A epoxy resin, the hydrogen terminated silicone oil, the catalyst and the tetramethyl dihydro disiloxane is (20-80): (1-6): (0.1-0.6): (10-40).
As a preferred embodiment of the present application, the solvent includes at least one of toluene, isopropyl alcohol, xylene, and acetone.
As a preferred embodiment of the present application, the catalyst comprises a platinum catalyst.
As a preferred embodiment of the application, the structural formula of the diallyl bisphenol A epoxy resin is shown as formula III:
as a preferred embodiment of the present application, the preparation method of the diallyl bisphenol A epoxy resin comprises the following steps:
stirring allyl bisphenol A, a phase transfer catalyst and epichlorohydrin at 75-90 ℃ for reaction for 1-6 hours, cooling to 55-70 ℃, adding sodium hydroxide solution for reaction for 1-4 hours, filtering, rotary evaporating, adding sodium hydroxide solution for reaction for 1-4 hours at 80-90 ℃, washing, extracting toluene, and distilling to obtain diallyl bisphenol A epoxy resin.
The reaction equation involved in the diallyl bisphenol A epoxy resin and the epoxy resin toughening agent of the application is as follows:
Step 1：Synthesis of DADGEBA
as a preferred embodiment of the present application, the mass ratio of the allyl bisphenol A, the phase transfer catalyst and the epichlorohydrin is (40 to 80): (0.1-0.5): (80-120).
As a preferred embodiment of the present application, the phase transfer catalyst comprises tetramethylammonium bromide.
As a preferred embodiment of the present application, the sodium hydroxide solution is 2 to 50wt% sodium hydroxide solution.
The application also provides an epoxy resin composition, which comprises a component A and a component B;
the component A comprises the following components in parts by mass: 60-80 parts of epoxy resin and 5-25 parts of epoxy resin toughening agent;
the component B comprises the following components in parts by mass: 85-95 parts of curing agent and 3-7 parts of accelerator;
the epoxy resin toughening agent is the epoxy resin toughening agent shown in the formula I or the epoxy resin toughening agent prepared by the preparation method.
As a preferred embodiment of the present application, the a component further comprises the following components in parts by mass: 5 to 10 parts of diluent and 0.3 to 1 part of defoamer.
As a preferred embodiment of the application, the mass ratio of the component A to the component B is (1-8): 1.
as a preferred embodiment of the present application, the epoxy resin includes at least one of bisphenol a type, bisphenol F type, and alicyclic epoxy resin.
As a preferred embodiment of the present application, the diluent is at least one of C12-C14 alkyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, benzyl alcohol, phenethyl alcohol, nonylphenol, propylene carbonate, trimethylolpropane triacrylate, diisopropyl methyl ether, toluene, xylene.
As a preferred embodiment of the present application, the antifoaming agent includes at least one of a polyacrylate type antifoaming agent and a modified silicone type antifoaming agent.
Illustratively, the defoamer includes at least one of BYK066N, BYKA, BYK141, BYK 354.
As a preferred embodiment of the present application, the curing agent comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, polyetheramine, diphenylmethanediamine, isophoronediamine and polyamide, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, polythiol.
As a preferred embodiment of the present application, the accelerators include bisphenol A, phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, cresol, tetrabutylammonium bromide.
In the present application, the method for preparing the epoxy resin composition is not limited to the present application, and those skilled in the art will know how to prepare the epoxy resin composition based on the disclosure of the present application.
Illustratively, the method of preparing the epoxy resin composition includes the steps of:
(1) Preparing a component A: uniformly stirring epoxy resin, an epoxy resin toughening agent, a diluent and a defoaming agent at 50-75 ℃ to obtain a component A;
(2) And (3) preparing a component B: and uniformly mixing the curing agent and the accelerator to obtain the component B.
(3) And uniformly mixing the component A and the component B to obtain the epoxy resin composition.
The epoxy resin composition can be applied to the fields of adhesives of electronic and electric appliances, coating adhesives of PCB circuit boards, pouring sealants, and electronic and electric appliance insulating paints, coatings, plastics and the like with higher requirements on toughness, mechanical properties and heat resistance, and has wide application prospects.
