CN113445323A - Preparation method of lignin-based sizing agent for composite carbon nano tube and application of lignin-based sizing agent in polyolefin - Google Patents

Preparation method of lignin-based sizing agent for composite carbon nano tube and application of lignin-based sizing agent in polyolefin Download PDF

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CN113445323A
CN113445323A CN202110769074.1A CN202110769074A CN113445323A CN 113445323 A CN113445323 A CN 113445323A CN 202110769074 A CN202110769074 A CN 202110769074A CN 113445323 A CN113445323 A CN 113445323A
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lignin
carbon fiber
sizing agent
epoxy resin
stirring
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CN113445323B (en
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张晨晨
呼微
赵文杰
刘碧莹
刘昱含
王艳淼
刘万利
王寒冰
张亮
张袅娜
徐义全
刘佰军
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Ningbo Lihe Bohui Photosensitive Materials Co ltd
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Changchun University of Technology
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    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Abstract

The invention provides a preparation method of lignin-based sizing agent of composite carbon nano tube and application thereof in polyolefin, the preparation method comprises the following steps: dissolving epoxy resin and ozonized lignin in an organic solvent, heating and stirring for reaction to obtain lignin-based epoxy resin, adding alcohol amine and carboxylic acid, heating and stirring for reaction, and adding a carbon nano tube and a silane coupling agent to obtain a lignin-based sizing agent of the composite carbon nano tube; and (3) soaking carbon fibers in the sizing agent, drying, placing in the polyolefin middle layer, and performing melt molding to obtain the carbon fiber reinforced polyolefin composite material. The sizing agent has good adhesive property, generates a bridge function between the carbon fiber and the polyolefin, overcomes the defects of poor adhesive property and the like between the carbon fiber and the polyolefin, and improves the mechanical property of the composite material. The sizing agent disclosed by the invention takes water as a medium, avoids the use of an organic solvent, and is low in cost, environment-friendly and good in stability.

Description

Preparation method of lignin-based sizing agent for composite carbon nano tube and application of lignin-based sizing agent in polyolefin
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a lignin-based sizing agent of a composite carbon nano tube and application of the lignin-based sizing agent in polyolefin.
Background
Polyolefin is a high molecular material with low density, rich raw materials, low price and wide application, and belongs to thermoplastic resin. However, the notch impact toughness of the polyolefin is low, the shrinkage rate is high, so that the polyolefin is affected by external force in the using process to cause stress whitening, and the application universality of the polyolefin 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 polyolefin 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. Polyolefin belongs to a nonpolar polymer, so that the interface bonding strength between the carbon fiber and the polyolefin composite material is poor when the carbon fiber and the polyolefin composite material are prepared, and the reinforcing effect of the carbon fiber is seriously influenced; in addition, the materials are very difficult to combine, the control requirement on the process is strict, the defects of air holes, layering, inclusion and the like are easy to occur, and the problems of cracking and delamination are easy to occur due to overlarge local impact in the using process.
At present, the sizing agent is adopted to enhance the interface performance between carbon fiber/polyolefin composite materials. The sizing agent has the following functions: (1) the electrostatic effect is reduced, the bundling capability of the carbon fiber is improved, and the subsequent weaving and spinning processing is facilitated; (2) air, moisture and dust are isolated, and the surface activity of the carbon fiber is kept; (3) filling the surface defects of the carbon fibers, and playing a role in assisting and reinforcing the carbon fibers to a certain extent; (4) the surface of the carbon fiber is smooth, the friction damage in subsequent processing is avoided, the burr is reduced, the service life of the carbon fiber is prolonged, and the carbon fiber is protected.
The sizing agent can be classified into a solution type sizing agent, an emulsion type sizing agent and a hydrophilic type sizing agent. The solution-type sizing agent is less used at present because a large amount of organic solvent is needed, the cost is relatively high, and the volatilization of the large amount of solvent has serious harm to the human health and the working environment. The emulsion sizing agent is a surfactant in nature because a large amount of emulsifier is needed, so that the surface of the carbon fiber is easy to absorb moisture; also, low molecular weight surfactants can affect the adhesion between the fibers and the resin. The addition of little or no emulsifier is an important direction for the development of sizing agents, the hydrophilic sizing agent is an improvement of the traditional emulsion sizing agent, hydrophilic groups are introduced into resin or functional groups are ionized to enable the resin to have self-emulsifying capacity, the resin can be self-emulsified and dispersed into emulsion in water without adding an emulsifier, and the emulsion is better dissolved in water, so that the use of the emulsifier is avoided, and the hydrophilic sizing agent has the advantages of small particle size, uniform particle size, high stability and the like. Therefore, the research on the hydrophilic environment-friendly and pollution-free sizing agent becomes the key point of the development of the sizing agent in the future. In addition, the addition of functional groups capable of forming a conjugated structure with the carbon fibers to the sizing agent will help the sizing agent to better bind the carbon fibers and the polyolefin.
