CN115162006A - Water-based epoxy resin sizing agent for large-tow carbon fibers and preparation method thereof - Google Patents
Water-based epoxy resin sizing agent for large-tow carbon fibers and preparation method thereof Download PDFInfo
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- CN115162006A CN115162006A CN202210671676.8A CN202210671676A CN115162006A CN 115162006 A CN115162006 A CN 115162006A CN 202210671676 A CN202210671676 A CN 202210671676A CN 115162006 A CN115162006 A CN 115162006A
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- Prior art keywords
- epoxy resin
- agent
- sizing agent
- carbon fibers
- preparation
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 113
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 103
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 103
- 238000004513 sizing Methods 0.000 title claims abstract description 87
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 72
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000080 wetting agent Substances 0.000 claims abstract description 10
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- -1 carboxylic acid compounds Chemical class 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 5
- 229940100242 glycol stearate Drugs 0.000 claims description 5
- 229940070765 laurate Drugs 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- WNLWBCIUNCAMPH-UHFFFAOYSA-N 2-n,2-n-dimethylpropane-1,2-diamine Chemical compound NCC(C)N(C)C WNLWBCIUNCAMPH-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- MAQDBUNNVYRNQL-UHFFFAOYSA-N pent-2-ene-1,1,1,2-tetramine Chemical compound NC(C(N)(N)N)=CCC MAQDBUNNVYRNQL-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 34
- 239000000835 fiber Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 28
- 238000002791 soaking Methods 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 210000002268 wool Anatomy 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 229960004275 glycolic acid Drugs 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a water-based epoxy resin sizing agent for large-tow carbon fibers and a preparation method thereof, wherein the water-based epoxy resin sizing agent comprises 20-35 parts by weight of modified epoxy resin, 5-10 parts by weight of water-based polyurethane, 3-10 parts by weight of neutralizing agent, 0.2-1 part by weight of defoaming agent, 0.5-2 parts by weight of flatting agent, 0.3-2 parts by weight of bundling agent, 0.5-3 parts by weight of wetting agent and 37-70.5 parts by weight of deionized water; the preparation method of the waterborne epoxy resin sizing agent comprises the following steps: the method comprises the following steps: preparing modified epoxy resin; step two: preparing a waterborne epoxy resin sizing agent; the sizing agent disclosed by the invention is low in production cost, high in particle size stability, strong in bundling property, excellent in wetting property, moderate in viscosity, capable of being uniformly spread on the surface of carbon fibers and quickly permeated among fiber tows, the aqueous polyurethane resin in the sizing agent has excellent properties such as high strength, good toughness, wear resistance and the like, the amount of broken filaments of the carbon fibers after sizing is low, the textile processing property of large-tow carbon fibers can be effectively improved, and the prepared composite material has excellent interface property and fracture toughness.
Description
Technical Field
The invention relates to the technical field of sizing agents, in particular to a water-based epoxy resin sizing agent for large-tow carbon fibers and a preparation method thereof.
Background
Carbon fibers are widely used in various industries such as electronic products, sporting goods, civil construction, medical equipment, automobiles, etc. due to their excellent properties such as high strength, high modulus, high temperature resistance, corrosion resistance, etc., and carbon fibers are also used in the top field of national defense, such as: aerospace, marine, energy, petrochemical, and the like.
Sizing is an essential step in the industrial production of carbon fibers, and can improve the phenomena of fine broken filaments and monofilament breakage caused by repeated friction in the processing process of the carbon fibers.
In the carbon fiber or epoxy resin composite material, the sizing agent has the effect similar to a bridge, the bonding strength between the carbon fiber and the epoxy resin matrix is effectively promoted, the interface performance of the carbon fiber composite material is improved, when the carbon fiber or epoxy resin composite material is subjected to an external force, the sizing agent can effectively transfer load from resin to the fiber, the initiation and the propagation of cracks at the interface are inhibited, and the interface bonding between the fiber and the matrix resin is improved.
Meanwhile, the epoxy resin composite material has high brittleness and poor impact resistance, so that the application and development of the epoxy resin composite material in some technical fields with high requirements on durability and reliability are limited, and the waterborne polyurethane has high toughness and impact resistance, so that the fracture toughness of the composite material can be effectively enhanced by introducing the waterborne polyurethane into a sizing agent, and the application range of the carbon fiber/epoxy resin composite material is widened.