The application has the beneficial effects that: (1) The main chain of the epoxy resin toughening agent contains an organosilicon long chain, an organosilicon short chain and a benzene ring, and the side chain contains an epoxy group, so that the epoxy resin toughening agent has good compatibility with an epoxy resin system, and the organosilicon main chain has good fluidity and is easy to mix with the epoxy resin for processing; the impact performance, the shearing performance and the tensile performance of the epoxy resin can be effectively improved, the purposes of toughening and reinforcing are achieved, meanwhile, the thermal stability, the water resistance and the ageing resistance of the material are not reduced, and the application range of the epoxy resin is further widened. (2) The epoxy resin toughening agent can solve the problems that toughening particles in physical toughening are difficult to control at a small level, the particle size is unstable, and the dispersing is difficult when the toughening particles are matched with epoxy resin for use, and the toughening agent has low viscosity although the molecular weight is high, so that the problems of high viscosity, large addition amount and environmental pollution caused by solvents in the use process are avoided. (3) The epoxy resin toughening agent and the epoxy component participate in the curing reaction together to form a uniformly dispersed cross-linking structure, so that the service life is longer, and the obvious reduction of the mechanical performance of the system caused by adopting a method for controlling the non-uniformity of the cross-linking state of molecules to form a structure favorable for plastic deformation to realize toughening is avoided.
Drawings
FIG. 1 is a graph showing the characterization of diallyl bisphenol A epoxy resin of example 1.
Fig. 2 and 3 are characterization graphs of the epoxy toughening agent of example 2.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
In the present application, the specific dispersing and stirring treatment method is not particularly limited.
The reagents or apparatus used in the present application are conventional products commercially available without the manufacturer's knowledge.
Example 1
The preparation of the diallyl bisphenol A epoxy resin comprises the following steps:
60 parts of allyl bisphenol A (DAPA) and 0.2 part of TMAB are placed in a four-neck round-bottom flask equipped with a magnetic stirrer, a thermometer and a reflux condenser, 100 parts of epichlorohydrin is dripped into the flask, the mixture is heated to 85 ℃ and reacted for 2 hours, then the mixture is cooled to 60 ℃, 50 parts of 48wt% sodium hydroxide aqueous solution is dripped into the flask through a dripping funnel under stirring, after 2 hours of reaction at 60 ℃, sodium chloride generated in the reaction process is filtered, and the excessive epichlorohydrin is distilled off by a rotary evaporator; 50 parts of 5% strength by weight aqueous sodium hydroxide (wt.%: 5%) are then added to the crude product and reacted further for 2h at 85 ℃. The crude product was repeatedly washed with sodium dihydrogen phosphate and deionized water until pH 7, then extracted with toluene, and finally toluene and the remaining water were separated by vacuum distillation to give allyl bisphenol a epoxy resin (DADGEBA) with a structural representation as shown in figure 1.
Example 2
Preparation of epoxy resin toughening agent-1:
42g of allyl bisphenol A epoxy resin prepared in example 1, 35ml of toluene, 0.210g of platinum catalyst, 1.35g of hydrogen-terminated silicone oil (R is methyl and has a structural formula of II) with hydrogen content of 0.18% are added into a three-neck flask, the three-neck flask is protected by nitrogen, stirred, reacted for 0.5h at 75 ℃, then heated to 80 ℃, 13.1g of tetramethyl dihydro disiloxane is dropwise added under the protection of nitrogen, the chain extension reaction is carried out for 2h, and the solvent is removed by vacuum distillation, thus obtaining the epoxy resin toughening agent-1.
The structural characterization of the synthetic epoxy resin toughening agent-1 is shown in figures 2 and 3.
Example 3
Preparation of epoxy resin toughening agent-2:
42g of allyl bisphenol A epoxy resin prepared in example 1, 35ml of toluene, 0.210g of platinum catalyst, 1.35g of hydrogen-terminated silicone oil (R is methyl and has a structural formula of II) with hydrogen content of 0.18% are added into a three-neck flask, the three-neck flask is protected by nitrogen, stirred, reacted for 0.5h at 75 ℃, then heated to 80 ℃, 12.06g of tetramethyl dihydro disiloxane is dropwise added under the protection of nitrogen, the chain extension reaction is carried out for 2h, and the solvent is removed by vacuum distillation, thus obtaining the epoxy resin toughening agent-2.
