CN114573950A - Epoxy resin system for high-strength and high-toughness composite material pultrusion frame and preparation method thereof - Google Patents
Epoxy resin system for high-strength and high-toughness composite material pultrusion frame and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
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- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 56
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000004014 plasticizer Substances 0.000 claims description 18
- 239000012745 toughening agent Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 16
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000012643 polycondensation polymerization Methods 0.000 claims description 12
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- 239000000843 powder Substances 0.000 claims description 11
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000010459 dolomite Substances 0.000 claims description 5
- 229910000514 dolomite Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 5
- 238000007039 two-step reaction Methods 0.000 claims description 5
- 238000009941 weaving Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 238000005491 wire drawing Methods 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
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- 238000005299 abrasion Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 10
- 229920001568 phenolic resin Polymers 0.000 description 10
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- 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 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001721 transfer moulding Methods 0.000 description 4
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- 238000006073 displacement reaction Methods 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 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
- C08L63/04—Epoxynovolacs
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame and a preparation method thereof, belonging to the technical field of epoxy resin systems and comprising the following raw materials in parts by weight: 52-64 parts of a binder; diluent agent: 24-32 parts; curing agent: 34-46 parts; accelerator (b): 5-16 parts; modified additive: 12-24 parts; functional additive: 6-14 parts; filling: 4-12 parts. The invention solves the problem of poor tensile strength, fracture toughness and wear resistance of the epoxy resin system, can effectively improve the tensile strength, fracture toughness and wear resistance of the epoxy resin system by adding the functional additive into the epoxy resin system, greatly improves the epoxy resin system, enables the composite material pultrusion frame to have the characteristics of high strength and high toughness, and has wide market prospect.
Description
Technical Field
The invention relates to the technical field of epoxy resin systems, in particular to an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame and a preparation method thereof.
Background
Since the advent of the epoxy resin, due to its excellent physical and chemical properties and simple molding process, it has been widely used in various industries, and is currently the most widely used thermosetting resin with optimal properties in the industry. In recent years, with the rapid development of industries such as wind power generation, automobiles, aerospace and the like, the status of the reinforced fiber/epoxy resin composite material is increasingly important. The fiber reinforced thermosetting resin composite material is a solid material of a multiphase system formed by thermosetting resin and a reinforced fiber composite material, fully exerts the characteristics and the performance of materials of all components, and presents excellent performance which cannot be possessed by the original single material through the reasonable matching and the synergistic effect of all the components.
At present, most of large-sized fiber-reinforced epoxy resin composite materials are manufactured by vacuum assisted resin transfer molding, resin transfer molding and reaction injection molding processes, and the forming process is simple and high in production efficiency, so that the large-sized fiber-reinforced epoxy resin composite materials become the mainstream of the low-cost manufacturing technology of advanced composite materials. The method is widely applied to the manufacturing of parts in the fields of wind power, automobiles, yachts, aerospace and the like; at present, most of epoxy resin systems for manufacturing the fiber reinforced epoxy resin composite material by vacuum assisted resin transfer molding, resin transfer molding and reaction injection molding processes are epoxy resin-amine curing agent systems, and compared with epoxy resin-anhydride curing systems, the epoxy resin-amine curing agent system has the advantages of low curing temperature and high curing speed, and becomes a mainstream system applied at present.
Chinese patent publication No. CN102040802A discloses an epoxy resin system comprising the following components: the epoxy resin, the diluent, the anhydride curing agent and the accelerator, wherein the epoxy resin and the diluent are mixed to form a component A in an epoxy resin system, the diluent accounts for no more than 30% of the component A by weight, and the diluent contains a polymer with more than one epoxy group; an anhydride curing agent is used as a component B of the epoxy resin system; the accelerant is a component C, and the weight portion ratio of the component A to the component B to the component C in the epoxy resin system is 100: 60-100: 0.5-10. The epoxy resin system is used for fiber reinforced composite materials, and low-toxicity and low-cost liquid anhydride curing agents are used for replacing amine curing agents commonly used in the industry at present, so that the production environment is improved, the glass transition temperature of composite material products is increased, the application range of the composite material products is expanded, the comprehensive performance of the composite material products is improved, and the cost is reduced. However, when the epoxy resin system is used for manufacturing the composite material pultrusion frame, the epoxy resin system has the following defects:
when the epoxy resin system is adopted to prepare the composite material pultrusion frame, the prepared composite material pultrusion frame has poor strength and toughness and cannot meet the market demand due to the poor tensile strength, fracture toughness and wear resistance of the epoxy resin system.
