CN104562698A - Preparation method of sizing agent of carbon fibers for reinforcement of thermoplastic resin - Google Patents
Preparation method of sizing agent of carbon fibers for reinforcement of thermoplastic resin Download PDFInfo
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- CN104562698A CN104562698A CN201310473074.2A CN201310473074A CN104562698A CN 104562698 A CN104562698 A CN 104562698A CN 201310473074 A CN201310473074 A CN 201310473074A CN 104562698 A CN104562698 A CN 104562698A
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Abstract
The invention discloses a preparation method of a sizing agent of carbon fibers for reinforcement of thermoplastic resin. The preparation method comprises the following steps of 1, preparing a special-purpose coupling agent, and 2, mixing an aqueous polyurethane emulsion, the special-purpose coupling agent, a dispersant and thermoplastic resin powder at a temperature of 20-40 DEG C to obtain the sizing agent applied for carbon fiber surfaces. The sizing agent comprises solid content of 1-4wt%, a use amount of the special-purpose coupling agent is 0.1-5wt% that of the aqueous polyurethane, a use amount of the thermoplastic resin powder is 0-10wt% that of the aqueous polyurethane, and a use amount of the dispersant is 0.5-5wt% of that of the thermoplastic resin powder. The preparation method has simple processes, a low cost and environmental friendliness and can improve wellability and interface interaction of carbon fibers and resin.
Description
Technical field
The invention belongs to materials application technical field, specifically, relate to a kind of preparation method strengthening carbon fiber for thermoplastic resin sizing agent.
Background technology
Carbon fiber is the important strongthener of high performance composite, is widely used in the fields such as aerospace, Leisure Sport articles for use, building, textile manufacturing machine, electronic product.Fibre reinforced thermoplas tic resin composite is rapidly developed because of features such as it are reusable, shaping speed is fast, anti-fatigue performance is good.
Carbon fiber surface modification is the gordian technique that carbon fiber is applied in the composite, needs to carry out the process such as electrochemical oxidation to carbon fiber in carbon fiber production process, makes carbon fiber surface produce oxygen-content active group, as hydroxyl, carboxyl and carbonyl etc.These active groups can produce chemical bonding with the various matrix resins of matrix material, thus significantly can improve the interface performance of matrix material.But carbon fiber itself enbrittles, easily in production, processing, produce lousiness, and the above active group through surface modification acquisition in atmosphere easily " inactivation ".So carrying out starching process to carbon fiber surface is operation indispensable during carbon fiber is produced; its object is except reducing lousiness, protecting carbon fiber surface, avoiding carbon fiber surface except " inactivation "; the wetting property of fiber and resin matrix can also be improved by sizing agent design, improve interface interaction intensity.
The carbon fiber sizing agent of current research mainly for carbon fiber-reinforced thermosetting resin composite materials, as disclosed a kind of sizing agent of epoxy resin latex in patent CN101736593A, is mainly used in carbon fiber-reinforced thermosetting epoxy resin composite material.The processing molding method of thermoplastic resin based composite material and thermoset ting resin composite has larger difference, and the principle of interface interaction is not identical yet, thus exploitation thermoplastic resin based composite material carbon fiber sizing agent to seem very urgent.The preparation method of the water-based emulsion sizing agent of a kind of thermoplastic polyimide resin and diglycidyl ether type epoxy resin is disclosed in patent CN10099867A, but above-mentioned sizing agent preparation process is complicated, after starching, carbon fiber surface is more crisp, and the consistency at thermoplastic resin interface is poor.Patent CN102660874A discloses a kind of carbon fiber thermoplasticity sizing agent, and its second-order transition temperature, higher than 267 DEG C, may be used for most high-temperature resistant thermoplastic resin.But this sizing agent is solvent-borne type sizing agent, pollutes greatly, production operation environment is poor, solvent recuperation cost is high.
The design of carbon fiber for thermoplastic resin sizing agent and processing should mainly be considered:
(1) the technical of carbon fiber is improved;
(2) wetting property of carbon fiber and high viscosity thermoplastic resin is improved;
(3) interface interaction of carbon fiber and thermoplastic resin is improved;
(4) at the bottom of cost, environmental friendliness.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method strengthening carbon fiber for thermoplastic resin sizing agent, its technique is simple, cost is low, environmental friendliness, wetting property and the interface interaction thereof of carbon fiber and resin can be improved.
A kind of preparation method strengthening carbon fiber for thermoplastic resin sizing agent provided by the invention; concrete steps comprise: (1) prepares special coupling agent: dissolved in organic solvent by the end-capping reagent containing reactive hydrogen; concentration controls at 1mol/L-5mol/L; be added drop-wise under inert atmosphere protection in isocyanic ester; the molar ratio of end-capping reagent and isocyanic ester is (1 ~ 2.5): 1; temperature of reaction is 60-105 DEG C; reaction times is 2-8 hour; after reaction terminates; removing excess blocking agent, obtains special coupling agent after washing, drying.
