CN103788322A - Polyurethane structure-modified bisphenol A epoxy resin composition, preparation method and application - Google Patents
Polyurethane structure-modified bisphenol A epoxy resin composition, preparation method and application Download PDFInfo
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- CN103788322A CN103788322A CN201210417800.4A CN201210417800A CN103788322A CN 103788322 A CN103788322 A CN 103788322A CN 201210417800 A CN201210417800 A CN 201210417800A CN 103788322 A CN103788322 A CN 103788322A
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- 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
- C08G18/58—Epoxy resins
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- 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
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- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane structure-modified epoxy resin sizing agent emulsion, which comprises 55-78wt% of polyurethane structure-modified epoxy resin composition, 20-40wt% of surfactant, 0.5-2wt% of anti-oxidant, 1-2wt% of levelling agent and 0.5-1wt% of antifreezing agent. A preparation method comprises the following steps: pumping bisphenol A epoxy resin under vacuum and dehydrating until the bubbles does not generate, cooling and adding isocyanate to prepare the epoxy resin composition; mixing and homogenizing the surfactant and anti-oxidant according to the above material fraction, and then gradually adding deionized water, the levelling agent and the antifreezing agent to obtain the product. The carbon fiber prepared by polyurethane structure-modified epoxy resin sizing agent emulsion has good convergence, wear resistance and toughness, the convergence and wear resistance are easily and freely adjusted through the amount of an isocyanate component; a sizing agent and on-site secondary mixing are not required at anaphase for the carbon fiber sizing agent, the application and stability are good, the carbon fiber sizing wellability is good, and the polyurethane structure-modified bisphenol A epoxy resin composition is benefit for industrial stabilization production of carbon fiber.
Description
Technical field
The invention belongs to the modification preparation field of epoxy resin in organic polymer material, particularly a kind of bisphenol A epoxide resin composition by polyurethane structural modification and preparation and application.
Background technology
Epoxy resin has higher intensity, good adhesiveproperties, chemical stability, easily machine-shaping and the advantage such as with low cost, and its polymer composites is by a large number for many industrial circles.But because the curing rear cross-linking density of pure epoxy resin is high, there is the shortcomings such as internal stress is large, curing material is crisp, thermotolerance is poor, limited its application in fibre reinforced composites.Interfacial layer plays an important role in matrix material, and it is the transition layer that reinforcement is connected with matrix, is the bridge that transmits stress, so its structure and performance directly have influence on the performance of matrix material simultaneously.
At present, importance based on sizing agent in high-performance carbon fibre and graphite fibre manufacturing engineering and fiber-reinforced resin matrix compound material application, sizing agent has become the important supplementary material of carbon fiber, graphite fibre through engineering approaches, the manufacturability of its performance impact carbon fiber manufacturing engineering and the comprehensive mechanical property of matrix material are also the important focuses of current high-performance carbon fibre and the research of graphite fibre industrialization technology.Chinese invention patent application 200510063352.2,201010300131.3,201010234852.9,2009102158.33,201010202372.4 discloses respectively preparation method and the application take epoxy resin, aqueous epoxy resins, Racemic glycidol ether-ether, polypropylene nitrile, epoxy vinyl compound resin as the carbon fiber sizing agent of main ingredient.In addition, in order further to improve the performance of emulsion property and starching carbon fiber, Chinese invention patent application 201010217247.0,201110102007.0,201110085545.3,200410064587.9 discloses respectively the preparation method and application that adopt the emulsion pasting agent of the modifications such as polyvalent alcohol, Graphene, carbon nanotube, nano silicon.Meanwhile, Chinese invention patent application 201010217240.9 and 201010125199.2 discloses respectively the synthesis preparation method of two kinds of self-emulsifying type epoxy group(ing) carbon fiber sizing agents.But from current application feature, adopt above-mentioned resin formula to prepare the sizing agent of gained, while being applied to carbon fiber, graphite fibre, there is under normal fiber starching amount (<1.40%) condition convergency and wear no resistance, open fibre and the problem such as expanding performance shortcoming and resilience toughness deficiency, especially ubiquity in the through engineering approaches application of the carbon fiber of 12K and above tow number, has restricted the practical engineering application of above-mentioned sizing agent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of bisphenol A epoxide resin composition by polyurethane structural modification and preparation and application, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduce polarity carbamate groups, be applied to the preparation of carbon fiber sizing agent, can improve the technique perviousness of sizing agent, improve convergency and the wear resisting property of sizing technique and carbon fiber, the manufacture that is conducive to 12K and above tow and counts carbon fiber through engineering approaches application and high performance composite; And preparation technology is simple for this composition epoxy resin, reaction raw materials convenient sources can complete preparation process in general-purpose equipment, and economic benefit is good, is conducive to realize suitability for industrialized production.
