CN117467244A - Epoxy resin material for pultrusion process and preparation method and application thereof - Google Patents
Epoxy resin material for pultrusion process and preparation method and application thereof Download PDFInfo
- Publication number
- CN117467244A CN117467244A CN202311366336.5A CN202311366336A CN117467244A CN 117467244 A CN117467244 A CN 117467244A CN 202311366336 A CN202311366336 A CN 202311366336A CN 117467244 A CN117467244 A CN 117467244A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- parts
- resin material
- pultrusion process
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 229920002545 silicone oil Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000009736 wetting Methods 0.000 claims abstract description 13
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 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
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- 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 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000003939 benzylamines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002955 isolation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 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 description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
Abstract
An epoxy resin material for a pultrusion process comprises, in mass ratio, 100: (80-120) a component A and a component B; the component A comprises the following components: 70-95 parts of epoxy resin, 5-15 parts of reactive diluent, 0.5-10 parts of hydroxyl silicone oil and 1-20 parts of wetting dispersant, wherein the component B comprises the following components: 70-90 parts of anhydride curing agent, 5-15 parts of toughening agent and 1-5 parts of accelerator. The invention also discloses a preparation method of the epoxy resin material. According to the invention, the hydroxy silicone oil is added into the epoxy resin material for the pultrusion process, the hydroxy silicone oil is completely compatible with the epoxy resin before the epoxy resin is cured, and the hydroxy silicone oil is partially incompatible with the epoxy resin after the epoxy resin is cured, so that little hydroxy silicone oil is separated out from the epoxy resin after the epoxy resin is cured, and a layer of isolation film is formed between a die and a product, so that a good demolding effect is achieved, and the epoxy resin material for the pultrusion process does not need to be added with a demolding agent.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an epoxy resin material for a pultrusion process, and a preparation method and application thereof.
Background
The pultrusion process is a process method for continuously producing composite materials, which is characterized in that reinforcing materials infiltrate into resin colloid, then enter a forming die for heating and curing, finally are pulled out by a traction device and cut into fixed-length products by a cutting device, and the method is focused on the advantages of low manufacturing cost, high raw material utilization rate, high automation degree, excellent mechanical properties of products, stable performance and the like, and has wide application in the fields of wind power, transportation, aerospace and the like.
With the wide application of the pultrusion process, the performance requirement on the epoxy resin matrix is higher and higher, and the cost requirement is lower and lower. However, the performance of the current epoxy resin for pultrusion is still to be improved, and the current epoxy resin must be added with a release agent in the pultrusion process, and the release agent is expensive, and the cost is usually more than 150 yuan/kg.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing an epoxy resin material for a pultrusion process with low cost, high toughness and no release agent, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an epoxy resin material for a pultrusion process, comprising the following components in percentage by mass: the component A and the component B of (80-120) comprise the following raw materials in parts by mass:
70-95 parts of epoxy resin, 5-15 parts of reactive diluent, 0.5-10 parts of hydroxyl silicone oil and 1-20 parts of wetting dispersant, wherein the hydroxyl end content of the hydroxyl silicone oil is 4-8%, the viscosity is 400-1000cp, and the number average molecular weight is 2000-8000;
the component B comprises the following raw materials:
70-90 parts of anhydride curing agent, 5-15 parts of toughening agent and 1-5 parts of accelerator.
The epoxy resin material for the pultrusion process is preferably one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin, wherein the epoxy value of the epoxy resin is 0.44-0.56mol/100g.
In the epoxy resin material for the pultrusion process, preferably, the reactive diluent is one or more of difunctional glycidyl ether and trifunctional glycidyl ether.
In the above epoxy resin material for pultrusion process, preferably, the wetting dispersant is one or more of BYK-310, digaKL 245, KYC-643 and BYK-W9010.
The epoxy resin material for the pultrusion process is preferably one or more of an F-100 toughening agent, a polyester polyol, a 'core-shell structure' toughening agent and a carboxyl-terminated nitrile rubber, wherein the 'core-shell structure' toughening agent refers to a core-shell emulsion polymer of the core-shell rubber.
In the epoxy resin material for the pultrusion process, preferably, the anhydride curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.
The epoxy resin material for the pultrusion process is preferably one in which the accelerator is at least two selected from tertiary amines, quaternary ammonium salts, imidazole compounds, benzylamine compounds and acetylacetonate metal chelates.