In addition, the aqueous polyurethane resin has excellent wear resistance, the amount of carbon fiber broken filaments after sizing is low, and the textile processing performance of the large-tow carbon fiber can be effectively improved.
The sizing agent is divided into a solvent sizing agent and a water-based sizing agent according to different dispersion media for preparing the sizing agent, and most of the solvent sizing agents adopt organic solvents as the dispersion media, so that the physical health of operators is harmed, the requirements of green chemistry are not met, and the production cost is increased.
Patent grant publication No. CN101858038B discloses a carbon fiber emulsion sizing agent, a preparation method and application thereof. In the process of preparing the epoxy resin sizing agent, a large amount of volatile organic solvent is used, and although the preparation process is simple and easy to operate, the volatile organic solvent is used, so that the specific concentration of the sizing agent is determined, the sizing agent is dispersed on the surface of carbon fibers unevenly, and the environment is polluted; the water is used as the solvent, so that the defects of the solvent sizing agent can be effectively overcome.
In recent years, an external emulsifier method is mostly adopted for preparing the waterborne epoxy resin sizing agent, although the emulsifier can be added to help epoxy resin to be better dispersed in water so as to prepare the waterborne sizing agent, residual micromolecular inactive substances such as the emulsifier and the like are easy to separate out in the sizing agent film forming process, and the chemical resistance, the water resistance and the mechanical property of the carbon fiber composite material are influenced finally.
Patent publication No. CN109183416B discloses an aqueous epoxy resin sizing agent prepared from furan-based epoxy resin, a surfactant and an auxiliary agent, which successfully avoids the problem of pollution caused by the use of an organic solvent, but the surfactant and the auxiliary agent are easy to remain and precipitate on the surface of carbon fibers, thereby reducing the mechanical properties of the carbon fibers or the epoxy resin composite material.
Patent No. CN107022901B discloses a composite water-based carbon fiber sizing agent, a preparation method and a use method thereof, the polyamide imide or epoxy resin composite water-based carbon fiber sizing agent prepared by the patent can be simultaneously applied to carbon fibers, thermosetting resin-based composite materials and carbon fibers or high-temperature resistant thermoplastic resin-based composite materials, but the problem of water absorption increase of the carbon fiber composite materials caused by precipitation of an emulsifier still cannot be solved, and the performances of water resistance, chemical resistance and the like of final products are influenced.
In recent years, the demand and the growth rate of the global market for carbon fibers show a trend of increasing year by year, and especially, the 25K large-tow carbon fibers produced by the company have obvious advantages compared with small-tow carbon fibers in price, so that the carbon fibers are widely applied to civil fields such as wind power generation, sports and leisure; however, because of more fiber bundles, the large-tow carbon fiber must ensure that the sizing agent is uniformly spread on the surface of the carbon fiber in the sizing process, and each carbon fiber is fully infiltrated, which puts higher requirements on the performance of the sizing agent.
Therefore, it is necessary to research a water-based epoxy resin sizing agent which is simple in preparation process and suitable for large-tow carbon fibers.
Disclosure of Invention
The invention aims to provide a water-based epoxy resin sizing agent for large-tow carbon fibers and a preparation method thereof, which solve the problems of poor wear resistance, spreadability, bundling property and wetting property of the existing universal epoxy resin sizing agent on the large-tow carbon fibers, poor toughness of the prepared carbon fiber reinforced epoxy resin composite material, and can also avoid the problems of precipitation of an emulsifier, strong hygroscopicity, environmental pollution caused by using an organic solvent and the like in the sizing agent preparation process by an additional emulsifier method.
In order to achieve the above purpose, the following technical scheme is provided:
the components of the aqueous epoxy resin sizing agent comprise, by weight, 20-35 parts of modified epoxy resin, 5-10 parts of aqueous polyurethane, 3-10 parts of a neutralizing agent, 0.2-1 part of a defoaming agent, 0.5-2 parts of a leveling agent, 0.3-2 parts of a bundling agent, 0.5-3 parts of a wetting agent and 37-70.5 parts of deionized water.
