CN103451951A - Preparation method of carbon fiber sizing agent - Google Patents
Preparation method of carbon fiber sizing agent Download PDFInfo
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- CN103451951A CN103451951A CN2012101784498A CN201210178449A CN103451951A CN 103451951 A CN103451951 A CN 103451951A CN 2012101784498 A CN2012101784498 A CN 2012101784498A CN 201210178449 A CN201210178449 A CN 201210178449A CN 103451951 A CN103451951 A CN 103451951A
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- sizing agent
- carbon fiber
- epoxy resin
- fiber sizing
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000004513 sizing Methods 0.000 title claims abstract description 39
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 30
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- -1 polyoxyethylene nonylphenol Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 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 claims description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical class C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- DZNGQMDVHXKOCV-UHFFFAOYSA-N poss®-octahydroxypropyldimethylsilyl Chemical compound O1[Si](O[Si](O[Si](C)(C)CCCO)(O2)O[Si](O[Si](C)(C)CCCO)(O3)O4)(O[Si](C)(C)CCCO)O[Si]4(O[Si](C)(C)CCCO)O[Si]4(O[Si](C)(CCCO)C)O[Si]1(O[Si](C)(C)CCCO)O[Si]2(O[Si](C)(C)CCCO)O[Si]3(O[Si](C)(C)CCCO)O4 DZNGQMDVHXKOCV-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a preparation method of a carbon fiber sizing agent, which is characterized in that epoxy resin is dissolved in acetone, hexahedral polysilsesquioxane and epoxy resin are added to prepare modified epoxy resin, and the hexahedral polysilsesquioxane: epoxy resin: the weight ratio of acetone is 20-100: 10000: 1000-3000; adjusting the proportion of the emulsifier to keep the hydrophilic-lipophilic balance value of the emulsifier mixture after mixing within the range of 8-12; melting and mixing an emulsifier and modified epoxy resin according to the weight ratio of 6-18: 100 to obtain a viscous solution; adding deionized water until the solid content is 5% by mass, controlling the temperature at 55 ℃, and stirring for 1h to obtain the carbon fiber sizing agent; the method can effectively improve the thermal stability of the carbon fiber sizing agent, is simple and convenient, is suitable for industrial production, and can improve the heat resistance of the sizing agent and the comprehensive performance of the carbon fiber composite material.
Description
Technical field:
The present invention relates to a kind of preparation method of carbon fiber sizing agent.
Background technology
Because carbon fiber has high ratio modulus, high specific strength, high temperature resistant, endurance, conduction, the series of advantages such as conduct heat and the coefficient of expansion is little, be widely used in the fortifying fibre polymer matrix composites.Carbon fiber wire easily produces lousiness and single wire fracture phenomenon in process of production, can reduce the mechanical property of material.In order to address this problem, usually with sizing agent, protect carbon fiber, simultaneously sizing agent can also play and improve the interface bonding degree between carbon fiber and matrix resin in composite, thereby improves the mechanical property of composite.
Carbon fiber sizing agent mainly is divided into two classes, solvent-borne type sizing agent and emulsion-type sizing agent at present.It is formulated that solvent type sizing agent mainly is dissolved in organic solvent by resin, as polyvinyl alcohol (PVA), vinyl acetate lipopolymer, acrylic acid polymer, polyurethane, polyimides, unsaturated polyester, epoxy resin or polystyrene etc. are dissolved in to formulated corresponding sizing agent in the acetone organic solvent.The shortcoming of this solvent-borne type sizing agent is to need a large amount of organic solvents, and this,, with regard to having brought the problem of the aspects such as a series of economy, safety, health, has restricted the use of solvent-borne type sizing agent to a certain extent.The emulsion-type sizing agent is to take a kind of resin as main body, is equipped with the emulsion that a certain amount of emulsifying agent and some auxiliary agents are made.The sizing agent of this class emulsion-type generally is difficult for residual lower resin on deflector roll, solvent-free contaminated environment again, and owing to containing surfactant in emulsion, can greatly improve the wettability of fiber surface, simultaneously by using different auxiliary agents can also improve interface shear strength (IFSS) and the interlaminar shear strength (ILSS) of carbon fibre composite.Because the emulsion-type sizing agent can overcome the problem that the solvent-borne type sizing agent exists at aspects such as economy, safety, health, thereby be widely applied.
