CN113265120A - Epoxy resin composition suitable for drawing agent process and epoxy resin drawing agent method - Google Patents
Epoxy resin composition suitable for drawing agent process and epoxy resin drawing agent method Download PDFInfo
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- CN113265120A CN113265120A CN202110535590.8A CN202110535590A CN113265120A CN 113265120 A CN113265120 A CN 113265120A CN 202110535590 A CN202110535590 A CN 202110535590A CN 113265120 A CN113265120 A CN 113265120A
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- epoxy resin
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- resin composition
- reactive diluent
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 132
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 132
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 48
- 239000003085 diluting agent Substances 0.000 claims abstract description 46
- 239000004952 Polyamide Substances 0.000 claims abstract description 38
- 229920002647 polyamide Polymers 0.000 claims abstract description 38
- 239000012745 toughening agent Substances 0.000 claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 6
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 3
- RWLRWONNIHIYGR-UHFFFAOYSA-N 18-[[3,5-bis[1-[17-carboxyheptadecyl(methyl)amino]ethyl]-2-hydroxyphenyl]methyl-methylamino]nonadecanoic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(C)N(C)CC1=CC(C(C)N(C)CCCCCCCCCCCCCCCCCC(O)=O)=CC(C(C)N(C)CCCCCCCCCCCCCCCCCC(O)=O)=C1O RWLRWONNIHIYGR-UHFFFAOYSA-N 0.000 claims description 3
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 3
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 3
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003292 glue Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 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 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 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 2
- 230000006872 improvement Effects 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002023 wood Substances 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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 provides an epoxy resin composition suitable for a drawing agent process and an epoxy resin drawing agent method, wherein the epoxy resin composition comprises the following raw materials: epoxy resin, reactive diluent, anhydride curing agent, accelerator and toughening agent. The reactive diluent adopts a long-chain type monofunctional epoxy reactive diluent and/or a long-chain type bifunctional epoxy reactive diluent, and the two diluents have high reactivity to an anhydride curing agent, can well participate in a curing reaction, and can play a role in toughening epoxy resin due to the long-chain structure; the toughening agent comprises low molecular polyamide, and the structure of the low molecular polyamide is provided with groups capable of participating in curing reaction, such as primary amine groups, secondary amine groups and amide groups; meanwhile, the structure of the epoxy resin is a long-chain carbon structure, so that the epoxy resin can be toughened, and the reactive diluent and the toughening agent can be well dispersed and combined in a resin system, so that the aim of effectively improving the toughness of the pultruded product is fulfilled.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an epoxy resin composition suitable for a drawing agent process and an epoxy resin drawing agent method.
Background
Compared with the glass fiber reinforced plastic prepared by a general forming method, the pultrusion product has high mechanical strength, and the specific performance is related to the type and structure of the used fiber, the variety and content of resin and process factors. Epoxy resins are also widely used in the production of pultruded products due to their excellent reactivity and good mechanical properties, heat resistance and chemical resistance. The fiber-based reinforcement material for epoxy pultruded articles is primarily glass fiber.
The glass fiber reinforced epoxy resin composite material has excellent mechanical property, and can be used as structural parts for various purposes instead of metal and wood products. But insufficient toughness is a big disadvantage of glass fiber reinforced epoxy resin, and limits the application of the glass fiber reinforced epoxy resin in certain fields. Moreover, the insufficient toughness causes the phenomena of die sticking and powder discharge in the actual production process, which affects the product quality and reduces the production efficiency.
Toughening of these materials is an effective way to improve the properties of the composite. At present, toughening modification of epoxy resin mainly comprises a series of toughening methods such as toughening of rubber elastomers, toughening of thermotropic liquid crystal polymers, toughening of thermoplastics, toughening of core-shell polymers, toughening of hyperbranched polymers and the like. However, most toughening methods have their own disadvantages, such as reducing the heat resistance and mechanical properties of the cured epoxy resin to some extent, and most toughening methods are costly and complicated to operate.
In view of the technical deficiencies of the current modifications to epoxy resins, there is a need to improve this.
Disclosure of Invention
In view of the above, the present invention provides an epoxy resin composition suitable for a drawing process and an epoxy drawing method, so as to solve or partially solve the technical problems in the prior art.