Disclosure of Invention
The invention aims to provide an epoxy resin system for a high-strength high-toughness composite material pultrusion frame and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
an epoxy resin system for a high-strength and high-toughness composite pultrusion frame comprises the following raw materials in parts by mass:
epoxy resin: 52-64 parts of a binder; diluent agent: 24-32 parts; curing agent: 34-46 parts; accelerator (b): 5-16 parts; modified additive: 12-24 parts; functional additive: 6-14 parts; filling: 4-12 parts.
Further, the epoxy resin is an epoxy resin containing two or more functional groups.
Further, the epoxy resin is novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acidic medium to obtain linear novolac resin, and the linear novolac resin and excessive propylene oxide are subjected to condensation polymerization in the presence of sodium hydroxide to obtain the epoxy resin, wherein the novolac epoxy resin is one or two of phenol novolac epoxy resin, o-cresol novolac epoxy resin and bisphenol A novolac epoxy resin.
Further, the diluent is one or two of epoxypropane butyl ether, epoxypropane phenyl ether and polyglycidyl ether, wherein the epoxypropane butyl ether is synthesized by two-step reaction by taking butanol and epichlorohydrin as raw materials; polyglycidyl ethers are organic ether compounds containing polyglycidyl groups.
Furthermore, the curing agent has a great influence on the performance of an epoxy resin system, is selected from the aspect of safety, generally requires low toxicity and is convenient for safe production, and the curing agent is one of an amine curing agent and an anhydride curing agent.
Further, the amine curing agent is used in an amount of MG/Hn, wherein M is amine molecular weight; hn is the number of active hydrogen-containing groups; g ═ epoxy value (number of epoxy equivalents per 100 grams of epoxy resin);
the amount of the anhydride curing agent is MG (0.6-1)/100, wherein M is the molecular weight of the anhydride; g ═ epoxy value; (0.6-1) is an experimental coefficient.
Further, the modified additive is one or two of vinyl resin, polyamide resin and polyvinyl butyral, wherein the vinyl resin is vinyl resin synthesized by reaction of methacrylic acid and bisphenol A epoxy resin and is easily soluble in styrene solution; the polyamide resin is a polycondensation type high molecular compound with a CONH structure in the molecule, and is obtained by polycondensation of dibasic acid and diamine; polyvinyl butyral is a product of condensation of polyvinyl alcohol and butyraldehyde under acid catalysis, and the PVB molecule contains longer branched chains.
Further, the functional additive comprises a plasticizer, a toughening agent and an anti-wear agent, wherein the mass part ratio of the plasticizer to the toughening agent to the anti-wear agent is 1: 0.5-0.8: 0.8-1.2.
Furthermore, the filler is one or two of glass fiber, quartz powder and alumina, wherein the glass fiber is prepared by taking six ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite as raw materials through high-temperature melting, wire drawing, winding and weaving processes, the diameter of each monofilament is several micrometers to twenty micrometers, which is equivalent to 1/20-1/5 of one hair strand, and each strand of fiber precursor consists of hundreds of monofilaments or even thousands of monofilaments; the quartz powder is prepared from pure quartz by crushing, sorting, cleaning, acid treatment, high-temperature melting, medium crushing, fine grinding, grading and iron removal.
