CN117467242A - Toughening type epoxy resin composition and preparation process thereof - Google Patents
Toughening type epoxy resin composition and preparation process thereof Download PDFInfo
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- CN117467242A CN117467242A CN202311440291.1A CN202311440291A CN117467242A CN 117467242 A CN117467242 A CN 117467242A CN 202311440291 A CN202311440291 A CN 202311440291A CN 117467242 A CN117467242 A CN 117467242A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 76
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000004593 Epoxy Substances 0.000 claims abstract description 80
- 239000012745 toughening agent Substances 0.000 claims abstract description 63
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 63
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 57
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000005770 Eugenol Substances 0.000 claims abstract description 53
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229960002217 eugenol Drugs 0.000 claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 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 abstract description 20
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims abstract description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 90
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 27
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- LIOBPVZSSVYQSS-UHFFFAOYSA-N 2-(3,4-diaminophenyl)acetic acid Chemical compound NC1=CC=C(CC(O)=O)C=C1N LIOBPVZSSVYQSS-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- KTIBRDNFZLYLNA-UHFFFAOYSA-N 2-(2-hydroxyethenoxy)ethenol Chemical compound OC=COC=CO KTIBRDNFZLYLNA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- IEZWOVIWXFLQTP-UHFFFAOYSA-N hydroperoxyethene Chemical compound OOC=C IEZWOVIWXFLQTP-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of epoxy resin, in particular to a toughening epoxy resin composition and a preparation process thereof. The epoxy resin comprises bisphenol A epoxy resin and difunctional silicon-based epoxy monomer; the mass ratio of the bisphenol A type epoxy resin to the difunctional silicon-based epoxy monomer is (50-52) to (5-8). The toughening epoxy resin composition comprises the following substances: 55-60 parts of epoxy resin, 5-8 parts of polymer toughening agent and 32-40 parts of curing agent. The raw materials of the polymer toughening agent comprise the following substances: 2 to 3 parts of hydroxyethyl acrylate, 2 to 3 parts of glycidyl methacrylate, 0.5 to 1 part of epoxy eugenol, 5 to 6 parts of 2-ethylhexyl acrylate, 3 to 3.8 parts of vinyl latent curing agent, 1.2 to 2 parts of lauryl acrylate and 1 to 1.5 parts of initiator.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a toughening epoxy resin composition and a preparation process thereof.
Background
Epoxy resin is an engineering material with good chemical resistance, mechanical property and electrical insulation property; but its brittleness and low impact toughness are limited due to its own characteristic limitations. In the prior art, the material is generally modified in the following way, firstly, high molecular polymers such as polyether, polyurethane and the like are introduced, so that the toughness and the ductility of the material are improved; secondly, elastic particles such as ethylene propylene rubber and the like are added, and then an elastic phase is formed, so that the toughness and the impact resistance of the material are improved; thirdly, amine curing agents such as polyamide and the like are introduced, and the three-dimensional net structure is formed through crosslinking modification, so that the mechanical property and toughness are improved; fourth, by introducing nanoscale fillers, the properties of the material are enhanced by the interactions between the remaining epoxy resins. In the scheme, the high molecular polymerization is not adopted (namely, the polymer toughening agent) and can obtain a good toughening effect on the premise of not influencing the resin, but the problem that the existing polymer toughening agent is poor in high temperature resistance and the stability is reduced is solved; secondly, the viscosity in the epoxy resin rises, the fluidity is poor, and the substances are unevenly mixed, so that the curing rate and the curing degree are affected, and the performance of the epoxy resin is reduced. In addition, the one-part epoxy resin composition is mixed with a curing agent, and there is a problem in that reaction precipitation occurs during storage, resulting in stability.
In summary, solving the above problems, optimizing the formation of a toughened epoxy resin composition is of great importance.