In a first aspect, the present invention provides an epoxy resin composition suitable for use in a drawing agent process, comprising the following raw materials: epoxy resin, reactive diluent, anhydride curing agent, accelerator and toughening agent; wherein the reactive diluent comprises a long chain type monofunctional epoxy reactive diluent and/or a long chain type difunctional epoxy reactive diluent.
On the basis of the technical scheme, preferably, the epoxy resin composition suitable for the pulling agent process comprises one or more of n-butyl glycidyl ether, 2-ethyl-hexyl glycidyl ether and tertiary carboxylic acid glycidyl ether as long-chain monofunctional epoxy reactive diluent;
and/or the long-chain bifunctional epoxy reactive diluent comprises one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether and neopentyl glycol diglycidyl ether.
On the basis of the above technical solution, preferably, the epoxy resin composition suitable for the drawing agent process is a liquid bisphenol a epoxy resin.
Further preferably, the epoxy resin composition suitable for use in a drawing agent process comprises an epoxy resin E-51 and/or an epoxy resin E-44.
On the basis of the above technical solutions, preferably, the epoxy resin composition suitable for the drawing agent process includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, and tung oil anhydride.
Based on the above technical solution, preferably, the accelerator for the epoxy resin composition suitable for the drawing agent process includes a tertiary amine accelerator and/or an acetylacetone metal salt accelerator.
Further preferably, the tertiary amine accelerator comprises one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, trioleate of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, triethylamine, triethanolamine, dimethylethanolamine, N-dimethylaniline, 1, 8-diazabicycloundece-7-ene, pyridine, o-hydroxybenzyldimethylamine;
and/or the acetylacetone metal salt promoter comprises one or more of aluminum acetylacetonate, copper acetylacetonate, zinc acetylacetonate, iron acetylacetonate, chromium acetylacetonate and cobalt acetylacetonate.
On the basis of the technical scheme, preferably, the epoxy resin composition suitable for the drawing agent process comprises a toughening agent and the toughening agent comprises low-molecular polyamide, wherein the low-molecular polyamide comprises one or more of polyamide 650, polyamide 651, polyamide 600, polyamide 300, polyamide 203 and polyamide 200.
On the basis of the technical scheme, the epoxy resin composition suitable for the drawing agent process is preferably used, wherein the mass ratio of the epoxy resin, the reactive diluent, the anhydride curing agent, the accelerator and the toughening agent is 100 (5-15): 70-95): 1-3): 5-15.
In a second aspect, the present invention also provides an epoxy resin drawing agent method, comprising the steps of:
placing the epoxy resin composition into a charging barrel, adding a release agent and a defoaming agent, stirring, and uniformly stirring to obtain a sizing material;
and placing the sizing material in a gum dipping tank to soak the glass yarns, and obtaining the epoxy resin product through a pultrusion process.
Compared with the prior art, the epoxy resin composition suitable for the drawing agent process and the epoxy resin drawing agent method have the following beneficial effects:
(1) according to the epoxy resin composition suitable for the drawing agent process, an epoxy resin/anhydride curing system is toughened through an in-situ reaction, the in-situ reaction toughening is mainly carried out from two directions, namely the reactive diluent and the toughening agent, the reactive diluent adopts a long-chain type monofunctional epoxy reactive diluent and/or a long-chain type bifunctional epoxy reactive diluent, the two types of diluents have high reactivity on an anhydride curing agent, can well participate in the curing reaction, and can play a role in toughening epoxy resin due to the long-chain structure; the toughening agent comprises low molecular polyamide, and the structure of the low molecular polyamide is provided with groups capable of participating in curing reaction, such as primary amine groups, secondary amine groups and amide groups; meanwhile, the structure of the epoxy resin is a long-chain carbon structure, so that the epoxy resin can be toughened. The reactive diluent and the toughening agent can directly react with the epoxy resin and the curing agent and participate in the curing reaction, so that the reactive diluent and the toughening agent can be well dispersed and combined in a resin system, the aim of effectively improving the toughness of the pultruded product is fulfilled, the process is simplified, and the production efficiency is improved.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides an epoxy resin composition suitable for a drawing agent process, which comprises the following raw materials: epoxy resin, reactive diluent, anhydride curing agent, accelerator and toughening agent; wherein the reactive diluent comprises a long-chain monofunctional epoxy reactive diluent and/or a long-chain difunctional epoxy reactive diluent.