According to another aspect of the invention, a preparation method of an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame is provided, which comprises the following steps:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into the stirring dispersion machine, stirring at the rotating speed of 2800-.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to an epoxy resin system for a high-strength high-toughness composite material pultrusion frame and a preparation method thereof, wherein a functional additive is added into the epoxy resin system, and the functional additive comprises a plasticizer, a toughening agent and a wear-resisting agent, wherein the mass part ratio of the plasticizer to the toughening agent to the wear-resisting agent is 1: 0.5-0.8: 0.8-1.2, can effectively improve the tensile strength, the fracture toughness and the wear resistance of the epoxy resin system, greatly improve the epoxy resin system, and have the characteristics of high strength and high toughness when the epoxy resin system is adopted to prepare the composite material pultrusion frame, thereby having wide market prospect.
Drawings
FIG. 1 is a flow diagram of the preparation of an epoxy resin system of the present invention;
FIG. 2 is a graph showing the effect of the addition of the functional admixture of the present invention on the tensile strength properties of an epoxy resin system;
FIG. 3 is a graph showing the effect of the addition of the functional admixture of the present invention on the fracture toughness performance of an epoxy resin system;
FIG. 4 is a graph showing the effect of the addition of the functional admixture of the present invention on the abrasion resistance of an epoxy resin system.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Referring to fig. 1, an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame comprises the following raw materials in parts by weight:
epoxy resin: 52 parts of (1); diluent agent: 24 parts of (1); curing agent: 34 parts of (a); accelerator (b): 5 parts of a mixture; modified additive: 12 parts of (1); functional additive: 6 parts of (1); filling: 4 parts.
The epoxy resin is phenol novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acidic medium to obtain linear phenolic resin, and the linear phenolic resin and excessive propylene oxide are subjected to condensation polymerization in the presence of sodium hydroxide to obtain the phenol novolac epoxy resin.
The diluent is epoxypropane butyl ether, wherein the epoxypropane butyl ether is synthesized by two-step reaction by taking butanol and epichlorohydrin as raw materials.
The curing agent has great influence on the performance of an epoxy resin system, is selected from safety, generally requires low toxicity and is convenient for safe production, and the curing agent is an amine curing agent.
The dosage of the amine curing agent is MG/Hn, wherein M is amine molecular weight; hn is the number of active hydrogen contained; g ═ epoxy value (number of epoxy equivalents per 100 grams of epoxy resin).
The modified additive is vinyl resin, wherein the vinyl resin is vinyl resin synthesized by reaction of methacrylic acid and bisphenol A epoxy resin and is easily soluble in styrene solution.
The functional additive comprises a plasticizer, a toughening agent and an abrasion-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the abrasion-resistant agent is 1: 0.6: 0.8.
the filler is glass fiber, wherein the glass fiber is prepared from six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding and weaving, the diameter of each monofilament is several micrometers to twenty micrometers, the monofilament is equivalent to 1/20-1/5 of one hair, and each bundle of fiber precursor consists of hundreds of monofilaments and even thousands of monofilaments.
In order to better show the preparation process of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, the embodiment now provides a preparation method of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, which includes the following steps:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into a stirring dispersion machine, stirring at the rotating speed of 2800-.
Example two
Referring to fig. 1, an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame comprises the following raw materials in parts by weight:
epoxy resin: 64 parts; diluent agent: 32 parts of (1); curing agent: 46 parts of (a); accelerator (b): 16 parts of a mixture; modified additive: 24 parts of (1); functional additive: 6 parts of (1); filling: 12 parts.
The epoxy resin is epoxy resin containing more than two functions, the epoxy resin is novolac epoxy resin, phenol and formaldehyde are subjected to polycondensation reaction in an acidic medium to obtain linear phenolic resin, and the linear phenolic resin and excessive propylene oxide are subjected to polycondensation reaction in the presence of sodium hydroxide to obtain the epoxy resin, wherein the novolac epoxy resin is o-cresol novolac epoxy resin.
The diluent is polyglycidyl ether, and the polyglycidyl ether is an organic ether compound containing polyglycidyl groups.