A kind of bisphenol A epoxide resin composition by polyurethane structural modification of the present invention, its component comprises: the isocyanic ester of the bisphenol A type epoxy resin of mass percent 88-99% and mass percent 1-12%.
Described bisphenol A type epoxy resin is selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51;
Described bisphenol A type epoxy resin, its molecular-weight average is 350～2500 grams/mol, preferably molecular-weight average is 350～1500 grams/mol;
Described isocyanic ester is aromatic series, aliphatics or alicyclic isocyanate;
Preferred isocyanic ester is aromatic series tolylene diisocyanate (TDI), aromatic series diphenylmethanediisocyanate (MDI), six methylene diisocyanates of aliphatics (HDI) or alicyclic isophorone diisocyanate (IPDI).
The preparation method of a kind of bisphenol A epoxide resin composition by polyurethane structural modification of the present invention, comprising:
(1) bisphenol A type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, the temperature of its vacuum hydro-extraction is 90-150 ℃, and the vacuum pressure of dehydration is 100-0.1mmHg;
(2) respectively the dry epoxy resin of above-mentioned vacuum hydro-extraction gained is cooled to 50 ~ 70 ℃; under the drying nitrogen protection of purity 99.999%, add isocyanate reaction thing; wherein the mass ratio of epoxy resin and isocyanic ester is 88 ~ 99:1 ~ 12; prior to 50 ~ 70 ℃; stirring reaction 1 ~ 2 hour; then be warming up to 80 ~ 100 ℃; continue reaction more than 2 hours; isocyanate functional group's content of controlling reaction product is less than 0.1% stopped reaction, makes the bisphenol A epoxide resin composition of polyurethane structural modification.
In described step (1) bisphenol A type epoxy resin be selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51;
In described step (1) bisphenol A type epoxy resin, its molecular-weight average is 350～2500 grams/mol, preferably molecular-weight average is 350～1500 grams/mol;
The temperature of the vacuum hydro-extraction in described step (1) is 90-120 ℃, and the vacuum pressure of dehydration is 10-0.5mmHg;
Isocyanic ester in described step (2) is aromatic series, aliphatics or alicyclic isocyanate;
Preferred isocyanic ester is aromatic series tolylene diisocyanate (TDI), aromatic series diphenylmethanediisocyanate (MDI), six methylene diisocyanates of aliphatics (HDI) or alicyclic isophorone diisocyanate (IPDI).
A kind of bisphenol A epoxide resin composition by polyurethane structural modification of the present invention preparation have good convergency and wear resistance epoxy group(ing) carbon fiber sizing agent in application.
Beneficial effect
(1) the present invention, by the method for the in-situ modified composition epoxy resin of polyurethane structural, introduces polarity carbamate groups, is applied to the preparation of sizing agent, can improve the technique perviousness of sizing agent; Meanwhile, by the molecular-weight average of free adjustment composition epoxy resin, improve convergency and the wear resisting property of sizing technique and carbon fiber, the manufacture that is conducive to 12K and above tow and counts carbon fiber through engineering approaches application and high performance composite;
(2) this preparation technology is simple, and reaction raw materials convenient sources can complete preparation process in general-purpose equipment, and economic benefit is good, is conducive to realize suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1-12
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 70 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative six methylene diisocyanates (HDI) are added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 70 ℃; be warming up to again 95 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol A epoxide resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, six methylene diisocyanates (HDI) consumption are in table 1.
Table 1, reaction raw materials quality table
Embodiment 13-24
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 70 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative isophorone diisocyanate (IPDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 70 ℃; be warming up to again 95 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol A epoxide resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, isophorone diisocyanate (IPDI) consumption are in table 2.
Table 2, reaction raw materials quality table
Embodiment 25-36
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 50 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative diphenylmethanediisocyanate (MDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 50 ℃; be warming up to again 85 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol A epoxide resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, diphenylmethanediisocyanate (MDI) consumption are in table 3.
Table 3, reaction raw materials quality table
Embodiment 37-48
Quantitative epoxy resin composition is placed in to the 250ml four-hole boiling flask with mechanical stirring device, is heated to 110 ℃, control vacuum pressure 100-0.1mmHg, vacuumize and dewater 2 hours extremely without Bubble formation.Be cooled to 50 ℃, remove vacuum extractor, insert prolong.Under high pure nitrogen protection; quantitative tolylene diisocyanate (TDI) is added drop-wise in flask very lentamente with Micro-metering Pumps; dropwise rear elder generation reacts 1 hour at 50 ℃; be warming up to again 85 ℃ of reactions more than 2 hours; infrared analysis is carried out in sampling; when result shows nothing-NCO group, make the bisphenol A epoxide resin composition of polyurethane structural modification.Epoxy resin composition kind used and consumption, tolylene diisocyanate (TDI) consumption are in table 4.