In some embodiments, the long chain monofunctional epoxy reactive diluent comprises one or more of n-butyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, tertiary carboxylic acid glycidyl ether;
and/or the long-chain bifunctional epoxy reactive diluent comprises one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether and neopentyl glycol diglycidyl ether.
In some embodiments, the epoxy resin is a liquid bisphenol a type epoxy resin.
In some embodiments, the liquid bisphenol A type epoxy resin includes epoxy resin E-51 and/or epoxy resin E-44.
In some embodiments, the anhydride curing agent comprises one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, eleostearic anhydride.
In some embodiments, the accelerator includes a tertiary amine-based accelerator and/or a metal acetylacetonate-based accelerator.
In some embodiments, the tertiary amine-based accelerator comprises one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, trioleate salt of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, triethylamine, triethanolamine, dimethylethanolamine, N-dimethylaniline, 1, 8-diazabicycloundece-7-ene, pyridine, o-hydroxybenzyldimethylamine;
the acetylacetone metal salt promoter comprises one or more of aluminum acetylacetonate, copper acetylacetonate, zinc acetylacetonate, ferric acetylacetonate, chromium acetylacetonate, and cobalt acetylacetonate.
In some embodiments, the toughening agent comprises a low molecular polyamide comprising one or more of polyamide 650, polyamide 651, polyamide 600, polyamide 300, polyamide 203, polyamide 200.
In the embodiment of the present application, the epoxy resin/anhydride curing system is toughened by an in-situ reaction, and the in-situ reaction toughening is mainly performed from two directions, namely, a reactive diluent and a toughening agent. The reactive diluent is a long-chain monofunctional epoxy reactive diluent and/or a long-chain bifunctional epoxy reactive diluent, and the two diluents have high reactivity to an anhydride curing agent, can well participate in a curing reaction, and can play a role in toughening epoxy resin due to the long-chain structure; the toughening agent comprises low molecular polyamide, and the structure of the low molecular polyamide is provided with groups capable of participating in curing reaction, such as primary amine groups, secondary amine groups and amide groups; meanwhile, the structure of the epoxy resin is a long-chain carbon structure, so that the epoxy resin can be toughened. The reactive diluent and the toughening agent can directly react with the epoxy resin and the curing agent and participate in the curing reaction, so that the reactive diluent and the toughening agent can be well dispersed and combined in a resin system, the aim of effectively improving the toughness of the pultruded product is fulfilled, the process is simplified, and the production efficiency is improved.
In some embodiments, the mass ratio of the epoxy resin, the reactive diluent, the anhydride curing agent, the accelerator and the toughening agent is 100 (5-15): 70-95): 1-3): 5-15.
In the embodiment of the application, the weight part of the used active agent is 5-15 parts per 100 parts by weight of the epoxy resin, when the weight part of the active diluent is more than 15 parts, the viscosity of the system is too low, glue is easy to drip and run off, and the hanging of the glue is not facilitated, so that the product lacks glue to form white spots, and the mechanical property of a cured product is greatly influenced; when the weight part of the reactive diluent is less than 5, the viscosity of the system is too high, which is not favorable for infiltrating and permeating glass yarns and fillers and removing air in glue during epoxy resin drawing agent forming, and reduces the production efficiency and the product quality.
Specifically, in the embodiment of the application, the viscosity of the reactive diluent is 200-2000 mpa · s/25 ℃, and preferably 200-1200 mpa · s/25 ℃. The long-chain type monofunctional epoxy reactive diluent and/or the long-chain type bifunctional epoxy reactive diluent are/is used, so that the viscosity of the system is reduced, and the toughening effect can be realized.
