CN107700213B - Carbon fiber sizing agent and preparation method thereof, and carbon fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Carbon fiber sizing agent and preparation method thereof, and carbon fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon fiber sizing agent which is a copolymer emulsion of maleic anhydride and long-chain olefin and/or long-chain alkyne. The composite material has good adhesion performance, greatly shortens the impregnation time, and plays a good bridging role between the carbon fiber and the polypropylene matrix, thereby further improving the mechanical property of the composite material. The carbon fiber sizing agent is adopted to pretreat carbon fibers, and the prepared carbon fiber reinforced polypropylene composite material has excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of carbon fiber composite materials, in particular to a carbon fiber sizing agent and a preparation method thereof, and a carbon fiber reinforced polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is a high polymer material with low density, rich raw materials, low price and wide application, and belongs to thermoplastic resin. However, the notch impact toughness of polypropylene is low, the shrinkage rate is high, so that the polypropylene is affected by external force in the using process to cause stress whitening, and the application universality of the polypropylene is limited to a certain extent. The carbon fiber is an excellent material with high specific modulus, high specific strength, low density, high temperature resistance and small thermal expansion coefficient, and is widely applied to the high-end fields of aerospace, automobile and the like.
By combining the advantages of polypropylene and carbon fiber, a high-strength and light-weight composite material can be prepared. However, carbon fibers exhibit surface chemical inertness, low surface energy and few chemical groups. In addition, polypropylene belongs to a non-polar polymer, which causes poor interface bonding strength between the carbon fiber and the polypropylene when the carbon fiber/polypropylene composite material is prepared, and seriously influences the reinforcing effect of the carbon fiber. For example, chinese patents CN201310698084.6, CN201510439653.4, and CN201610253742.4 all specifically mention that the mechanical properties of the carbon fiber/polypropylene composite material can be improved by soaking the carbon fiber in an aqueous solution of a silane coupling agent for a long time and adding a certain amount of a compatibilizer during the compounding process. However, the small-molecule silane coupling agent used in the above method has poor adhesion properties and has very limited improvement in interface properties.
Based on the above, it has become an important direction for development to develop a high-molecular carbon fiber sizing agent with high adhesion property to treat carbon fibers to improve the compatibility of the carbon fibers and polypropylene, reduce the usage amount of the compatilizer and simultaneously satisfy the mechanical properties of materials.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a carbon fiber sizing agent and a preparation method thereof, and a carbon fiber reinforced polypropylene composite material and a preparation method thereof, wherein the carbon fiber sizing agent has a good adhesion property, and the impregnation time is greatly shortened.
The invention provides a carbon fiber sizing agent which is a copolymer emulsion of maleic anhydride and long-chain olefin and/or long-chain alkyne.
The long-chain olefin is one or more of 1-dodecene, 1-hexadecene, 1-octadecene and 1-eicosene.
The long-chain alkyne is one or more of 1-nonyne, 1-decyne, 1-dodecyne and 1-hexadecyne.
The molar ratio of the maleic anhydride to the total amount of long-chain alkenes and long-chain alkynes is preferably 1: (0.05-3).
The invention provides a preparation method of the carbon fiber sizing agent, which comprises the following steps:
A) under the protection of nitrogen and at the temperature of 30-70 ℃, dissolving long-chain olefin and/or long-chain alkyne and maleic anhydride in an organic solvent;
B) adding an initiator, controlling the temperature to be 80-130 ℃, stirring at the speed of 200-1000 rpm, and reacting for 0.5-6 hours;
C) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 500-30000 rpm, dropwise adding deionized water while stirring, continuously stirring for 0.5-3 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The organic solvent is preferably a mixture of one or more of xylene, N dimethylformamide and N, N dimethylacetamide.
The initiator is preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and diacetyl peroxide.
The molecular weight of the prepared carbon fiber sizing agent is 5000-100000 Kg/mol.
The invention provides a preparation method of a carbon fiber reinforced polypropylene composite material, which comprises the following steps:
A) soaking the carbon fiber in the carbon fiber sizing agent at normal temperature for 1-3 min;
B) adding polypropylene, carbon fiber, an antioxidant and a lubricant into an internal mixer, kneading for 3-5 min at 170-200 ℃, and discharging to obtain a rubber compound;
C) and (3) performing hot press molding and cold pressing qualitative treatment on the rubber compound in sequence to obtain the carbon fiber reinforced polypropylene composite material.