Based on the above, the development of a hydrophilic environment-friendly sizing agent with high adhesion performance for treating carbon fibers, which improves the compatibility between the carbon fibers and polyolefin, reduces the usage amount of a compatilizer or does not use the compatilizer, and simultaneously satisfies the mechanical properties of materials, has become a technical problem to be solved at present.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of lignin-based sizing agent of composite carbon nano-tube and application thereof in polyolefin, which comprises the following steps:
(1) placing 5-20g lignin in an ozonization device, and treating for 0.5-1.5h under the conditions of ozone concentration of 4.5-20mg/L, mixed gas flow rate of 200-;
(2) dissolving the ozonized modified lignin and epoxy resin obtained in the step (1) in an organic solvent, stirring for 5-25 minutes at room temperature, then heating to 70-100 ℃, and stirring for reaction for 1-4 hours to obtain lignin-based epoxy resin;
(3) adding an organic solvent into the lignin-based epoxy resin obtained in the step (2), adding alcohol amine, and stirring at the temperature of 70-100 ℃ for reaction for 1-4h, wherein the stirring speed is 200-600rpm, so as to obtain lignin-based epoxy resin grafted with the alcohol amine;
(4) adding a carboxylic acid solution into the lignin-based epoxy resin grafted with alcohol amine obtained in the step (3), stirring and reacting at 50-80 ℃ for 0.5-2 hours at the stirring speed of 200-600rpm, adding a carbon nano tube and a silane coupling agent, reacting for 1-5 hours, and then, according to the mass ratio: the mass ratio of the silane coupling agent, the epoxy resin in the step (2), the lignin in the step (1), the alcohol amine in the step (3), the carboxylic acid and the carbon nano tube is 0.2-2: 5-11: 0.5-3: 1-4: 1-4: 0.005-0.02, and removing the solvent by rotary evaporation to obtain the lignin-based sizing agent of the composite carbon nano tube.
Further, the lignin in the step (1) is one or two of enzymatic hydrolysis lignin, alkali lignin, sulfonate lignin, ground wood lignin or organic solvent lignin.
Further, the epoxy resin in the step (2) is any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydroxymethyl bisphenol A type epoxy resin or bisphenol S type epoxy resin; the organic solvent is N, N-dimethylformamide.
Further, the organic solvent in the step (3) is one or any combination of methanol, ethanol or ethylene glycol monobutyl ether; the alcohol amine is one or any combination of ethanolamine, diethanolamine, dimethylethanolamine or triethanolamine.
Further, the carboxylic acid in the step (4) is one or any combination of oxalic acid, formic acid, acetic acid or propionic acid; the carbon nano tube is one or any combination of a single-walled carbon nano tube, a multi-walled carbon nano tube, a hydroxylated carbon nano tube or a carboxylated carbon nano tube; the silane coupling agent is one or any combination of vinyl triethoxysilane, vinyl trimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane or gamma-aminopropyl triethoxysilane.
The invention also provides an application of the lignin-based sizing agent of the composite carbon nano tube in the field of carbon fiber reinforced polyolefin composite materials, which comprises the following steps:
(1) soaking the carbon fiber cloth in 0.5-4wt% lignin-based sizing agent of the composite carbon nanotube for 2-6min at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 2-6cm/min, and drying at 70-100 ℃ for 1-4h to obtain the carbon fiber cloth after sizing pretreatment;
(2) spreading polyolefin powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a middle layer of the polyolefin powder, placing the carbon fiber cloth and the polyolefin powder in a mass ratio of 6-10:80-100 in a flat-plate vulcanizer, preheating at the temperature of 170-200 ℃ for 1-7min, then applying 10-25 tons of pressure to carry out hot pressing for 3-5min, cooling to room temperature, and keeping the pressure for 10-30 tons for 2-8min to obtain the carbon fiber reinforced polyolefin composite material.