(2) special coupling agent and water or organic solvent are mixed, be mixed with suspension or solution that concentration is 5wt-15wt%, aqueous polyurethane emulsion, special coupling agent, dispersion agent and thermoplastic resin powder are carried out being mixed to get the carbon fiber surface sizing agent that solid content is 1wt% ~ 4wt% under the condition of 20-40 DEG C, wherein the add-on of special coupling agent is the 0.1wt% ~ 5wt% of aqueous polyurethane, the add-on of thermoplastic resin powder is the 1wt% ~ 10wt% of aqueous polyurethane, and the add-on of dispersion agent is thermoplastic resin powder 0.5wt% ~ 5wt%.
The end-capping reagent containing reactive hydrogen described in above-mentioned steps 1 is one or more in N-methylacetamide, Acetanilide, hexanolactam, sodium bisulfite, pyrosulphite hydrogen sodium.
Isocyanic ester described in above-mentioned steps (1) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 1, one in 5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate, sub-xylylene diisocyanate, PPDI, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, HMDI, isophorone diisocyanate, Methylcyclohexyl diisocyanate.
Organic solvent described in above-mentioned steps (1) is selected from the one in toluene, benzene or dimethylbenzene.
Organic solvent described in above-mentioned steps (2) is selected from ethylene glycol, Virahol, butanone, acetone, any one in methyl ether or tetrachloroethylene.
Aqueous polyurethane emulsion described in above-mentioned steps (2), its particle diameter is at 0.1 ~ 1.0 micron.
Thermoplastic resin powder described in above-mentioned steps (2) is selected from any one in nylon 6, nylon66 fiber, nylon 1010, polyester, polypropylene, polyethylene or polyphenylene sulfide, diameter of particle 5 ~ 20 microns.
Dispersion agent described in above-mentioned steps (2) is selected from one in polyoxyethylene glycol, polyacrylamide or aminopropyl triethoxysilane or two kinds.
In the present invention, carbon fiber reinforced thermoplastic resin can be identical with the thermoplastic resin powder described in step (2), also can be different.
Beneficial effect of the present invention is: its preparation method, and its technique is simple, cost is low, environmental friendliness, can improve wetting property and the interface interaction thereof of carbon fiber and resin.
Embodiment
Aqueous polyurethane is purchased from Bayer (bayer), and particle diameter concentrates on 100 ~ 600nm, and particle diameter peak value is at 260nm.
Embodiment (1)-(6)
(1) special coupling agent is prepared: dissolved in organic solvent by end-capping reagent; the selection of strength of solution, end-capping reagent and organic solvent is as shown in table 1; be added drop-wise under the protection of rare gas element in isocyanic ester, the kind of isocyanic ester and feed ratio are also as shown in table 1.React according to the reaction conditions of table 1, terminate the end-capping reagent that rear removing is excessive, after washing, drying, obtain special coupling agent
(2) by special coupling agent and water or organic solvent mixing, be made into suspension liquid or solution, kind and the concentration of coupling agent, organic solvent are as shown in table 2, temperature condition aqueous polyurethane emulsion, special coupling agent, dispersion agent and thermoplastic resin powder are carried out being mixed to get carbon fiber surface sizing agent, wherein the add-on of sizing agent total solid content and coupling agent, aqueous polyurethane, thermoplastic resin split, dispersion agent is as shown in table 2.
As shown in table 1 is preparation condition and the result of special coupling agent in embodiment.
As shown in table 2 is preparation condition in embodiment on carbon fiber and result.
Table 1
Table 2
Performance test
Method for sizing: select the sizing agent of suitable solid content as sizing liquor according to the starching amount of required carbon fiber, by roller pickling process or roller contact process etc., sizing liquor is evenly adhered to also on carbon fiber, finally makes solvent evaporates by methods such as hot blast, warming mill, Infrared Heating again.
By carbon fiber prepared by embodiment 1, starching amount is 3%, and tow convergency is good, and surface is glossy, and fiber does not disperse few fluffing, and linear density is even.
The PA66EPR27 of Henan Shen Ma group is selected to be resin matrix, 1
#the 12K carbon fiber of conventional sizing agent starching that what sample strongthener was selected is, 2
#the 12K carbon fiber of sizing agent starching prepared by embodiment 3 that what sample strongthener was selected is, 1
#with 2
#the carbon fiber of sample is identical is only that sizing agent is different, and the composite property that both prepare is as table 3.
Table 3
Visible 1
#although sample carbon fiber content is slightly high, its Performance Ratio 2
#really poor, illustrate 2
#carbon fiber sizing agent have better keying action to carbon fiber and resin matrix.