The curing agent has great influence on the performance of an epoxy resin system, is selected from safety, generally requires low toxicity and is convenient for safe production, and the curing agent is an anhydride curing agent.
The amount of the anhydride curing agent is MG (0.6-1)/100, wherein M is the molecular weight of the anhydride; g ═ epoxy value; (0.6-1) is an experimental coefficient.
The modified additive is polyamide resin, wherein the polyamide resin is a polycondensation type high molecular compound with a CONH structure in the molecule, and is obtained by polycondensation of dibasic acid and diamine.
The functional additive comprises a plasticizer, a toughening agent and an abrasion-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the abrasion-resistant agent is 1: 0.6: 1.0.
the filler is quartz powder, wherein the quartz powder is powder which is processed by pure quartz through multiple procedures of crushing, sorting, cleaning, acid treatment, high-temperature melting, medium crushing, fine grinding, grading and iron removal and meets the use requirement.
In order to better show the preparation process of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, the embodiment now provides a preparation method of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, which includes the following steps:
s1: adding epoxy resin and a diluent into an emulsification dispersion machine, stirring and dispersing at the rotating speed of 3400-;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into the stirring dispersion machine, stirring at the rotating speed of 2800-.
EXAMPLE III
Referring to fig. 1, an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame comprises the following raw materials in parts by mass:
epoxy resin: 52 parts of (1); diluent agent: 24 parts of (1); curing agent: 34 parts of a binder; accelerator (b): 5 parts of a mixture; modified additive: 12 parts of (1); functional additive: 10 parts of (A); filling: 4 parts.
The epoxy resin is epoxy resin containing more than two functions, the epoxy resin is novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acidic medium to obtain linear phenolic resin, and the linear phenolic resin and excessive propylene oxide are subjected to condensation polymerization in the presence of sodium hydroxide to obtain the epoxy resin, wherein the novolac epoxy resin is bisphenol A type novolac epoxy resin.
The diluent is epoxypropane butyl ether, wherein the epoxypropane butyl ether is synthesized by two-step reaction by taking butanol and epichlorohydrin as raw materials.
The curing agent has great influence on the performance of an epoxy resin system, is selected from safety, generally requires low toxicity and is convenient for safe production, and the curing agent is an amine curing agent.
The dosage of the amine curing agent is MG/Hn, wherein M is amine molecular weight; hn is the number of active hydrogen contained; g ═ epoxy value (number of epoxy equivalents per 100 grams of epoxy resin).
The modified additive is polyvinyl butyral, wherein the polyvinyl butyral is a product obtained by condensing polyvinyl alcohol and butyraldehyde under the catalysis of acid, and PVB molecules of the polyvinyl butyral contain longer branched chains.
The functional additive comprises a plasticizer, a toughening agent and an abrasion-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the abrasion-resistant agent is 1: 0.8: 1.2.
the filler is glass fiber, wherein the glass fiber is prepared from six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding and weaving, the diameter of each monofilament is several micrometers to twenty micrometers, the monofilament is equivalent to 1/20-1/5 of one hair, and each bundle of fiber precursor consists of hundreds of monofilaments and even thousands of monofilaments.
In order to better show the preparation process of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, the embodiment now provides a preparation method of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, which includes the following steps:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into a stirring dispersion machine, stirring at the rotating speed of 2800-.
Example four
Referring to fig. 1, an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame comprises the following raw materials in parts by weight:
epoxy resin: 52 parts of (1); diluent (b): 24 parts of (1); curing agent: 34 parts of (a); accelerator (b): 5 parts of a mixture; modified additive: 12 parts of (1); functional additive: 8 parts; filling: 4 parts.
The epoxy resin is phenol novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acidic medium to obtain linear phenolic resin, and the linear phenolic resin and excessive propylene oxide are subjected to condensation polymerization in the presence of sodium hydroxide to obtain the phenol novolac epoxy resin.
The diluent is epoxypropane butyl ether, wherein the epoxypropane butyl ether is synthesized by two-step reaction by taking butanol and epichlorohydrin as raw materials.