Further, the polyolefin in the step (2) is any one of polypropylene, polyethylene, polyvinyl chloride or ethylene-vinyl acetate copolymer.
The lignin-based sizing agent of the composite carbon nano tube is a copolymer hydrophilic emulsion of lignin, a silane coupling agent, epoxy resin, alcohol amine, carboxylic acid and the carbon nano tube. The carbon fiber/polyolefin composite material has good adhesion performance, the dipping time is greatly shortened, the sizing operation is simple, the implementation is easy, and good bridging and interface reinforcing effects are achieved between the carbon fiber and the polyolefin matrix, so that the mechanical property of the composite material is further improved. The carbon fiber reinforced polyolefin composite material prepared by pretreating the carbon fiber by adopting the sizing agent has excellent mechanical property.
Drawings
FIG. 1 is a comparison graph of IR spectra of organosolv lignin before and after ozonation in example 1;
FIG. 2 is an infrared spectrum of lignin-based sizing agent for composite carbon nanotubes of example 1;
fig. 3 shows the flexural strength and interlaminar shear strength of the carbon fiber composite materials obtained in example 2 and comparative example 2.
Detailed Description
The following examples adopt carbon fiber cloth obtained by desizing a carbon fiber cloth of T700 to 12K, wherein the carbon fiber cloth is a carbon fiber cloth of type T700 to 12K manufactured by eastern beauty ltd, japan, and the desizing treatment is carried out before the sizing, and the desizing treatment adopts a method comprising: under the ultrasonic condition, soaking the carbon fiber cloth in a mixed solution of acetone, ethanol and water for 10-30min, then placing the soaked carbon fiber cloth in concentrated nitric acid for 24h, washing the carbon fiber cloth with deionized water, then drying the carbon fiber cloth at 80-100 ℃ to obtain the carbon fiber cloth subjected to de-sizing treatment, cutting the carbon fiber cloth into the size of 8 x 10cm, cooling and placing the carbon fiber cloth in a dryer for later use. The acetone, the ethanol and the water are mixed according to the volume ratio: 1.5:1: 1.
Example 1
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 14mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 1.5g of ozonized organic solvent lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) and (3) adding 1.8g of acetic acid solution and 0.008g of multi-walled carbon nano-tubes into the lignin-based epoxy resin grafted with diethanol amine obtained in the step (3), stirring at the temperature of 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain the lignin-based sizing agent of the composite carbon nano-tubes.
Example 2
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 1.5wt% of the sizing agent aqueous solution obtained in the example 1 at room temperature for 5 minutes, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3cm/min, and drying the carbon fiber cloth at the temperature of 90 ℃ for 1 hour to obtain the carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 3
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 2.0wt% aqueous solution of the sizing agent obtained in example 1 at room temperature for 5 minutes, then pulling the carbon fiber cloth out of the aqueous solution of the sizing agent at the speed of 3cm/min, and drying at 90 ℃ for 1 hour to obtain carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 4
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 2.5wt% aqueous solution of the sizing agent obtained in example 1 at room temperature for 5 minutes, then pulling the carbon fiber cloth out of the aqueous solution of the sizing agent at the speed of 3cm/min, and drying the carbon fiber cloth at 90 ℃ for 1 hour to obtain carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 5
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 3.0wt% aqueous solution of the sizing agent obtained in example 1 at room temperature for 5 minutes, then pulling the carbon fiber cloth out of the aqueous solution of the sizing agent at the speed of 3cm/min, and drying at 90 ℃ for 1 hour to obtain carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 6
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 2.5wt% aqueous solution of the sizing agent obtained in example 1 at room temperature for 6 minutes, then pulling the carbon fiber cloth out of the aqueous solution of the sizing agent at the speed of 4 cm/min, and drying the carbon fiber cloth at 90 ℃ for 4 hours to obtain carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 7% to 90% in a flat vulcanizing instrument, preheating for 6 minutes at the temperature of 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons of pressure for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 7
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the carbon fiber cloth in 2.5wt% aqueous solution of the sizing agent obtained in example 1 at room temperature for 3 minutes, then pulling the carbon fiber cloth out of the aqueous solution of the sizing agent at the speed of 2 cm/min, and drying the carbon fiber cloth at 100 ℃ for 2 hours to obtain carbon fiber cloth subjected to sizing pretreatment;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 6% to 100% for preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure for hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 8
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of enzymatic hydrolysis lignin in an ozonization device, and treating for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 14mg/L to obtain ozonized enzymatic hydrolysis lignin;
(2) dissolving 1.5g of ozonized enzymatic lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in DMF, mixing at room temperature, stirring for 20 minutes, heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol and methanol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of single-walled carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 9
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: 7g of alkali lignin is placed in an ozonization device, and ozonized alkali lignin is obtained after treatment for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 14 mg/L;