Preferably, the modified epoxy resin is any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenolic aldehyde type epoxy resin or a combination of any several of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin and the phenolic aldehyde type epoxy resin.
Preferably, the preparation method of the waterborne epoxy resin sizing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Placing epoxy resin to be modified, absolute ethyl alcohol and a catalyst into a three-neck flask provided with a condensation reflux device, heating to 45-60 ℃, and mechanically stirring for 10min;
(2) And (2) adding carboxylic acid compounds into the step (1), heating to 90-125 ℃, and reacting for 2-6 hours to obtain the modified epoxy resin.
Step two: preparation of waterborne epoxy resin sizing agent
And (2) cooling the modified epoxy resin in the step one to 50-60 ℃, adding a neutralizing agent for neutralization and salt formation, continuously stirring for 30-60 min, slowly dropwise adding deionized water containing a defoaming agent, a leveling agent, a bundling agent and a wetting agent into the reactant, adding waterborne polyurethane, fully stirring for 10min, and then removing absolute ethyl alcohol under a vacuum condition to obtain the self-emulsifying epoxy resin waterborne sizing agent.
Preferably, the carboxylic acid compound is any one or combination of any several of p-hydroxybenzoic acid, p-tert-butylbenzoic acid, terephthalic acid, acrylic acid, methacrylic acid, phenyl-alpha-acrylic acid, acrylic acid-beta-glycolic acid, dimethylolpropionic acid, dihydroxybenzoic acid, itaconic acid, maleic acid or maleic acid.
Preferably, the catalyst is any one of benzyltriethylammonium chloride, tetra-N-butylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and N, N-dimethylbenzylamine or a combination of any several of the benzyltriethylammonium chloride, the tetrabutylammonium bromide, the tetrabutylammonium chloride, the tetrabutyltrimethylammonium sulfate, the dodecyltrimethylammonium chloride and the N, N-dimethylbenzylamine.
Preferably, the neutralizing agent is any one of triethylamine, ammonia water, sodium hydroxide, potassium hydroxide, trimethylamine, tripropylamine ethylenediamine, propylenediamine, dimethylpropylenediamine, divinyltriamine, diethylenetriamine, triethylenetetramine, diethanolamine, triethanolamine, pentaenetetramine or polyetherpolyamine, or a combination of any several of them.
Preferably, the defoamer is one or a combination of any several of silicone water defoamer, silicone defoamer, polyalkylene glycol defoamer and higher alcohol emulsion defoamer.
Preferably, the leveling agent is one or a combination of any several of polyether modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane and alkyl modified organosiloxane.
Preferably, the bundling agent is one or a combination of two of alkyl phosphate ester surfactant of polyethylene glycol and maleic anhydride modified polypropylene.
Preferably, the wetting agent is one or a combination of any several of polyoxyethylene ether compounds, polyethylene glycol laurate and polyethylene glycol stearate.
Preferably, the large tow is any one of 24K or more carbon fibers.
The invention has the beneficial effects that:
(1) The waterborne epoxy resin sizing agent prepared by the self-emulsifying method is prepared by chemically modifying epoxy resin and then carrying out salt-forming reaction to obtain the ionic waterborne epoxy resin sizing agent, and the ionic waterborne epoxy resin sizing agent is self-emulsifying, so that the sizing agent can be prepared without an additional emulsifier.
(2) The prepared carbon fiber has excellent wettability, bundling property and wear resistance on the surface of the carbon fiber, has low hygroscopicity and proper viscosity, can be uniformly spread on the surface of the carbon fiber, can realize quick infiltration, has strong bundling property, and is suitable for large-tow carbon fibers.
(3) The water-based sizing agent prepared by the invention has small particle size and uniform distribution, can accurately regulate and control the particle size of the sizing agent by regulating the salt forming rate, has excellent stability, and can meet the requirements of long-distance transportation and long-term storage.
(4) The water-based sizing agent prepared by the invention takes water as a solvent, does not cause harm to operators and the environment, has low preparation cost, simple operation and good industrialization prospect, has excellent interface bonding performance between carbon fibers and epoxy resin after sizing, and the prepared composite material has better fracture toughness and impact resistance, solves the problem of larger brittleness of the composite material after curing, and can effectively improve the durability of the composite material.