Disclosure of Invention
The invention aims to provide a toughening epoxy resin composition and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of a toughened epoxy resin composition comprises the following steps:
step 1: preparation of a polymer toughening agent:
1.1. preparation of epoxy eugenol:
sequentially adding eugenol, epoxy chloropropane and benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2-2.5 hours at the temperature of 105-115 ℃ to obtain epoxy eugenol;
1.2. preparation of vinyl latent curing agent:
sequentially adding 3, 4-diaminophenylacetic acid, hydroxy vinyl ether and zeolite into a reaction kettle, and uniformly mixing; dropwise adding concentrated sulfuric acid, and reacting for 5-7 hours at the constant temperature of 155-160 ℃ under the protection of nitrogen to obtain vinyl monomers;
sequentially adding salicylaldehyde, sodium bisulphite and ethanol into a reaction kettle, and stirring for reaction for 3-5 hours; then dripping vinyl monomer-DMF solution, setting the temperature to be 80-85 ℃ and reacting for 3-5 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent:
sequentially adding hydroxyethyl acrylate, glycidyl methacrylate, epoxy eugenol, 2-ethylhexyl acrylate, vinyl latent curing agent, lauryl acrylate, initiator and ethyl acetate into a reaction kettle, heating to 80-90 ℃, stirring and reacting for 24 hours; then pouring the reaction solution into a methanol-water solution for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: dispersing the polymer toughening agent in acetone, adding epoxy resin, stirring uniformly, removing acetone at 55-60 ℃, adding a curing agent, stirring uniformly at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
More preferably, the raw materials of the epoxy eugenol comprise the following substances: 1 part of eugenol, 3 to 3.5 parts of epoxy chloropropane and 0.02 to 0.08 part of benzyl triethyl ammonium chloride.
More preferably, the raw materials of the vinyl latent curing agent comprise the following substances: 1.5 to 2.5 parts of salicylaldehyde, 2 to 2.3 parts of sodium bisulfite and 2 to 3 parts of vinyl monomer; the vinyl monomer comprises the following raw materials: 1 part of 3, 4-diaminophenylacetic acid, 1.5 to 2 parts of hydroxy vinyl ether and 2.3 to 2.6 parts of concentrated sulfuric acid.
More preferably, the raw materials of the polymer toughening agent comprise the following substances: 2 to 3 parts of hydroxyethyl acrylate, 2 to 3 parts of glycidyl methacrylate, 0.5 to 1 part of epoxy eugenol, 5 to 6 parts of 2-ethylhexyl acrylate, 3 to 3.8 parts of vinyl latent curing agent, 1.2 to 2 parts of lauryl acrylate and 1 to 1.5 parts of initiator.
More preferably, the toughening epoxy resin composition comprises the following substances: 55-60 parts of epoxy resin, 5-8 parts of polymer toughening agent and 32-40 parts of curing agent.
More preferably, the epoxy resin comprises bisphenol a type epoxy resin and difunctional silicon-based epoxy monomer; the mass ratio of the bisphenol A type epoxy resin to the difunctional silicon-based epoxy monomer is (50-52) to (5-8).
More optimally, the preparation process of the difunctional silicon-based epoxy monomer comprises the following steps: sequentially adding 1, 3-tetramethyl disiloxane, epoxy eugenol, a catalyst and toluene into a reaction kettle, setting the temperature to be 60-100 ℃ for reaction for 4-12 hours, cooling, and removing the solvent by rotary evaporation to obtain the difunctional silicon-based epoxy monomer.
More preferably, the raw materials of the difunctional silicon-based epoxy monomer comprise the following components: 1 to 1.5 parts of 1, 3-tetramethyl disiloxane, 2 to 3 parts of epoxy eugenol, 0.03 to 0.05 part of catalyst and 100 parts of toluene.
More preferably, the curing agent is an anhydride curing agent.
More optimally, the toughening epoxy resin composition is prepared by the preparation process of the toughening epoxy resin composition.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polymer toughening agent with similar compatibility and reaction compatibility is prepared, the fluidity and stability of the polymer toughening agent in the epoxy resin composition are ensured, the polymer toughening agent can be effectively and uniformly dispersed in the epoxy resin composition for effective toughening, and the thermal stability of the epoxy resin composition is not reduced.