The curing agent has great influence on the performance of an epoxy resin system, is selected from safety, generally requires low toxicity and is convenient for safe production, and the curing agent is an amine curing agent.
The dosage of the amine curing agent is MG/Hn, wherein M is amine molecular weight; hn is the number of active hydrogen contained; g ═ epoxy value (number of epoxy equivalents per 100 grams of epoxy resin).
The modified additive is vinyl resin, wherein the vinyl resin is vinyl resin synthesized by reaction of methacrylic acid and bisphenol A epoxy resin and is easily soluble in styrene solution.
The functional additive comprises a plasticizer, a toughening agent and an abrasion-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the abrasion-resistant agent is 1: 0.6: 0.8.
the filling material is quartz powder, wherein the quartz powder is powder which meets the use requirement and is processed by pure quartz through a plurality of procedures of crushing, sorting, cleaning, acid treatment, high-temperature melting, medium crushing, fine grinding, grading and iron removal.
In order to better show the preparation process of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, the embodiment now provides a preparation method of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, which includes the following steps:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into a stirring dispersion machine, stirring at the rotating speed of 2800-.
EXAMPLE five
Referring to fig. 1, an epoxy resin system for a high-strength and high-toughness composite material pultrusion frame comprises the following raw materials in parts by weight:
epoxy resin: 52 parts of (1); diluent agent: 24 parts of (1); curing agent: 34 parts of (a); accelerator (b): 5 parts of a mixture; modified additive: 12 parts of (1); functional additive: 12 parts of (1); filling: 4 parts.
The epoxy resin is epoxy resin with more than two functions, the epoxy resin is novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acid medium to obtain linear phenolic resin, and the linear phenolic resin and excessive propylene oxide are subjected to condensation polymerization in the presence of sodium hydroxide to obtain the epoxy resin, wherein the novolac epoxy resin is o-cresol novolac epoxy resin.
The diluent is polyglycidyl ether, wherein the polyglycidyl ether is an organic ether compound containing polyglycidyl groups.
The curing agent has great influence on the performance of an epoxy resin system, is selected from safety, generally requires low toxicity and is convenient for safe production, and the curing agent is an anhydride curing agent.
The dosage of the anhydride curing agent is MG (0.6-1)/100, wherein M is anhydride molecular weight; g ═ epoxy value; (0.6-1) is an experimental coefficient.
The modified additive is vinyl resin, wherein the vinyl resin is vinyl resin synthesized by reaction of methacrylic acid and bisphenol A epoxy resin and is easily soluble in styrene solution.
The functional additive comprises a plasticizer, a toughening agent and an abrasion-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the abrasion-resistant agent is 1: 0.6: 1.1.
the filler is glass fiber, wherein the glass fiber is prepared from six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding and weaving, the diameter of each monofilament is several micrometers to twenty micrometers, the monofilament is equivalent to 1/20-1/5 of one hair, and each bundle of fiber precursor consists of hundreds of monofilaments and even thousands of monofilaments.
In order to better show the preparation process of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, the embodiment now provides a preparation method of the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame, which includes the following steps:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into a stirring dispersion machine, stirring at the rotating speed of 2800-.
Comparative example
An epoxy resin system comprises the following raw materials in parts by weight:
epoxy resin: 52 parts of (1); diluent agent: 24 parts of (1); curing agent: 34 parts of (a); accelerator (b): 5 parts of a mixture; modified additive: 12 parts of (1); filling: 4 parts.