Detailed Description
The present design will be described in detail below.
The aqueous epoxy resin sizing agent comprises, by weight, 20-35 parts of modified epoxy resin, 5-10 parts of aqueous polyurethane, 3-10 parts of a neutralizing agent, 0.2-1 part of a defoaming agent, 0.5-2 parts of a leveling agent, 0.3-2 parts of a bundling agent, 0.5-3 parts of a wetting agent and 37-70.5 parts of deionized water, wherein the modified epoxy resin is any one or a combination of any more of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic epoxy resin, preferably, the carboxylic acid compound is any one or a combination of any more of p-hydroxybenzoic acid, p-tert-butylbenzoic acid, terephthalic acid, acrylic acid, methacrylic acid, phenyl-alpha-acrylic acid, acrylic acid-beta-hydroxyacetic acid, dimethylolpropionic acid, dihydroxybenzoic acid, itaconic acid, maleic acid or maleic acid, the catalyst is any one or the combination of any several of benzyltriethylammonium chloride, tetra-N-butylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and N, N-dimethylbenzylamine, the neutralizer is any one or combination of any more of triethylamine, ammonia water, sodium hydroxide, potassium hydroxide, trimethylamine, tripropylamine ethylenediamine, propylenediamine, dimethylpropylenediamine, divinyltriamine, diethylenetriamine, triethylenetetramine, diethanolamine, triethanolamine, pentaenetetramine or polyether polyamine, and the defoamer is organosilicon aqueous defoamer, silicone defoamer, polyalkylene glycol defoamer, polyether polyamine, or the like, one or the combination of any more of the high alcohol emulsion defoaming agent, the leveling agent is one or the combination of any more of polyether modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane and alkyl modified organosiloxane, the bundling agent is one or the combination of two of alkyl phosphate surfactant of polyethylene glycol and maleic anhydride modified polypropylene, and the wetting agent is one or the combination of any more of polyoxyethylene ether compound, polyethylene glycol laurate and polyethylene glycol stearate.
The preparation method of the waterborne epoxy resin sizing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Placing epoxy resin to be modified, absolute ethyl alcohol and a catalyst into a three-neck flask provided with a condensation reflux device, heating to 45-60 ℃, and mechanically stirring for 10min;
(2) And (2) adding carboxylic acid compounds into the step (1), heating to 90-125 ℃, and reacting for 2-6 hours to obtain the modified epoxy resin.
Step two: preparation of waterborne epoxy resin sizing agent
And (2) cooling the modified epoxy resin in the step one to 50-60 ℃, adding a neutralizing agent for neutralization and salt formation, continuously stirring for 30-60 min, slowly dropwise adding deionized water containing a defoaming agent, a leveling agent, a bundling agent and a wetting agent into the reactant, adding waterborne polyurethane, fully stirring for 10min, and then removing absolute ethyl alcohol under a vacuum condition to obtain the self-emulsifying epoxy resin waterborne sizing agent.
Wherein the large tows are any one of carbon fibers of more than 24K.
Example 1
(1) 37g of epoxy resin E51, 20mL of absolute ethanol and 0.5g of tetra-n-butylammonium bromide are added into a three-neck flask provided with a condensation reflux device, mechanical stirring is carried out for 10min at 50 ℃, then 13g of itaconic acid is added, the temperature is raised to 110 ℃, and the reaction is carried out for 3 hours at the rotating speed of 200rpm, thus obtaining the modified epoxy resin.
(2) Cooling the modified epoxy resin obtained in the step (1) to 50 ℃, dropwise adding 10.1g of triethylamine to neutralize and salify, after reacting for 30 minutes, increasing the rotating speed to 300rpm, slowly dropwise adding a mixture of 0.5g of organic silicon water-based defoaming agent, 0.6g of polyether modified polysiloxane, 0.8g of alkyl phosphate surfactant of polyethylene glycol and maleic anhydride modified polypropylene, 1g of polyethylene glycol laurate and 90mL of deionized water, then adding 5g of waterborne polyurethane to fully stir for 10 minutes, and then removing anhydrous ethanol in the emulsion under a vacuum condition to obtain the waterborne epoxy resin sizing agent.