In the embodiment of the application, the weight part of the anhydride curing agent is 70-95 parts per 100 parts of the epoxy resin, and the anhydride curing agent is calculated according to the concrete weight; in the case of methyltetrahydrophthalic anhydride as an example, the optimum amount to be used as a curing agent for E-51 epoxy resin in the presence of a tertiary amine as an accelerator was calculated to be 85 parts. When the using amount of the anhydride curing agent is less than the optimal using amount, epoxy resin is remained due to incomplete curing reaction, so that the mechanical property of a cured product is reduced; when the amount is more than the optimum amount, the mechanical properties of the cured product may be deteriorated by the acid anhydride remaining.
In the embodiment of the application, the weight part of the used accelerant is 1-3 parts per 100 parts of epoxy resin, the accelerant is mainly used for accelerating the curing reaction, and the gel temperature and the curing time of the curing system are controlled within 130-150 ℃ and 2-6 min. When the weight part of the accelerator is less than 1 part, the accelerating effect is not obvious, and the cured product is not completely cured after passing through the die cavity, so that the production of the pultrusion product cannot be met; when the weight part of the accelerator exceeds 3 parts, the accelerator can play a role of a curing agent in a system, the reaction activity of the system is increased, the pot life of the curing system is reduced, the glue is gelled or thickened in a glue dipping tank until glass yarns cannot be soaked, and meanwhile, the phenomenon that the product is yellow in color and even a machine is halted due to too fast reaction occurs.
In the embodiment of the application, the weight part of the toughening agent used is 5-15 parts per 100 parts by weight of the epoxy resin, the specific amount depends on the type of the low molecular polyamide used, the amount with a lower amine value is higher, and the amount with a higher amine value is lower. Active reaction groups in the molecular structure of the low molecular polyamide can enable the low molecular polyamide to directly participate in curing reaction, so that flexible long chains in the structure of the low molecular polyamide are well dispersed in a system to play a toughening role. When the used weight part of the toughening agent is less than 5 parts, the toughening agent can play a toughening role, but the toughening effect is not obvious, and the improvement on the phenomena of die sticking and powder discharging is not enough; when the weight part of the toughening agent is more than 15 parts, the active reaction group in the molecular structure of the toughening agent can play a role of a curing agent in a curing system, so that an agglomeration phenomenon occurs, and the pot life of the system is greatly reduced.
Based on the same inventive concept, the embodiment of the application also provides an epoxy resin drawing agent method, which comprises the following steps:
s1, placing the epoxy resin composition into a charging barrel, adding a release agent and a defoaming agent, and uniformly stirring to obtain a sizing material;
s2, placing the sizing material in a glue dipping tank to soak the glass yarn, and obtaining the epoxy resin product through a pultrusion process.
In the embodiment of the present application, the drawing process refers to a method for continuously producing a glass steel wire molded product by dipping glass fiber or a fabric thereof in glue, extruding, molding, heating, curing, and cutting to a fixed length under the traction of an external force. Adding glass yarns in the impregnation process, wherein the types of the glass yarns are ECT 560T-19200. In practice, the added release agent can be formed by combining one or more paraffin substances, the mass ratio is not required when a plurality of substances are mixed, the addition amount is 0.3-0.5% of the total mass of the epoxy resin composition, and the release agent mainly plays a role in releasing the mold; in practice, silane coupling agent such as KH-550 can be used as the coupling agent, the addition amount is 0.2-0.5%, the wettability and the binding power of the glass yarn and the resin can be effectively enhanced, and a defoaming agent, a delustering agent, a dispersing agent, an antioxidant and the like can be properly added when necessary.
The epoxy resin composition and the epoxy resin drawing method suitable for the drawing process are further described below in specific examples.
Example 1
The embodiment of the application provides an epoxy resin composition suitable for a drawing agent process, which comprises a mixture of E-51 epoxy resin, methyltetrahydrophthalic anhydride, ethylene glycol diglycidyl ether, DMP-30 (namely 2,4, 6-tris (dimethylaminomethyl) phenol) and polyamide 650 in a mass ratio of 100:85:10:2: 10.