(2) dissolving 1.5g of ozonized alkali lignin obtained in the step (1) and 8.5g of hydrogenated bisphenol A epoxy resin in DMF, mixing at room temperature, stirring for 20 minutes, heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethanol into the lignin-based epoxy resin obtained in the step (2), adding 3g of triethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with triethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of multi-walled carbon nano-tubes into the triethanolamine-grafted lignin-based epoxy resin obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano-tubes;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 10
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: 7g of sulfonate lignin is placed in an ozonization device, and is treated for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 14mg/L to obtain the sulfonate lignin subjected to ozonization;
(2) dissolving 1.5g of ozonized sulfonate lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in DMF, mixing at room temperature, stirring for 20 minutes, heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of single-walled carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 11
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of wood grinding lignin in an ozonization device, and treating for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 14mg/L to obtain ozonized wood grinding lignin;
(2) dissolving 1.5g of ozonized ground wood lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in DMF, mixing at room temperature, stirring for 20 minutes, heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol and methanol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of single-walled carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 12
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 60 minutes under the conditions that the flow rate of mixed gas is 400L/h and the concentration of ozone is 16mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 2g of ozonized organic solvent lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of hydroxylated carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 190 ℃, then applying 12 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 12 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 13
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 14mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 1.5g of ozonized organic solvent lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of carboxylated carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 190 ℃, then applying 12 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 12 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 14
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 50 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 14mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 1.5g of ozonized organic solvent lignin obtained in the step (1) and 8.5g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.8g of acetic acid solution and 0.008g of multi-walled carbon nano-tubes into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at the temperature of 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 0.94g of vinyltrimethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano-tubes;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 10 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fibers subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 7% to 95%, preheating for 4 minutes at the temperature of 200 ℃, applying 14 tons of pressure to carry out hot pressing for 5 minutes, cooling to room temperature, keeping the pressure for 14 tons and keeping for 5 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 15
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 60 minutes under the conditions that the flow rate of mixed gas is 450L/h and the ozone concentration is 16mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 2g of ozonized organic solvent lignin obtained in the step (1) and 10g of bisphenol F type epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3.5g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 2g of acetic acid solution and 0.01g of carboxylated carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 1g of gamma-methacryloxypropyl-trimethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 190 ℃, then applying 12 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 12 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 16
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 45 minutes under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 20mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 1.8g of ozonized organic solvent lignin obtained in the step (1) and 9g of bisphenol A type epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3.2g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.86g of acetic acid solution and 0.15g of hydroxylated carbon nanotube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 1g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nanotube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 190 ℃, then applying 12 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 12 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 17
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 7g of organic solvent lignin in an ozonization device, and treating for 45 minutes under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 20mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 1.8g of ozonized organic solvent lignin obtained in the step (1) and 9g of bisphenol A type epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 20 minutes, then heating to 75 ℃, and stirring for 110 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 3.2g of diethanolamine, stirring at 70 ℃ for 2h, and then stirring at the speed of 350rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1.86g of acetic acid solution and 0.15g of multi-walled carbon nano-tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 65 ℃ for 40 minutes at the stirring speed of 350rpm, adding 1g of gamma-aminopropyltriethoxysilane, reacting for 3.5 hours, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano-tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 2.5wt% obtained in the step (4) for 5 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 3 cm/minute, and drying the carbon fiber cloth for 1 hour at the temperature of 90 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fibers subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 7.5% to 100% in a flat vulcanizing instrument, preheating for 6 minutes at 190 ℃, then applying 12 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, keeping the pressure for 12 tons of pressure for 4 minutes, and obtaining the carbon fiber reinforced polypropylene composite material.