(3) Soaking and running carbon fibers in a sizing agent for 15s, drying at 110 ℃, soaking the obtained carbon fibers in an epoxy resin tank for 1min, taking out, removing excess epoxy resin on the surfaces of the fibers by using a glass rod, and then putting the fibers into a mold coated with a release agent (the fiber laying direction is 0 ℃) for hot press molding to obtain the composite material.
The sizing agent obtained in example 1 has the particle size, viscosity and composite materialThe shearing strength between material layers, the quantity of the wool and the fracture toughness of the II-type layer are tested, the grain diameter of the sizing agent is 235nm, the viscosity is 1450 Pa.s, the shearing strength between the layers of the composite material is 69.3MPa, the quantity of the wool is 0.0027g, and the fracture toughness between the layers is 453.2J/m 2 (the specific data are shown in Table 1, table 2 and Table 3).
Example 2
(1) Adding 44g of epoxy resin E44, 20mL of absolute ethyl alcohol and 0.5g of tetra-n-butylammonium bromide into a three-neck flask provided with a condensation reflux device, mechanically stirring for 10min at 50 ℃, then adding 13g of itaconic acid, heating to 115 ℃, and reacting for 2.5 h at the rotation speed of 200rpm to obtain the modified epoxy resin.
(2) Cooling the modified epoxy resin obtained in the step (1) to 50 ℃, dropwise adding 10.1g of triethylamine to neutralize and salify, after reacting for 30 minutes, increasing the rotating speed to 300rpm, slowly dropwise adding a mixture of 0.5g of organic silicon water-based defoaming agent, 0.6g of polyether modified polysiloxane, 0.8g of alkyl phosphate ester surfactant of polyethylene glycol and maleic anhydride modified polypropylene, 1g of polyethylene glycol stearate and 105mL of deionized water, then adding 10g of waterborne polyurethane to fully stir for 10 minutes, and then removing absolute ethyl alcohol in the emulsion under a vacuum condition to obtain the epoxy resin water-based sizing agent.
(3) Soaking and running carbon fibers in a sizing agent for 15s, drying at 110 ℃, soaking the obtained carbon fibers in an epoxy resin tank for 1min, taking out, removing excess epoxy resin on the surfaces of the fibers by using a glass rod, and then putting the fibers into a mold coated with a release agent (the fiber laying direction is 0 ℃) for hot press molding to obtain the composite material.
The grain diameter, viscosity, interlaminar shear strength of the composite material, the amount of the wool and the interlaminar fracture toughness of the II layer obtained in the example 2 are tested, and the grain diameter of the sizing agent is 253nm, the viscosity is 1570 Pa.s, the interlaminar shear strength of the composite material is 68.2MPa, the amount of the wool is 0.0032g, and the interlaminar fracture toughness is 467.8J/m 2 (the specific data are shown in Table 1, table 2 and Table 3).
Example 3
(1) 37g of epoxy resin E51, 20mL of absolute ethanol and 0.5g of tetra-n-butylammonium bromide are added into a three-neck flask provided with a condensation reflux device, mechanical stirring is carried out for 10min at 50 ℃, then 13g of itaconic acid is added, the temperature is raised to 100 ℃, and the reaction is carried out for 4 hours at the rotating speed of 200rpm, thus obtaining the modified epoxy resin.
(2) And (2) cooling the modified epoxy resin obtained in the step (1) to 50 ℃, dropwise adding 14.9g of triethanolamine to neutralize and salify, reacting for 30 minutes, increasing the rotating speed to 300rpm, slowly dropwise adding a mixture of 0.5g of organic silicon water-based defoaming agent, 0.6g of polyether modified polysiloxane, 0.8g of alkyl phosphate ester surfactant of polyethylene glycol and maleic anhydride modified polypropylene, 1g of polyethylene glycol stearate and 159mL of deionized water, then adding 10g of waterborne polyurethane, fully stirring for 10 minutes, and removing absolute ethyl alcohol in the emulsion under a vacuum condition to obtain the epoxy resin waterborne sizing agent.