The embodiment of the application also provides an epoxy resin drawing agent method, which comprises the following steps: the epoxy resin composition in the example 1 is added into a cylinder of a drawing agent forming device, a release agent zinc stearate accounting for 0.5 percent of the total mass of the epoxy resin composition and a silicone defoaming agent accounting for 0.1 percent of the total mass of the epoxy resin composition are added, the mixture is stirred for 15min to be completely uniform, then the mixture is poured into a dipping tank to be soaked with glass yarns, the type of the used glass yarns is ECT560T-19200, and a product is obtained through pultrusion, wherein the gel content of the product is 20 percent.
Example 2
The embodiment of the application provides an epoxy resin composition suitable for a drawing agent process, which comprises a mixture of E-51 epoxy resin, methyltetrahydrophthalic anhydride, n-butyl glycidyl ether, aluminum acetylacetonate and polyamide 651 in a mass ratio of 100:85:10:2: 5.
The embodiment of the application also provides an epoxy resin drawing agent method, which comprises the following steps: the epoxy resin composition in the example 2 is added into a cylinder of a drawing agent forming device, a release agent zinc stearate accounting for 0.5 percent of the total mass of the epoxy resin composition and a silicone defoaming agent accounting for 0.1 percent of the total mass of the epoxy resin composition are added, the mixture is stirred for 15min to be completely uniform, then the mixture is poured into a dipping tank to be soaked with glass yarns, the type of the used glass yarns is ECT560T-19200, and a product is obtained through pultrusion, wherein the gel content of the product is 20 percent.
Example 3
The embodiment of the application provides an epoxy resin composition suitable for a drawing agent process, which comprises a mixture of E-51 epoxy resin, methylhexahydrophthalic anhydride, n-butyl glycidyl ether, DMP-30 and polyamide 650 in a mass ratio of 100:85:10:2: 10.
The embodiment of the application also provides an epoxy resin drawing agent method, which comprises the following steps: the epoxy resin composition in the above example 3 was added to a cylinder of a drawing agent molding apparatus, and a release agent zinc stearate in an amount of 0.5% by total mass of the epoxy resin composition and a silicone defoaming agent in an amount of 0.1% by total mass of the epoxy resin composition were added, stirred for 15min to be completely uniform, and then poured into a dipping tank to impregnate glass yarns, the type of the glass yarns used was ECT560T-19200, and a product was obtained by pultrusion, the gel content of the product being 20%.
Example 4
The embodiment of the application provides an epoxy resin composition suitable for a drawing agent process, which comprises a mixture of E-51 epoxy resin, methylhexahydrophthalic anhydride, ethylene glycol diglycidyl ether, aluminum acetylacetonate and polyamide 651 in a mass ratio of 100:85:10:2: 5.
The embodiment of the application also provides an epoxy resin drawing agent method, which comprises the following steps: the epoxy resin composition in the above example 4 was added to a cylinder of a drawing agent molding apparatus, and a release agent zinc stearate in an amount of 0.5% by total mass of the epoxy resin composition and a silicone defoaming agent in an amount of 0.1% by total mass of the epoxy resin composition were added, stirred for 15min to be completely uniform, and then poured into a dipping tank to impregnate glass yarns, the type of the glass yarns used was ECT560T-19200, and a product was obtained by pultrusion, the gel content of the product being 20%.
Comparative example 1
The composition of the epoxy resin composition suitable for the drawing agent process is the same as that of the epoxy resin composition in example 1, except that the epoxy resin composition does not contain polyamide 650, and the mass ratio of the rest raw materials is the same as that of the epoxy resin composition in example 1.
This comparative example provides an epoxy resin drawing method which is the same as example 1 except that the epoxy resin composition of comparative example 1 is used and the rest of the process is the same.
Comparative example 2
The composition of the epoxy resin composition suitable for the drawing agent process provided by the comparative example is the same as that of example 2, except that the comparative example does not include polyamide 651, and the mass ratio of the rest raw materials is the same as that of example 1.
This comparative example provides an epoxy resin drawing method which is the same as example 2 except that the epoxy resin composition of comparative example 2 is used and the rest of the process is the same.
Comparative example 3
The composition of the epoxy resin composition suitable for the pulling agent process is the same as that of example 3, except that n-butyl glycidyl ether is replaced by benzyl glycidyl ether, and the mass ratio of the rest raw materials is the same as that of example 3.
