CN113882155A - Polyethylene glycol maleimide-styrene copolymer sizing agent and preparation method and application thereof - Google Patents
Polyethylene glycol maleimide-styrene copolymer sizing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polyethylene glycol maleimide-styrene copolymer sizing agent and a preparation method and application thereof. The sizing agent comprises polyethylene glycol maleimide-styrene type copolymer, an emulsifier and water, wherein the emulsifier is an aqueous emulsifier. The polyethylene glycol maleimide-styrene copolymer sizing agent disclosed by the invention has good compatibility with a common maleimide resin matrix, can improve the bonding strength of carbon fibers and the maleimide resin matrix, and can play a role in improving the wear resistance of the carbon fibers, reducing the filament quantity of the carbon fibers and adjusting the stiffness of the carbon fibers. The preparation method is simple and convenient to operate, easy to implement and good in commercial prospect.
Description
Technical Field
The invention relates to the field of fiber manufacturing, in particular to a polyethylene glycol maleimide-styrene copolymer sizing agent and a preparation method and application thereof. The sizing agent can effectively improve the heat resistance of the carbon fiber and improve the interface performance between the carbon fiber and polyethylene glycol maleimide and polystyrene resin matrixes.
Background
Carbon fiber is a special fiber material composed of carbon elements, and a carbon fiber reinforced composite material (CFRP) is a material prepared by compounding carbon fibers serving as a reinforcing material with a matrix such as resin, metal, ceramic and the like. For example, the carbon fiber can be compounded with the polymaleimide to prepare the carbon fiber/polymaleimide composite material, and the carbon fiber has the characteristics of high specific strength and high specific modulus, so that the mechanical property of the composite material can be obviously improved. Copolymers composed of N-substituted maleimide monomers and styrene-based monomers have the characteristics of good heat resistance, multiple polymerization methods and good manufacturability, and are often used in the manufacture of automobiles, televisions and refrigerators. Polystyrene is an amorphous high molecular polymer, and because the benzene ring of the side chain has larger volume, the polystyrene has higher rigidity and is more brittle, so the performance of the polystyrene can be improved by adding a comonomer. The N-substituted maleimide has a five-membered planar ring structure, and is often used as a heat-resistant monomer to be copolymerized with other monomers so as to improve the heat resistance of the polymer material. Because the surface active groups of the carbon fibers are less, and the water solubility of the copolymer consisting of the N-substituted maleimide monomer and the styrene monomer is poor, the two monomers are difficult to be tightly combined. Although the carbon fiber sizing agents designed by polyimide on the market at present are various in variety, the sizing agents designed aiming at the copolymer of the N-substituted maleimide monomer and the styrene monomer are less, so that the sizing agent designed and suitable for the carbon fiber/maleimide-styrene copolymer composite material has high practical value.
Epoxy resin is thermosetting resin with excellent mechanical property, stability and insulativity, is a commonly used matrix in carbon fiber reinforced composite materials, and is widely applied to the fields of aviation materials, engineering materials and the like. In recent years, the development of the aerospace industry has made higher demands on the heat resistance of composite materials, and epoxy sizing agents are liable to decompose during high-temperature processing and long-term use due to insufficient heat resistance and cannot be used in high-temperature environments. Therefore, a high-temperature-resistant polymer can be added in the preparation of the sizing agent to improve the high-temperature resistance of the composite material, and patent CN104695228A discloses a preparation method of a thermoplastic emulsion sizing agent for carbon fibers, wherein a method for preparing the sizing agent by using polyphenyl maleimide copolymer and ABS (acrylonitrile butadiene styrene) blended as a main sizing agent is introduced, namely epoxy resin is prepared into a solution, and then the solution is stirred with an emulsifier and deionized water to form an emulsion.
Disclosure of Invention
In order to solve the problems in the prior art, the invention firstly prepares a polyethylene glycol maleimide-styrene type copolymer, and then mixes the polyethylene glycol maleimide-styrene type copolymer with resin emulsion to prepare a polyethylene glycol maleimide-styrene type copolymer sizing agent, wherein the sizing agent has variable main agent configuration and has stronger hydrophilic property and heat resistance, thus having better application prospect in the field of preparing composite materials.
One of the purposes of the invention is to provide a polyethylene glycol maleimide-styrene type copolymer sizing agent, which comprises a polyethylene glycol maleimide-styrene type copolymer, an emulsifier and water, wherein the emulsifier is an aqueous emulsifier.