Claims (8)
1. strengthen a preparation method for carbon fiber for thermoplastic resin sizing agent, it is characterized in that concrete steps are as follows:
(1) special coupling agent is prepared: dissolved in organic solvent by the end-capping reagent containing reactive hydrogen, concentration controls at 1mol/L-5mol/L, be added drop-wise under nitrogen protection in isocyanic ester, the molar ratio of end-capping reagent and isocyanic ester is (1 ~ 2.5): 1, temperature of reaction is 60-105 DEG C, and the reaction times is 2-8 hour, after reaction terminates, removing excess blocking agent, obtains special coupling agent after washing, drying;
(2) special coupling agent and water or organic solvent is carried out being hybridly prepared into the suspension that concentration is 5wt-15wt% or solution, under the condition of 20-40 DEG C, aqueous polyurethane emulsion, special coupling agent, dispersion agent and thermoplastic resin powder are mixed, obtain the carbon fiber surface sizing agent that solid content is 1wt% ~ 4wt%; Wherein: the add-on of special coupling agent is the 0.1wt% ~ 5wt% of aqueous polyurethane, the add-on of thermoplastic resin powder is the 1wt% ~ 10wt% of aqueous polyurethane, and the add-on of dispersion agent is thermoplastic resin powder 0.5wt% ~ 5wt%.
2. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, is characterized in that: the end-capping reagent containing reactive hydrogen described in step (1) is one or more in N-methylacetamide, Acetanilide, hexanolactam, sodium bisulfite or pyrosulphite hydrogen sodium.
3. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, it is characterized in that: the isocyanic ester described in step (1) is selected from 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4, 4 '-'-diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate, sub-xylylene diisocyanate, PPDI, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, 4, 4 '-dicyclohexyl methane diisocyanate, any one in isophorone diisocyanate or Methylcyclohexyl diisocyanate.
4. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, is characterized in that: the organic solvent described in step (1) is the one in toluene, benzene, dimethylbenzene.
5. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, is characterized in that: the organic solvent described in step (2) is the one in ethylene glycol, Virahol, butanone, acetone, methyl ether or tetrachloroethylene.
6. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, its feature exists: the aqueous polyurethane emulsion described in step (2), its particle diameter is between 0.1-1.0 micron.
7. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, it is characterized in that: the thermoplastic resin powder described in step (2) is selected from any one in nylon 6, nylon66 fiber, nylon 1010, polyester, polypropylene, polyethylene or polyphenylene sulfide, diameter of particle 5-20 micron.
8. the preparation method of enhancing carbon fiber for thermoplastic resin sizing agent according to claim 1, is characterized in that: the dispersion agent described in step (2) is selected from one in polyoxyethylene glycol, polyacrylamide or aminopropyl triethoxysilane or two kinds.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107509380A (en) * | 2017-09-13 | 2017-12-22 | 苏州南尔材料科技有限公司 | A kind of preparation method of environmental-protecting electromagnetic shielding composite |
| CN108976476A (en) * | 2018-08-03 | 2018-12-11 | 安徽旭升新材料有限公司 | The processing method of carbon fiber in carbon fiber PA6 thermoplastic composite |
| CN109054368A (en) * | 2018-08-03 | 2018-12-21 | 安徽旭升新材料有限公司 | The preparation method of carbon fiber PA6 thermoplastic composite |
| CN109096748A (en) * | 2018-07-18 | 2018-12-28 | 安徽旭升新材料有限公司 | A kind of thermoplasticity carbon fibre composite midsole and preparation method thereof |
| CN109181288A (en) * | 2018-09-18 | 2019-01-11 | 安徽旭升新材料有限公司 | The preparation process of carbon fiber PA6 thermoplastic composite |
| CN109722894A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyolefin resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN110130109A (en) * | 2019-04-17 | 2019-08-16 | 镇江市高等专科学校 | A kind of novel carbon fiber sizing agent |
| 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 |
| CN111088699A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Sizing agent for polypropylene/carbon fiber interface and preparation method and application thereof |
| CN111116930A (en) * | 2019-12-31 | 2020-05-08 | 中山大学 | Hyper-dispersant, thermoplastic resin-based carbon fiber composite material and preparation method thereof |
| CN112591729A (en) * | 2020-12-16 | 2021-04-02 | 彭浩波 | Cured carbon fiber felt and preparation method thereof |
| CN114318878A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | Polyphenylene sulfide linear oligomer graft modified carbon fiber and preparation method and application thereof |
