CN113882155B - 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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- CN113882155B CN113882155B CN202010619834.6A CN202010619834A CN113882155B CN 113882155 B CN113882155 B CN 113882155B CN 202010619834 A CN202010619834 A CN 202010619834A CN 113882155 B CN113882155 B CN 113882155B
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The invention provides a polyethylene glycol maleimide-styrene copolymer sizing agent, 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 has good compatibility with a common maleimide resin matrix, can improve the bonding strength of carbon fibers and the maleimide resin matrix, and can simultaneously play roles in improving the wear resistance of the carbon fibers, reducing the quantity of carbon fiber hairiness and adjusting the stiffness of the carbon fibers. The preparation method is simple and convenient to operate, easy to implement and has good 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, 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 matrix.
Background
Carbon fiber is a special fiber material composed of carbon elements, and carbon fiber reinforced composite material (CFRP) is a material prepared by compounding carbon fiber 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 polymaleimide to prepare a 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 remarkably improved. The copolymer composed of N-substituted maleimide monomer and styrene monomer has the characteristics of good heat resistance, various polymerization methods and good manufacturability, and is often used in the manufacture of automobiles, televisions and refrigerators. Polystyrene is an amorphous high molecular polymer, and since the benzene ring of the side chain is larger in volume, the polystyrene is more rigid and more brittle, so that the performance of the polystyrene can be improved by adding a comonomer. 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 to improve the heat resistance of the polymer material. Because the carbon fiber has few surface active groups, and the copolymer composed of the N-substituted maleimide monomer and the styrene monomer has poor water solubility, the N-substituted maleimide monomer and the styrene monomer are difficult to be tightly combined. The polyimide resin sizing agent which is designed by polyimide is a carbon fiber sizing agent which is commercially available at present, but the sizing agent which is designed by aiming at the copolymer of N-substituted maleimide monomer and styrene monomer is less, so the sizing agent which is designed by aiming at the carbon fiber/maleimide-styrene copolymer composite material has high practical value.
The epoxy resin is a thermosetting resin with excellent mechanical property, stability and insulativity, is a common 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 aviation industry has put 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 the blending of a polyphenylene maleimide copolymer and ABS as main sizing agent is introduced, namely, after epoxy resin is prepared into a solution, the solution is stirred with an emulsifying agent and deionized water to form emulsion, and the preparation method can be used for preparing various different types of sizing agents, namely, a heat resistant polymaleimide copolymer is added into the sizing agent to obtain the heat resistant sizing agent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention firstly prepares the polyethylene glycol maleimide-styrene type copolymer, and then mixes the polyethylene glycol maleimide-styrene type copolymer with resin emulsion to prepare the polyethylene glycol maleimide-styrene type copolymer sizing agent, wherein the sizing agent has a 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 a formula I:
wherein n is 1 to 50, preferably n is 2 to 20;
R 1 is that One of the following;
p is 1 to 50, q is 1 to 50, preferably p is 3 to 20, q is 4 to 20;
R 2 is-OH, -O-CH 3 、-CH 2 -COOH、-SH、One of the following;
R 3 is-H, -CH 3 、-OH、-O-CH 3 、COOH、-CH 2 -COOH、-F、-Cl、-Br、-I、-NH 2 、One of them.
The polyethylene glycol maleimide-styrene copolymer is obtained by polymerizing polyethylene glycol maleimide monomers and styrene monomers.
Preferably, the polyethylene glycol maleimide-styrene-based copolymer may be prepared by the steps of: and adding polyethylene glycol maleimide monomers and styrene monomers into a solvent at room temperature under nitrogen atmosphere, and adding an initiator to react. Preferably, the reaction temperature is 50 to 80 ℃, the reaction time is 12 to 36 hours, more preferably, the reaction temperature is 55 to 75 ℃, and the reaction time is 12 to 30 hours.
The steps for preparing the polyethylene glycol maleimide-styrene copolymer further comprise the usual post-treatment steps of precipitation, filtration, washing, drying and the like, and the solvents used are all solvents commonly used.