The epoxy resin material for the pultrusion process preferably contains no release agent.
The present invention also provides a method for preparing the epoxy resin material for the pultrusion process, which comprises the following steps:
(1) Adding epoxy resin and an active diluent into a reaction kettle, heating to 80-90 ℃, stirring and mixing, then cooling to 50-60 ℃, adding hydroxyl silicone oil and a wetting and dispersing agent, continuously stirring for 40-60 min, and then vacuum defoaming to obtain a component A;
(2) Adding an anhydride curing agent into a reaction kettle, stirring and heating to 80-90 ℃, adding a toughening agent, stirring for 1-3 h, cooling to 40-50 ℃, adding a promoter, and stirring for 60-90 min at a constant temperature to obtain a component B;
(3) And weighing the component A and the component B according to the weight ratio to finish the preparation of the epoxy resin material for the pultrusion process.
The invention also provides an application of the epoxy resin material for the pultrusion process or the epoxy resin material obtained by the preparation method in the reinforced fiber composite material.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the hydroxy silicone oil is added into the epoxy resin material for the pultrusion process, the hydroxy silicone oil is completely compatible with the epoxy resin before the epoxy resin is cured, and the hydroxy silicone oil is partially incompatible with the epoxy resin after the epoxy resin is cured, so that little hydroxy silicone oil is separated out from the epoxy resin after the epoxy resin is cured, and a layer of isolation film is formed between a die and a product, so that a good demolding effect is achieved, and the epoxy resin material for the pultrusion process does not need to be added with a demolding agent, and the cost of the hydroxy silicone oil is 75% lower than that of the demolding agent in the prior art, and can greatly reduce the cost of the epoxy resin material.
(2) After the component A and the component B of the epoxy resin material for the pultrusion process are mixed and cured, hydroxyl silicone oil can also play a synergistic effect with the toughening agent, and the homogeneous phase system of the epoxy resin cured product is changed into a multiphase system, namely, a sea-island structure is formed, so that the mechanical property and fatigue property of the pultrusion product are synergistically improved.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the specific embodiments described below.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The various reagents and materials used in the present invention are commercially available or may be prepared by known methods unless otherwise specified.
Example 1:
the invention relates to an epoxy resin material for a pultrusion process, which comprises the following components in percentage by mass: 105, a component a and a component B; the component A comprises the following raw materials in parts by mass:
88 parts of E51 bisphenol A epoxy resin, 6 parts of reactive diluent (1, 4-butanediol diglycidyl ether), 5 parts of hydroxyl silicone oil (with 5% of terminal hydroxyl group content, 800cp of viscosity and 3000 of number average molecular weight), and 1 part of wetting dispersant (digaKL 245);
the component B comprises the following raw materials:
90 parts of methyltetrahydrophthalic anhydride, 12 parts of F-100 toughening agent and the accelerator is as follows: 2 parts of dimethylbenzylamine and 1 part of DMP-30.
The preparation method of the epoxy resin material for the pultrusion process in the embodiment specifically comprises the following steps:
(1) Adding 88 parts of E51 bisphenol A epoxy resin and 6 parts of 1, 4-butanediol diglycidyl ether active diluent into a reaction kettle, heating to 80 ℃, stirring and mixing, then cooling to 50 ℃, adding 5 parts of hydroxyl-terminated silicone oil with 5% of hydroxyl-terminated content, viscosity of 800cp, number average molecular weight of 3000 and 1 part of wetting dispersant diGao KL245, continuously stirring for 50min, and then carrying out vacuum defoaming to obtain a component A;
(2) 90 parts of methyltetrahydrophthalic anhydride is added into a reaction kettle, stirred and heated to 80 ℃, 12 parts of F-100 toughening agent is added, stirred for 2 hours, cooled to 40 ℃, 2 parts of dimethylbenzylamine and 1 part of DMP-30 are added, and the temperature is kept for 90 minutes, and after the solution is completely dissolved, the component B is obtained.
When in use, the component A and the component B are mixed according to the weight ratio of 100:105 mass ratio was mixed.