With trace, nano-silicon dioxide modified epoxy resin latex makes the epoxide group of this resin form with nano particle the effect that is greater than Van der Waals force on interface, has good compatibility simultaneously, and can form ideal interface phase.Patent CN1632217 can effectively improve both mechanical properties of composite of carbon fiber wire monofilament with this emulsion pasting agent, reaches enhancing, toughness reinforcing effect.But this nanoscale SiO
2the shortcoming of the sizing agent of modification is nanoscale SiO
2the dispersion of particle in emulsion is inhomogeneous, has had a strong impact on the character of sizing agent, has further affected the performance of carbon fibre composite.
In the last few years, hexahedron polysilsesquioxane (POSS) had caused that vast researcher showed great attention to.The structure of POSS has two essential characteristics: one, chemical composition is between silica (SiO
2) and silicones (R
2siO) between, it is the most typical hybrid structure, it can be considered to minimum silica dioxide granule, but the difference between it and silica is, its cage shape surface is associated with a plurality of organic substituents, and the POSS compound generally has good dissolubility, can be dissolved in conventional solvent (as chloroform, carrene, THF etc.), it also has good polymer-compatible, biocompatibility and surface compatability simultaneously.Two, single POSS bulk of molecule is between 1-3nm, and average-size is the 1.5nm left and right, can on molecular level, to the functional material performance, be strengthened.No matter POSS adulterates or the form of grafting is incorporated in material, all can improve heat endurance and the heat decomposition temperature of flame-retardant heat-resistant, hardness, scratch resistance and the material of material.At present, it has been widely used in the fields such as every field comprises in polymer, crosslinked resin, polyurethane, the catalyst that contains silicon, luminescent material, biomedicine.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of functional form carbon fiber emulsion pasting agent of applicable industrial applications, solve SiO
2the SiO existed in the modification sizing agent
2disperse inhomogeneous and problem poor stability.
It is raw material that carbon fiber emulsion pasting agent of the present invention be take epoxy resin, emulsifying agent and simple function group POSS, and its preparation process is as follows:
(1) hexahedron polysilsesquioxane (POSS) and epoxy resin are dissolved in acetone, high-speed stirred is even, then vacuumizes except organic solvent, makes modified epoxy, POSS: epoxy resin: the weight ratio of acetone is 20～100:10000:1000～3000;
(2) regulate the proportioning between emulsifying agent, the equilibrium valve (HLB) of the mixed hydrophilic and oleophilic of emulsifier mixture is remained between 8～12 scopes, then be heated to after molten condition start to stir it is mixed;
(3) epoxy resin of blended emulsifier and modification is become to viscous solution according to the weight ratio melting mixing of 6～18:100;
(4) slowly add deionized water, until the mass fraction of solid content is 5%, temperature is controlled at 55 ℃, the while rapid stirring, and the control rotating speed is 14000～18000r/min, mixing time is 1h, obtains carbon fiber emulsion pasting agent.
Hexahedron polysilsesquioxane as above (POSS) can be eight (the 3-hydroxypropyl dimethyl is silica-based) polysilsesquioxane (PSS-Octa[(3-hydroxypropyl) dimethylsiloxy] substituted), the hexahedron polysilsesquioxane of the hydroxyl such as 3-hydroxypropyl seven isobutyl group polysilsesquioxanes (PSS-(3-Hydroxypropyl)-heptaisobutyl substituted).
Epoxy resin as above can be one or more the mixture in glycidol fundamental mode epoxy resin, epoxidation of olefins, bisphenol A type epoxy resin, and glycidol fundamental mode epoxy resin is as epoxy resin 618,665,6101, AG-80 etc.; Epoxidation of olefins can be epoxy resin D-17 etc.
Emulsifying agent as above can be OP series, as OP-10, OP-7 etc.; This coils series, as S-40, S-60, S-80 etc.; Tween series is as T-40, T-60, T-80 etc.
The present invention has following advantage:
The present invention can effectively improve the heat endurance of carbon fiber sizing agent.The preparation method of this sizing agent is easy, is suitable for industrial production and can improves the heat resistance of sizing agent and the combination property of carbon fibre composite.
The specific embodiment:
Embodiment 1:
Reactor kind at 2L adds 3-hydroxypropyl seven isobutyl group polysilsesquioxanes (PSS-(3-Hydroxypropyl)-heptaisobutyl substituted), epoxy resin AG-80 and acetone, weight ratio is 20:10000:1000, and mixture stirs and makes modified epoxy.By emulsifying agent alkylphenol-polyethenoxy base ether (OP-10) and dehydration sorb fatty acid ester, with the weight ratio of 3:5, be mixed and heated to 80 ℃ in the stirred autoclave of another 2L, make blended emulsifier.After the weight ratio melting by 100:6 of the epoxy resin AG-80 of modification and blended emulsifier, stir, slowly add deionized water, until the mass fraction of solid content is 5%, temperature is controlled at 55 ℃, use the mulser rapid stirring simultaneously, mixing speed is 14000r/min, stirs 1h, makes carbon fiber sizing agent of the present invention.