The polyethylene glycol maleimide monomer is at least one selected from hydroxy polyethylene glycol maleimide, methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide, mercapto polyethylene glycol maleimide, acrylic ester polyethylene glycol maleimide and tert-butoxycarbonyl imine polyethylene glycol maleimide, preferably at least one selected from methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide and hydroxy polyethylene glycol maleimide;
the molecular weight of the polyethylene glycol maleimide monomer is 150-5000, preferably 300-3000;
the styrene monomer is at least one selected from styrene, p-methylstyrene, p-hydroxystyrene, p-methoxystyrene, 4-vinylbenzoic acid, 4-vinylphenylacetic acid, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-aminostyrene and p-isobutylstyrene, preferably at least one selected from styrene, p-methylstyrene, 4-vinylbenzoic acid and 4-hydroxystyrene.
The solvent is a general organic solvent such as tetrahydrofuran.
The initiator is a general initiator such as azobisisobutyronitrile and the like.
In the method, the molar ratio of the polyethylene glycol maleimide monomer to the styrene monomer is (0.2-5): 1, preferably (0.5 to 2): 1, a step of;
the mol ratio of the solvent to the total monomer is (1-50): 1, preferably (5 to 20): 1, more preferably (10 to 15): 1, a step of;
the molar ratio of the initiator to the total monomer 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 comprising bisphenol A resin and polyethylene glycol, preferably the emulsifier is prepared from components comprising bisphenol A resin, polyethylene glycol, emulsifier I and emulsifier II. More preferably, the polyethylene glycol is mixed with bisphenol A resin at 50-100 ℃, heated to be molten, and added with the emulsifier I and the emulsifier II to obtain the emulsifier. And stirring for 5-10 hours until the reaction is completed. The temperature is more preferably 60 to 90 ℃.
Among the above emulsifiers, the molecular weight of polyethylene glycol is 200 to 4000, preferably 400 to 2000;
the bisphenol A resin is at least one of bisphenol A epoxy resin, bisphenol A phenolic resin, bisphenol A polyether resin, bisphenol A vinyl ester resin and bisphenol A polyester resin, preferably at least one of bisphenol A epoxy resin and bisphenol A polyether resin;
the emulsifier I is at least one of sorbitan monostearate (span-60) and sorbitan monooleate (span-80);
the emulsifier II 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 mole ratio of bisphenol A resin to polyethylene glycol is (2-50): 1, preferably (10 to 45): 1, more preferably (20 to 45): 1, a step of;
the mol ratio of the emulsifier I to the polyethylene glycol is (0.05-5): 1, preferably (0.1 to 2): 1, a step of;
the molar ratio of the emulsifier II to the polyethylene glycol is (0.05-5): 1, preferably (0.1 to 2): 1.
in the technical scheme of the invention, the content of the polyethylene glycol maleimide-styrene copolymer and the emulsifying agent in the sizing agent is 10-50wt%, preferably 15-45wt%,
in the technical scheme of the invention, in the sizing agent, the molar ratio of polyethylene glycol in the aqueous emulsifier to the total monomer in the polyethylene glycol maleimide-styrene copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003 to 0.01): 1.
the second purpose of the invention is to provide a preparation method of the polyethylene glycol maleimide-styrene copolymer sizing agent, which comprises the following steps: mixing components including polyethylene glycol maleimide-styrene copolymer and emulsifier, and adding water to obtain the sizing agent. The mixing is preferably carried out at 60 to 80 ℃, more preferably 65 to 75 ℃.
In the sizing agent, the content of the polyethylene glycol maleimide-styrene type copolymer and the emulsifier is 10 to 50wt%, preferably 15 to 45wt%,
in the sizing agent, the molar ratio of polyethylene glycol in the aqueous emulsifier to the total monomer in the polyethylene glycol maleimide-styrene type copolymer is (0.001-0.1): 1, preferably (0.001 to 0.05): 1, preferably (0.003 to 0.01): 1.