(3) And (2) soaking and running the carbon fibers in the sizing agent for 15s, drying at 110 ℃, soaking the obtained carbon fibers in an epoxy resin tank for 1min, taking out, removing the redundant epoxy resin on the surfaces of the fibers by using a glass rod, and then putting the fibers into a mold coated with a release agent (the fiber layering direction is 0 degrees) for hot press molding to obtain the composite material.
The grain diameter, viscosity, interlaminar shear strength of the composite material, the amount of the wool and the interlaminar fracture toughness of the II-type layer obtained in the example 3 are tested, and the grain diameter of the sizing agent is 244nm, the viscosity is 1320Pa s, the interlaminar shear strength of the composite material is 66.9MPa, the amount of the wool is 0.0029g, and the interlaminar fracture toughness is 436.9J/m 2 (the specific data are shown in Table 1, table 2 and Table 3).
Example 4
(1) 37g of epoxy resin E51, 20mL of absolute ethanol and 0.7g of tetra-n-butylammonium bromide are added into a three-neck flask provided with a condensation reflux device, mechanical stirring is carried out for 10min at 50 ℃, then 13g of itaconic acid is added, the temperature is raised to 120 ℃, and the reaction is carried out for 3 hours at the rotating speed of 200rpm, thus obtaining the modified epoxy resin.
(2) And (2) cooling the modified epoxy resin obtained in the step (1) to 50 ℃, dropwise adding 8g of triethylamine to neutralize and salify, reacting for 30 minutes, increasing the rotating speed to 300rpm, slowly dropwise adding 0.5g of organic silicon aqueous defoaming agent, 0.5g of polyether modified polysiloxane, 1g of bisphenol unsaturated polyester, 1g of polyethylene glycol laurate and 115mL of deionized water, then adding 10g of aqueous polyurethane to fully stir for 10min, and removing absolute ethyl alcohol in the emulsion under a vacuum condition to obtain the epoxy resin aqueous sizing agent.
(3) Soaking and running carbon fibers in a sizing agent for 15s, drying at 110 ℃, soaking the obtained carbon fibers in an epoxy resin tank for 1min, taking out, removing excess epoxy resin on the surfaces of the fibers by using a glass rod, and then putting the fibers into a mold coated with a release agent (the fiber laying direction is 0 ℃) for hot press molding to obtain the composite material.
The sizing agent obtained in example 4 was tested for particle size, viscosity, interlaminar shear strength of the composite material, amount of filaments, and interlaminar fracture toughness of layer II, and the measured particle size of the sizing agent was 315nm, viscosity was 1720Pa · s, interlaminar shear strength of the composite material was 65.6MPa, amount of filaments was 0.0034g, and interlaminar fracture toughness was 441.3J/m 2 (the specific data are shown in Table 1, table 2 and Table 3).
Comparative example 1
The carbon fiber which is not subjected to sizing treatment is used as a comparative example, the abrasion resistance of the carbon fiber, the interlaminar shear strength of the composite material, the amount of the fuzz and the II-type interlaminar fracture toughness are examined, and the preparation process of the composite material is the same as that of the example (the specific data are shown in tables 2 and 3).
Comparative example 2
The commercial carbon fiber is used as a comparative example, the abrasion resistance of the carbon fiber, the interlaminar shear strength of the composite material, the amount of the fuzz and the II-type interlaminar fracture toughness are examined, and the preparation process of the composite material is the same as that of the embodiment (the specific data are shown in tables 2 and 3).
The data show that the broken filament amount of the carbon fiber treated by the sizing agent is obviously less than that of carbon fiber which is not sized, and is slightly superior to that of commercial carbon fiber, and the sizing agent has excellent wear resistance.
Table 1 comparison of the properties of different sizing agents
TABLE 2 comparison of the Properties of different carbon fiber composites
TABLE 3 comparative data for different amounts of carbon fiber filaments
It should be understood that the application of the present invention is not limited to the above examples, and the design concept of the present invention is not limited thereto, and that the invention shall fall within the scope of protection of the present invention by making insubstantial changes to the concept. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The aqueous epoxy resin sizing agent is characterized by comprising, by weight, 20-35 parts of modified epoxy resin, 5-10 parts of aqueous polyurethane, 3-10 parts of a neutralizing agent, 0.2-1 part of a defoaming agent, 0.5-2 parts of a leveling agent, 0.3-2 parts of a bundling agent, 0.5-3 parts of a wetting agent and 37-70.5 parts of deionized water.
2. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 1, wherein the modified epoxy resin is any one of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic epoxy resin or a combination of any several of the bisphenol A epoxy resin, the bisphenol F epoxy resin and the phenolic epoxy resin.
3. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 1 are characterized in that the preparation method of the aqueous epoxy resin sizing agent comprises the following steps:
the method comprises the following steps: preparation of modified epoxy resin
(1) Placing epoxy resin to be modified, absolute ethyl alcohol and a catalyst into a three-neck flask provided with a condensation reflux device, heating to 45-60 ℃, and mechanically stirring for 10min;
(2) And (2) adding carboxylic acid compounds into the step (1), heating to 90-125 ℃, and reacting for 2-6 hours to obtain the modified epoxy resin.
Step two: preparation of waterborne epoxy resin sizing agent
And (2) cooling the modified epoxy resin in the step one to 50-60 ℃, adding a neutralizing agent for neutralization and salt formation, continuously stirring for 30-60 min, slowly dropwise adding deionized water containing a defoaming agent, a leveling agent, a bundling agent and a wetting agent into the reactant, adding waterborne polyurethane, fully stirring for 10min, and then removing absolute ethyl alcohol under a vacuum condition to obtain the self-emulsifying epoxy resin waterborne sizing agent.
4. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 3, characterized in that the carboxylic acid compound is any one or a combination of any several of p-hydroxybenzoic acid, p-tert-butylbenzoic acid, terephthalic acid, acrylic acid, methacrylic acid, phenyl-alpha-acrylic acid, acrylic acid-beta-glycolic acid, dimethylolpropionic acid, dihydroxybenzoic acid, itaconic acid, maleic acid or maleic acid.
5. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 3, wherein the catalyst is any one or a combination of any several of benzyltriethylammonium chloride, tetra-N-butylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride and N, N-dimethylbenzylamine.
6. The aqueous epoxy resin sizing agent for large tow carbon fibers and the preparation method thereof according to claim 1, wherein the neutralizing agent is any one or a combination of any several of triethylamine, ammonia water, sodium hydroxide, potassium hydroxide, trimethylamine, tripropylamine ethylenediamine, propylenediamine, dimethylpropylenediamine, divinyltriamine, diethylenetriamine, triethylenetetramine, diethanolamine, triethanolamine, pentaenetetramine or polyetherpolyamine.
7. The aqueous epoxy resin sizing agent for large tow carbon fibers and the preparation method thereof according to claim 1, wherein the defoamer is one or a combination of any of silicone waterborne defoamer, silicone defoamer, polyalkylene glycol defoamer and higher alcohol emulsion defoamer.
8. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 1, wherein the leveling agent is one or a combination of any several of polyether modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane and alkyl modified organosiloxane.
9. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof as claimed in claim 1, wherein the sizing agent is one or a combination of two of alkyl phosphate ester surfactant of polyethylene glycol and maleic anhydride modified polypropylene.
10. The aqueous epoxy resin sizing agent for large-tow carbon fibers and the preparation method thereof according to claim 1 are characterized in that the wetting agent is one or a combination of any several of polyoxyethylene ether compounds, polyethylene glycol laurate and polyethylene glycol stearate.
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| CN106592242A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin large tow general-purpose type carbon fiber sizing agent, preparation method and applications thereof |
| CN112679717A (en) * | 2020-12-04 | 2021-04-20 | 吉林乾仁新材料有限公司 | Preparation method of multipurpose self-emulsifying anionic unsaturated polyester carbon fiber sizing agent, product and application thereof |
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| CN106592242A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Modified epoxy resin large tow general-purpose type carbon fiber sizing agent, preparation method and applications thereof |
| CN112679717A (en) * | 2020-12-04 | 2021-04-20 | 吉林乾仁新材料有限公司 | Preparation method of multipurpose self-emulsifying anionic unsaturated polyester carbon fiber sizing agent, product and application thereof |
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| CN117449102B (en) * | 2023-12-21 | 2024-03-29 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid fiber composition and preparation method thereof |
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