CN116641237A - Self-emulsifying polyurethane resin sizing agent for carbon fiber - Google Patents
Self-emulsifying polyurethane resin sizing agent for carbon fiber Download PDFInfo
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- CN116641237A CN116641237A CN202310741091.3A CN202310741091A CN116641237A CN 116641237 A CN116641237 A CN 116641237A CN 202310741091 A CN202310741091 A CN 202310741091A CN 116641237 A CN116641237 A CN 116641237A
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- CN
- China
- Prior art keywords
- polyurethane resin
- soybean oil
- dimethylformamide
- epoxidized soybean
- present
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- 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.)
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 78
- 238000004513 sizing Methods 0.000 title claims abstract description 57
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 56
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 228
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 122
- 235000012424 soybean oil Nutrition 0.000 claims description 100
- 239000003549 soybean oil Substances 0.000 claims description 100
- 229960003638 dopamine Drugs 0.000 claims description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 229920002635 polyurethane Polymers 0.000 claims description 35
- 239000004814 polyurethane Substances 0.000 claims description 35
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000000839 emulsion Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- BLORRZQTHNGFTI-ZZMNMWMASA-L calcium-L-ascorbate Chemical compound [Ca+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] BLORRZQTHNGFTI-ZZMNMWMASA-L 0.000 description 35
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 35
- 125000004122 cyclic group Chemical group 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 125000003700 epoxy group Chemical group 0.000 description 14
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 7
- 230000002238 attenuated effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- ZMXDDKWLCZADIW-WFVSFCRTSA-N 1-deuterio-n,n-dimethylformamide Chemical compound [2H]C(=O)N(C)C ZMXDDKWLCZADIW-WFVSFCRTSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-IMJSIDKUSA-N L-threitol Chemical group OC[C@H](O)[C@@H](O)CO UNXHWFMMPAWVPI-IMJSIDKUSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 241000904692 Syrgis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 108010004563 mussel adhesive protein Proteins 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of carbon fiber surface modification, and in particular relates to a self-emulsifying polyurethane resin sizing agent for carbon fibers and a preparation method thereof, wherein the self-emulsifying polyurethane resin sizing agent for the carbon fibers comprises the following raw materials in parts by weight: 5-10 parts of aqueous polyurethane resin, 0.2-0.3 part of silane coupling agent and 89.7-94.8 parts of deionized water, and the materials are discharged after being mixed according to a proportion and uniformly stirred. The self-emulsifying polyurethane resin sizing agent for the carbon fiber solves the problem of poor wettability of the sizing agent and main resin in a composite material in the prior art through self-made waterborne polyurethane resin, and has the advantages of excellent emulsion stability, safety, environmental protection and easy operation.
Description
Technical Field
The invention belongs to the field of carbon fiber surface modification, and particularly relates to a self-emulsifying polyurethane resin sizing agent for carbon fibers.
Background
The carbon fiber is a fibrous carbon material with carbon content above 90%, which is obtained by a series of processes of spinning, oxidizing, heat treating, sizing and the like, and has a diameter of 5-10 mu m. The carbon fiber is invented in the 50 th century of 20 th century, has the advantages of high strength, high modulus, light weight and the like, and is widely applied to the fields of aerospace, energy conservation, new energy automobiles, wind power, military industry and the like.
However, the carbon fiber is worn in the subsequent processing process, and a hairline is generated, which not only affects the smooth proceeding of the subsequent process, but also reduces the overall performance of the carbon fiber, so that the carbon fiber needs to be sized. The proper sizing agent not only can improve the bundling property of the carbon fiber and improve the process performance, but also can be used as a transitional bonding layer between the carbon fiber and the matrix resin, improve the chemical combination between the carbon fiber and the resin and improve the interface performance of the composite material. Common composite materials are epoxy resins, unsaturated polyester resins, vinyl resins, and the like. Because the carbon fiber is combined with different types of resin to prepare the composite material, according to the principle of similar compatibility, different resin matrixes are selected with corresponding sizing agents, so that the universality of the sizing agents is relatively narrow.