according to a preferred embodiment of the present invention, the sizing agent may be prepared by the steps of:
step a), adding polyethylene glycol maleimide monomer and styrene monomer according to the proportion of (0.2-5) at room temperature under nitrogen atmosphere: 1, preferably (0.5 to 2): 1, and the mole ratio of the solvent tetrahydrofuran to the total monomers is (1-50) based on the total amount of the added monomers: 1, preferably (5 to 20): 1, more preferably (10 to 15): 1. the mole ratio of the initiator azodiisobutyronitrile to the total monomers is (0.0001-0.01): 1, preferably (0.001 to 0.005): 1, sequentially adding tetrahydrofuran, polyethylene glycol maleimide monomer, styrene monomer and azodiisobutyronitrile into a reactor, reacting for 12-36 hours at 50-80 ℃, and then reducing the temperature to 0 ℃ according to the molar ratio of methanol to total monomer of (10-20): 1, adding methanol into a reactor, standing for 1-2 h, filtering, wherein the molar ratio of each time of use to total monomers is (1-5): 1, washing a filter cake with methanol for 2-3 times, and vacuum drying at room temperature for 1-6 hours to obtain a polyethylene glycol maleimide-styrene copolymer;
step b) at 50-100 ℃, the mole ratio of bisphenol A resin to polyethylene glycol is (2-50) based on the amount of polyethylene glycol added: 1, preferably (10 to 45): 1, more preferably (20 to 45): 1, adding polyethylene glycol and bisphenol A resin into a reactor, heating to melt, wherein the molar ratio of the emulsifier I to the polyethylene glycol is (0.05-5) based on the amount of the added polyethylene glycol: 1, preferably (0.1 to 2): 1. the mol ratio of the emulsifier II to the polyethylene glycol is (0.05-5): 1, preferably (0.1 to 2): 1, adding the first emulsifier and the second emulsifier into a reactor, and stirring for 5-10 hours to obtain the water-based emulsifier.
Step c) at 60-80 ℃ in terms of the amount of polyethylene glycol maleimide-styrene type copolymer added, the molar ratio of polyethylene glycol to 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): 1, adding an emulsifying agent and a polyethylene glycol maleimide-styrene type copolymer into a reactor, stirring uniformly, then continuously adding deionized water, and diluting the mixed system until the solid content is 10-50wt%, preferably 15-45wt%, thus obtaining the polyethylene glycol maleimide-styrene type 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 sizing agent components.
The invention further provides an application of the polyethylene glycol maleimide-styrene copolymer sizing agent in carbon fiber composite materials.
When in use, the common sizing agent treatment method is adopted. For example, the polyethylene glycol maleimide-styrene copolymer sizing agent is diluted to 2.5 percent and used for sizing treatment of carbon fibers on a carbon fiber production line, and is dried at 120-150 ℃ and then is taken up.
The sizing agent has moderate sizing amount (0.5-1.5%), low saturated water absorption (< 0.15%), moderate interlayer shear strength (90-115 MPa), controllable particle size (200-500 nm) and good stability (> 6 months).
The polyethylene glycol maleimide-styrene copolymer sizing agent has good compatibility with a common maleimide resin matrix, can improve the bonding strength of carbon fibers and the maleimide resin matrix, and can simultaneously play roles in improving the wear resistance of the carbon fibers, reducing the quantity of carbon fiber hairiness and adjusting the stiffness of the carbon fibers. The preparation method is simple and convenient to operate, easy to implement and has good commercial prospect.
The invention is characterized in that:
(1) The polyethylene glycol maleimide-styrene copolymer of the main agent has an adjustable molecular structure, and because polyethylene glycol is hydrophilic group and benzene ring is hydrophobic group, the polarity of the polymer can be adjusted by adjusting the copolymerization ratio of polyethylene glycol maleimide and styrene and the side chain functional group of the copolymer, thereby improving the affinity energy of sizing agent and resin.
(2) The aqueous emulsifier adopts bisphenol A epoxy resin and polyethylene glycol, and an emulsifier I and an emulsifier II are added, the bisphenol A resin, the emulsifier I and the emulsifier II can be adjusted according to the resin type of the composite material, the type with the best crosslinking effect is selected, and the molecular weight of the polyethylene glycol, the type of the emulsifier I and the type of the emulsifier II are adjusted, so that the aqueous emulsifier forms stable emulsion.