The carbon fiber is preferably chopped carbon fiber with the diameter of 7 mu m and the length of 2-10 mm.
After the impregnation in the step A), preferably, the carbon fiber is dried at the temperature of 20-80 ℃ for 0.5-1 h.
The mass ratio of the polypropylene to the carbon fiber to the antioxidant to the lubricant to the carbon fiber sizing agent is preferably 100: (3-50): (0.1-3): (1-3): (0.1-2).
The antioxidant is preferably one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 '-methylenebis (4-methyl-6-tert-butylphenol), 4' -thiobis (6-tert-butyl-3-methylphenol) and tris [2, 4-di-tert-butylphenyl ] phosphite.
The lubricant is preferably one or more of chlorinated polyethylene, paraffin oil, sodium stearate and silicone powder.
The hot press molding is preferably as follows:
and flatly spreading the obtained rubber compound in a flat plate mold, placing the flat plate mold in a flat plate vulcanizing instrument, controlling the temperature to be 160-190 ℃ and preheating for 10-50 min under the pressure of 0.5 ton. Further applying a pressure of 10-25 tons for hot pressing for 5-20 min.
The cold pressing qualitative optimization specifically comprises the following steps:
and reducing the temperature of the vulcanizing press to normal temperature and keeping the pressure for 5-20 tons for 10-30 min.
The invention also provides the carbon fiber reinforced polypropylene composite material prepared by the preparation method.
The invention provides a carbon fiber sizing agent which is a copolymer emulsion of maleic anhydride and long-chain olefin and/or long-chain alkyne. The composite material has good adhesion performance, greatly shortens the impregnation time, and plays a good bridging role between the carbon fiber and the polypropylene matrix, thereby further improving the mechanical property of the composite material. The carbon fiber sizing agent is adopted to pretreat carbon fibers, and the prepared carbon fiber reinforced polypropylene composite material has excellent mechanical properties.
Drawings
FIG. 1 is a scanning electron microscope image of an impact cross section of the carbon fiber reinforced polypropylene composite material prepared in example 2;
FIG. 2 is a scanning electron microscope image of an impact cross section of the carbon fiber reinforced polypropylene composite material prepared in example 3.
Detailed Description
In order to further illustrate the present invention, the following will describe the carbon fiber sizing agent, the preparation method thereof and a carbon fiber reinforced polypropylene composite material in detail with reference to the examples.
Example 1
Preparation of sizing agent
(1) Under the protection of nitrogen and at the temperature of 30 ℃, dissolving the decadiene and the maleic anhydride in the dimethylbenzene according to the mass ratio of 1.0: 1.0;
(2) adding azodiisobutyronitrile, controlling the temperature at 80 ℃, and reacting for 0.5 hour at the stirring speed of 200 rpm;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 500rpm, dropwise adding deionized water while stirring, continuously stirring for 0.5 hour, and then performing rotary evaporation on the solution to remove acetone to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: the carbon fiber is dipped in the sizing agent at normal temperature for 1min and then is dried at 20 ℃ for 0.5 h.
(5) Mixing: 100 parts of polypropylene, 3 parts of carbon fiber and 1010 parts of antioxidant: 0.1 part of chlorinated polyethylene and 1 part of chlorinated polyethylene are added into an internal mixer, the temperature is controlled at 170 ℃, and the materials are kneaded for 3min and then discharged to obtain the rubber compound.
(6) Hot-press molding: the mixed rubber is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 160 ℃, and the pressure is 0.5 ton for preheating for 10 min. Further, 10 tons of pressure was applied to conduct hot pressing for 5 min.
(7) Cold pressing and shaping: and (3) reducing the temperature of the flat vulcanizing machine to normal temperature and maintaining the pressure for 5 tons for 10min to obtain the carbon fiber reinforced polypropylene composite material.
Example 2
Preparation of sizing agent
(1) Under the protection of nitrogen and at the temperature of 30-70 ℃, dissolving dodecyne and maleic anhydride in N, N-dimethylformamide according to the mass ratio of 1.0: 2.0;
(2) adding benzoyl peroxide, controlling the temperature at 90 ℃, stirring at 500rpm, and reacting for 3 hours;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 10000rpm, dropwise adding deionized water while stirring, continuously stirring for 1.5 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: soaking the carbon fiber in the sizing agent at normal temperature for 2min, and drying at 60 ℃ for 40 min.