In the technical scheme of the invention, the polyethylene glycol maleimide-styrene type copolymer preferably has a structural formula shown in formula I:
wherein n is 1-50, preferably n is 2-20;
R1is composed of
One of (1);
p is 1-50, q is 1-50, preferably p is 3-20, and q is 4-20;
R2is-OH, -O-CH3、-CH2-COOH、-SH、
One of (1);
R3is-H, -CH3、-OH、-O-CH3、COOH、-CH2-COOH、-F、-Cl、-Br、-I、-NH2、
One kind of (1).
The polyethylene glycol maleimide-styrene type copolymer is obtained by polymerizing a polyethylene glycol maleimide monomer and a styrene monomer.
Preferably, the polyethylene glycol maleimide-styrene type copolymer can be prepared by the following steps: adding polyethylene glycol maleimide monomer and styrene monomer into solvent at room temperature under nitrogen atmosphere, and adding initiator for reaction. Preferably, the reaction temperature is 50-80 ℃, the reaction time is 12-36 hours, more preferably, the reaction temperature is 55-75 ℃, and the reaction time is 12-30 hours.
The above-mentioned step of preparing the polyethylene glycol maleimide-styrene type copolymer further comprises the usual post-treatment steps of precipitation, filtration, washing and drying, and all the solvents are the ones usually used.
The polyethylene glycol maleimide monomer is selected from at least one of hydroxyl polyethylene glycol maleimide, methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide, sulfydryl polyethylene glycol maleimide, acrylate polyethylene glycol maleimide and tert-butyloxycarbonyl imide polyethylene glycol maleimide, and preferably at least one of methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide and hydroxyl polyethylene glycol maleimide;
the molecular weight of the polyethylene glycol maleimide monomer is 150-5000, preferably 300-3000;
the styrene monomer is selected from at least one of styrene, p-methylstyrene, p-hydroxystyrene, p-methoxystyrene, 4-vinylbenzoic acid, 4-vinyl phenylacetic acid, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-aminostyrene and p-isobutylstyrene, and preferably at least one of styrene, p-methylstyrene, 4-vinylbenzoic acid and 4-hydroxystyrene.
The solvent is a common organic solvent such as tetrahydrofuran.
The initiator is a common initiator such as azobisisobutyronitrile.
In the method, the molar ratio of the polyethylene glycol maleimide monomer to the styrene monomer is (0.2-5): 1, preferably (0.5-2): 1;
the molar ratio of the solvent to the total monomers is (1-50): 1, preferably (5-20): 1, more preferably (10-15): 1;
the molar ratio of the initiator to the total monomers is (0.0001-0.01): 1, preferably (0.001 to 0.005): 1.
in the technical scheme of the invention, the emulsifier is prepared from components including bisphenol A resin and polyethylene glycol, preferably, the emulsifier is prepared from components including bisphenol A resin, polyethylene glycol, emulsifier I and emulsifier II. More preferably, the emulsifier is obtained by mixing polyethylene glycol and bisphenol A resin at 50-100 ℃, heating to melt, and adding the emulsifier I and the emulsifier II. And stirring for 5-10 hours until the reaction is finished. The temperature is further preferably 60 to 90 ℃.
In the emulsifier, the molecular weight of the polyethylene glycol is 200-4000, preferably 400-2000;
the bisphenol A type resin is at least one of bisphenol A type epoxy resin, bisphenol A type phenolic resin, bisphenol A type polyether resin, bisphenol A type vinyl ester resin and bisphenol A type polyester resin, preferably at least one of bisphenol A type epoxy resin and bisphenol A type polyether resin;
the first emulsifier is at least one of sorbitan monostearate (span-60) and sorbitan monooleate (span-80);
and the second emulsifier is at least one of polyoxyethylene sorbitan monopalmitate (Tween-40), polyoxyethylene sorbitan monostearate (Tween-60), polyoxyethylene sorbitan monooleate (Tween-80) and polyoxyethylene octyl phenol ether-10 (OP-10).