Table 4, reaction raw materials quality table
Application Example
One, the preparation of epoxy group(ing) carbon fiber sizing agent
Get 60g above-described embodiment and prepare the composition epoxy resin of the polyurethane structural modification of gained, add 0.32g2,6-ditertbutylparacresol (group produces by traditional Chinese medicines), 21.30g octadecanol polyoxyethylene ether surface active agent (ethylene oxide polymerization degree 20) (being produced by Hai'an, Jiangsu petrochemical plant) stirs 1 hour at 90 ℃.Then be cooled to 80 ℃, slowly drip the high-speed stirring emulsification simultaneously of 100g deionized water, after completing, add 0.32g Siloxane-Oxyalkylene Copolymers BNK-LK380(to be produced by BNK company of the U.S.), 0.32g butyl glycol ether (group produces by traditional Chinese medicines), prepare water-based emulsion.
The viscosity that the present embodiment is prepared gained water-based emulsion adopts the test of Brookfield DV-II Pro rotational viscosimeter to obtain, emulsion PH adopts the examination of the U.S. DELTA 320pH of Mettler Toledo Inc. instrumentation to obtain, emulsion surface tension adopts the DCAT21 type dynamic contact angle of German DataPhysics company and surface tension instrument test to obtain, emulsion median size adopts the Zetasizer NanoZS90 type dynamic laser scatterometer test of Ma Erwen instrument company of Britain to obtain, and prepared emulsion property indices is in table 5.
Table 5, emulsion property index test result
Two, the starching of carbon fiber
The above-mentioned gained emulsion pasting agent of preparing is carried out to starching in self-control on small-sized starching instrument, and selected fiber is 12K T300 grade carbon fiber, dipping time 30s, 130 ℃ of drying temperatures, time of drying 2min.
The present embodiment is according to document (" new carbon ", 2006,21(4): 337-341; Exercise question: temp, resisting type carbon fibre emulsion sizing agent) method test obtains wear resistance, lousiness figureofmerit; According to GB3357-1982 unidirectional fibre reinforced plastics interlayer shear strength test method test carbon-fibre composite interlaminar shear strength ILSS; After adopting feel appearance method to starching, carbon fiber cluster performance is graded, and gained starching carbon fiber Evaluation results is in table 6.
Table 6, starching carbon fiber Evaluation results
| Convergency | Wear resistance/time | Lousiness amount/mg | ILSS/Mpa | |
| Comparative example 1 | × | 1855 | 3.81 | 66.5 |
| Comparative example 2 | × | 1801 | 3.76 | 68.2 |
| Comparative example 3 | × | 1793 | 3.59 | 68.6 |
| Comparative example 4 | × | 1779 | 3.62 | 69.1 |
| Embodiment 1 | ● | 4222 | 0.46 | 113.5 |
| Embodiment 7 | ○ | 3851 | 0.84 | 112.9 |
| Embodiment 18 | ● | 3805 | 0.61 | 109.8 |
| Embodiment 23 | ● | 4047 | 0.29 | 105.3 |
| Embodiment 28 | ● | 3286 | 0.71 | 98.8 |
| Embodiment 38 | ○ | 2734 | 1.09 | 81.9 |
| Embodiment 41 | ● | 3003 | 0.83 | 86.9 |
| Embodiment 48 | ○ | 2669 | 1.17 | 87.6 |
Note: convergency Index grading ●-fine zero-good △-bad ×-poor
Although the present invention discloses preferred embodiment as above; so it is not in order to limit content of the present invention; anyly be familiar with this skill person; not departing from main spirits of the present invention and context; when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the basic right claimed range of applying for a patent.
Claims (14)
1. by a bisphenol A epoxide resin composition for polyurethane structural modification, its component comprises: the isocyanic ester of the bisphenol A type epoxy resin of mass percent 88-99% and mass percent 1-12%.
2. a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 1, is characterized in that: described bisphenol A type epoxy resin is selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51.
3. a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 1 and 2, is characterized in that: described bisphenol A type epoxy resin, its molecular-weight average is 350～2500 grams/mol.
4. a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 3, is characterized in that: described bisphenol A type epoxy resin, its molecular-weight average is 350～1500 grams/mol.
5. a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 1, is characterized in that: described isocyanic ester is aromatic series, aliphatics or alicyclic isocyanate.