The polymer toughening agent is based on the synthesis of polyacrylic acid substances, and firstly, acrylic acid-2-ethylhexyl ester and acrylic acid laurate are introduced in the polymerization process, so that the toughness is improved. Secondly, glycidyl methacrylate and epoxy eugenol are introduced to provide similar compatibility, so that the fluidity and dispersibility of the epoxy resin composition are ensured; the epoxy eugenol is obtained by the reaction of eugenol and epichlorohydrin, contains benzene ring, can ensure high-temperature performance by being introduced into a polymer toughening agent, and can also increase the compatibility with epoxy resin. Thirdly, the vinyl latent curing agent is introduced, and the crosslinking can be initiated only at high temperature, so that the polymer toughening agent has long-term storage stability at room temperature, and the combination of the reaction monomers effectively ensures the superiority of the polymer toughening agent. The vinyl latent curing agent is based on 3, 4-diaminophenylacetic acid, carboxyl is esterified and grafted with hydroxyl vinyl ether, and then o-phenylenediamine is utilized to react with aldehyde groups of salicylaldehyde, so that the vinyl curing agent with imidazole rings is formed, and because of the existence of hydroxyl groups in the salicylaldehyde, the vinyl curing agent can be in intramolecular hydrogen bonds with the imidazole rings; the epoxy resin composition has long-term stability, and can break the intermolecular effect only at a higher temperature (170-190 ℃), the activity of nitrogen in an imidazole ring and promote crosslinking.
(2) In a further scheme, the conventional single bisphenol A epoxy resin is replaced by a difunctional silicon-based epoxy monomer, so that the high temperature resistance is ensured and the dispersibility and the crosslinking property of the polymer toughening agent are improved while the polymer toughening agent is toughened. The difunctional silicon-based epoxy monomer is prepared by hydrosilylation of 1, 3-tetramethyl disiloxane and epoxy eugenol and contains a silicon chain, so that the epoxy monomer has certain toughness; meanwhile, the epoxy eugenol has similar compatibility with the polymer toughening agent, so that the fluidity and uniform dispersibility of the epoxy composition are further promoted, and meanwhile, the phase crosslinking can be further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
It should be noted that the manufacturers of all the raw materials according to the present invention include, without any particular limitation: in the following examples, the following parts are parts by weight, 3, 4-diaminophenylacetic acid (CAS number 621-43-2), hydroxyvinyl ether (CAS number 111-45-5), eugenol (CAS number 97-53-0), concentrated sulfuric acid at 98%, salicylaldehyde (CAS number 90-02-8), hydroxyethyl acrylate (CAS number 818-61-1), glycidyl methacrylate (CAS number 106-91-2), 2-ethylhexyl acrylate (CAS number 103-11-7), lauryl acrylate (CAS number 2156-97-0), 1, 3-tetramethyldisiloxane (CAS number 32277-26-7); the curing agent is methyl hexahydrophthalic anhydride, the model of bisphenol A type epoxy resin is E51, and the curing agent is provided by Hunan chemical industry Co.