(5) Mixing: 100 parts of polypropylene, 11 parts of carbon fiber and 300 parts of antioxidant: 0.1 part of chlorinated polyethylene and 5 parts of chlorinated polyethylene are added into an internal mixer, the temperature is controlled at 190 ℃, and the materials are discharged after kneading for 5min, so that the rubber compound is obtained.
(6) Hot-press molding: the rubber compound is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 185 ℃, and the pressure is 1 ton, and the rubber compound is preheated for 30 min. Further, 20 tons of pressure was applied to conduct hot pressing for 10 min.
(7) Cold pressing and shaping: and (3) reducing the temperature of the flat vulcanizing instrument to normal temperature and maintaining the pressure for 15 tons for 15min to obtain the carbon fiber reinforced polypropylene composite material.
The mechanical property test of the prepared composite material is shown in figure 1, and figure 1 is an impact section scanning electron microscope image of the carbon fiber reinforced polypropylene composite material prepared in the application, and a certain amount of matrix resin is adhered to the surface of a carbon fiber pulling-out section as can be observed from figure 1, so that the interface between the carbon fiber and the matrix has a good adhesion effect in the impact process, and the reinforcing effect is improved.
Example 3
Preparation of sizing agent
(1) Under the protection of nitrogen and at 50 ℃, octadecene and maleic anhydride are dissolved in xylene according to the mass ratio of 1.0: 0.8;
(2) adding benzoyl peroxide, controlling the temperature at 90 ℃, stirring at the speed of 600rpm, and reacting for 4 hours;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 3000rpm, dropwise adding deionized water while stirring, continuously stirring for 2 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: and (3) soaking the carbon fiber in the sizing agent at normal temperature for 3min, and drying at 80 ℃ for 1 h.
(5) Mixing: 100 parts of polypropylene, 20 parts of carbon fiber and 1010 parts of antioxidant: 0.5 part of the mixed rubber and 2 parts of paraffin oil are added into an internal mixer, the temperature is controlled to 187 ℃, and the mixed rubber is obtained after 3.5min of kneading.
(6) Hot-press molding: the mixed rubber is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 190 ℃, and the pressure is 0.5 ton for preheating for 25 min. Further, hot pressing was performed for 10min with a pressure of 25 tons.
(7) Cold pressing and qualitative determination: and (3) reducing the temperature of the vulcanizing press to normal temperature and maintaining the pressure for 20 tons for 20min to obtain the carbon fiber reinforced polypropylene composite material.
The mechanical property test of the prepared composite material is carried out, the result is shown in figure 2, figure 2 is a scanning electron microscope image of the impact section of the carbon fiber reinforced polypropylene composite material prepared by the method, and it can be known from figure 2 that the interface action between the fiber and the matrix becomes stronger along with the increase of the content of the fiber sizing agent.
Example 4
Preparation of sizing agent
(1) Under the protection of nitrogen and at 60 ℃, dissolving decene and maleic anhydride in N, N-dimethylacetamide according to the mass ratio of 1.0: 0.5;
(2) adding benzoyl peroxide, controlling the temperature at 100 ℃, stirring at 700rpm, and reacting for 6 hours;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 1000rpm, dropwise adding deionized water while stirring, continuously stirring for 3 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: the carbon fiber is dipped in the sizing agent at normal temperature for 1min and then is dried at 30 ℃ for 0.5 h.
(5) Mixing: 100 parts of polypropylene, 5 parts of carbon fiber and 300 parts of antioxidant: 0.1 part of silicone powder and 1.9 parts of silicone powder are added into an internal mixer, the temperature is controlled at 177 ℃, and the materials are discharged after kneading for 5min, so that the rubber compound is obtained.
(6) Hot-press molding: the rubber compound is flatly laid in a flat plate mold and placed in a flat plate vulcanizing machine, and the temperature is controlled at 185 ℃ and the pressure is controlled at 0.5 ton for preheating for 16 min. Further, 13 tons of pressure was applied to perform hot pressing for 15 min.