(3) The sizing agent adopts common raw materials such as polyethylene glycol maleimide and styrene, and the like as raw materials, and the blending preparation mode can effectively reduce the manufacturing cost of the sizing agent, so that the prepared sizing agent has good economic value.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the specific embodiment of the present invention are commercially available.
The sized carbon fibers were tested for sizing and saturated water absorption, and the interlaminar shear strength (ILSS) test was performed according to JC/T773-82 (96).
Example 1:
200g of tetrahydrofuran, 35g of methoxy polyethylene glycol maleimide (M.W.331) and 10.5g of styrene are added into a reactor under the nitrogen atmosphere at room temperature, 0.1g of azodiisobutyronitrile is added, the temperature is reduced to 0 ℃ after 20 hours of reaction, 100g of methanol is added, the filtration is carried out, 20g of methanol is used for washing filter cakes each time, residual methoxy polyethylene glycol maleimide and styrene are removed by washing 3 times, and 37.2g of methoxy polyethylene glycol maleimide-styrene copolymer is obtained after vacuum drying at 50 ℃ for 12 hours.
12g of bisphenol A type epoxy resin (618) is added into a reactor at 80 ℃ and 2g of polyethylene glycol (PEG-2000) is added, after the raw materials are stirred to be molten, 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 ℃, 25g of methoxy polyethylene glycol maleimide-styrene 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 35%, so that 100g of methoxy polyethylene glycol maleimide-styrene sizing agent is prepared.
The methoxy polyethylene glycol maleimide-styrene copolymer sizing agent prepared in the embodiment is diluted to 2.5 percent and used for sizing treatment of carbon fibers on a carbon fiber production line, and is dried at 120 ℃ and is used for filament collection. The sizing attachment amount of the sized carbon fiber is 1.0%, the saturated water absorption is 0.08%, and the ILSS is 105MPa.
Example 2:
200g of tetrahydrofuran, 40g of carboxyl polyethylene glycol maleimide (M.W.402) and 10.5g of styrene are added into a reactor under the nitrogen atmosphere at room temperature, 0.1g of azodiisobutyronitrile is added, the temperature is reduced to 0 ℃ after 20 hours of reaction, 100g of methanol is added, the filtration is carried out, 20g of methanol is used for washing filter cakes each time, residual carboxyl polyethylene glycol maleimide and styrene are removed by washing 3 times, and 42.1g of carboxyl polyethylene glycol maleimide-styrene copolymer is obtained after vacuum drying at 50 ℃ for 12 hours.
15g bisphenol A epoxy resin (616) was added to the reactor at 80℃and 2g polyethylene glycol (PEG-2000) was added, after stirring the raw materials to melt, the temperature was raised to 100℃and 0.2g span-80 and 0.6g Tween-60 were added, and stirring was carried out for 8 hours to obtain 17.8g of aqueous emulsifier.
At 70 ℃, adding 25g of carboxyl polyethylene glycol maleimide-styrene copolymer and 10g of aqueous emulsifier into a reactor, stirring uniformly, then continuously adding deionized water, diluting the mixed system until the solid content is 35%, and obtaining 100g of carboxyl polyethylene glycol maleimide-styrene sizing agent.
The prepared carboxyl polyethylene glycol maleimide-styrene copolymer sizing agent in the embodiment is diluted to 2.5 percent and is used for sizing treatment of carbon fibers on a carbon fiber production line, and the carbon fibers are dried at 120 ℃ and are harvested. The sizing attachment amount of the sized carbon fiber is 0.9%, the saturated water absorption is 0.07%, and the ILSS is 102MPa.
Example 3:
200g of tetrahydrofuran, 35g of methoxy polyethylene glycol maleimide (M.W.331) and 12g of p-methylstyrene are added into a reactor under the nitrogen atmosphere at room temperature, 0.1g of azodiisobutyronitrile is added, the temperature is reduced to 0 ℃ after 20 hours of reaction, 100g of methanol is added, the filtration is carried out, 20g of methanol is used for washing filter cakes each time, residual methoxy polyethylene glycol maleimide and p-methylstyrene are removed by washing 3 times, and 37.6g of methoxy polyethylene glycol maleimide-p-methylstyrene copolymer is obtained after vacuum drying at 50 ℃ for 12 hours.