The polyurethane has the advantages of good wear resistance, wide hardness range, high strength, high elongation and the like, and is widely applied to the fields of textile, national defense in the forms of emulsion, resin and the like. The non-isocyanate polyurethane is prepared by the copolymerization reaction of the multi-ring carbonate prepolymer and the polyamine, so that the use of isocyanate with higher toxicity in the prior art is avoided, and the mechanical property of the product is greatly improved due to the intramolecular hydrogen bond on the main chain structure; in addition, the synthesis of polyurethane emulsions is often supplemented with external emulsifiers, the presence of which can affect the storage stability of the emulsion. On the other hand, development of bionic polymers finds that the super-strong adhesion capability of marine organism mussels is due to catechol groups and amino structures contained in mussel adhesive proteins, and the structures have excellent wettability to various materials.
In consideration of the above factors, in combination with the premise of poor wettability of the current sizing agent, it is important to develop a sizing agent with strong universality, excellent wettability and good storage stability.
Disclosure of Invention
The invention aims at solving the problem of poor wettability of sizing agent and main resin in composite materials in the prior art, and provides a self-emulsifying polyurethane resin sizing agent for carbon fibers and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
the self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
5-10 parts of aqueous polyurethane resin;
0.2-0.3 part of silane coupling agent;
89.7-94.8 parts of deionized water.
Preferably, the aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 2-6 hours, and then performing reduced pressure distillation to obtain dopamine-modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and a catalyst in N, N-dimethylformamide C, stirring, heating to 100-130 ℃, preserving heat for 1-3 hours, cooling to room temperature, and distilling under reduced pressure to obtain the epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.30-0.35mol:0.1mol:300mL;
the catalyst is used in an amount of 2wt% of the total mass of the reactants;
(3) Ethylene carbonate is dissolved in N, N-dimethyl formyl D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethyl formyl E dissolved with mercapto-containing epoxidized soybean oil and a photoinitiator, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, and UV irradiation is carried out for 15-60min; vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the dosage of the photoinitiator is 0-3wt% of the total mass of the reactants;
(4) N is led to 2 Dissolving epoxy soybean oil and polyether diamine modified by cyclic carbonate in N, N-dimethyl formyl F, heating to 70-120 ℃ for reaction for 8-14h, adding dopamine, and heating to 120-130 DEG CReacting for 1-2h, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxy soybean oil modified by the cyclic carbonate, the polyether diamine, the N, N-dimethyl formyl F and the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain the water-based polyurethane resin with the solid content of 30%.
Preferably, the catalyst is triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
Preferably, the photoinitiator is 184, 1173, 369, 2959 or TPO.
Preferably, the polyetherdiamine is polyetheramine D400, polyetheramine ED600 or polyetheramine ED900.
Preferably, the silane coupling agent is 3-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane or vinyl trimethoxysilane.
The preparation method of the self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following steps:
and mixing the aqueous polyurethane resin, the silane coupling agent and the deionized water in proportion, uniformly stirring, and discharging to obtain the self-emulsifying polyurethane resin sizing agent for the carbon fiber.
The invention has the following beneficial effects:
(1) The invention provides a self-emulsifying polyurethane resin sizing agent for carbon fibers, which uses self-made self-emulsifying polyurethane and contains a large number of N, O, S heteroatoms and mercapto structures. Firstly, the existence of a large number of N atoms, O atoms and sulfhydryl groups can provide a large number of hydrogen bonds with carbon fibers or composite materials, so that the interface strength between two phases is enhanced; the surface tension of the sizing agent on the surface of the carbon fiber is increased, and the wettability of the sizing agent on carbon fiber yarns and resin is better. Second, the presence of mercapto groups can chemically react with vinyl resins ("mercapto-ene" click reaction), epoxy resins, and the like, increasing selectivity to the resin.
(2) The invention provides a self-emulsifying polyurethane resin sizing agent for carbon fibers, which uses self-made self-emulsifying polyurethane resin. Firstly, the polyurethane structure provides excellent wear resistance and improved brittleness of the carbon fiber filaments; secondly, the polyurethane is synthesized by adopting a non-isocyanate method to open a ring, and the formed non-isocyanate polyurethane can form a six-membered ring in a molecule, so that the mechanical property and the water resistance are better; thirdly, the polyurethane resin structure contains catechol structure, and has excellent adhesive force to the base material; meanwhile, the proportion of soft and hard segments of the resin can be balanced, and excellent mechanical properties are given to the material; fourth, polyurethane resin contains diamine with hydrophilicity and catechol structure, has excellent self-emulsifying property, and forms emulsion with better storage stability; finally, the plant-based raw materials are wide in source and environment-friendly.