This comparative example provides an epoxy resin drawing method which is the same as example 3 except that the epoxy resin composition of comparative example 3 is used and the rest of the process is the same.
Comparative example 4
The composition of the epoxy resin composition suitable for the drawing agent process is the same as that of example 4, except that ethylene glycol diglycidyl ether is replaced by benzyl glycidyl ether, and the mass ratio of the rest raw materials is the same as that of example 4.
This comparative example provides an epoxy resin drawing method which is the same as example 4 except that the epoxy resin composition of comparative example 4 was used and the rest of the process was the same.
The elongation at break (%) and tensile strength (Mpa) of the finally obtained article, and the die-bonding condition at the die outlet and the powder output per hour during the drawing process were measured according to the epoxy resin drawing method in examples 1 to 4 and comparative examples 1 to 4, and the results are shown in table 1 below.
TABLE 1-elongation at break (%) and tensile strength (MPa) of the final articles obtained in the different examples
As can be seen from table 1, the elongation at break and the tensile strength of the epoxy resin products prepared by the agent-pulling methods of examples 1 to 4 of the present application are superior to those of the comparative examples, which indicates that the epoxy resin products prepared by the agent-pulling method of the present application have good elongation at break and tensile strength; further, as can be seen from table 1, the epoxy resin drawing method provided by the present application has a very small powder output during the drawing process and does not stick to the mold.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An epoxy resin composition suitable for a drawing agent process is characterized by comprising the following raw materials: epoxy resin, reactive diluent, anhydride curing agent, accelerator and toughening agent; wherein the reactive diluent comprises a long chain type monofunctional epoxy reactive diluent and/or a long chain type difunctional epoxy reactive diluent.
2. The epoxy resin composition suitable for use in a zipper process according to claim 1, wherein the long chain type monofunctional epoxy reactive diluent comprises one or more of n-butyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, and tertiary carboxylic acid glycidyl ether;
and/or the long-chain bifunctional epoxy reactive diluent comprises one or more of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether and neopentyl glycol diglycidyl ether.
3. The epoxy resin composition suitable for use in a pulling agent process of claim 1, wherein the epoxy resin is a liquid bisphenol a type epoxy resin.
4. The epoxy resin composition suitable for use in a pulling agent process of claim 3, wherein the liquid bisphenol a type epoxy resin comprises epoxy resin E-51 and/or epoxy resin E-44.
5. The epoxy resin composition suitable for use in a pulling agent process of claim 1, wherein the anhydride curing agent comprises one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, eleostearic anhydride.
6. The epoxy resin composition suitable for use in a pulling agent process of claim 1, wherein the accelerator comprises a tertiary amine type accelerator and/or an acetylacetone metal salt type accelerator.
7. The epoxy resin composition suitable for use in a pulling agent process of claim 6, wherein the tertiary amine accelerator comprises one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, trioleate of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, triethylamine, triethanolamine, dimethylethanolamine, N-dimethylaniline, 1, 8-diazabicycloundece-7-ene, pyridine, o-hydroxybenzyldimethylamine;
and/or the acetylacetone metal salt promoter comprises one or more of aluminum acetylacetonate, copper acetylacetonate, zinc acetylacetonate, iron acetylacetonate, chromium acetylacetonate and cobalt acetylacetonate.
8. The epoxy resin composition suitable for use in a drawing agent process according to claim 1, wherein the toughening agent comprises a low molecular polyamide comprising one or more of polyamide 650, polyamide 651, polyamide 600, polyamide 300, polyamide 203, polyamide 200.
9. The epoxy resin composition suitable for use in a drawing agent process as claimed in claim 1, wherein the mass ratio of the epoxy resin, the reactive diluent, the anhydride curing agent, the accelerator and the toughening agent is 100 (5-15): 70-95): 1-3: (5-15).
10. An epoxy resin drawing agent method is characterized by comprising the following steps:
placing the epoxy resin composition as defined in any one of claims 1 to 9 in a cylinder, adding a release agent and a defoaming agent, stirring, and uniformly stirring to obtain a sizing material;
and placing the sizing material in a gum dipping tank to soak the glass yarns, and obtaining the epoxy resin product through a pultrusion process.
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Application publication date: 20210817 |