Example 18
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 5g of organic solvent lignin in an ozonization device, and treating for 30 minutes under the conditions of the flow rate of mixed gas of 200L/h and the concentration of ozone of 4.5mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 0.5g of ozonized organic solvent lignin obtained in the step (1) and 5g of bisphenol A type epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 5 minutes, then heating to 70 ℃, and stirring for 60 minutes to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 1g of diethanolamine, stirring at 70 ℃ for 1h, and then stirring at the speed of 200rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 1g of acetic acid solution and 0.005g of multi-walled carbon nano-tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 50 ℃ for 30 minutes at the stirring speed of 200rpm, adding 0.2g of gamma-aminopropyltriethoxysilane, reacting for 1 hour, and then performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano-tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 0.5wt% obtained in the step (4) for 2 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 2 cm/minute, and drying the carbon fiber cloth for 1 hour at 70 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 6% to 100% for preheating for 1 minute at the temperature of 170 ℃, then applying 10 tons of pressure for hot pressing for 3 minutes, cooling to room temperature, and keeping the pressure for 10 tons for 2 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 19
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 20g of organic solvent lignin in an ozonization device, and treating for 1.5h under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 20mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 3g of ozonized organic solvent lignin obtained in the step (1) and 11g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 25 minutes, then heating to 100 ℃, and stirring for 4 hours to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 4g of diethanolamine, stirring at 100 ℃ for 4 hours at the stirring speed of 600rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 4g of acetic acid solution and 0.02g of multi-wall carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 80 ℃ for 2h at the stirring speed of 600rpm, adding 0.2g of gamma-aminopropyltriethoxysilane, reacting for 5h, and performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 4wt% obtained in the step (4) for 6 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 6 cm/minute, and drying the carbon fiber cloth for 4 hours at the temperature of 100 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polypropylene powder in a mold, arranging the carbon fibers subjected to sizing pretreatment in the step (5) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to the mass ratio of 10% to 80% for preheating for 7 minutes at the temperature of 200 ℃, then applying 25 tons of pressure for hot pressing for 5 minutes, cooling to room temperature, and keeping the pressure for 30 tons and 8 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Example 20
The preparation method of the sizing agent comprises the following steps:
(1) ozonization treatment of lignin: placing 20g of organic solvent lignin in an ozonization device, and treating for 1.5h under the conditions that the flow rate of mixed gas is 450L/h and the concentration of ozone is 20mg/L to obtain ozonized organic solvent lignin;
(2) dissolving 3g of ozonized organic solvent lignin obtained in the step (1) and 11g of bisphenol A epoxy resin in N, N-Dimethylformamide (DMF), stirring at room temperature for 25 minutes, then heating to 100 ℃, and stirring for 4 hours to obtain lignin-based epoxy resin;
(3) adding absolute ethyl alcohol into the lignin-based epoxy resin obtained in the step (2), adding 4g of diethanolamine, stirring at 100 ℃ for 4 hours at the stirring speed of 600rpm to obtain the lignin-based epoxy resin grafted with the diethanolamine;
(4) adding 4g of acetic acid solution and 0.02g of multi-wall carbon nano tube into the lignin-based epoxy resin grafted with diethanolamine obtained in the step (3), stirring at 80 ℃ for 2h at the stirring speed of 600rpm, adding 0.2g of gamma-aminopropyltriethoxysilane, reacting for 5h, and performing rotary evaporation to remove the solvent to obtain a lignin-based sizing agent of the composite carbon nano tube;
the preparation method of the carbon fiber reinforced polyethylene composite material comprises the following steps:
(5) soaking the carbon fiber cloth in the sizing agent aqueous solution with the concentration of 4wt% obtained in the step (4) for 6 minutes at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 6 cm/minute, and drying the carbon fiber cloth for 4 hours at the temperature of 100 ℃ to obtain the carbon fiber cloth subjected to sizing pretreatment;
(6) and (3) flatly paving polyethylene powder in a mould, arranging the carbon fiber subjected to sizing pretreatment in the step (5) in a polyethylene powder middle layer, placing the carbon fiber cloth and the polyethylene powder in a flat-plate vulcanizing instrument according to the mass ratio of 10% to 80% for preheating for 7 minutes at the temperature of 200 ℃, then applying 25 tons of pressure for hot pressing for 5 minutes, then cooling to room temperature, keeping the pressure for 30 tons and 8 minutes, and obtaining the carbon fiber reinforced polyethylene composite material.