(7) Cold pressing and qualitative determination: and (3) reducing the temperature of the flat vulcanizing instrument to normal temperature and maintaining the pressure for 15 tons for 30min to obtain the carbon fiber reinforced polypropylene composite material.
Example 5
Preparation of sizing agent
(1) Dissolving tetradecene and maleic anhydride in xylene according to the mass ratio of 1.0:1.0 under the protection of nitrogen and at the temperature of 30 ℃;
(2) adding azodiisobutyronitrile, controlling the temperature at 80 ℃, and reacting for 4.5 hours at the stirring speed of 800 rpm;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 7000rpm, dropwise adding deionized water while stirring, continuously stirring for 2 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: the carbon fiber is dipped in the sizing agent at normal temperature for 2min and then is dried at 50 ℃ for 0.5 h.
(5) Mixing: 100 parts of polypropylene, 27 parts of carbon fiber and 2246 parts of antioxidant: 0.2 part of chlorinated polyethylene and 1.8 parts of chlorinated polyethylene are added into an internal mixer, the temperature is controlled at 190 ℃, and the materials are discharged after kneading for 5min, so that the rubber compound is obtained.
(6) Hot-press molding: the mixed rubber is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 190 ℃, and the pressure is 0.5 ton for preheating for 20 min. Further, 25 tons of pressure was applied to perform hot pressing for 15 min.
(7) Cold pressing and qualitative determination: and (3) reducing the temperature of the vulcanizing press to normal temperature and maintaining the pressure for 20 tons for 25min to obtain the carbon fiber reinforced polypropylene composite material.
Example 6
Preparation of sizing agent
(1) Under the protection of nitrogen and at 70 ℃, dissolving tetradecyne and maleic anhydride in xylene according to the mass ratio of 1.0: 1.2;
(2) adding benzoyl peroxide, controlling the temperature at 110 ℃, stirring at 1000rpm, and reacting for 4 hours;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 1000rpm, dropwise adding deionized water while stirring, continuously stirring for 2 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: the carbon fiber is dipped in the sizing agent at normal temperature for 1min and then is dried at 30 ℃ for 0.5 h.
(5) Mixing: 100 parts of polypropylene, 30 parts of carbon fiber and 1010 parts of antioxidant: 0.1 part of sodium stearate and 1.9 parts of sodium stearate are added into an internal mixer, the temperature is controlled at 200 ℃, and the materials are discharged after kneading for 4min, so that the rubber compound is obtained.
(6) Hot-press molding: the mixed rubber is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 190 ℃, and the pressure is controlled at 0.5 ton for preheating for 16 min. Further, 25 tons of pressure was applied to perform hot pressing for 15 min.
(7) Cold pressing and qualitative determination: and (3) reducing the temperature of the flat vulcanizing machine to normal temperature and maintaining the pressure for 25 tons for 30min to obtain the carbon fiber reinforced polypropylene composite material.
Example 7
Preparation of sizing agent
(1) Under the protection of nitrogen and at 70 ℃, dodecene and maleic anhydride are dissolved in xylene according to the mass ratio of 1.0: 1.0;
(2) adding benzoyl peroxide, controlling the temperature at 130 ℃, stirring at 1000rpm, and reacting for 6 hours;
(3) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 30000rpm, dropwise adding deionized water while stirring, continuously stirring for 3 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
The carbon fiber reinforced polypropylene composite material is prepared by the following method:
(4) carbon fiber pretreatment: and (3) soaking the carbon fiber in the sizing agent at normal temperature for 1min, and drying at 80 ℃ for 1 h.
(5) Mixing: 100 parts of polypropylene, 50 parts of carbon fiber and 1010 parts of antioxidant: 3 parts of chlorinated polyethylene and 3 parts of chlorinated polyethylene are added into an internal mixer, the temperature is controlled at 200 ℃, and the materials are discharged after kneading for 5min, so that the rubber compound is obtained.
(6) Hot-press molding: the mixed rubber is flatly laid in a flat plate die and placed in a flat plate vulcanizing instrument, the temperature is controlled at 190 ℃, and the pressure is 0.5 ton for preheating for 50 min. Further, 25 tons of pressure was applied to perform hot pressing for 20 min.
(7) Cold pressing and qualitative determination: and (3) reducing the temperature of the vulcanizing press to normal temperature and maintaining the pressure for 20 tons for 30min to obtain the carbon fiber reinforced polypropylene composite material.