| CN115162004A (en) * | 2022-07-15 | 2022-10-11 | 江苏先诺新材料科技有限公司 | Polyimide chopped fiber and preparation method thereof |
| CN115450050A (en) * | 2022-09-30 | 2022-12-09 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
| TWI843665B (en) * | 2023-10-13 | 2024-05-21 | 陳英仁 | Method for enhancing the interface strength between carbon fiber and acrylic resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314157A2 (en) * | 1987-10-29 | 1989-05-03 | Nitto Boseki Co., Ltd. | Method of surface treating carbon fiber with a sizing agent |
| CN100999867A (en) * | 2006-12-20 | 2007-07-18 | 中国科学院山西煤炭化学研究所 | Temp, resisting type carbon fibre emulsion sizing agent and its preparation process and application |
| CN102660874A (en) * | 2012-06-06 | 2012-09-12 | 哈尔滨工业大学 | Thermoplasticity sizing agent for carbon fiber and preparation and usage thereof |
| CN102912637A (en) * | 2012-11-16 | 2013-02-06 | 中复神鹰碳纤维有限责任公司 | Carbon fiber sizing agent |
| CN102912641A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Preparation method of aqueous sizing agent for carbon fibers |
-
2013
- 2013-10-11 CN CN201310473074.2A patent/CN104562698A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0314157A2 (en) * | 1987-10-29 | 1989-05-03 | Nitto Boseki Co., Ltd. | Method of surface treating carbon fiber with a sizing agent |
| CN100999867A (en) * | 2006-12-20 | 2007-07-18 | 中国科学院山西煤炭化学研究所 | Temp, resisting type carbon fibre emulsion sizing agent and its preparation process and application |
| CN102660874A (en) * | 2012-06-06 | 2012-09-12 | 哈尔滨工业大学 | Thermoplasticity sizing agent for carbon fiber and preparation and usage thereof |
| CN102912637A (en) * | 2012-11-16 | 2013-02-06 | 中复神鹰碳纤维有限责任公司 | Carbon fiber sizing agent |
| CN102912641A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Preparation method of aqueous sizing agent for carbon fibers |
Cited By (21)
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| CN107509380A (en) * | 2017-09-13 | 2017-12-22 | 苏州南尔材料科技有限公司 | A kind of preparation method of environmental-protecting electromagnetic shielding composite |
| CN109722894A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyolefin resin base carbon fibre suspension sizing agent and preparation method thereof |
| CN109722894B (en) * | 2017-10-27 | 2022-01-21 | 中国石油化工股份有限公司 | Polyolefin resin-based carbon fiber suspension sizing agent and preparation method thereof |
| CN109096748A (en) * | 2018-07-18 | 2018-12-28 | 安徽旭升新材料有限公司 | A kind of thermoplasticity carbon fibre composite midsole and preparation method thereof |
| CN108976476A (en) * | 2018-08-03 | 2018-12-11 | 安徽旭升新材料有限公司 | The processing method of carbon fiber in carbon fiber PA6 thermoplastic composite |
| CN109054368A (en) * | 2018-08-03 | 2018-12-21 | 安徽旭升新材料有限公司 | The preparation method of carbon fiber PA6 thermoplastic composite |
| CN109181288A (en) * | 2018-09-18 | 2019-01-11 | 安徽旭升新材料有限公司 | The preparation process of carbon fiber PA6 thermoplastic composite |
| CN111088699B (en) * | 2018-10-23 | 2023-01-24 | 中国石油化工股份有限公司 | Sizing agent for polypropylene/carbon fiber interface and preparation method and application thereof |
| CN111088699A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Sizing agent for polypropylene/carbon fiber interface and preparation method and application thereof |
| CN110130109A (en) * | 2019-04-17 | 2019-08-16 | 镇江市高等专科学校 | A kind of novel carbon fiber sizing agent |
| 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 |
| CN111116930A (en) * | 2019-12-31 | 2020-05-08 | 中山大学 | Hyper-dispersant, thermoplastic resin-based carbon fiber composite material and preparation method thereof |
| CN114318878A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院宁波材料技术与工程研究所 | Polyphenylene sulfide linear oligomer graft modified carbon fiber and preparation method and application thereof |
| CN114318878B (en) * | 2020-09-30 | 2023-11-03 | 中国科学院宁波材料技术与工程研究所 | Polyphenylene sulfide linear oligomer grafted modified carbon fiber and preparation method and application thereof |
| CN112591729A (en) * | 2020-12-16 | 2021-04-02 | 彭浩波 | Cured carbon fiber felt and preparation method thereof |
| CN112591729B (en) * | 2020-12-16 | 2022-10-11 | 彭浩波 | Cured carbon fiber felt and preparation method thereof |
| CN115162004A (en) * | 2022-07-15 | 2022-10-11 | 江苏先诺新材料科技有限公司 | Polyimide chopped fiber and preparation method thereof |
| CN115450050A (en) * | 2022-09-30 | 2022-12-09 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
| CN115450050B (en) * | 2022-09-30 | 2023-10-17 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
| TWI843665B (en) * | 2023-10-13 | 2024-05-21 | 陳英仁 | Method for enhancing the interface strength between carbon fiber and acrylic resin |
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