The molar ratio of the bisphenol A type resin to the polyethylene glycol is (2-50): 1, preferably (10-45): 1, more preferably (20-45): 1;
the molar ratio of the first emulsifier to the polyethylene glycol is (0.05-5): 1, preferably (0.1-2): 1;
the molar ratio of the emulsifier II to the polyethylene glycol is (0.05-5): 1, preferably (0.1-2): 1.
in the technical scheme of the invention, the content of the polyethylene glycol maleimide-styrene copolymer and the emulsifier in the sizing agent is 10-50 wt%, preferably 15-45 wt%,
in the technical scheme of the invention, in the sizing agent, the molar ratio of polyethylene glycol in the aqueous emulsifier to total monomers in the polyethylene glycol maleimide-styrene copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003-0.01): 1.
the invention also provides a preparation method of the polyethylene glycol maleimide-styrene type copolymer sizing agent, which comprises the following steps: mixing components including the polyethylene glycol maleimide-styrene type copolymer and an emulsifier, and adding water to obtain the sizing agent. The mixing is preferably carried out at 60-80 ℃, and more preferably 65-75 ℃.
In the sizing agent, the content of the polyethylene glycol maleimide-styrene type copolymer and the emulsifier is 10-50 wt%, preferably 15-45 wt%,
in the sizing agent, the molar ratio of the polyethylene glycol in the aqueous emulsifier to the total monomers in the polyethylene glycol maleimide-styrene copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003-0.01): 1.
according to a preferred embodiment of the present invention, the sizing agent can be prepared by the following steps:
step a) adding polyethylene glycol maleimide monomers and styrene monomers at room temperature under nitrogen atmosphere according to the weight ratio of (0.2-5): 1, preferably (0.5-2): 1, and the molar ratio of the solvent tetrahydrofuran to the total monomers is (1-50): 1, preferably (5-20): 1, more preferably (10-15): 1. according to the molar ratio of the initiator azodiisobutyronitrile to the total monomers being (0.0001-0.01): 1, preferably (0.001 to 0.005): 1, sequentially adding tetrahydrofuran, polyethylene glycol maleimide monomers, styrene monomers and azobisisobutyronitrile into a reactor, reacting for 12-36 hours at 50-80 ℃, reducing to 0 ℃, and mixing according to the molar ratio of methanol to total monomers (10-20): 1, adding methanol into a reactor, standing for 1-2 h, and filtering, wherein the molar ratio of the methanol to the total monomers used each time is (1-5): 1, washing a filter cake with methanol for 2-3 times, and vacuum-drying at room temperature for 1-6 h to obtain a polyethylene glycol maleimide-styrene copolymer;
and b) at 50-100 ℃, based on the amount of the added polyethylene glycol, the molar ratio of the bisphenol A type resin to the polyethylene glycol is (2-50): 1, preferably (10-45): 1, more preferably (20-45): adding polyethylene glycol and bisphenol A resin into a reactor, heating to melt, wherein the molar ratio of an emulsifier I to the polyethylene glycol is (0.05-5) based on the amount of the added polyethylene glycol: 1, preferably (0.1-2): 1. and (3) according to the molar ratio of the emulsifier II to the polyethylene glycol of (0.05-5): 1, preferably (0.1-2): 1, adding the emulsifier I and the emulsifier II into a reactor, and stirring for 5-10 hours to obtain the water-based emulsifier.
And c) at the temperature of 60-80 ℃, based on the amount of the added polyethylene glycol maleimide-styrene type copolymer, the molar ratio of the polyethylene glycol to the total monomers in the polyethylene glycol maleimide-styrene type copolymer in the aqueous emulsifier is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, more preferably (0.003 to 0.01): adding an emulsifier and a polyethylene glycol maleimide-styrene copolymer into a reactor, stirring uniformly, then continuously adding deionized water, diluting a mixed system until the solid content is 10-50 wt%, preferably 15-45 wt%, and preparing the polyethylene glycol maleimide-styrene copolymer sizing agent.
The sizing agent has good stability, can improve the post-processing performance of the carbon fiber and the interface bonding strength of the carbon fiber and the maleimide resin, and can be applied to different types of maleimide resin matrixes by changing the structure of a main agent copolymer in the sizing agent and adjusting the proportion of components of the sizing agent.
The invention also aims to provide the application of the polyethylene glycol maleimide-styrene copolymer sizing agent in the carbon fiber composite material.
When in use, the common sizing agent treatment method is adopted. For example, the polyethylene glycol maleimide-styrene type copolymer sizing agent is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120-150 ℃ and collecting filaments.
The sizing agent has moderate sizing amount (0.5-1.5%), low saturated water absorption rate (< 0.15%), moderate interlaminar shear strength (90-115 MPa), controllable particle size (200-500 nm) and good stability (>6 months).