Comparative example 1
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the T700-12K carbon fiber cloth in deionized water for 5min at room temperature, then pulling the carbon fiber cloth out of the deionized water at the speed of 3cm/min, and drying at 90 ℃ for 1 hour to obtain the pretreated carbon fiber cloth;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
Comparative example 2
The preparation method of the carbon fiber reinforced polypropylene composite material comprises the following steps:
(1) soaking the de-sized T700-12K carbon fiber cloth in deionized water for 5min at room temperature, then pulling the carbon fiber cloth out of the deionized water at the speed of 3cm/min, and drying at 90 ℃ for 1 hour to obtain the pretreated carbon fiber cloth;
(2) and (2) flatly paving polypropylene powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a polypropylene powder middle layer, placing the carbon fiber cloth and the polypropylene powder in a flat vulcanizing instrument according to a mass ratio of 7% to 95% in a flat vulcanizing instrument, preheating for 6 minutes at 180 ℃, then applying 15 tons of pressure to carry out hot pressing for 4 minutes, cooling to room temperature, and keeping the pressure for 15 tons for 4 minutes to obtain the carbon fiber reinforced polypropylene composite material.
FIG. 1 is a comparison spectrum of infrared spectra of organosolv lignin before and after ozonization in example 1, in which the three-dimensional network structure of benzene ring in organosolv lignin is destroyed by ozonization, and active groups such as hydroxyl groups are exposed. As can be seen from FIG. 1, 2990cm appears for both spectrograms-1The characteristic peak is the vibration absorption peak of weak free phenolic hydroxyl group existing on the lignin, and the hydroxyl peak is obviously enhanced through ozonization, which indicates that the ozonization successfully increases the content of the hydroxyl group in the organic solvent lignin. At 1709cm-1A strong vibration peak occurs, which is attributed to the C = O stretching vibration, at 1600cm-1The peak corresponding to the aromatic benzene skeleton is reduced, which indicates that the benzene ring on the organic solvent lignin is broken to expose more active groups through ozonization.
FIG. 2 shows the production of composite carbon nanotubes in example 1The infrared spectrum of the lignin-based sizing agent is 1043cm-1，1118cm-1，1385cm-1The peak at is Si-O-CH2CH3All of which represent successful grafting of the sizing agent with the silane coupling agent. At 1640cm-1、1430cm-1The peaks at (a) represent the C = O and C-H bending vibration peaks, which are reinforced by the characteristic peaks, also resulting from the addition of carbon nanotubes.
The results of the stability tests of the sizing agents of examples 2 to 5, which were described above, were shown in Table 1, with respect to the concentrations of the sizing agents and the concentrations of the sizing agents described in the literature.
The carbon fiber cloth of the above examples 2 to 5 and the literature was subjected to a carbon fiber fuzz amount test, and the results are shown in table 2.
Mechanical tests were performed on the carbon fiber/polypropylene composite materials prepared in the above examples 2 to 5 and comparative examples 1 to 2, and the results are shown in Table 3.
Table 1: sizing stability test
Comparison of conditions Stability (Tian)
Example 2 35
Example 3 35
Example 4 35
Example 5 35
PEG4000 modified epoxy resin sizing agent 14
Graphene oxide modified emulsion type carbon fiber sizing agent 30
In table 1, the PEG4000 modified epoxy resin sizing agent is derived from modification of polyethylene glycol and a study on properties of an aqueous epoxy resin emulsion [ J ] (a novel chemical material, yankunming, lieng, cheng, and yankeeping 2019, 47(07): 94-98.), and the graphene oxide modified emulsion type carbon fiber sizing agent is derived from a formula of a carbon fiber sizing agent for reinforcing polypropylene and a preparation method [ P ] (wangting, majon, ge.
As can be seen from table 1, the lignin-based sizing agent for the composite carbon nanotubes prepared by the present invention has better and excellent stability, thereby demonstrating that the lignin-based sizing agent for the composite carbon nanotubes prepared by the present invention has a significant stabilizing effect in production and transportation.
Table 2 shows the comparison of the amounts of broken filaments of the carbon fiber cloth and the T700-12K carbon fiber cloth after the sizing pretreatment, the carbon fiber cloth after the desizing treatment of the T700-12K carbon fiber cloth and the HS-12K carbon fiber material after the sizing treatment in examples 2-5.