Embodiment 2:
Reactor kind at 2L adds eight (the 3-hydroxypropyl dimethyl is silica-based) polysilsesquioxane (PSS-Octa[(3-hydroxypropyl) dimethylsiloxy] substituted), epoxy resin 618 and acetone, weight ratio is 20:10000:2000, and mixture stirs and makes modified epoxy.By emulsifying agent alkylphenol-polyethenoxy base ether (OP-7) and dehydration sorb fatty acid ester, with the weight ratio of 3:5, be mixed and heated to 80 ℃ in the stirred autoclave of another 2L, make blended emulsifier.After the epoxy resin 618 of modification and the weight ratio melting of blended emulsifier by 100:7, stir, slowly add deionized water, until the mass fraction of solid content is 5%, temperature is controlled at 55 ℃, use the mulser rapid stirring simultaneously, mixing speed is 18000r/min, stirs 1h, makes carbon fiber sizing agent of the present invention.
Embodiment 3:
Reactor kind at 2L adds eight (the 3-hydroxypropyl dimethyl is silica-based) polysilsesquioxane (PSS-Octa[(3-hydroxypropyl) dimethylsiloxy] substituted), epoxy resin D-17 and acetone, weight ratio is 20:10000:2000, and mixture stirs and makes modified epoxy.By emulsifying agent alkylphenol-polyethenoxy base ether (OP-7) and dehydration sorb fatty acid ester, with the weight ratio of 3:5, be mixed and heated to 80 ℃ in the stirred autoclave of another 2L, make blended emulsifier.After the weight ratio melting by 100:11 of the epoxy resin D-17 of modification and blended emulsifier, stir, slowly add deionized water, until the mass fraction of solid content is 5%, temperature is controlled at 55 ℃, use the mulser rapid stirring simultaneously, mixing speed is 18000r/min, stirs 1h, makes carbon fiber sizing agent of the present invention.
Claims (9)
1. the preparation method of a carbon fiber sizing agent, is characterized in that: comprise the steps:
(1) epoxy resin is dissolved in acetone, add hexahedron polysilsesquioxane and epoxy resin high-speed stirred even, then vacuumize except organic solvent, make modified epoxy, hexahedron polysilsesquioxane: epoxy resin: the weight ratio of acetone is: 20～100:10000:1000～3000;
(2) regulate the proportioning between emulsifying agent, the equilibrium valve of the mixed hydrophilic and oleophilic of emulsifier mixture is remained between 8～12 scopes, then be heated to after molten condition start to stir it is mixed;
(3) epoxy resin of blended emulsifier and modification is become to viscous solution according to the weight ratio melting mixing of 6～18:100;
(4) slowly add deionized water, until the mass fraction of solid content is 5%, temperature is controlled at 55 ℃, the while rapid stirring, and the control rotating speed is 14000～18000r/min, mixing time is 1h, obtains carbon fiber sizing agent.
2. the preparation method of carbon fiber sizing agent according to claim 1, it is characterized in that: described hexahedron polysilsesquioxane is selected from eight (the 3-hydroxypropyl dimethyl is silica-based) polysilsesquioxanes or 3-hydroxypropyl seven isobutyl group polysilsesquioxanes.
3. the preparation method of carbon fiber sizing agent according to claim 1 is characterized in that: described epoxy resin is one or more the mixture in glycidol fundamental mode epoxy resin, epoxidation of olefins, bisphenol A type epoxy resin.
4. the preparation method of carbon fiber sizing agent according to claim 3, it is characterized in that: described glycidol fundamental mode epoxy resin is epoxy resin 618,665,6101 or AG-80.
5. the preparation method of carbon fiber sizing agent according to claim 3, it is characterized in that: described epoxidation of olefins is epoxy resin D-17.
6. the preparation method of carbon fiber sizing agent according to claim 1 is characterized in that: it is OP series, this dish series or tween series that described emulsifying agent is selected from.
7. the preparation method of carbon fiber sizing agent according to claim 6, it is characterized in that: described polyoxyethylene nonylphenol ether series is OP-10 or OP-7.
8. the preparation method of carbon fiber sizing agent according to claim 6, it is characterized in that: described emolsifier span series is S-40, S-60 or S-80.