12g of bisphenol A type epoxy resin (618) is added into a reactor at 80 ℃ and 3g of polyethylene glycol (PEG-2000) is added, after the raw materials are stirred to be molten, 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 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 to a solid content of 36%, so that 100g of methoxy polyethylene glycol maleimide-p-methylstyrene sizing agent is prepared.
The methoxy polyethylene glycol maleimide-p-methylstyrene copolymer sizing agent prepared in the embodiment is diluted to 2.5 percent and is used for sizing treatment of carbon fibers on a carbon fiber production line, and the carbon fibers are dried at 120 ℃ and are harvested. The sizing attachment amount of the sized carbon fiber is 1.1 percent, the saturated water absorption is 0.09 percent, and the ILSS is 106MPa.
Example 4:
200g of tetrahydrofuran, 35g of carboxyl polyethylene glycol maleimide (M.W.350) and 15g of 4-vinylbenzoic acid are added into a reactor under the nitrogen atmosphere at room temperature, 0.1g of azodiisobutyronitrile is added, the temperature is reduced to 0 ℃ after 20 hours of reaction, 100g of methanol is added, the filtration is carried out, 20g of methanol is used for washing filter cakes each time, residual carboxyl polyethylene glycol maleimide and 4-vinylbenzoic acid are removed 3 times, and 40.2g of carboxyl polyethylene glycol maleimide-4-vinylbenzoic acid copolymer is obtained after vacuum drying at 50 ℃ for 12 hours.
12g of bisphenol A type epoxy resin (618) was added to a reactor at 80℃and 2g of polyethylene glycol (PEG-2000) were added, and after the raw materials were stirred to melt, the temperature was raised to 100℃and 0.5g of span-80 and 1.5g of Tween-40 were added thereto and stirred for 8 hours to obtain 16g of an aqueous emulsifier.
At 70 ℃, adding 20g of carboxyl polyethylene glycol maleimide-4-vinylbenzoic acid copolymer and 12g of aqueous emulsifier into a reactor, stirring uniformly, then continuously adding deionized water, diluting the mixed system until the solid content is 32%, and obtaining 100g of carboxyl polyethylene glycol maleimide-4-vinylbenzoic acid copolymer sizing agent.
The prepared carboxyl polyethylene glycol maleimide-4-vinylbenzoic acid copolymer sizing agent in the embodiment is diluted to 2.5 percent and is used for sizing treatment of carbon fibers on a carbon fiber production line, and the carbon fibers are dried at 120 ℃ and are harvested. The sizing attachment amount of the sized carbon fiber is 1.2%, the saturated water absorption is 0.1%, and the ILSS is 108MPa.
Example 5:
200g of tetrahydrofuran, 35g of hydroxypolyethylene glycol maleimide (M.W.350) and 12g of 4-hydroxystyrene are added into a reactor under the nitrogen atmosphere at room temperature, 0.1g of azodiisobutyronitrile is added, the temperature is reduced to 0 ℃ after 20 hours of reaction, 100g of methanol is added, the filtration is carried out, 20g of methanol is used for washing filter cakes each time, residual hydroxypolyethylene glycol maleimide and 4-hydroxystyrene are removed 3 times, and 37.1g of hydroxypolyethylene glycol maleimide-4-hydroxystyrene copolymer is obtained after vacuum drying at 50 ℃ for 12 hours.
12g of bisphenol A type epoxy resin (618) was added to the reactor at 80℃and 2g of polyethylene glycol (PEG-2000) were added, the raw materials were stirred until molten, the temperature was raised to 100℃and 0.3g of span-60 and 0.9g of Tween-40 were added, and the mixture was stirred for 8 hours to obtain 15.2g of an aqueous emulsifier.
At 70 ℃, 25g of the hydroxypolyethylene glycol maleimide-4-hydroxystyrene copolymer and 10g of the aqueous emulsifier are added into a reactor, deionized water is continuously added after the mixture is stirred uniformly, and the mixed system is diluted until the solid content is 35%, so that 100g of hydroxypolyethylene glycol maleimide-4-hydroxystyrene sizing agent is prepared.