The carbon fiber bundle is dragged between two polyurethane foams with the specification of 40 mm in length, 10 mm in width and 5 mm in thickness at a constant speed of 15 m/min, the load of the polyurethane is 200 g, and the amount of the fuzz on the polyurethane foam is recorded after 50 m.
Table 2: carbon fiber fuzz amount test
Comparison of conditions Amount of carbon fiber filaments（mg）
Example 2 3.3 ± 0.1
Example 3 3.4 ± 0.1
Example 4 3.6 ± 0.1
Example 5 3.8 ± 0.1
T700-12K carbon fiber cloth 5.0 ±0.1
Carbon fiber cloth after desizing treatment of T700-12K carbon fiber cloth 25 ± 0.2
HS-12K carbon fiber material subjected to sizing treatment 6.0 ± 0.5
The data presented in Table 2 for the amount of filaments in the sized HS-12K carbon fiber material was derived from a domestic T800S grade carbon fiber surface structure and abrasion resistance study [ J ] (solid rocket technology, Huiyume, Hough, Cushing, Zuoshuang, Zhao-Xiaoran. 1-7).
As can be seen from Table 2, the amount of fuzz of the carbon fiber pretreated by sizing is significantly reduced after the addition of the sizing agent. Compared with the carbon fiber cloth after the desizing treatment of the T700-12K carbon fiber cloth, the carbon fiber material of the embodiment 2 added with the sizing agent has the carbon fiber fuzz amount reduced by 86.8 percent. Therefore, the lignin-based sizing agent of the composite carbon nano tube prepared by the invention has obvious effect on reducing the broken filament quantity of the carbon fiber. The wear resistance of the carbon fiber is obviously improved after the sizing agent disclosed by the invention is used for sizing, and the subsequent processing of the carbon fiber is facilitated.
Table 3: comparison of mechanical properties of carbon fiber reinforced polypropylene composite materials prepared in examples 2-5 and comparative examples 1-2
Figure 600149DEST_PATH_IMAGE001
The mechanical properties of the DCF/PP composite and CF-5CNTs carbon fiber/polypropylene composites listed in Table 3 were derived from the carbon fiber surface modification and its resin-based composite properties [ D ] (Jinan university, canula Junior. 2020).
From the comparison, compared with the comparative example, the carbon fiber reinforced polyolefin composite material prepared by pretreating the carbon fibers by using the lignin-based sizing agent of the composite carbon nanotube with the specific component has excellent mechanical properties.
As can be seen from Table 3, FIG. 5, which is published on page 46 of the Master thesis "surface modification of carbon fibers and their resin-based composite properties", shows: compared with a carbon fiber reinforced polypropylene composite material (DCF/PP composite material), the bending strength of the carbon fiber reinforced polypropylene composite material added with the 5CNTs sizing agent is improved by 22.5%. Compared with the carbon fiber reinforced polypropylene composite materials of comparative example 2 and comparative example 1, the mechanical properties of the carbon fiber reinforced polypropylene composite material added with the sizing agent in the embodiment 2 of the invention are obviously improved, wherein compared with the comparative example 2, the bending strength is improved by 38.1%, the bending modulus is improved by 59.3%, the impact strength is improved by 139.3%, and the interlaminar shear strength is improved by 93.9%; compared with comparative example 1, the flexural strength is improved by 18.2%, the flexural modulus is improved by 26.5%, the impact strength is improved by 63.4%, and the interlaminar shear strength is improved by 68.4%. Therefore, the lignin-based sizing agent of the composite carbon nano tube prepared by the invention is superior to the prior art in the aspect of improving the mechanical property of the composite material.
The sizing agent reasonably utilizes lignin and the carbon nano tube, and enhances the interface bonding force of the sizing agent and the carbon fiber by utilizing the pi-pi conjugation function between the benzene ring of the lignin and the carbon six-membered ring on the carbon fiber substrate; the sizing agent is grafted with the silane coupling agent, and the alkyl chains on the epoxy resin and the silane coupling agent and polyolefin matrix molecules generate physical entanglement while the hydrophilicity is maintained, so that the interface binding force is enhanced, and the comprehensive mechanical property of the composite material is improved.