The specific embodiment is as follows:
the present invention will be described in detail with reference to examples. It is to be understood that the following examples are illustrative of embodiments of the present invention and are not intended to limit the scope of the invention.
The epoxidized soybean oil used in the following examples of the present invention was 99% pure and purchased from ala Ding Gongsi.
Example 1
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 5 hours, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and N, N-dimethylbenzylamine in N, N-dimethylformamide C, stirring, heating to 120 ℃, preserving heat for 2 hours, cooling to room temperature, and distilling under reduced pressure to obtain epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.35mol:0.1mol:300mL;
the dosage of the N, N-dimethylbenzylamine is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethylformamide D and is placed in a constant-pressure dropping funnel, the constant-pressure dropping funnel is dripped into N, N-dimethylformamide E dissolved with sulfhydryl-containing epoxidized soybean oil and photoinitiator 1173, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant-pressure dropping funnel is controlled, UV irradiation is carried out for 20min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the photoinitiator 1173 is used in an amount of 2wt% based on the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil modified by cyclic carbonate and polyether amine ED600 in N, N-dimethylformamide F, heating to 100 ℃ for reaction for 12 hours, adding dopamine, reacting at 125 ℃ for 1.2 hours, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyether amine ED600 to the N, N-dimethylformamide F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
Example 2
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
5 parts of aqueous polyurethane resin;
0.2 parts of vinyl trimethoxy silane;
94.8 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 2 hours, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and N, N-dimethylbenzylamine in N, N-dimethylformamide C, stirring, heating to 100 ℃, preserving heat for 3 hours, cooling to room temperature, and distilling under reduced pressure to obtain epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.35mol:0.1mol:300mL;
the dosage of the N, N-dimethylbenzylamine is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethyl formyl D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethyl formyl E dissolved with sulfhydryl-containing epoxidized soybean oil, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, UV irradiation is carried out for 60min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil and polyether amine D400 modified by cyclic carbonate in N, N-dimethyl formyl F, heating to 70 ℃ for reaction for 14h, adding dopamine, reacting at 120 ℃ for 2h, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyetheramine D400 to the N, N-dimethylformamide F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
Example 3
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
8 parts of aqueous polyurethane resin;
0.3 parts of 3-aminopropyl triethoxysilane;
91.7 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 6 hours, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and tetrabutylammonium bromide in N, N-dimethylformamide C, stirring, heating to 110 ℃, preserving heat for 2 hours, cooling to room temperature, and distilling under reduced pressure to obtain the epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.32mol:0.1mol:300mL;
the dosage of tetrabutylammonium bromide is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethylformamide D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethylformamide E dissolved with sulfhydryl-containing epoxidized soybean oil and photo initiator TPO, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, UV irradiation is carried out for 15min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Reduced pressure distillation to obtain modified cyclic carbonateEpoxidized soybean oil;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the dosage of the photo initiator TPO is 0.5wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil modified by cyclic carbonate and polyether amine ED900 in N, N-dimethyl formyl F, heating to 110 ℃ for reaction for 8 hours, adding dopamine, reacting at 130 ℃ for 1 hour, and decompressing to remove solvent after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyether amine ED900 to the N, N-dimethyl formyl F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : carbamates (Carbamates)-NH-present; 2551cm -1 : SH is present.
Example 4
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
6 parts of aqueous polyurethane resin;
0.2 parts of vinyl trimethoxy silane;
93.8 parts of deionized water.