Epoxy resin systems were prepared according to the mass parts of the raw materials described in examples 1 to 5 and comparative examples, and the prepared epoxy resin systems were subjected to performance tests as follows:
1. tensile strength property test (test according to relevant provisions of GB/T3354):
taking 5 parts of standard sample and 1 part of comparison sample, wherein the size of the sample is 12.5 x 2.2mm, symmetrically clamping the sample in an upper clamp and a lower clamp, starting a testing machine, and loading at a stable speed within 5mm/min, wherein the tensile strength T is F/(b.l), and the formula is as follows: f is the maximum load of the sample for shearing failure; b is the sample width; l is the length of the sample; and the maximum load of shear failure of the sample was recorded as shown in table 1:
table 1: tensile Strength Performance test
Referring to fig. 2, the epoxy resin systems prepared according to the raw materials of examples 1 to 5 have a higher tensile strength than the epoxy resin systems prepared according to the comparative examples, and the tensile strength of the epoxy resin systems can be significantly improved by the functional additives added to the epoxy resin systems.
2. Fracture toughness property test (test according to relevant regulations of GB/T37900):
measuring the thickness B of a sample at the ligament part at the front edge of the fatigue crack, measuring the width W of the sample near a notch, measuring for 3 times, taking an average value, installing a three-point bending test base, enabling a loading line to pass through the middle point of a span S, enabling the central line of the notch to just fall on the middle point of the span when the sample is placed, enabling the axial line of the sample and a supporting roller to form a right angle, connecting the wiring of a load sensor and a displacement sensor into a dynamic strain gauge according to a full bridge method respectively, carrying out balance adjustment, connecting the load and displacement output signals to Y and X wiring terminals of a function recorder respectively by using a dynamic output gear, adjusting the amplification ratio of the function recorder to enable the initial slope of a recording curve to be between 0.7 and 1.5, starting a testing machine, slowly and uniformly loading the sample, selecting a loading speed, and recording the numerical values of any initial load and breaking load on a P-V curve during loading, so as to calibrate the load on the P-V curve, crush the sample after the loading is finished, take the recorded curve from the X-Y series experiment recorder, and record the fracture toughness property of the sample, as shown in Table 2:
table 2: fracture toughness Property test
Referring to fig. 3, the epoxy resin systems prepared according to the raw materials of examples 1 to 5 have better fracture toughness than the epoxy resin systems prepared according to the comparative example, and the functional additive added into the epoxy resin system can significantly improve the fracture toughness of the epoxy resin systems.
3. Abrasion resistance test (test according to the relevant regulations of GB/T3903.2):
the weight change of the sample before and after the abrasion test is measured by a weighing method, the difference is the abrasion loss, and the abrasion loss W is G1-G2, wherein: w is the abrasion loss of the sample; g1 is the specimen weight before the abrasion test; g2 is the sample weight after the abrasion test; and the amount of wear of the test specimens was recorded as shown in table 3:
table 3: abrasion resistance test
Referring to fig. 4, the epoxy resin systems prepared according to the raw materials of examples 1 to 5 have better wear resistance than the epoxy resin systems prepared according to the comparative examples, and the functional additive added into the epoxy resin systems can significantly improve the wear resistance of the epoxy resin systems.
In summary, according to the epoxy resin system for the high-strength and high-toughness composite material pultrusion frame and the preparation method thereof, the functional additive is added into the epoxy resin system, and the functional additive comprises the plasticizer, the toughening agent and the wear-resisting agent, wherein the mass part ratio of the plasticizer to the toughening agent to the wear-resisting agent is 1: 0.5-0.8: 0.8-1.2, can effectively improve the tensile strength, the fracture toughness and the wear resistance of the epoxy resin system, greatly improve the epoxy resin system, and have the characteristics of high strength and high toughness when the epoxy resin system is adopted to prepare the composite material pultrusion frame, thereby having wide market prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. The high-strength high-toughness epoxy resin system for the pultrusion frame of the composite material is characterized by comprising the following raw materials in parts by mass:
epoxy resin: 52-64 parts of; diluent agent: 24-32 parts; curing agent: 34-46 parts; accelerator (b): 5-16 parts; modified additive: 12-24 parts; functional additive: 6-14 parts; filling: 4-12 parts.
2. The epoxy resin system for the high strength and high toughness composite pultruded edge frame of claim 1, wherein said epoxy resin is an epoxy resin comprising two or more functionalities.