Example 4
Preparation of epoxy resin composition-1 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 17.1g of epoxy resin E-51, 0.9g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 5.4g of polyetheramine epoxy hardener (D230) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Example 5
Preparation of epoxy resin composition-2 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 16.2g of epoxy resin E-51, 1.8g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 5.4g of polyetheramine epoxy hardener (D230) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Example 6
Preparation of epoxy resin composition-3 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 17.1g of epoxy resin E-51, 0.9g of epoxy resin toughening agent-2, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 5.4g of polyetheramine epoxy hardener (D230) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Example 7
Preparation of epoxy resin composition-4 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 17.1g of epoxy resin E-51, 0.9g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 13.5g of tetramethyl hexahydrophthalic anhydride (MeHHPA) and 0.45g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and allowed to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:75, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Example 8
Preparation of epoxy resin composition-5 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 17.1g of epoxy resin E-51, 0.9g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 2.7g of polyetheramine epoxy hardener (D230), 3.6g of polythiol hardener and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) are mixed, stirred well and then left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the condition of 80 ℃/2 h. The properties were measured.
Example 9
Preparation of epoxy resin composition-6 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 8.1g of epoxy resin E-51, 8.1g of alicyclic epoxy ERL4221D, 1.8g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, uniformly mixed and stood.
(2) Preparation of a component B curing agent: 13.5g of tetramethyl hexahydrophthalic anhydride (MeHHPA) and 0.45g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and allowed to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:75, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 120 ℃/2h+150 ℃/2 h. The properties were measured.
Example 10
Preparation of epoxy resin composition-7 and performance test:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 8.1g of epoxy resin E-51, 8.1g of alicyclic epoxy ERL4221D, 1.8g of epoxy resin toughening agent-1, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, uniformly mixed and stood.
(2) Preparation of a component B curing agent: 5.4g of tetramethyl hexahydrophthalic anhydride (MeHHPA) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and allowed to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:75, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Comparative example 1
Comparative example 1 differs from examples 4-6 in that comparative example 1 uses an equal amount of epoxy resin E-51 in place of either epoxy resin toughening agent-1 or epoxy resin toughening agent-2, all of which are identical.
Preparation and performance test of comparative epoxy resin composition-1:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 18g of epoxy resin E-51, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 5.4g of polyetheramine epoxy hardener (D230) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Comparative example 2
Comparative example 2 differs from example 7 in that comparative example 2 uses an equivalent amount of epoxy resin E-51 in place of epoxy resin toughening agent-1, all of which are identical.
Preparation and performance test of comparative epoxy resin composition-2:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 18g of epoxy resin E-51, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 13.5g of tetramethyl hexahydrophthalic anhydride (MeHHPA) and 0.45g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and allowed to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:75, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Comparative example 3
Comparative example 3 differs from example 8 in that comparative example 3 uses an equivalent amount of epoxy resin E-51 in place of epoxy resin toughening agent-1, all other things being equal.
Preparation and performance test of comparative epoxy resin composition-3:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 18g of epoxy resin E-51, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 2.7g of polyetheramine epoxy hardener (D230), 3.6g of polythiol hardener and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) are mixed, stirred well and then left to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:30, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the condition of 80 ℃/2 h. The properties were measured.
Comparative example 4
Comparative example 4 differs from example 10 in that comparative example 4 uses an equivalent amount of epoxy resin E-51, cycloaliphatic epoxy ERL4221D in place of epoxy resin toughener-1, all of which are identical.
Preparation and performance test of comparative epoxy resin composition-4:
(1) And (3) preparing a main agent of the epoxy resin of the component A: 9g of epoxy resin E-51, 9g of cycloaliphatic epoxy ERL4221D, 0.3g of polyethylene glycol diglycidyl ether and 0.03g of defoamer BYKA530 are mixed, heated to 60 ℃, stirred for 20min, mixed uniformly and stood.
(2) Preparation of a component B curing agent: 5.4g of tetramethyl hexahydrophthalic anhydride (MeHHPA) and 0.18g of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) were mixed, stirred well and allowed to stand.
(3) The prepared A, B components are uniformly mixed according to the mass ratio of 100:75, kept stand for 15min, defoamed, poured into a stainless steel die, uniformly coated on a stainless steel plate and then cured under the conditions of 80 ℃/2h+120 ℃/2 h. The properties were measured.
Test case
1. The impact strengths of the epoxy resin compositions of examples 4 to 10 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
| Formulation of | Impact Strength (kJ/m) 2 ) |
| Example 4 | 76.5 |
| Example 5 | 78.5 |
| Example 6 | 76.8 |
| Example 7 | 21.6 |
| Example 8 | 51.0 |
| Example 9 | 16.2 |
| Example 10 | 16.7 |
| Comparative example 1 | 9.9 |
| Comparative example 2 | 7.1 |
| Comparative example 3 | 8.8 |
| ComparisonExample 4 | 6.0 |
From Table 1, it can be seen that the toughening agent prepared by the application has good toughening effect on the epoxy resin system, and the impact strength is greatly improved.