Example 1: a preparation process of a toughened epoxy resin composition comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 2.8 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 8 parts of polymer toughening agent in acetone, adding 58 parts of epoxy resin (52 parts of bisphenol A type epoxy resin and 6 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 34 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Example 2: a preparation process of a toughened epoxy resin composition comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 2.8 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 5 parts of polymer toughening agent in acetone, adding 60 parts of epoxy resin (52 parts of bisphenol A type epoxy resin and 8 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 35 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Example 3: a preparation process of a toughened epoxy resin composition comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 2.8 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 8 parts of polymer toughening agent in acetone, adding 55 parts of epoxy resin (50 parts of bisphenol A type epoxy resin and 5 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 37 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Comparative example 1: referring to example 1, no vinyl latent curing agent was incorporated in the polymeric toughening agent; the method comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of a polymer toughening agent: sequentially adding 2.9 parts of hydroxyethyl acrylate, 6 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate into a reaction kettle, heating to 85 ℃, stirring and reacting for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 8 parts of polymer toughening agent in acetone, adding 58 parts of epoxy resin (52 parts of bisphenol A type epoxy resin and 6 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 34 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Comparative example 2: referring to example 1, no epoxy eugenol was incorporated in the polymeric toughening agent; the method comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.2. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 3.6 parts of glycidyl methacrylate, 5.2 parts of 2-ethylhexyl acrylate, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 8 parts of polymer toughening agent in acetone, adding 58 parts of epoxy resin (52 parts of bisphenol A type epoxy resin and 6 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 34 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Comparative example 3: referring to example 1, no difunctional silicon-based epoxy monomer was introduced into the toughened epoxy resin composition; the method comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 2.8 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 8 parts of polymer toughening agent in acetone, adding 58 parts of bisphenol A epoxy resin, stirring uniformly, removing acetone at 58 ℃, adding 34 parts of curing agent, stirring uniformly at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Comparative example 4: referring to example 1, the amount of toughening agent was increased; the method comprises the following steps:
step 1: preparation of a polymer toughening agent: 1.1. preparation of epoxy eugenol: sequentially adding 1 part of eugenol, 3.2 parts of epichlorohydrin and 0.05 part of benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2 hours at the temperature of 110 ℃ to obtain the epoxyeugenol;
1.2. preparation of vinyl latent curing agent: sequentially adding 1 part of 3, 4-diaminophenylacetic acid, hydroxyl vinyl ether and 0.1 part of zeolite into a reaction kettle, and uniformly mixing; 2.5 parts of concentrated sulfuric acid is added dropwise, and the temperature is set to 160 ℃ for reaction for 6 hours under the protection of nitrogen, so as to obtain vinyl monomers;
sequentially adding 2 parts of salicylaldehyde, 2.2 parts of sodium bisulphite and 120 parts of ethanol into a reaction kettle, and stirring for reaction for 4 hours; then, a vinyl monomer-DMF solution (2.4 parts of vinyl monomer, 30 parts of DMF) was added dropwise, and the reaction was carried out at 80℃for 4 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent: 2.9 parts of hydroxyethyl acrylate, 2.8 parts of glycidyl methacrylate, 0.8 part of epoxy eugenol, 5.2 parts of acrylic acid-2-ethylhexyl ester, 3.2 parts of vinyl latent curing agent, 1.5 parts of lauryl acrylate, 1.3 parts of azobisisobutyronitrile and 80 parts of ethyl acetate are sequentially added into a reaction kettle, and the temperature is raised to 85 ℃ for stirring reaction for 24 hours; then pouring the reaction solution into a methanol-water solution (the mass ratio of methanol to water is 1:1) for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: preparation of difunctional silicon-based epoxy monomer: 1.3 parts of 1, 3-tetramethyl disiloxane, 2.3 parts of epoxy eugenol, 0.05 part of chloroplatinic acid catalyst and 100 parts of toluene are sequentially added into a reaction kettle, the temperature is set at 70 ℃ for reaction for 12 hours, cooling is carried out, and the solvent is removed by rotary evaporation, thus obtaining the difunctional silicon-based epoxy monomer.