The polyethylene glycol maleimide-styrene copolymer sizing agent disclosed by the invention has good compatibility with a common maleimide resin matrix, can improve the bonding strength of carbon fibers and the maleimide resin matrix, and can play a role in improving the wear resistance of the carbon fibers, reducing the filament quantity of the carbon fibers and adjusting the stiffness of the carbon fibers. The preparation method is simple and convenient to operate, easy to implement and good in commercial prospect.
The invention has the characteristics that:
(1) the polyethylene glycol maleimide-styrene type copolymer of the main agent has an adjustable molecular structure, and because polyethylene glycol is a hydrophilic group and a benzene ring is a hydrophobic group, the polarity of the polymer can be adjusted by adjusting the copolymerization proportion of the polyethylene glycol maleimide and styrene and the side chain functional group of the copolymer, thereby improving the affinity performance of the sizing agent and resin.
(2) The water-based emulsifier adopts bisphenol A epoxy resin and polyethylene glycol, and is added with the first emulsifier and the second emulsifier, the bisphenol A resin, the first emulsifier and the second emulsifier can be adjusted according to the resin type of the composite material, the category with the best crosslinking effect is selected, and the molecular weight of the polyethylene glycol and the types of the first emulsifier and the second emulsifier are adjusted, so that the water-based emulsifier forms stable emulsion.
(3) The sizing agent adopts raw materials comprising common raw materials such as polyethylene glycol maleimide, styrene and the like, the preparation method of blending can effectively reduce the manufacturing cost of the sizing agent, and the prepared sizing agent has good economic value.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the embodiments of the present invention are commercially available.
The sized carbon fiber is tested for sizing amount and saturated water absorption, and the interlaminar shear strength (ILSS) test is carried out according to JC/T773-82 (96).
Example 1:
at room temperature, under nitrogen atmosphere, 200g of tetrahydrofuran is added into a reactor, 35g of methoxy polyethylene glycol maleimide (M.W.331) and 10.5g of styrene are added, 0.1g of azobisisobutyronitrile is added, after the reaction is carried out for 20 hours at 65 ℃, the temperature is reduced to 0 ℃, 100g of methanol is added, the filtration is carried out, 20g of methanol is respectively used for washing a filter cake each time, the washing is carried out for 3 times to remove residual methoxy polyethylene glycol maleimide and styrene, and the vacuum drying is carried out for 12 hours at 50 ℃ to obtain 37.2g of methoxy polyethylene glycol maleimide-styrene copolymer.
At the temperature of 80 ℃, 12g of bisphenol A type epoxy resin (618) is added into a reactor, 2g of polyethylene glycol (PEG-2000) is added, the raw materials are stirred until the raw materials are melted, the temperature is raised to 100 ℃, 0.5g of span-60 and 0.5g of Tween-80 are added, and the mixture is stirred for 8 hours to obtain 15g of aqueous emulsifier.
At 70 ℃, adding 25g of methoxy polyethylene glycol maleimide-styrene copolymer and 10g of aqueous emulsifier into a reactor, stirring uniformly, continuing adding deionized water, diluting the mixed system until the solid content is 35%, and preparing 100g of methoxy polyethylene glycol maleimide-styrene sizing agent.
The sizing agent of the methoxy polyethylene glycol maleimide-styrene copolymer prepared in the embodiment is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120 ℃ and collecting filaments. The carbon fiber sizing adhesion amount after sizing was 1.0%, the saturated water absorption was 0.08%, and the ILSS was 105 MPa.
Example 2:
at room temperature, under nitrogen atmosphere, 200g of tetrahydrofuran is added into a reactor, 40g of carboxyl polyethylene glycol maleimide (M.W.402) and 10.5g of styrene are added, 0.1g of azobisisobutyronitrile is added, after the reaction is carried out for 20 hours at 65 ℃, the temperature is reduced to 0 ℃, 100g of methanol is added, the filtration is carried out, 20g of methanol is respectively used for washing a filter cake each time, the washing is carried out for 3 times to remove residual carboxyl polyethylene glycol maleimide and styrene, and the vacuum drying is carried out for 12 hours at 50 ℃ to obtain 42.1g of carboxyl polyethylene glycol maleimide-styrene copolymer.