6. a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 5, is characterized in that: described isocyanic ester is aromatic series tolylene diisocyanate TDI, aromatic series diphenylmethanediisocyanate MDI, six methylene diisocyanate HDI of aliphatics or alicyclic isophorone diisocyanate IPDI.
7. by a preparation method for the bisphenol A epoxide resin composition of polyurethane structural modification, comprising:
(1) bisphenol A type epoxy resin reactant is at high temperature vacuumized to dehydration extremely without Bubble formation, the temperature of its vacuum hydro-extraction is 90-150 ℃, and the vacuum pressure of dehydration is 100-0.1mmHg;
(2) respectively the dry epoxy resin of above-mentioned vacuum hydro-extraction gained is cooled to 50 ~ 70 ℃; under the drying nitrogen protection of purity 99.999%, add isocyanate reaction thing; wherein the mass ratio of epoxy resin and isocyanic ester is 88 ~ 99:1 ~ 12; prior to 50 ~ 70 ℃; stirring reaction 1 ~ 2 hour; then be warming up to 80 ~ 100 ℃; continue reaction more than 2 hours; isocyanate functional group's content of controlling reaction product is less than 0.1% stopped reaction, makes the bisphenol A epoxide resin composition of polyurethane structural modification.
8. the preparation method of a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 7, is characterized in that: in described step (1) bisphenol A type epoxy resin be selected from one or more the mixture in bisphenol A-type E20, bisphenol A-type E21, bisphenol A-type E44, bisphenol A-type E51.
9. according to the preparation method of a kind of bisphenol A epoxide resin composition by polyurethane structural modification described in claim 7 or 8, it is characterized in that: in described step (1) bisphenol A type epoxy resin, its molecular-weight average is 350～2500 grams/mol.
10. the preparation method of a kind of bisphenol A epoxide resin composition by polyurethane structural modification according to claim 9, is characterized in that: described bisphenol A type epoxy resin, its molecular-weight average is 350～1500 grams/mol.
The preparation method of 11. a kind of bisphenol A epoxide resin compositions by polyurethane structural modification according to claim 7, is characterized in that: the temperature of the vacuum hydro-extraction in described step (1) is 90-120 ℃, and the vacuum pressure of dehydration is 10-0.5mmHg.
The preparation method of 12. a kind of bisphenol A epoxide resin compositions by polyurethane structural modification according to claim 7, is characterized in that: the isocyanic ester in described step (2) is aromatic series, aliphatics or alicyclic isocyanate.
The preparation method of 13. a kind of bisphenol A epoxide resin compositions by polyurethane structural modification according to claim 12, is characterized in that: described isocyanic ester is aromatic series tolylene diisocyanate TDI, aromatic series diphenylmethanediisocyanate MDI, six methylene diisocyanate HDI of aliphatics or alicyclic isophorone diisocyanate IPDI.
The application in preparation epoxy group(ing) carbon fiber sizing agent of 14. 1 kinds of bisphenol A epoxide resin compositions by polyurethane structural modification.
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| CN109957969A (en) * | 2017-12-25 | 2019-07-02 | 比亚迪股份有限公司 | A kind of carbon fiber sizing agent, preparation method, enhancing carbon fiber and carbon fibre composite |
| CN110615988A (en) * | 2019-08-29 | 2019-12-27 | 江苏沃特新材料科技有限公司 | High-wear-resistance polyphenylene sulfide material and preparation method thereof |
| CN111574719A (en) * | 2020-04-09 | 2020-08-25 | 深圳航天科技创新研究院 | Thermoplastic epoxy resin, application thereof and surface modifier for carbon fibers |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106498740A (en) * | 2016-11-11 | 2017-03-15 | 北京化工大学 | A kind of polyurethane modified epoxy resin sizing agent and preparation method thereof |
| CN109957969A (en) * | 2017-12-25 | 2019-07-02 | 比亚迪股份有限公司 | A kind of carbon fiber sizing agent, preparation method, enhancing carbon fiber and carbon fibre composite |
| CN109957969B (en) * | 2017-12-25 | 2022-01-07 | 比亚迪股份有限公司 | Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material |
| CN110615988A (en) * | 2019-08-29 | 2019-12-27 | 江苏沃特新材料科技有限公司 | High-wear-resistance polyphenylene sulfide material and preparation method thereof |
| CN110615988B (en) * | 2019-08-29 | 2022-03-11 | 江苏沃特新材料科技有限公司 | High-wear-resistance polyphenylene sulfide material and preparation method thereof |
| CN111574719A (en) * | 2020-04-09 | 2020-08-25 | 深圳航天科技创新研究院 | Thermoplastic epoxy resin, application thereof and surface modifier for carbon fibers |
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