The prepared hydroxypolyethylene glycol maleimide-4-hydroxystyrene sizing agent in the embodiment is diluted to 2.5 percent and is used for sizing treatment of carbon fibers on a carbon fiber production line, and is dried at 120 ℃ and is used for filament collection. The sizing attachment amount of the sized carbon fiber is 1.2%, the saturated water absorption is 0.11%, and the ILSS is 109MPa.
Comparative example 1:
10 kg of epoxy resin (trade name 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 (Tweer 81), 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 a mixed system is 50%, so that the organic resin emulsion is prepared.
Slowly adding 5g of single-layer graphene into the organic resin emulsion, and uniformly stirring; and then continuing to add deionized water, and diluting the mixed system until the solid content is 5%, thus preparing the graphene modified sizing agent.
Adhering diluted sizing agent to the surface of carbon fiber by dipping method for 10s, drying at 120deg.C for 30s to remove solvent, and placing sample in N 2 The atmosphere is kept in a dryer for use. ILSS was 89.8MPa.
Claims (22)
1. A polyethylene glycol maleimide-styrene copolymer sizing agent comprises polyethylene glycol maleimide-styrene copolymer, an emulsifier and water, wherein the emulsifier is an aqueous emulsifier,
the polyethylene glycol maleimide-styrene type copolymer has a structural formula shown in formula I:
wherein n is 1 to 50;
R 1 is that One of the following;
p is 1-50, q is 1-50;
R 2 is thatOne of the following;
R 3 is-H, -CH 3 、-OH、-O-CH 3 、-COOH、-CH 2 -COOH、-F、-Cl、-Br、-I、-NH 2 、One of the following;
the polyethylene glycol maleimide-styrene copolymer is obtained by polymerizing polyethylene glycol maleimide monomers and styrene monomers, wherein the molar ratio of the polyethylene glycol maleimide monomers to the styrene monomers is (0.2-5) to 1;
the emulsifier is prepared from components comprising bisphenol A type resin, polyethylene glycol, emulsifier I and emulsifier II, wherein 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; the emulsifier I is at least one of sorbitan monostearate and sorbitan monooleate; the emulsifier II is at least one of polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene octyl phenol ether-10.
2. Sizing agent according to claim 1, characterized in that:
n is 2-20; p is 3-20, q is 4-20.
3. Sizing agent according to claim 1, characterized in that:
the polyethylene glycol maleimide-styrene type copolymer is prepared by the following steps: under the room temperature and nitrogen atmosphere, adding polyethylene glycol maleimide monomers and styrene monomers into a solvent, and adding an initiator to perform polymerization reaction.
4. A sizing agent according to claim 3, characterized in that:
the polyethylene glycol maleimide monomer is at least one selected from hydroxy polyethylene glycol maleimide, methoxy polyethylene glycol maleimide, carboxyl polyethylene glycol maleimide, mercapto polyethylene glycol maleimide, acrylic ester polyethylene glycol maleimide and tert-butoxycarbonyl imine polyethylene glycol maleimide; and/or the number of the groups of groups,
the molecular weight of the polyethylene glycol maleimide monomer is 150-5000; and/or the number of the groups of groups,
the styrene monomer is at least one selected from styrene, p-methylstyrene, p-hydroxystyrene, p-methoxystyrene, 4-vinylbenzoic acid, 4-vinylphenylacetic acid, p-fluorostyrene, p-chlorostyrene, p-bromostyrene, p-iodostyrene, p-aminostyrene and p-isobutylstyrene; and/or the number of the groups of groups,
the reaction temperature is 50-80 ℃ and the reaction time is 12-36 hours.
5. The sizing agent of claim 4, wherein:
the molecular weight of the polyethylene glycol maleimide monomer is 300-3000.
6. A sizing agent according to claim 3, characterized in that:
the molar ratio of the polyethylene glycol maleimide monomer to the styrene monomer is (0.5-2): 1, a step of; and/or the number of the groups of groups,
the mol ratio of the solvent to the total monomer is (1-50): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the initiator to the total monomer is (0.0001-0.01): 1.