9. the preparation method of carbon fiber sizing agent according to claim 6, it is characterized in that: described emulsifier tween series is T-40, T-60, T-80.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101784498A CN103451951A (en) | 2012-06-01 | 2012-06-01 | Preparation method of carbon fiber sizing agent |
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|---|---|---|---|
| CN2012101784498A CN103451951A (en) | 2012-06-01 | 2012-06-01 | Preparation method of carbon fiber sizing agent |
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| CN103451951A true CN103451951A (en) | 2013-12-18 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628323A (en) * | 2013-11-25 | 2014-03-12 | 宜兴市飞舟高新科技材料有限公司 | Carbon fiber sizing agent |
| CN104005232A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | Bismaleimide emulsion type sizing agent and preparation method thereof |
| CN105064030A (en) * | 2015-08-19 | 2015-11-18 | 国网智能电网研究院 | Carbon fiber sizing agent and preparation method thereof |
| CN105178025A (en) * | 2015-09-02 | 2015-12-23 | 哈尔滨工业大学 | High-temperature resistance type nanometer POSS modified epoxy emulsion carbon fiber sizing agent preparation method |
| CN105506962A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Capacity increasing method for nano particle modified carbon fiber sizing agent |
| CN114438791A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Covalent organic framework material modified epoxy resin sizing agent and preparation and application thereof |
| CN114438790A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Modified epoxy resin sizing agent and preparation and application thereof |
| CN116356574A (en) * | 2023-04-11 | 2023-06-30 | 哈尔滨工业大学 | Preparation method of carbon fiber sizing agent capable of improving CAI (carbon fiber) performance of composite material |
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| CN1632217A (en) * | 2004-12-07 | 2005-06-29 | 中国科学院山西煤炭化学研究所 | Process for preparing nano SiO2 modified carbon fiber emulsion pasting agent |
| WO2010021971A1 (en) * | 2008-08-18 | 2010-02-25 | Massachusetts Institute Of Technology | Highly reactive multilayer assembled coating of metal oxides on organic and inorganic substrates |
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2012
- 2012-06-01 CN CN2012101784498A patent/CN103451951A/en active Pending
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| WO2010021971A1 (en) * | 2008-08-18 | 2010-02-25 | Massachusetts Institute Of Technology | Highly reactive multilayer assembled coating of metal oxides on organic and inorganic substrates |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628323A (en) * | 2013-11-25 | 2014-03-12 | 宜兴市飞舟高新科技材料有限公司 | Carbon fiber sizing agent |
| CN104005232A (en) * | 2014-06-10 | 2014-08-27 | 中国科学院山西煤炭化学研究所 | Bismaleimide emulsion type sizing agent and preparation method thereof |
| CN104005232B (en) * | 2014-06-10 | 2015-11-11 | 中国科学院山西煤炭化学研究所 | A kind of BMI emulsion-type sizing agent and method for making thereof |
| CN105064030A (en) * | 2015-08-19 | 2015-11-18 | 国网智能电网研究院 | Carbon fiber sizing agent and preparation method thereof |
| CN105178025B (en) * | 2015-09-02 | 2017-07-04 | 哈尔滨工业大学 | A kind of preparation method of high temperature resistant nano POSS modified epoxy emulsion carbon fiber sizing agents |
| CN105178025A (en) * | 2015-09-02 | 2015-12-23 | 哈尔滨工业大学 | High-temperature resistance type nanometer POSS modified epoxy emulsion carbon fiber sizing agent preparation method |
| CN105506962A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Capacity increasing method for nano particle modified carbon fiber sizing agent |
| CN114438791A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Covalent organic framework material modified epoxy resin sizing agent and preparation and application thereof |
| CN114438790A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Modified epoxy resin sizing agent and preparation and application thereof |
| CN114438791B (en) * | 2020-10-30 | 2024-04-02 | 中国石油化工股份有限公司 | Covalent organic framework material modified epoxy resin sizing agent, preparation and application thereof |
| CN114438790B (en) * | 2020-10-30 | 2024-04-09 | 中国石油化工股份有限公司 | Modified epoxy resin sizing agent and preparation and application thereof |
| CN116356574A (en) * | 2023-04-11 | 2023-06-30 | 哈尔滨工业大学 | Preparation method of carbon fiber sizing agent capable of improving CAI (carbon fiber) performance of composite material |
| CN116356574B (en) * | 2023-04-11 | 2024-08-13 | 哈尔滨工业大学 | Preparation method of carbon fiber sizing agent capable of improving CAI (carbon fiber) performance of composite material |
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Application publication date: 20131218 |