At the temperature of 80 ℃, 15g of bisphenol A type epoxy resin (616) is added into a reactor, 2g of polyethylene glycol (PEG-2000) is added, the raw materials are stirred until the raw materials are melted, the temperature is raised to 100 ℃, 0.2g of span-80 and 0.6g of Tween-60 are added, and the mixture is stirred for 8 hours to obtain 17.8g of the aqueous emulsifier.
At 70 ℃, adding 25g of carboxyl polyethylene glycol maleimide-styrene copolymer and 10g of aqueous emulsifier into a reactor, stirring uniformly, continuing adding deionized water, diluting the mixed system until the solid content is 35%, and preparing 100g of carboxyl polyethylene glycol maleimide-styrene sizing agent.
The sizing agent of the carboxyl polyethylene glycol maleimide-styrene copolymer prepared in the embodiment is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120 ℃ and collecting filaments. The carbon fiber sizing adhesion amount after sizing was 0.9%, the saturated water absorption was 0.07%, and the ILSS was 102 MPa.
Example 3:
adding 200g of tetrahydrofuran into a reactor at room temperature under nitrogen atmosphere, adding 35g of methoxy polyethylene glycol maleimide (M.W.331) and 12g of p-methylstyrene, adding 0.1g of azobisisobutyronitrile, reacting at 65 ℃ for 20 hours, cooling to 0 ℃, adding 100g of methanol, filtering, washing a filter cake with 20g of methanol each time, washing for 3 times to remove residual methoxy polyethylene glycol maleimide and p-methylstyrene, and drying under vacuum at 50 ℃ for 12 hours to obtain 37.6g of methoxy polyethylene glycol maleimide-p-methylstyrene copolymer.
At 80 ℃, 12g of bisphenol A epoxy resin (618) is added into a reactor, 3g of polyethylene glycol (PEG-2000) is added, the raw materials are stirred until the raw materials are melted, the temperature is raised to 100 ℃, 0.5g of span-80 and 0.5g of Tween-80 are added, and the mixture is stirred for 8 hours to obtain 16g of the aqueous emulsifier.
At 70 ℃, 26g of methoxy polyethylene glycol maleimide-p-methylstyrene copolymer and 10g of aqueous emulsifier are added into a reactor, deionized water is continuously added after uniform stirring, and the mixed system is diluted until the solid content is 36 percent to prepare 100g of methoxy polyethylene glycol maleimide-p-methylstyrene sizing agent.
The sizing agent of the methoxy polyethylene glycol maleimide-p-methylstyrene copolymer prepared in the embodiment is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120 ℃ and collecting filaments. The carbon fiber sizing adhesion amount after sizing was 1.1%, the saturated water absorption was 0.09%, and the ILSS was 106 MPa.
Example 4:
adding 200g of tetrahydrofuran into a reactor at room temperature under nitrogen atmosphere, adding 35g of carboxyl polyethylene glycol maleimide (M.W.350) and 15g of 4-vinyl benzoic acid, adding 0.1g of azobisisobutyronitrile, reacting at 65 ℃ for 20 hours, cooling to 0 ℃, adding 100g of methanol, filtering, washing a filter cake with 20g of methanol each time, washing for 3 times to remove residual carboxyl polyethylene glycol maleimide and 4-vinyl benzoic acid, and vacuum drying at 50 ℃ for 12 hours to obtain 40.2g of carboxyl polyethylene glycol maleimide-4-vinyl benzoic acid copolymer.
At 80 ℃, 12g of bisphenol A epoxy resin (618) is added into a reactor, 2g of polyethylene glycol (PEG-2000) is added, the raw materials are stirred until the raw materials are melted, the temperature is raised to 100 ℃, 0.5g of span-80 and 1.5g of Tween-40 are added, and the mixture is stirred for 8 hours to obtain 16g of the aqueous emulsifier.
At 70 ℃, 20g of carboxyl polyethylene glycol maleimide-4-vinyl benzoic acid copolymer and 12g of aqueous emulsifier are added into a reactor, deionized water is continuously added after uniform stirring, and the mixed system is diluted until the solid content is 32%, so that 100g of carboxyl polyethylene glycol maleimide-4-vinyl benzoic acid copolymer sizing agent is prepared.
The sizing agent of the carboxyl polyethylene glycol maleimide-4-vinyl benzoic acid copolymer prepared in the embodiment is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120 ℃ and collecting filaments. The carbon fiber sizing adhesion amount after sizing is 1.2%, the saturated water absorption is 0.1%, and the ILSS is 108 MPa.