Preferably, the aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 3 hours, and then carrying out reduced pressure distillation to obtain dopamine-modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and triphenylphosphine in N, N-dimethylformamide C, stirring, heating to 130 ℃, preserving heat for 2 hours, cooling to room temperature, and distilling under reduced pressure to obtain the epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.32mol:0.1mol:300mL;
the dosage of the triphenylphosphine is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethyl formyl D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethyl formyl E dissolved with sulfhydryl-containing epoxidized soybean oil and a photoinitiator 184, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, UV irradiation is carried out for 15min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the photoinitiator 184 was used in an amount of 3wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil and polyether amine D400 modified by cyclic carbonate in N, N-dimethyl formyl F, heating to 90 ℃ for reaction for 12 hours, adding dopamine, reacting at 120 ℃ for 1.5 hours, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyetheramine D400 to the N, N-dimethylformamide F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
Example 5
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution for 4 hours at room temperature, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and N, N-dimethylbenzylamine in N, N-dimethylformamide C, stirring, heating to 130 ℃, preserving heat for 1h, cooling to room temperature, and distilling under reduced pressure to obtain epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.30mol:0.1mol:300mL;
the dosage of the N, N-dimethylbenzylamine is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethylformamide D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethylformamide E dissolved with sulfhydryl-containing epoxidized soybean oil and photoinitiator 2959, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, UV irradiation is carried out for 40min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the photoinitiator 2959 is used in an amount of 1wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil modified by cyclic carbonate and polyether amine ED600 in N, N-dimethylformamide F, heating to 80 ℃ for reaction for 14h, adding dopamine, reacting at 120 ℃ for 1.5h, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyether amine ED600 to the N, N-dimethylformamide F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
Example 6
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
10 parts of aqueous polyurethane resin;
0.3 parts of 3-aminopropyl triethoxysilane;
89.7 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 5 hours, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and tetrabutylammonium bromide in N, N-dimethylformamide C, stirring, heating to 120 ℃, preserving heat for 3 hours, cooling to room temperature, and distilling under reduced pressure to obtain the epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.32mol:0.1mol:300mL;
the dosage of tetrabutylammonium bromide is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethylformamide D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethylformamide E dissolved with sulfhydryl-containing epoxidized soybean oil and photoinitiator 369, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, UV irradiation is carried out for 30min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the dosage of the photoinitiator 369 is 1.5wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : SH is present and attenuated; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil modified by cyclic carbonate and polyether amine ED900 in N, N-dimethyl formyl F, heating to 120 ℃ for reaction for 8 hours, adding dopamine, reacting at 130 ℃ for 1 hour, and decompressing to remove solvent after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyether amine ED900 to the N, N-dimethyl formyl F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-present; 2551cm -1 : SH is present.
The preparation method of the self-emulsifying polyurethane resin sizing agent for the carbon fiber, which is described in examples 1-6, comprises the following steps:
and mixing the aqueous polyurethane resin, the silane coupling agent and the deionized water in proportion, uniformly stirring, and discharging to obtain the self-emulsifying polyurethane resin sizing agent for the carbon fiber.
Comparative examples 1-5 are all compared to example 1:
comparative example 1
Sizing-free carbon fibers.
Comparative example 2
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
93 parts of deionized water.
The preparation method of the aqueous polyurethane resin is the same as that of example 1.
Comparative example 3
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The preparation method of the aqueous polyurethane resin is the same as that of the specific example 1, except that the dopamine is replaced with L-threitol.
Comparative example 4
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The preparation method of the aqueous polyurethane resin is the same as that of the specific example 1, except that the polyetheramine ED600 is replaced with polyetheramine D230.
Comparative example 5
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The preparation method of the aqueous polyurethane resin is the same as that of the specific example 1, except that the polyetheramine ED600 is replaced with polyetheramine ED2003.
Comparative example 5
The self-emulsifying polyurethane resin sizing agent for the carbon fiber comprises the following raw materials in parts by weight:
7 parts of aqueous polyurethane resin;
0.25 parts of gamma-glycidoxypropyl trimethoxysilane;
92.75 parts of deionized water.
The aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 5 hours, and then carrying out reduced pressure distillation to obtain dopamine modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.4mol:200mL:0.1mol:300mL;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o present; 943cm -1 、829cm -1 : the epoxy groups weaken.
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and N, N-dimethylbenzylamine in N, N-dimethylformamide C, stirring, heating to 120 ℃, preserving heat for 2 hours, cooling to room temperature, and distilling under reduced pressure to obtain epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.25mol:0.1mol:300mL;
the dosage of the N, N-dimethylbenzylamine is 2wt% of the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1743cm -1 : ester-c=o is present and enhanced; 943cm -1 、829cm -1 : the epoxy group disappears; 2551cm -1 : SH is present.
(3) Ethylene carbonate is dissolved in N, N-dimethylformamide D and is placed in a constant-pressure dropping funnel, the constant-pressure dropping funnel is dripped into N, N-dimethylformamide E dissolved with sulfhydryl-containing epoxidized soybean oil and photoinitiator 1173, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant-pressure dropping funnel is controlled, UV irradiation is carried out for 20min, and the UV intensity is set to 300mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Reduced pressure steamingDistilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the photoinitiator 1173 is used in an amount of 2wt% based on the total mass of the reactants;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o present; 1743cm -1 : ester-c=o present; 2551cm -1 : -SH vanishes; 1620cm -1 : -c=c-is absent.