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 (8)

1. A lignin-based sizing agent for composite carbon nanotubes is characterized in that: the preparation method comprises the following steps:
(1) placing 5-20g lignin in an ozonization device, and treating for 0.5-1.5h under the conditions that the ozone concentration is 4.5-20mg/L and the flow rate of mixed gas is 200-;
(2) dissolving the ozonized modified lignin and epoxy resin obtained in the step (1) in an organic solvent, stirring for 5-25 minutes at room temperature, then heating to 70-100 ℃, and stirring for reaction for 1-4 hours to obtain lignin-based epoxy resin;
(3) adding an organic solvent into the lignin-based epoxy resin obtained in the step (2), adding alcohol amine, and stirring at the temperature of 70-100 ℃ for reaction for 1-4h, wherein the stirring speed is 200-600rpm, so as to obtain lignin-based epoxy resin grafted with the alcohol amine;
(4) adding a carboxylic acid solution into the lignin-based epoxy resin grafted with alcohol amine obtained in the step (3), stirring and reacting at 50-80 ℃ for 0.5-2 hours at the stirring speed of 200-600rpm, adding a carbon nano tube and a silane coupling agent, reacting for 1-5 hours, and then, according to the mass ratio: the mass ratio of the silane coupling agent, the epoxy resin in the step (2), the lignin in the step (1), the alcohol amine in the step (3), the carboxylic acid and the carbon nano tube is 0.2-2: 5-11: 0.5-3: 1-4: 1-4: 0.005-0.02, and removing the solvent by rotary evaporation to obtain the lignin-based sizing agent of the composite carbon nano tube.
2. The lignin-based sizing agent for composite carbon nanotubes according to claim 1, wherein: the lignin in the step (1) is one or two of enzymatic hydrolysis lignin, alkali lignin, sulfonate lignin, ground wood lignin or organic solvent lignin.
3. The lignin-based sizing agent for composite carbon nanotubes according to claim 1, wherein: the epoxy resin in the step (2) is any one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydroxymethyl bisphenol A epoxy resin or bisphenol S epoxy resin; the organic solvent is N, N-dimethylformamide.
4. The lignin-based sizing agent for composite carbon nanotubes according to claim 1, wherein: the organic solvent in the step (3) is one or any combination of methanol, ethanol or ethylene glycol monobutyl ether; the alcohol amine is one or any combination of ethanolamine, diethanolamine, dimethylethanolamine or triethanolamine.
5. The lignin-based sizing agent for composite carbon nanotubes according to claim 1, wherein: the carboxylic acid in the step (4) is one or any combination of oxalic acid, formic acid, acetic acid or propionic acid; the carbon nano tube is one or any combination of a single-walled carbon nano tube, a multi-walled carbon nano tube, a hydroxylated carbon nano tube or a carboxylated carbon nano tube; the silane coupling agent is one or any combination of vinyl triethoxysilane, vinyl trimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane or gamma-aminopropyl triethoxysilane.
6. The use of the lignin-based sizing agent for carbon nanotubes of any one of claims 1 to 5 in the field of carbon fiber reinforced polyolefin composites.
7. The application of the lignin-based sizing agent for carbon nanotubes in the field of carbon fiber reinforced polyolefin composite material according to claim 6, wherein the lignin-based sizing agent comprises: it comprises the following steps:
(1) soaking the carbon fiber cloth in 0.5-4wt% lignin-based sizing agent of the composite carbon nanotube for 2-6min at room temperature, then pulling the carbon fiber cloth out of the sizing agent aqueous solution at the speed of 2-6cm/min, and drying at 70-100 ℃ for 1-4h to obtain the carbon fiber cloth after sizing pretreatment;
(2) spreading polyolefin powder in a mold, arranging the carbon fiber subjected to sizing pretreatment in the step (1) in a middle layer of the polyolefin powder, placing the carbon fiber cloth and the polyolefin powder in a mass ratio of 6-10:80-100 in a flat-plate vulcanizer, preheating at the temperature of 170-200 ℃ for 1-7min, then applying 10-25 tons of pressure to carry out hot pressing for 3-5min, cooling to room temperature, and keeping the pressure for 10-30 tons for 2-8min to obtain the carbon fiber reinforced polyolefin composite material.
8. The application of the lignin-based sizing agent for carbon nanotubes in the field of carbon fiber reinforced polyolefin composite materials according to claim 7 is characterized in that: the polyolefin in the step (2) is any one of polypropylene, polyethylene, polyvinyl chloride or ethylene-vinyl acetate copolymer.
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