7. the sizing agent of claim 6, wherein:
the mol ratio of the solvent to the total monomer is (5-20): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the initiator to the total monomer is (0.001-0.005): 1.
8. the sizing agent of claim 7, wherein:
the mol ratio of the solvent to the total monomer is (10-15): 1.
9. sizing agent according to claim 1, characterized in that:
the molecular weight of the polyethylene glycol is 200-4000.
10. Sizing agent according to claim 9, characterized in that:
the molecular weight of the polyethylene glycol is 400-2000.
11. Sizing agent according to claim 1, characterized in that:
the mole ratio of bisphenol A resin to polyethylene glycol is (2-50): 1, a step of; and/or the number of the groups of groups,
the mol ratio of the emulsifier I to the polyethylene glycol is (0.05-5): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the emulsifier II to the polyethylene glycol is (0.05-5): 1.
12. a sizing agent according to claim 11, wherein:
the mole ratio of bisphenol A resin to polyethylene glycol is (10-45): 1, a step of; and/or the number of the groups of groups,
the mol ratio of the emulsifier I to the polyethylene glycol is (0.1-2): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the emulsifier II to the polyethylene glycol is (0.1-2): 1.
13. a sizing agent according to claim 12, wherein:
the mole ratio of bisphenol A resin to polyethylene glycol is (20-45): 1.
14. sizing agent according to claim 1, characterized in that:
mixing polyethylene glycol with bisphenol A resin at 50-100 ℃, heating to melt, and adding an emulsifier I and an emulsifier II to obtain the emulsifier.
15. Sizing agent according to claim 1, characterized in that:
in the sizing agent, the content of polyethylene glycol maleimide-styrene copolymer and emulsifier is 10-50wt%; and/or the number of the groups of groups,
in the sizing agent, the molar ratio of polyethylene glycol in the aqueous emulsifier to the total monomer in the polyethylene glycol maleimide-styrene type copolymer is (0.001-0.1): 1.
16. a sizing agent according to claim 15, wherein:
the content of the polyethylene glycol maleimide-styrene copolymer and the emulsifier is 15-45 wt%; and/or the number of the groups of groups,
the molar ratio of polyethylene glycol to the total monomer in the polyethylene glycol maleimide-styrene type copolymer in the aqueous emulsifier is (0.001-0.05): 1.
17. a sizing agent according to claim 16, wherein:
the molar ratio of polyethylene glycol to the total monomer in the polyethylene glycol maleimide-styrene type copolymer in the aqueous emulsifier is (0.003-0.01): 1.
18. a process for preparing a polyethylene glycol maleimide-styrene-type copolymer sizing agent according to any one of claims 1 to 17, comprising the steps of:
mixing components including polyethylene glycol maleimide-styrene copolymer and emulsifier, and adding water to obtain the sizing agent.
19. The method for producing a sizing agent according to claim 18, wherein:
in the sizing agent, the content of polyethylene glycol maleimide-styrene copolymer and emulsifier is 10-50wt%; and/or the number of the groups of groups,
in the sizing agent, the molar ratio of polyethylene glycol in the aqueous emulsifier to the total monomer in the polyethylene glycol maleimide-styrene type copolymer is (0.001-0.1): 1, a step of; and/or the number of the groups of groups,
the mixing is carried out at 60-80 ℃.
20. The method of preparing a sizing agent of claim 19, wherein:
the content of the polyethylene glycol maleimide-styrene copolymer and the emulsifier is 15-45 wt%; and/or the number of the groups of groups,
the molar ratio of polyethylene glycol to the total monomer in the polyethylene glycol maleimide-styrene type copolymer in the aqueous emulsifier is (0.001-0.05): 1.
21. the method for producing a sizing agent according to claim 20, wherein:
the molar ratio of polyethylene glycol to the total monomer in the polyethylene glycol maleimide-styrene type copolymer in the aqueous emulsifier is (0.003-0.01): 1.
22. use of a polyethylene glycol maleimide-styrene-type copolymer sizing agent according to any of claims 1 to 17 in carbon fiber composites.
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