Step 3: dispersing 12 parts of polymer toughening agent in acetone, adding 54 parts of epoxy resin (50 parts of bisphenol A type epoxy resin and 4 parts of difunctional silicon-based epoxy monomer), uniformly stirring, removing acetone at 58 ℃, adding 34 parts of curing agent, uniformly stirring at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
Experiment: the toughened epoxy resin compositions obtained in examples 1 to 3 and comparative examples 1 to 4 were cured to prepare a sample, the curing temperature was 90℃for 1 hour, the temperature was increased to 150℃for 1 hour, and the temperature was increased to 190℃for 2 hours. Testing the tensile strength of a sample by taking GB/T2567-2008 as a standard and the tensile rate of 1 mm/min; the notched impact strength was measured at 80mm by 10mm by 4 mm. The heat distortion temperature of the test specimen was measured using GB/T1634-2004 as a standard. The data obtained are shown below:
| sample preparation | Tensile strength Mpa | Impact strength kj/m 2 | Heat distortion temperature (DEG C) |
| Example 1 | 107.5 | 24.4 | 182 |
| Example 2 | 103.7 | 23.7 | 179 |
| Example 3 | 105.3 | 24.0 | 183 |
| Comparative example 1 | 95.4 | 22.22 | 161 |
| Comparative example 2 | 102.0 | 23.4 | 171 |
| Comparative example 3 | 94.6 | 21.7 | 156 |
| Comparative example 4 | 97.8 | 22.6 | 168 |
From the data in the table above, it can be seen that: according to the preparation method, the polymer toughening agent is prepared by utilizing the epoxy eugenol and the vinyl latent curing agent, and is applied to the epoxy resin, so that the stability is ensured, the mechanical property is effectively enhanced, and meanwhile, the excellent heat resistance is ensured. From the data of example 1 compared with the data of comparative examples 1 to 4, it was found that: in comparative example 1, since the polymer toughening agent does not incorporate a vinyl latent curing agent, the crosslinking compatibility is reduced, so that the tensile strength, impact strength and heat resistance are lowered; in comparative example 2, since epoxyeugenol is not introduced, the mechanical properties and heat resistance are lowered; in comparative example 3, performance was degraded by the absence of the incorporation of the difunctional silicon-based epoxy monomer; in comparative example 4, the performance was decreased due to the increased amount of the toughening agent. The above shows that: the importance of vinyl latent curing agent and epoxy eugenol in the polymer toughening agent is shown, meanwhile, the introduction of the difunctional silicon-based epoxy monomer and the polymer toughening agent have a synergistic effect, and in addition, the polymer toughening agent is not introduced more and better, and the problems of phase separation and compatibility are caused too much or too much, so that the performance is reduced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation process of a toughened epoxy resin composition is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparation of a polymer toughening agent:
1.1. preparation of epoxy eugenol:
sequentially adding eugenol, epoxy chloropropane and benzyl triethyl ammonium chloride into a reaction kettle, uniformly mixing, and reacting for 2-2.5 hours at the temperature of 105-115 ℃ to obtain epoxy eugenol;
1.2. preparation of vinyl latent curing agent:
sequentially adding 3, 4-diaminophenylacetic acid, hydroxy vinyl ether and zeolite into a reaction kettle, and uniformly mixing; dropwise adding concentrated sulfuric acid, and reacting for 5-7 hours at the constant temperature of 155-160 ℃ under the protection of nitrogen to obtain vinyl monomers;
sequentially adding salicylaldehyde, sodium bisulphite and ethanol into a reaction kettle, and stirring for reaction for 3-5 hours; then dripping vinyl monomer-DMF solution, setting the temperature to be 80-85 ℃ and reacting for 3-5 hours; obtaining vinyl latent curing agent;
1.3. preparation of a polymer toughening agent:
sequentially adding hydroxyethyl acrylate, glycidyl methacrylate, epoxy eugenol, 2-ethylhexyl acrylate, vinyl latent curing agent, lauryl acrylate, initiator and ethyl acetate into a reaction kettle, heating to 80-90 ℃, stirring and reacting for 24 hours; then pouring the reaction solution into a methanol-water solution for precipitation, washing and drying to obtain a polymer toughening agent;
step 2: dispersing the polymer toughening agent in acetone, adding epoxy resin, stirring uniformly, removing acetone at 55-60 ℃, adding a curing agent, stirring uniformly at 40-45 ℃, degassing, and cooling to obtain the toughened epoxy resin composition.
2. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the raw materials of the epoxy eugenol comprise the following substances: 1 part of eugenol, 3 to 3.5 parts of epoxy chloropropane and 0.02 to 0.08 part of benzyl triethyl ammonium chloride.
3. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the raw materials of the vinyl latent curing agent comprise the following substances: 1.5 to 2.5 parts of salicylaldehyde, 2 to 2.3 parts of sodium bisulfite and 2 to 3 parts of vinyl monomer; the vinyl monomer comprises the following raw materials: 1 part of 3, 4-diaminophenylacetic acid, 1.5 to 2 parts of hydroxy vinyl ether and 2.3 to 2.6 parts of concentrated sulfuric acid.
4. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the raw materials of the polymer toughening agent comprise the following substances: 2 to 3 parts of hydroxyethyl acrylate, 2 to 3 parts of glycidyl methacrylate, 0.5 to 1 part of epoxy eugenol, 5 to 6 parts of 2-ethylhexyl acrylate, 3 to 3.8 parts of vinyl latent curing agent, 1.2 to 2 parts of lauryl acrylate and 1 to 1.5 parts of initiator.
5. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the toughening epoxy resin composition comprises the following substances: 55-60 parts of epoxy resin, 5-8 parts of polymer toughening agent and 32-40 parts of curing agent.
6. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the epoxy resin comprises bisphenol A epoxy resin and difunctional silicon-based epoxy monomer; the mass ratio of the bisphenol A type epoxy resin to the difunctional silicon-based epoxy monomer is (50-52) to (5-8).
7. The process for preparing a toughened epoxy resin composition as claimed in claim 6, wherein: the preparation process of the difunctional silicon-based epoxy monomer comprises the following steps: sequentially adding 1, 3-tetramethyl disiloxane, epoxy eugenol, a catalyst and toluene into a reaction kettle, setting the temperature to be 60-100 ℃ for reaction for 4-12 hours, cooling, and removing the solvent by rotary evaporation to obtain the difunctional silicon-based epoxy monomer.
8. The process for preparing a toughened epoxy resin composition as claimed in claim 7, wherein: the raw materials of the difunctional silicon-based epoxy monomer comprise the following components: 1 to 1.5 parts of 1, 3-tetramethyl disiloxane, 2 to 3 parts of epoxy eugenol, 0.03 to 0.05 part of catalyst and 100 parts of toluene.
9. The process for preparing a toughened epoxy resin composition as claimed in claim 1, wherein: the curing agent is an anhydride curing agent.
10. The toughened epoxy resin composition prepared by the preparation process of the toughened epoxy resin composition according to any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040970A (en) * | 2001-07-27 | 2003-02-13 | Arakawa Chem Ind Co Ltd | Method for producing silane-modified epoxy resin, resin composition, semicured material and cured material |
| US20160053045A1 (en) * | 2013-04-17 | 2016-02-25 | 3M Innovative Properties Company | Multiple accelerator systems for epoxy adhesives |
| CN113897032A (en) * | 2021-09-22 | 2022-01-07 | 广东华彩复合材料有限公司 | Epoxy resin composite material for fiber winding and preparation method thereof |
| CN114907670A (en) * | 2021-02-06 | 2022-08-16 | 东莞市力源复合材料有限公司 | Single-component fast curing epoxy resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040970A (en) * | 2001-07-27 | 2003-02-13 | Arakawa Chem Ind Co Ltd | Method for producing silane-modified epoxy resin, resin composition, semicured material and cured material |
| US20160053045A1 (en) * | 2013-04-17 | 2016-02-25 | 3M Innovative Properties Company | Multiple accelerator systems for epoxy adhesives |
| CN114907670A (en) * | 2021-02-06 | 2022-08-16 | 东莞市力源复合材料有限公司 | Single-component fast curing epoxy resin and preparation method thereof |
| CN113897032A (en) * | 2021-09-22 | 2022-01-07 | 广东华彩复合材料有限公司 | Epoxy resin composite material for fiber winding and preparation method thereof |
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