(4) N is led to 2 Dissolving epoxy soybean oil modified by cyclic carbonate and polyether amine ED600 in N, N-dimethylformamide F, heating to 100 ℃ for reaction for 12 hours, adding dopamine, reacting at 125 ℃ for 1.2 hours, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxidized soybean oil modified by the cyclic carbonate to the polyether amine ED600 to the N, N-dimethylformamide F to the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o shoulder present; 1547cm -1 : urethane-NH-is present.
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain waterborne polyurethane resin with solid content of 30%;
the infrared data are as follows: 3300-3600cm -1 : -OH, -NH-present and enhanced; 1637cm -1 、1480cm -1 : the benzene ring exists; 1798cm -1 : cyclic carbonate-c=o vanishes; 1743cm -1 : ester-c=o present; 1732cm -1 : carbamate-c=o present; 1547cm -1 : carbamate-NH-presence。
The self-emulsifying polyurethane resin sizing agents obtained in specific examples 1 to 6 and comparative examples 2 to 6 are respectively used as base materials and applied to carbon fibers for sizing treatment process: and (3) sizing the fibers by using modified polyurethane sizing agents with different concentrations, wherein the yarn tension is 180N, the grouting force is 0.2MPa, the pre-drying temperature is 100 ℃, the drying room temperature is 120 ℃, and the yarn winding speed is 3m/min in the sizing process.
The carbon fiber is 3K specification.
The physical properties of the sizing agents and the carbon fibers after sizing treatment prepared in examples 1 to 6 of the present invention and comparative examples 1 to 6 were measured, respectively, and the results are shown in Table 1.
Table 1 physical test performance of various examples
First, as can be seen from Table 1, it can be seen from examples 1 to 6 and comparative examples 1 to 6 that the sizing agent of the present invention has excellent wetting properties (lower water contact angle);
second, as can be seen from example 1 and comparative example 1, the sizing agent of the present invention has excellent abrasion resistance, interfacial strength and wettability; from comparison of example 1 with comparative examples 1-5, it can be seen that the presence of heteroatoms such as N, S increases the surface tension of the sizing agent on the surface of the carbon fiber, and the wettability to the carbon fiber filaments and resin is better; from a comparison of example 1 with comparative examples 4-5, it can be seen that the molecular weight of the polyether diamine is preferably selected between 400 and 900; compared with comparative example 6, the mercapto group and the vinyl resin have click reaction of 'mercapto-ene', are bonded to the surface of the carbon fiber, and have better wettability and wear resistance.
Thirdly, the sizing agent provided by the invention has high universality on matrix resin; and the self-emulsifying polyurethane resin has small particle size and excellent emulsion stability.
The test method comprises the following steps:
(1) Concentration: the measurement was carried out according to GB/T1721-1995.
(2) Particle size: sizing particle size was characterized using a dynamic light scattering instrument (Zetasizer NanoZS-90, malvern). The sizing agent was diluted to a concentration of 0.1mg/L of sample solution, and 4mL of sample solution was taken to a quartz dish, and each sample was tested three times.
(3) Storage stability: the emulsion was prepared to a solids content of 5% and placed in a 25ml graduated cuvette, and allowed to stand at room temperature for observation of the time of precipitation, stratification and demulsification.
(4) Abrasion resistance: the tests were carried out according to the method described in the literature (synthetic fibre industry, 2009,32 (2), 1-3).
(5) Interface strength: according to JC/T773-2010 standard, the interface strength of the composite material is obtained by adopting a three-point bending method on an Instron-5567 universal mechanical experiment machine, and the composite material is respectively epoxy resin and vinyl resin. Epoxy resin (TDE-85#): the relative molecular weight is 298.29, the epoxy value is 0.86, and the Tianjin Jindong chemical composite material is available from the company Limited; vinyl resin: technical grade, jilin dry kernel New Material Co., ltd; vinyl resin curing agent: analytical grade, syrgis group limited, usa.