3. The epoxy resin system for pultrusion of the composite material with high strength and high toughness as claimed in claim 2, wherein the epoxy resin is novolac epoxy resin, phenol and formaldehyde are subjected to condensation polymerization in an acidic medium to obtain novolac resin, and then the novolac epoxy resin is subjected to condensation polymerization with excess propylene oxide in the presence of sodium hydroxide, wherein the novolac epoxy resin is one or two of phenol novolac epoxy resin, o-cresol novolac epoxy resin and bisphenol a novolac epoxy resin.
4. The epoxy resin system for the high-strength and high-toughness composite material pultrusion frame as claimed in claim 1, wherein the diluent is one or two of propylene oxide butyl ether, propylene oxide phenyl ether and polyglycidyl ether, wherein the propylene oxide butyl ether is synthesized by two-step reaction by using butanol and epichlorohydrin as raw materials; polyglycidyl ethers are organic ether compounds containing polyglycidyl groups.
5. The epoxy resin system for the high-strength high-toughness composite material pultruded jamb according to claim 1, wherein said curing agent is one of amine curing agent and acid anhydride curing agent.
6. The epoxy resin system for pultrusion of high-strength and high-toughness composite material as claimed in claim 5, wherein said amine curing agent is used in an amount of MG/Hn, where M is amine molecular weight; hn is the number of active hydrogen contained; g ═ epoxy value;
the amount of the anhydride curing agent is MG/100, wherein M is the molecular weight of the anhydride; g ═ epoxy value; are experimental coefficients.
7. The epoxy resin system for the pultrusion frame of the high-strength and high-toughness composite material as claimed in claim 1, wherein the modification additive is one or two of vinyl resin, polyamide resin and polyvinyl butyral, wherein the vinyl resin is vinyl resin synthesized by reaction of methacrylic acid and bisphenol A epoxy resin and is easily soluble in styrene solution; the polyamide resin is a polycondensation type high molecular compound with a CONH structure in the molecule, and is obtained by polycondensation of dibasic acid and diamine; polyvinyl butyral is a product of condensation of polyvinyl alcohol and butyraldehyde under acid catalysis, and the PVB molecule contains longer branched chains.
8. The epoxy resin system for the high-strength high-toughness composite material pultrusion frame as claimed in claim 1, wherein the functional additive comprises a plasticizer, a toughening agent and a wear-resistant agent, wherein the mass part ratio of the plasticizer to the toughening agent to the wear-resistant agent is 1: 0.5-0.8: 0.8-1.2.
9. The epoxy resin system for the pultrusion frame made of the high-strength and high-toughness composite material as claimed in claim 1, wherein the filler is one or two of glass fiber, quartz powder and alumina, wherein the glass fiber is made of six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through high-temperature melting, wire drawing, winding and weaving, the diameter of a monofilament is several micrometers to twenty-several micrometers, and the quartz powder is powder which is processed by pure quartz through multiple processes of crushing, sorting, cleaning, acid treatment, high-temperature melting, medium crushing, fine grinding, grading and iron removal and meets the use requirement.
10. A method for preparing the epoxy resin system for the high-strength high-toughness composite material pultruded jamb according to any of claims 1 to 9, comprising the steps of:
s1: adding epoxy resin and a diluent into an emulsifying and dispersing machine, stirring and dispersing at the rotating speed of 3400 plus 6200r/min for 20-30min until the solid content is 1% -4%, and dispersing until the particle size is 120 plus 260nm to obtain epoxy resin emulsion;
s2: adding epoxy resin emulsion and a curing agent into a stirring and dispersing machine, stirring and dispersing at the rotating speed of 2400-3600r/min for 10-24min, after stirring and dispersing, adding an accelerant and a modified additive into the stirring and dispersing machine, stirring and dispersing at the rotating speed of 2600-4200r/min for 14-26min, and fully dissolving and mixing;
s3: adding the functional additive and the filler into a stirring dispersion machine, stirring at the rotating speed of 2800-.
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