Example 2:
the invention relates to an epoxy resin material for a pultrusion process, which comprises the following components in percentage by mass: 102, a component A and a component B; the component A comprises the following raw materials in parts by mass:
40 parts of E51 bisphenol A epoxy resin, 45 parts of bisphenol F epoxy resin (with an epoxy value of 0.56mol/100 g), 10 parts of reactive diluent (1, 4-butanediol diglycidyl ether), 4 parts of hydroxyl silicone oil (with a hydroxyl end content of 7%, a viscosity of 600cp and a molecular weight of 2500) and 1 part of wetting dispersant (BYK-310);
the component B comprises the following raw materials:
35 parts of methyltetrahydrophthalic anhydride, 40 parts of methylhexahydrophthalic anhydride, 12 parts of methylnadic anhydride, 12 parts of carboxyl terminated nitrile rubber and an accelerator: 2 parts of tetrabutylammonium iodide and 1 part of DMP-30.
The preparation method of the epoxy resin material for the pultrusion process in the embodiment specifically comprises the following steps:
(1) Adding 40 parts of E51 bisphenol A epoxy resin, 45 parts of bisphenol F epoxy resin and 10 parts of 1, 4-butanediol diglycidyl ether active diluent into a reaction kettle, heating to 85 ℃, stirring and mixing, then cooling to 50 ℃, adding 4 parts of hydroxyl silicone oil and 1 part of wetting dispersant BYK-310, continuing stirring for 50min, and vacuum defoaming to obtain a component A;
(2) Adding 35 parts of methyltetrahydrophthalic anhydride, 40 parts of methylhexahydrophthalic anhydride and 12 parts of methylnadic anhydride into a reaction kettle, stirring and heating to 80 ℃, adding 12 parts of toughener carboxyl-terminated nitrile rubber, stirring for 3 hours, cooling to 40 ℃, adding 2 parts of tetrabutylammonium iodide and 1 part of DMP-30 as accelerators, preserving heat and stirring for 90 minutes, and obtaining the component B after complete dissolution.
When in use, the component A and the component B are mixed according to the weight ratio of 100: 102.
Example 3:
the invention relates to an epoxy resin material for a pultrusion process, which comprises the following components in percentage by mass: 103, an A component and a B component; the component A comprises the following raw materials in parts by mass:
85 parts of E54 bisphenol A epoxy resin, 9 parts of 1, 6-hexanediol diglycidyl ether active diluent, 5 parts of hydroxyl silicone oil (with 7% of terminal hydroxyl group content, 900cp of viscosity and 5000 of molecular weight) and 1 part of wetting dispersant (digao KL 245);
the component B comprises the following raw materials:
88 parts of methyl hexahydrophthalic anhydride, 12 parts of a 'core-shell structure' flexibilizer (Brillouin chemical MX-125), 2 parts of a promoter, namely benzyl triethyl ammonium chloride and 1 part of tetrabutyl ammonium bromide.
The preparation method of the epoxy resin material for the pultrusion process in the embodiment specifically comprises the following steps:
(1) 85 parts of E54 bisphenol A epoxy resin and 9 parts of 1,6 hexanediol diglycidyl ether active diluent are added into a reaction kettle, the temperature is raised to 90 ℃, stirring and mixing are carried out, then the temperature is lowered to 50 ℃, 5 parts of hydroxyl silicone oil with the hydroxyl end content of 7 percent and the viscosity of 900cp and 1 part of wetting dispersant diGao KL245 are added, and after stirring is continued for 60 minutes, the component A is obtained through vacuum defoaming.
(2) 88 parts of methyl hexahydrophthalic anhydride is added into a reaction kettle, stirred and heated to 90 ℃, 12 parts of a core-shell structure toughening agent Brillouin chemical MX-125 is added, stirred for 3 hours, then cooled to 50 ℃, 2 parts of benzyl triethyl ammonium chloride and 1 part of tetrabutylammonium bromide are added as accelerators, and the mixture is stirred for 90 minutes under heat preservation, so that the component B is obtained after complete dissolution.
When in use, the component A and the component B are mixed according to the weight ratio of 100:103, and mixing them.
Comparative example 1:
the epoxy resin material for the pultrusion process of this comparative example is different from comparative document 1 in that no hydroxy silicone oil is added to the a component, and the remaining formulation is the same as in example 1.
When in use, the component A and the component B are mixed according to the weight ratio of 100:100, and 1.5 parts of an AXEL 1890 internal mold release agent was added for mixing during the pultrusion.
Comparative example 2:
in this comparative example, a commercial pultrusion epoxy resin and curing agent composition (Hui Bai AP-3009) was used, and samples were prepared according to the proportions described in the specification, and 1.5 parts of an AXEL 1890 internal mold release agent was added and mixed during the pultrusion.