Comparative example 1
(1) Carbon fiber pretreatment: and (3) soaking the carbon fiber in deionized water at normal temperature for 3min, and drying at 80 ℃ for 1 h.
The steps (2) to (4) were the same as the steps (5) to (7) in example 3, and a carbon fiber-reinforced polypropylene composite material was obtained.
The composite materials prepared in examples 1 to 7 and comparative example 1 were subjected to mechanical testing, and the results are shown in table 1.
TABLE 1 mechanical test results for composites prepared in examples 1-7 and comparative example 1
As can be seen from the examples and the comparative examples, the sizing agent with specific components is adopted to pretreat the carbon fibers, so that the dipping time is shortened, and the prepared composite material has excellent mechanical properties.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. The preparation method of the carbon fiber reinforced polypropylene composite material is characterized by comprising the following steps:
A) soaking the carbon fiber in a carbon fiber sizing agent at normal temperature for 1-3 min, and then drying;
the carbon fiber sizing agent is a copolymer emulsion of maleic anhydride and long-chain olefin and/or long-chain alkyne;
the long-chain olefin is one or more of 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, and the long-chain alkyne is one or more of 1-nonyne, 1-decyne, 1-dodecyne, 1-tetradecyne and 1-hexadecyne;
B) adding polypropylene, carbon fiber, an antioxidant and a lubricant into an internal mixer, kneading for 3-5 min at 170-200 ℃, and discharging to obtain a rubber compound;
C) sequentially carrying out hot press molding and cold press qualitative treatment on the rubber compound to obtain a carbon fiber reinforced polypropylene composite material;
the mass ratio of the polypropylene to the carbon fiber to the antioxidant to the lubricant to the carbon fiber sizing agent is 100: (3-50): (0.1-3): (1-3): (0.1-2);
the hot press forming specifically comprises the following steps:
and flatly spreading the obtained rubber compound in a flat plate mold, placing the flat plate mold in a flat plate vulcanizing instrument, controlling the temperature to be 160-190 ℃, preheating for 10-50 min under the pressure of 0.5 ton, and then applying the pressure of 10-25 ton for hot pressing for 5-20 min.
2. The process according to claim 1, wherein the molar ratio of maleic anhydride to the total amount of long-chain alkenes and long-chain alkynes is 1: (0.05-3).
3. The method for preparing a carbon fiber sizing agent according to claim 1, comprising the steps of:
A) under the protection of nitrogen and at the temperature of 30-70 ℃, dissolving long-chain olefin and/or long-chain alkyne and maleic anhydride in an organic solvent;
B) adding an initiator, controlling the temperature to be 80-130 ℃, stirring at the speed of 200-1000 rpm, and reacting for 0.5-6 hours;
C) stirring the solution by using a high-speed shearing dispersion emulsifying machine at the stirring speed of 500-30000 rpm, dropwise adding deionized water while stirring, continuously stirring for 0.5-3 hours, and then carrying out rotary evaporation on the solution to remove the organic solvent to obtain the polymer emulsion sizing agent.
4. The method according to claim 3, wherein the organic solvent is a mixture of one or more of xylene, N-dimethylformamide and N, N-dimethylacetamide.
5. The method according to claim 1, wherein the antioxidant is one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2 '-methylenebis (4-methyl-6-tert-butylphenol), 4' -thiobis (6-tert-butyl-3-methylphenol), and tris [2, 4-di-tert-butylphenyl ] phosphite.
6. The method of claim 1, wherein the lubricant is one or more of chlorinated polyethylene, paraffin oil, sodium stearate, and silicone powder.
7. The carbon fiber reinforced polypropylene composite material prepared by the preparation method of any one of claims 1 to 6.
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| 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 |
| CN113717389B (en) * | 2021-07-07 | 2022-08-26 | 东北师范大学 | Preparation method of lignin-based hydrophilic sizing agent and application of lignin-based hydrophilic sizing agent in polyolefin composite material |
| CN113445323B (en) * | 2021-07-07 | 2022-05-27 | 长春工业大学 | Preparation method of lignin-based sizing agent for composite carbon nano tube and application of lignin-based sizing agent in polyolefin |
| CN114213751B (en) * | 2021-12-09 | 2022-07-15 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
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