Example 5:
at room temperature, under nitrogen atmosphere, adding 200g tetrahydrofuran, adding 35g hydroxypolyethylene glycol maleimide (M.W.350) and 12g 4-hydroxystyrene, adding 0.1g azobisisobutyronitrile, reacting at 65 ℃ for 20 hours, cooling to 0 ℃, adding 100g methanol, filtering, washing the filter cake with 20g methanol each time, washing for 3 times to remove residual hydroxypolyethylene glycol maleimide and 4-hydroxystyrene, and vacuum drying at 50 ℃ for 12 hours to obtain 37.1g hydroxypolyethylene glycol maleimide-4-hydroxystyrene copolymer.
At the temperature of 80 ℃, 12g of bisphenol A type epoxy resin (618) is added into a reactor, 2g of polyethylene glycol (PEG-2000) is added, the raw materials are stirred until the raw materials are melted, the temperature is raised to 100 ℃, 0.3g of span-60 and 0.9g of Tween-40 are added, and the mixture is stirred for 8 hours to obtain 15.2g of the aqueous emulsifier.
At 70 ℃, adding 25g of hydroxypolyethylene glycol maleimide-4-hydroxystyrene copolymer and 10g of aqueous emulsifier into a reactor, stirring uniformly, continuing adding deionized water, diluting the mixed system until the solid content is 35%, and preparing 100g of hydroxypolyethylene glycol maleimide-4-hydroxystyrene sizing agent.
The prepared hydroxypolyethylene glycol maleimide-4-hydroxystyrene sizing agent in the embodiment is diluted to 2.5 percent and is used for sizing carbon fibers on a carbon fiber production line, drying at 120 ℃ and collecting filaments. The carbon fiber sizing adhesion amount after sizing was 1.2%, the saturated water absorption was 0.11%, and the ILSS was 109 MPa.
Comparative example 1:
10 kg of epoxy resin (trade mark 601) was dissolved in 3 kg of acetone at 30 ℃ to form an organic resin solution.
After the organic resin solution is cooled to normal temperature, 0.2 kg of emulsifier polyoxyethylene sorbitan monooleate (Tweer81), 0.05 kg of lubricant fatty alcohol polyoxyethylene ether (O-10) and 1 kg of deionized water are uniformly mixed and added into the organic resin solution, and after stirring for 30min, the deionized water is added until the solid content of the mixed system is 50%, so as to prepare the organic resin emulsion.
Slowly adding 5g of single-layer graphene into the organic resin emulsion, and uniformly stirring; and then, continuously adding deionized water, diluting the mixed system until the solid content is 5%, and preparing the graphene modified sizing agent.
Attaching diluted sizing agent to the surface of carbon fiber by dipping method, wherein the dipping time is 10s, drying at 120 ℃ for 30s to remove solvent, putting the sample in N2The atmosphere desiccator was ready for use. ILSS was 89.8 MPa.
Claims (14)
1. The sizing agent comprises a polyethylene glycol maleimide-styrene copolymer, an emulsifier and water, wherein the emulsifier is an aqueous emulsifier.
2. The sizing agent according to claim 1, characterized in that:
the polyethylene glycol maleimide-styrene type copolymer has a structural formula shown in a formula I:
wherein n is 1-50, preferably n is 2-20;
R1is composed of
p is 1-50, q is 1-50, p is preferably 3-20, and q is preferably 4-20;
R2is-OH, -O-CH3、-CH2-COOH、-SH、
One of (1);
R3is-H, -CH3、-OH、-O-CH3、-COOH、-CH2-COOH、-F、-Cl、-Br、-I、-NH2、
One kind of (1).
3. The sizing agent according to claim 1, characterized in that:
the polyethylene glycol maleimide-styrene type copolymer is obtained by polymerizing a polyethylene glycol maleimide monomer and a styrene monomer; and/or the presence of a gas in the gas,
the emulsifier is prepared from components including bisphenol A type resin and polyethylene glycol.
4. The sizing agent according to claim 3, characterized in that:
the polyethylene glycol maleimide-styrene type copolymer is prepared by the following steps: adding polyethylene glycol maleimide monomer and styrene monomer into solvent at room temperature under nitrogen atmosphere, adding initiator to carry out polymerization reaction.