The epoxy resin materials in each of the examples and comparative examples were subjected to performance test, and the results are shown in table 1.
Table 1 performance parameters of the epoxy resin materials in each of examples and comparative examples
As can be seen from Table 1, the properties of each example are better than those of comparative example 1 without the addition of the hydroxy silicone oil and better than those of comparative example 2, which is a commercially available epoxy resin for pultrusion, due to the combination of the hydroxy silicone oil and the toughening agent.
The components A and B in the examples and the comparative examples are uniformly mixed according to the respective mass ratio and then transferred into a dipping glue groove (wherein the comparative examples need to be added with a release agent), the glue content of 20wt% and reinforcing fiber (model TM+468GE-2000 of Chongqing International composite material Co., ltd.) are controlled, and the epoxy resin-based composite material is prepared by a pultrusion process and cured and molded, wherein the main process comprises the following steps: and (3) three sections of pultrusion, namely setting the temperature of a die: the first stage area is pre-cured at 140-150 ℃, the second stage area is basically cured at 170-180 ℃, the third stage area is further cured at 190 ℃, and the performance parameters of the prepared pultruded composite are shown in the following table 2 after being cured and molded by a three-stage mold.
Table 2 performance parameters of pultruded composites prepared in examples and comparative examples
As can be seen from table 2, the performance of the composite material products obtained by pultrusion of the epoxy resin materials in comparative examples 1 and 2 is lower than that of the composite material products obtained by pultrusion of the epoxy resin materials in examples at 0 ° and 90 ° in terms of tensile and compression, and particularly, the fatigue performance is more outstanding, which also proves that the toughness of the epoxy resin materials of the invention is improved well.
Then, a single pultrusion test was performed using the composite epoxy resin material of comparative example 1 (no release agent was added), and the remaining conditions were identical to those of the pultrusion of comparative example 1. In the process of pultrusion trial without adding a release agent, serious sticking phenomenon exists, and abnormal sound appears on a die along with the time, so that the pultrusion work can not be finally performed. The composite epoxy resin material has good demolding effect because no internal demolding agent is added, and the resin and the mold have good bonding effect, so that the friction between the resin and the mold cannot be reduced, and further the technical effect of continuous demolding cannot be achieved.
In summary, the epoxy resin material of the invention enables the epoxy resin composition to have higher glass transition temperature and better mechanical property through the synergistic effect of the components, the composite material prepared by the technology and taking the glass fiber reinforced material and the epoxy resin composition of the invention as the base materials does not need a release agent, and the finally prepared composite material has excellent static performance and fatigue performance, is suitable for a pultrusion process, and has good application prospect and market value.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the embodiments and the protection scope of the present invention, although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. An epoxy resin material for a pultrusion process, which is characterized by comprising the following components in percentage by mass: (80-120) a component A and a component B; the component A comprises the following raw materials in parts by mass:
70-95 parts of epoxy resin, 5-15 parts of reactive diluent, 0.5-10 parts of hydroxyl silicone oil and 1-20 parts of wetting dispersant, wherein the hydroxyl-terminated group content of the hydroxyl silicone oil is 4-8%, the viscosity is 400-1000cp, and the number average molecular weight is 2000-8000;
the component B comprises the following raw materials:
70-90 parts of anhydride curing agent, 5-15 parts of toughening agent and 1-5 parts of accelerator.
2. The epoxy resin material for a pultrusion process according to claim 1, wherein the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin, and the epoxy value of the epoxy resin is 0.44-0.56mol/100g.
3. The epoxy resin material for a pultrusion process according to claim 1, wherein the reactive diluent is one or more of difunctional glycidyl ether and trifunctional glycidyl ether.
4. The epoxy resin material for a pultrusion process according to claim 1, wherein the wetting dispersant is one or more of BYK-310, DYhigh KL245, KYC-643 and BYK-W9010.
5. The epoxy resin material for a pultrusion process according to claim 1, wherein the toughening agent is one or more of an F-100 toughening agent, a polyester polyol, a "core shell structure" toughening agent and a carboxyl terminated nitrile rubber.
6. The epoxy resin material for a pultrusion process according to claim 1, wherein the acid anhydride curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.
7. The epoxy resin material for a pultrusion process according to claim 1, wherein the accelerator is at least two selected from tertiary amines, quaternary ammonium salts, imidazole compounds, benzylamine compounds and acetylacetonate metal chelates.