(6) Water contact angle: the contact angles of the carbon fibers and the resin of the sizing agents with different concentrations are measured by adopting an JC98A type contact angle measuring instrument.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (7)
1. A self-emulsifying polyurethane resin sizing agent for carbon fibers is characterized in that: the material comprises the following raw materials in parts by weight:
5-10 parts of aqueous polyurethane resin;
0.2-0.3 part of silane coupling agent;
89.7-94.8 parts of deionized water.
2. The self-emulsifying polyurethane resin sizing agent for carbon fibers according to claim 1, wherein: the aqueous polyurethane resin is prepared by the following method:
(1) Dissolving dopamine in N, N-dimethylformamide A, placing the N, N-dimethylformamide A in a constant pressure dropping funnel, dropwise adding the solution into N, N-dimethylformamide B dissolved with epoxidized soybean oil, slowly dropwise adding the solution, stirring the solution at room temperature for 2-6 hours, and then performing reduced pressure distillation to obtain dopamine-modified epoxidized soybean oil;
the dosage ratio of the dopamine to the N, N-dimethylformamide A to the epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.3mol:200mL:0.1mol:300mL;
(2) Dissolving thioglycollic acid, dopamine modified epoxidized soybean oil and a catalyst in N, N-dimethylformamide C, stirring, heating to 100-130 ℃, preserving heat for 1-3 hours, cooling to room temperature, and distilling under reduced pressure to obtain the epoxidized soybean oil containing sulfhydryl;
the dosage ratio of the thioglycollic acid to the dopamine modified epoxidized soybean oil to the N, N-dimethylformamide B is as follows: 0.30-0.35mol:0.1mol:300mL;
the catalyst is used in an amount of 2wt% of the total mass of the reactants;
(3) Ethylene carbonate is dissolved in N, N-dimethyl formyl D and is placed in a constant pressure dropping funnel, the constant pressure dropping funnel is dripped into N, N-dimethyl formyl E dissolved with mercapto-containing epoxidized soybean oil and a photoinitiator, magnetic stirring is started, a UV light source is added to irradiate a glass reaction kettle, the dropping speed of the constant pressure dropping funnel is controlled, and UV irradiation is carried out for 15-60min; vacuum distilling to obtain epoxidized soybean oil modified by cyclic carbonate;
the dosage ratio of ethylene carbonate to N, N-dimethyl formyl D to mercapto-containing epoxidized soybean oil to N, N-dimethyl formyl E is as follows: 0.2mol:200mL:0.1mol:300mL;
the dosage of the photoinitiator is 0-3wt% of the total mass of the reactants;
(4) N is led to 2 Dissolving epoxy soybean oil and polyether diamine modified by cyclic carbonate in N, N-dimethyl formyl F, heating to 70-120 ℃ for reaction for 8-14h, adding dopamine, reacting for 1-2h at 120-130 ℃, and removing solvent under reduced pressure after the reaction is finished to obtain polyurethane;
the dosage ratio of the epoxy soybean oil modified by the cyclic carbonate, the polyether diamine, the N, N-dimethyl formyl F and the dopamine is as follows: 0.1mol:0.95mol:500mL:0.05mol;
(5) Slowly adding polyurethane into deionized water at 50 ℃, stirring until the polyurethane is completely dissolved, cooling to room temperature, filtering, discharging to obtain the water-based polyurethane resin with the solid content of 30%.
3. The self-emulsifying polyurethane resin sizing agent for carbon fibers according to claim 2, wherein: the catalyst is triphenylphosphine, tetrabutylammonium bromide or N, N-dimethylbenzylamine.
4. The self-emulsifying polyurethane resin sizing agent for carbon fibers according to claim 2, wherein: the photoinitiator was 184, 1173, 369, 2959 or TPO.
5. The self-emulsifying polyurethane resin sizing agent for carbon fibers according to claim 2, wherein: the polyether diamine is polyether amine D400, polyether amine ED600 or polyether amine ED900.
6. The self-emulsifying polyurethane resin sizing agent for carbon fibers according to claim 1, wherein: the silane coupling agent is 3-aminopropyl triethoxy silane, gamma-glycidol ether oxypropyl trimethoxy silane or vinyl trimethoxy silane.
7. A preparation method of a self-emulsifying polyurethane resin sizing agent for carbon fibers is characterized by comprising the following steps: comprises the following steps:
and mixing the aqueous polyurethane resin, the silane coupling agent and the deionized water in proportion, uniformly stirring, and discharging to obtain the self-emulsifying polyurethane resin sizing agent for the carbon fiber.
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