5. The sizing agent according to claim 4, characterized in that:
the polyethylene glycol maleimide monomer is at least one selected from hydroxyl polyethylene glycol maleimide, methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide, sulfydryl polyethylene glycol maleimide, acrylate polyethylene glycol maleimide and tert-butyloxycarbonyl imide polyethylene glycol maleimide; and/or the presence of a gas in the gas,
the molecular weight of the polyethylene glycol maleimide monomer is 150-5000, preferably 300-3000; and/or the presence of a gas in the gas,
the styrene monomer is selected from at least one of styrene, p-methylstyrene, p-hydroxystyrene, p-methoxystyrene, 4-vinylbenzoic acid, 4-vinyl phenylacetic acid, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-aminostyrene and p-isobutylstyrene; and/or the presence of a gas in the gas,
the reaction temperature is 50-80 ℃, and the reaction time is 12-36 hours.
6. The sizing agent according to claim 4, characterized in that:
the molar ratio of the polyethylene glycol maleimide monomer to the styrene monomer is (0.2-5): 1, preferably (0.5-2): 1; and/or the presence of a gas in the gas,
the molar ratio of the solvent to the total monomers is (1-50): 1, preferably (5-20): 1, more preferably (10-15): 1; and/or the presence of a gas in the gas,
the molar ratio of the initiator to the total monomers is (0.0001-0.01): 1, preferably (0.001 to 0.005): 1.
7. the sizing agent according to claim 3, characterized in that:
the emulsifier is prepared from components including bisphenol A type resin, polyethylene glycol, emulsifier I and emulsifier II.
8. The sizing agent according to claim 7, characterized in that:
the molecular weight of the polyethylene glycol is 200-4000, preferably 400-2000; and/or the presence of a gas in the gas,
the bisphenol A type resin is at least one of bisphenol A type epoxy resin, bisphenol A type phenolic resin, bisphenol A type polyether resin, bisphenol A type vinyl ester resin and bisphenol A type polyester resin; and/or the presence of a gas in the gas,
the first emulsifier is at least one of sorbitan monostearate and sorbitan monooleate; and/or the presence of a gas in the gas,
and the second emulsifier is at least one of polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene octyl phenol ether-10.
9. The sizing agent according to claim 7, characterized in that:
the molar ratio of the bisphenol A type resin to the polyethylene glycol is (2-50): 1, preferably (10-45): 1, more preferably (20-45): 1; and/or the presence of a gas in the gas,
the molar ratio of the first emulsifier to the polyethylene glycol is (0.05-5): 1, preferably (0.1-2): 1; and/or the presence of a gas in the gas,
the molar ratio of the emulsifier II to the polyethylene glycol is (0.05-5): 1, preferably (0.1-2): 1.
10. the sizing agent according to claim 7, characterized in that:
mixing polyethylene glycol and bisphenol A resin at 50-100 ℃, heating to melt, and adding an emulsifier I and an emulsifier II to obtain the emulsifier.
11. The polyethylene glycol maleimide-styrene type copolymer sizing agent according to claim 3, wherein:
in the sizing agent, the content of the polyethylene glycol maleimide-styrene type copolymer and the emulsifier is 10-50 wt%, preferably 15-45 wt%; and/or the presence of a gas in the gas,
in the sizing agent, the molar ratio of the polyethylene glycol in the aqueous emulsifier to the total monomers in the polyethylene glycol maleimide-styrene copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003-0.01): 1.
12. a method for preparing a sizing agent for polyethylene glycol maleimide-styrene type copolymer according to any one of claims 1 to 11, comprising the steps of:
mixing components including the polyethylene glycol maleimide-styrene type copolymer and an emulsifier, and adding water to obtain the sizing agent.
13. The method for producing a sizing agent according to claim 12, wherein:
in the sizing agent, the content of the polyethylene glycol maleimide-styrene type copolymer and the emulsifier is 10-50 wt%, preferably 15-45 wt%; and/or the presence of a gas in the gas,
in the sizing agent, the molar ratio of the polyethylene glycol in the aqueous emulsifier to the total monomers in the polyethylene glycol maleimide-styrene copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003-0.01): 1; and/or the presence of a gas in the gas,
the mixing is carried out at 60-80 ℃.
14. Use of the polyethylene glycol maleimide-styrene type copolymer sizing agent according to any one of claims 1 to 11 in a carbon fiber composite material.
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