2. The tensile strength, elongation at break and glass transition temperature of examples 4 to 6 and comparative example 1 are shown in Table 2.
TABLE 2
As can be seen from Table 2, the toughening agent can also improve the tensile strength and the elongation at break to a certain extent and maintain the vitrification temperature on the premise of greatly toughening.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present application without departing from the spirit and scope of the technical solution of the present application.
Claims (11)
1. An epoxy resin toughening agent is characterized in that the structural formula is shown as formula I:
wherein R is CH 3 Phenyl, CF 3 Or C 2 H 5 ；
m＝60～100，n＝0～20。
2. The method of preparing an epoxy resin toughening agent according to claim 1, comprising the steps of:
stirring diallyl bisphenol A epoxy resin, hydrogen terminated silicone oil and a catalyst uniformly in the presence of a solvent, reacting for 0.5-4 h at 60-75 ℃, adding tetramethyl dihydro disiloxane, performing chain extension reaction for 0.5-6 h at 75-85 ℃, and removing the solvent to obtain the epoxy resin toughening agent.
3. The method for preparing the epoxy resin toughening agent according to claim 2, wherein the structural formula of the hydrogen terminated silicone oil is shown as formula II:
wherein R is CH 3 Phenyl, CF 3 Or C 2 H 5 。
4. The method for preparing the epoxy resin toughening agent according to claim 2, wherein the mass ratio of the diallyl bisphenol a epoxy resin to the hydrogen terminated silicone oil to the catalyst to the tetramethyl dihydro disiloxane is (20-80): (1-6): (0.1-0.6): (10-40).
5. The method for preparing the epoxy resin toughening agent according to claim 2, wherein the structural formula of the diallyl bisphenol a epoxy resin is shown as formula III:
6. the method for preparing the epoxy resin toughening agent according to claim 5, wherein the method for preparing the diallyl bisphenol a epoxy resin comprises the following steps:
stirring allyl bisphenol A, a phase transfer catalyst and epichlorohydrin at 75-90 ℃ for reaction for 1-6 hours, cooling to 55-70 ℃, adding sodium hydroxide solution for reaction for 1-4 hours, filtering, rotary evaporating, adding sodium hydroxide solution for reaction for 1-4 hours at 80-90 ℃, washing, extracting toluene, and distilling to obtain diallyl bisphenol A epoxy resin.
7. The method for preparing the epoxy resin toughening agent according to claim 6, wherein the mass ratio of the allyl bisphenol A to the phase transfer catalyst to the epichlorohydrin is (40-80): (0.1-0.5): (80-120); and/or
The phase transfer catalyst comprises tetramethyl ammonium bromide.
8. An epoxy resin composition, which is characterized by comprising an A component and a B component;
the component A comprises the following components in parts by mass: 60-80 parts of epoxy resin and 5-25 parts of epoxy resin toughening agent;
the component B comprises the following components in parts by mass: 85-95 parts of curing agent and 3-7 parts of accelerator;
the epoxy resin toughening agent is the epoxy resin toughening agent according to claim 1 or the epoxy resin toughening agent prepared by the preparation method according to any one of claims 2 to 7.
9. The epoxy resin composition according to claim 8, wherein the a component further comprises the following components in parts by mass: 5 to 10 parts of diluent and 0.3 to 1 part of defoamer.
10. The epoxy resin composition according to claim 9, wherein the mass ratio of the component a to the component B is (1 to 8): 1, a step of; and/or
The epoxy resin comprises at least one of bisphenol A type, bisphenol F type and alicyclic epoxy resin; and/or
At least one of the diluents C12-C14 alkyl glycidyl ether, butyl glycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, benzyl alcohol, phenethyl alcohol, nonylphenol, propylene carbonate, trimethylolpropane triacrylate, diisopropyl methyl ether, toluene, xylene; and/or
The defoaming agent comprises at least one of polyacrylate defoaming agent and modified organic silicon defoaming agent; and/or
The curing agent comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, polyetheramine, diphenylmethane diamine, isophorone diamine, polyamide, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, nadic anhydride and polythiol; and/or
The promoter comprises bisphenol A, phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, cresol and tetrabutylammonium bromide.
11. The use of the epoxy resin composition according to any one of claims 8 to 10 in adhesives for electronic appliances, coating adhesives for PCB boards, potting adhesives, electronic insulating paints, electric insulating paints, plastics.
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