8. The epoxy resin material for a pultrusion process according to any one of claims 1 to 7, wherein the epoxy resin material does not contain a release agent.
9. A method for producing an epoxy resin material for a pultrusion process according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) Adding epoxy resin and an active diluent into a reaction kettle, heating to 80-90 ℃, stirring and mixing, then cooling to 50-60 ℃, adding hydroxyl silicone oil and a wetting and dispersing agent, continuously stirring for 40-60 min, and then vacuum defoaming to obtain a component A;
(2) Adding an anhydride curing agent into a reaction kettle, stirring and heating to 80-90 ℃, adding a toughening agent, stirring for 1-3 h, cooling to 40-50 ℃, adding a promoter, and stirring for 60-90 min at a constant temperature to obtain a component B;
(3) And weighing the component A and the component B according to the weight ratio for standby, and completing the preparation of the epoxy resin material for the pultrusion process.
10. Use of an epoxy resin material for a pultrusion process according to any of claims 1-8 or obtained by a method of preparation according to claim 9 in a reinforced fibre composite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311366336.5A CN117467244A (en) | 2023-10-20 | 2023-10-20 | Epoxy resin material for pultrusion process and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311366336.5A CN117467244A (en) | 2023-10-20 | 2023-10-20 | Epoxy resin material for pultrusion process and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117467244A true CN117467244A (en) | 2024-01-30 |
Family
ID=89638887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311366336.5A Pending CN117467244A (en) | 2023-10-20 | 2023-10-20 | Epoxy resin material for pultrusion process and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117467244A (en) |
-
2023
- 2023-10-20 CN CN202311366336.5A patent/CN117467244A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110511536B (en) | Epoxy resin composition and preparation method thereof | |
WO2024037194A1 (en) | Epoxy resin composition having two-phase sea-island structure, composite material, and preparation methods therefor | |
CN114907548A (en) | Epoxy resin batch for pultrusion of composite material and preparation method thereof | |
JPH11302507A (en) | Epoxy resin composition for fiber-reinforced composite material, intermediate substrate for fiber-reinforced composite material and fiber-reinforced composite material | |
CN111732715B (en) | Epoxy resin system used at high temperature in normal-temperature curing and preparation method thereof | |
CN113943473B (en) | High-toughness epoxy resin composition and preparation process thereof | |
CN113897027A (en) | High-toughness and high-heat-resistance alicyclic epoxy resin and preparation method thereof | |
CN110845829A (en) | Low-temperature curing epoxy resin composition and preparation method of prepreg and composite material thereof | |
CN116535820B (en) | Epoxy anhydride resin system material for pultrusion as well as preparation method and application thereof | |
CN117467244A (en) | Epoxy resin material for pultrusion process and preparation method and application thereof | |
CN106496944B (en) | A kind of wind electricity blade high tenacity hand pasting forming composition epoxy resin and preparation method thereof | |
CN116285228A (en) | Modification method for epoxy resin synergistic toughening | |
CN114806087A (en) | Epoxy resin-anhydride system for vacuum infusion of wind power blade and preparation method thereof | |
CN115926377A (en) | Epoxy resin system for vacuum infusion process and preparation method thereof | |
JPS63221122A (en) | Prepreg and its production | |
CN1262601C (en) | High temperature resistant epoxy resin composite with lasting storage stability and temperature thixotropy | |
CN113789034A (en) | Low-heat-release epoxy resin composition and preparation method thereof | |
CN112552486A (en) | Pre-accelerated toughening anhydride curing agent, preparation method thereof and epoxy resin composition for producing pultrusion composite material | |
CN116515253B (en) | Epoxy resin curing agent, epoxy resin composition, glass fiber reinforced plastic pavement panel and preparation method thereof | |
CN115044076B (en) | Surface-modified milled fiber, preparation method thereof, high-toughness modified epoxy resin prepared from surface-modified milled fiber and preparation method of high-toughness modified epoxy resin | |
CN117362598B (en) | Epoxy resin composition with low viscosity, high strength and difficult crystallization | |
CN114230980B (en) | Dry-method cold-drawn molding prepreg and preparation method thereof | |
JPS63221139A (en) | Prepreg and its production | |
CN115960337B (en) | Epoxy resin curing agent for composite material pultrusion and preparation method thereof | |
CN114276667B (en) | Crystalline polyaryletherketone microsphere toughened polyaryletherketone material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |