CN110820315B - Crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber and preparation method thereof - Google Patents
Crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber and preparation method thereof Download PDFInfo
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Abstract
A crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber and a preparation method thereof belong to the technical field of carbon fiber surface treatment. The invention utilizes a difluoride monomer containing an aniline side group and a bisphenol monomer to carry out polymerization, or modifies a crystalline polyaryletherketone to obtain a soluble amorphous polyaryletherketone polymer, and then thermally induced crosslinking groups are blocked at two ends of the polymer; simultaneously, carrying out surface electrochemical reduction on the carbon fiber, and grafting the same crosslinking group to the surface of the carbon fiber; then, the carbon fiber with the surface subjected to electrochemical reduction treatment is pulled to pass through a sizing agent solution for sizing, and acidification is carried out to recover the crystallinity of the polyaryletherketone sizing agent; and finally, after the carbon fiber is processed and formed to prepare the composite material, high-temperature heat treatment is carried out to initiate a crosslinking reaction, the crystallization degree of the polyaryletherketone polymer is perfected, so that the sizing agent has a crystallization structure and is connected with the surface of the carbon fiber through chemical bonds, the interface shear strength is improved, and the composite material is high-temperature resistant and corrosion resistant.
Description
Technical Field
The invention belongs to the technical field of carbon fiber surface treatment, and particularly relates to a crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber and a preparation method thereof.
Background
Composite materials are widely used in various fields due to their good mechanical properties and processability. In various composite materials, the application of special engineering plastic-based composite materials represented by polyaryletherketone/carbon fiber is more and more extensive, but the interface strength between a polyaryletherketone resin matrix and the surface of the carbon fiber is weaker, so that the performance of the carbon fiber reinforced polyaryletherketone composite material is influenced, and the wider application of the polyaryletherketone/carbon fiber composite material is limited.
The sizing agent coating is used as a common carbon fiber surface treatment method, and can form a uniform protective layer on the surface of the carbon fiber, so that the fiber filaments are bundled, the mechanical property of the carbon fiber is enhanced to a certain extent, and the interface property of the carbon fiber and the enhanced matrix is improved. However, most carbon fibers use epoxy resin or coupling agent as sizing agent, and the interfacial compatibility with polyaryletherketone resin matrix is poor, which results in low interfacial strength of polyaryletherketone/carbon fiber composite material and influences the comprehensive performance of the composite material. In addition, most sizing agents enhance the interface with the carbon fibers by mechanical friction, meshing or intermolecular forces, and do not form a robust chemical bond. Therefore, it is necessary to perform a surface treatment on the carbon fiber before using the sizing agent to activate the inert carbon fiber surface so that the sizing agent forms a chemical bonding effect with the carbon fiber. The currently adopted treatments such as acid liquor, plasma, surface oxidation and the like can damage the carbon fibers, damage the surface morphology of the fibers and influence the mechanical properties such as tensile strength and the like of the fibers.
Patent No. CN109505135A discloses a polyetherketoneketone sizing agent, which is prepared by dissolving polyetherketoneketone resin with sulfuric acid solution and doping graphite oxide. However, the high-concentration sulfuric acid solution can sulfonate the polyether ketone resin, the regular molecular structure of the polyether ketone molecular chain is damaged, and the interaction between the sizing agent and the resin matrix is influenced. Meanwhile, the sulfonated polyether ketone loses crystallization capacity and is dissolved in an organic solvent, so that the solvent resistance, the heat resistance and the like of the composite material are influenced. In addition, the graphene oxide is utilized to enhance the mechanical friction effect between the sizing agent and the resin matrix, effective chemical bond connection is not formed, and the further improvement of the interface performance is influenced.
Patent No. CN109930388A discloses a polyether ether ketone based sizing agent. The soluble sizing agent is prepared by grafting the acidified polyether-ether-ketone polymer and the functionalized modified carbon nano material. In the patent, the molecular chain regularity of the polyether-ether-ketone is destroyed after sulfonation, and the polyether-ether-ketone has no crystallization property, so that the strength of an interface layer is reduced, the polyether-ether-ketone does not tolerate an organic solvent, and the interface bonding between a sizing agent and a resin matrix is not facilitated. In addition, the use of large amounts of strong acid at high concentration during the treatment process requires strict experimental conditions, which is not conducive to large-scale production. Finally, the sizing agent increases the mechanical friction between interfaces through the addition of nanomaterials without creating effective chemical bonds.
Patent No. CN108004779A discloses a polyaryletherketone powder suspension sizing agent. The polyaryletherketone powder is suspended in water containing a stabilizer to size the fibers. In the method, although the dispersing agent is added into water to improve the dispersibility of the polyaryletherketone powder, the polyaryletherketone powder cannot uniformly and effectively coat the surface of the carbon fiber compared with a sizing agent solution. Meanwhile, the alkylphenol polyvinyl ether serving as a dispersant in water cannot be removed after sizing, remains in an interface phase in the processing process, and has a decomposition temperature lower than that of polyaryletherketone. Thus, the interface properties are affected by-products generated by decomposition during processing. In addition, this method also does not form an effective chemical bond between the sizing agent and the carbon fiber.
Patent No. CN102926204A discloses an epoxy-based sizing agent with a polyarylether structure. It is desirable to improve the interaction of sizing agents with polyetheretherketone by a similar chemical structure. But epoxy groups are remained due to no epoxy resin curing agent in the formula, the thermal decomposition temperature of the epoxy groups is lower than the processing temperature (400 ℃) of the polyether-ether-ketone material, and by-products generated by thermal decomposition can cause interface defects and influence the interface performance; meanwhile, uncured epoxy resin is dissolved in an organic solvent, so that the interface is failed; the hydroquinone used in this patent is easily oxidized in air, is lower than the processing temperature of the polyetheretherketone composite, and also affects the mechanical properties of the polyetheretherketone composite product. In addition, this method also does not form an effective chemical bond between the sizing agent and the carbon fiber.
Disclosure of Invention
Aiming at the problems, in order to enable the sizing agent to uniformly and uniformly infiltrate the surface of the carbon fiber, generate good interface bonding with a polyarylether resin matrix, generate good chemical bond connection with the carbon fiber through a crosslinking reaction group, and simultaneously maintain the crystallization capability of the sizing agent, and have good interface strength, high temperature resistance and solvent resistance, the invention provides the carbon fiber modified by the crystalline crosslinkable polyaryletherketone sizing agent and the preparation method thereof.
The invention is realized by the following method: polymerizing a difluoride monomer containing a side group and a bisphenol monomer, or modifying crystalline polyaryletherketone to obtain a soluble amorphous polyaryletherketone polymer, and then terminating thermally-induced crosslinking groups at two ends of the polymer; simultaneously, carrying out surface electrochemical reduction on the carbon fiber, and grafting the same crosslinking group to the surface of the carbon fiber; then, the carbon fiber with the surface subjected to electrochemical reduction treatment is pulled to pass through a sizing agent solution for sizing, and acidification is carried out to recover the crystallinity of the polyaryletherketone sizing agent; finally, the fiber is thermally treated in the process of processing the carbon fiber into the composite material to initiate a crosslinking reaction, and the crystallization degree of the polyaryletherketone polymer is perfected, so that the sizing agent has a crystallization structure and is connected with the surface of the carbon fiber by chemical bonds. Researches show that the interface shear strength (IFSS) of the carbon fiber and the polyether-ether-ketone resin matrix after treatment can reach 120MPa, is improved by 200 percent compared with the interface shear strength of the untreated carbon fiber and the polyether-ether-ketone resin matrix, and has the specific steps of:
(1) dissolving a difluoride monomer (structure is shown as I) containing an aniline side group and a bisphenol monomer (structure is shown as II) in sulfolane for polymerization, or substituting carbonyl in a crystalline polyaryletherketone (structure is shown as III) into 1, 4-dioxolane to obtain soluble polyaryletherketone; then adding a crosslinking group end-capping agent (one of IV in the structure) into soluble polyaryletherketone cooled to 120-180 ℃ for end-capping to obtain crosslinking group end-capped soluble crosslinkable polyaryletherketone, and dissolving the crosslinking group end-capped soluble crosslinkable polyaryletherketone in acetone to prepare a solution with the mass fraction of 1-10 wt% to obtain a crosslinking group end-capped soluble crosslinkable polyaryletherketone sizing agent;
(2) dissolving 0.1-10 mmol of diazonium salt (structure is shown as V) containing a crosslinking group and 15-30 mmol of tetrabutyl tetrafluoroborate in 1L of acetonitrile to prepare electrolyte; then, drawing the carbon fibers (with a drawing speed of 15-50 mm/min) into the electrolyte, and simultaneously introducing a current of 0.01-0.5A to the carbon fibers at room temperature to carry out electrochemical reduction grafting on the surfaces of the carbon fibers so as to graft a crosslinking group onto the surfaces of the carbon fibers; finally, the carbon fiber is pulled into acetonitrile to wash away the attached unreacted diazonium salt, and the carbon fiber grafted by the crosslinking group is obtained after drying; the diazonium salt has the same crosslinking group as the capping agent used in step (1);
(3) sizing the carbon fiber grafted by the crosslinking group obtained in the step (2) by using the crosslinking group-terminated soluble crosslinkable polyaryletherketone sizing agent obtained in the step (1), wherein the traction rate of the carbon fiber is 1-100 mm/min;
(4) evaporating the solvent of the carbon fiber subjected to sizing treatment obtained in the step (3); for example, when tetrahydrofuran is used as the solvent, an infrared heater can be used, and the evaporation temperature is 100-150 ℃;
(5) introducing the sizing carbon fiber of which the solvent is evaporated to dryness obtained in the step (4) into a hydrolysis tank, and carrying out acidification hydrolysis treatment to convert soluble crosslinkable polyaryletherketone into insoluble crystalline crosslinkable polyaryletherketone; for example, after non-sized carbon fibers are treated by using a sizing agent with the mass fraction of ketimine polyether-ether-ketone being 1 wt% and a solvent is evaporated to dryness, the carbon fibers are introduced into a hydrolysis tank with a benzenesulfonic acid solution of 5-30 wt% to carry out a chemical reaction of a formula (VI), so that the crystallinity of the soluble crosslinkable polyaryletherketone is recovered;
(6) pulling the sized carbon fiber subjected to the acidification and hydrolysis treatment in the step (5) to be washed by deionized water, and then drying the carbon fiber by an infrared heater to obtain a crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber;
the soluble polyaryletherketone obtained in the step (1) is ketimine polyetheretherketone, ketimine polyetherketone, ketimine biphenyl polyetheretherketone, ketimine polydiphenyl polyetheretherketone, polyetheretherketone-1, 3-dioxolane, polyetherketone-1, 3-dioxolane, biphenyl polyetheretherketone-1, 3-dioxolane or biphenyl polyetheretherketone-1, 3-dioxolane, and the structural formula is shown in (VII).
The crosslinking group in the step (2) is maleimide group, benzocyclobutene group, ethynyl group, styryl group, biphenyl alkenyl group, phenyl maleimide group and phenylethynyl group, the groups have different thermal crosslinking treatment temperatures, and the structural formula and the treatment temperature are shown in table 1.
Table 1: structural formula and name of crosslinking group and thermal crosslinking treatment temperature
The polymer and the crosslinking group can efficiently form soluble crosslinkable polyaryletherketone compounds by using a one-pot method, so that carbon fibers can be uniformly and sufficiently sized, and the crystallinity of the polymer can be recovered by hydrolysis after sizing. The crosslinking group can be reduced to the surface of the carbon fiber through corresponding diazonium salt through electrochemistry, and the crosslinking group in the sizing agent are subjected to crosslinking reaction at different heat treatment temperatures, so that the interface interaction and the strength of the interface layer are enhanced, and the interface shear strength is improved to 120 MPa. The crystalline cross-linkable polymer is used as a sizing agent, and electrochemical reduction grafting of cross-linking groups is carried out on the surface of the carbon fiber, so that continuous production is realized, the operation condition is mild, effective interface chemical bond connection is formed, the use conditions of high temperature and corrosion resistance are met, and the interface bonding strength of the composite material is improved.
The number average molecular weight of the crosslinking group end-capped soluble crosslinkable polyaryletherketone prepared in the step (1) is 4000-20000 g/mol. The molecular weight and the mass fraction of the soluble crosslinkable polyaryletherketone terminated by the crosslinking group influence the interfacial property between the carbon fiber and the resin matrix after sizing. The number average molecular weight of 4000-20000 g/mol is an optimal value screened by experiments, when the polymer with the number average molecular weight of less than 4000g/mol is used as an effective component of the sizing agent, a sizing agent layer cannot be well formed due to the fact that the molecular chain of the polymer is short, and when the polymer with the number average molecular weight of more than 20000g/mol is used as the effective component of the sizing agent, the content of a cross-linking group is too low, an effective cross-linking structure cannot be formed, and the formation of chemical bond combination is influenced.
The cross-linking group end-capping reagent in the step (1) is maleimide fluorone, benzocyclobutene fluorone, ethynyl fluorone, styryl fluorone, biphenyl alkenyl fluorone, phenyl maleimide fluorone, or phenylethynyl fluorone; the end capping agent with the structure has good reaction activity with the soluble polyaryletherketone in the step (1), has high grafting success rate, can be directly cooled for reaction after polymerization or modification is finished, and does not need to change a reaction system.
The diazonium salt in the electrochemical reduction in the step (2) is maleimide diazonium salt, benzocyclobutene diazonium salt, ethynyl diazonium salt, styryl diazonium salt, biphenyl diazonium salt, phenyl maleimide diazonium salt and phenylethynyl diazonium salt; and (3) dissolving the diazonium salt in the electrolyte, and carrying out small-current and rapid electrochemical grafting reaction on the surface of the carbon fiber. The grafting method has the advantages of short time, little pollution, continuous operation and little damage to carbon fibers.
The sizing rate in the step (3) is a test result comprehensively considering fiber tension, frictional damage, fiber spreading effect, sizing time and sizing efficiency during sizing. The sizing rate is lower than 1mm/min, the sizing efficiency is too low, and the fiber spreading effect is poor; the fiber friction damage is serious when the sizing rate is higher than 100 mm/min. The specific sizing rate needs to be combined with the effective stroke of the fibers in the sizing tank, and the effective sizing time is ensured to be 5-20 min.
The acidifying hydrolysis reagent in the step (5) is a sulfuric acid solution with the mass concentration of 5-30% or a benzenesulfonic acid aqueous solution with the mass concentration of 5-30%. The acidification treatment time is 1-5 h. The soluble polyaryletherketone polymer in the step (1) can be hydrolyzed into a crystalline polyaryletherketone polymer in water, and the hydrolysis rate is accelerated under an acidic condition to ensure complete hydrolysis.
The deionized water is drawn in the step (6) to further complete the hydrolysis reaction, recover the carbonyl structure in the resin matrix, and simultaneously wash off the micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, thereby facilitating the next processing.
The carbon fiber modified by the crystalline crosslinkable polyaryletherketone sizing agent can be used for preparing high-performance resin matrix composite materials. After the carbon fiber is processed and molded to prepare the composite material, the preliminarily molded composite material is subjected to proper high-temperature heat treatment according to the crosslinking temperatures of different crosslinking groups, so that the crosslinking groups on the surface of the carbon fiber and the crosslinking groups in the sizing agent are subjected to crosslinking reaction to generate chemical bond connection. Meanwhile, the crystal structures of the sizing agent layer and the resin matrix are improved after high-temperature heat treatment, the sizing agent and the resin matrix interface are combined more tightly after melting, and the interface bonding strength is improved. For example, a phenylacetylene-terminated ketimine polyether ether ketone sizing agent with the mass fraction of 1 wt% is used for sizing carbon fibers with phenylacetylene crosslinking groups modified on the surfaces, the carbon fibers are dried and washed, then introduced into a hydrolysis tank with 5-30 wt% of benzenesulfonic acid solution for hydrolysis, and then dried to obtain the phenylacetylene-terminated crystalline polyether ether ketone surface-modified carbon fibers. The carbon fiber is processed to obtain the polyetheretherketone carbon fiber composite material, then the composite material is subjected to heat treatment, and phenylacetylene crosslinking groups on the surface of the carbon fiber and phenylacetylene groups in the sizing agent are subjected to crosslinking reaction to form an interface with chemical bond connection.
The high-temperature heat treatment refers to the heat treatment of the preliminarily molded composite material after the carbon fiber is processed and molded to prepare the composite material, wherein the heat treatment has two purposes, namely, the carbon fiber reacts with a crosslinking group in a sizing agent to form a crosslinking network, and the crystal structure of the polyaryletherketone resin sizing agent is more complete through the heat treatment. This enhances the interface adhesion and also enhances the strength of the interface itself.
Features and advantages
(1) The invention relates to a method for sizing carbon fibers by using a crystalline crosslinkable polyaryletherketone polymer and carrying out electrochemical reduction treatment on the surfaces of the carbon fibers. Has the characteristics of uniform sizing, capability of simultaneously keeping crystallization crosslinking performance of sizing agent, improvement of interface interaction and capability of generating strong interaction with polyaryletherketone special engineering plastics.
(2) The invention establishes chemical crosslinking connection between the sizing agent and the carbon fibers by a simple and rapid method, generates stronger interface bonding between the sizing agent and the resin matrix, greatly improves the interface shearing property of the special engineering plastic resin matrix of polyaryletherketone such as polyetheretherketone and the like and the carbon fiber composite material, can be improved to 120MPa in the experimental range to the maximum extent, and improves the interface bonding strength between the resin matrix and the carbon fibers;
(3) the crosslinking group selected in the invention is a thermally induced crosslinking group, and can generate crosslinking reaction under the high-temperature condition without adding a coupling agent or a curing agent. Therefore, the homogeneous phase and stability of the sizing agent layer can be kept, and meanwhile, micromolecular impurities generated by decomposition of the coupling agent and the curing agent in the subsequent high-temperature processing process are avoided, and the interaction of the interface layer is weakened.
(4) The raw materials are easy to obtain (the ketimine polymer can be obtained by polymerizing ketimine monomers, the energy consumption in the polymerization process is lower than that of commercial polyether sulfone; and the 1, 3-dioxolane polymer can be obtained by post-treating commercial polyaryletherketone), and the method can be used for continuous production, and has room-temperature sizing and mild post-treatment means.
(5) Compared with other carbon fiber surface treatment methods, the electrochemical reduction grafting process has the advantages of short time, small pollution, continuous operation and small damage to the carbon fibers. Grafting different types of crosslinking groups can allow it to adapt to different crosslinking temperatures.
(6) The polyaryl ether ketone sizing agent has a wide molecular weight range, and can meet different composite materials and application requirements.
Drawings
FIG. 1: (a) scanning electron micrographs of untreated carbon fibers described in example 1;
FIG. 1: (b) scanning electron micrographs of the electrochemically treated carbon fibers described in example 1;
FIG. 1: (c) scanning electron micrographs of the sized carbon fibers described in example 1;
FIG. 2: the interfacial shear strength test curve of the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber prepared in the example;
Detailed Description
The method of the present invention is further described by the following specific examples, which are merely specific descriptions of the claims of the present invention, including but not limited to the contents of the examples. The ranges of the polymeric monomer, the crosslinking group capping agent, the crosslinking group diazonium salt, the heat treatment temperature, the mass fraction, the sizing rate, the number average molecular weight, the acid solution concentration and the like are limited to only select representative examples.
Example 1:
adding 20mmol of ketimine fluorone and 20mmol of hydroquinone into sulfolane, polymerizing for 10h at reflux temperature, reducing the temperature of the polymer solution to 120 ℃ after the polymerization is finished, and directly adding 1mmol of phenylethynyl fluorone for end capping. Discharging the reaction product into methanol after the reaction is finished, and washing the reaction product for three times to obtain phenylacetylene-terminated soluble crosslinkable ketimine polyether-ether-ketone (the number average molecular weight is 20000 g/mol);
adding 10g of p-phenylaminophenylacetylene into 100mL of aqueous solution containing 15g of sodium nitrite and 0.1mol of hydrochloric acid at zero degree, and recrystallizing to obtain phenylacetylene diazonium salt. The carbon fiber is pulled into acetonitrile solution added with phenylacetylene diazonium salt with the concentration of 1mmol/L, and 0.5A current is introduced by an electric brush for grafting reaction, so that a crosslinking group is grafted on the surface of the carbon fiber to provide an active reaction group; the carbon fiber drawing rate was 50 mm/min. Then the carbon fiber is pulled into acetonitrile to be washed and dried by an infrared heater.
Dissolving 2.5g of soluble phenylacetylene-terminated ketimine polyether-ether-ketone in 997.5mL of THF (tetrahydrofuran), and obtaining a phenylacetylene-terminated ketimine polyether-ether-ketone sizing agent with the mass fraction of 1% after complete dissolution; placing the sizing agent in a sizing tank with an effective stroke of 1m, and drawing the carbon fiber with the surface grafted with the crosslinking group into the sizing tank at the speed of 50mm/min to perform sizing treatment on the carbon fiber.
The sized carbon fibers are drawn through an infrared heater and the solvent is dried at 100 ℃.
And (3) introducing the fiber bundle from which the solvent is removed into a hydrolysis tank of dilute sulfuric acid with the mass fraction of 30%, and carrying out acidification treatment for 1h, thus obtaining the crystal type cross-linkable polyetheretherketone sized carbon fiber bundle after hydrolysis.
And (3) drawing the acidified and hydrolyzed sized carbon fiber through a deionized water tank, washing off micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, and then drying to obtain the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber.
The carbon fibers are pulled by acetone solution suspended by polyether-ether-ketone powder at the speed of 50mm/min, then the fibers are arranged in order, the carbon fiber unidirectional tape is obtained by hot pressing at the temperature of 5MPa and 340 ℃ for 30min, the multi-layer unidirectional tape is subjected to mould pressing at the temperature of 350 ℃ and the pressure of 10MPa to obtain a polyether-ether-ketone carbon fiber composite material plate, then the pressure is kept to be continuously increased to 370 ℃ for heat treatment for 30min, and the crystalline cross-linkable polyether-ether-ketone sized carbon fiber composite material is obtained.
The surface topography of the carbon fiber before and after electrochemical reduction is shown in fig. 1a and 1b, and the surface topography of the carbon fiber after sizing is shown in fig. 1 c. FIG. 1b illustrates that the chemical groups have been successfully grafted to the carbon fiber surface, and FIG. 1c illustrates that the sizing agent has completely coated the carbon fiber.
After the treatment by the method, the interface shear strength of the carbon fiber and the pure polyether-ether-ketone resin matrix in the composite material is 120MPa, and is increased by 200 percent compared with the interface shear strength (40MPa) of the carbon fiber and the pure polyether-ether-ketone without sizing (the test curve of the interface shear strength is shown in figure 2).
Example 2:
adding 20mmol of ketimine fluorone and 20mmol of hydroquinone into sulfolane, polymerizing for 5h at reflux temperature, reducing the temperature of the polymer solution to 120 ℃ after the polymerization is finished, and directly adding 1mmol of biphenyl alkenyl fluorone for end capping. After the reaction is finished, discharging the mixture into methanol, and washing the mixture for three times to obtain phenyl maleimide terminated soluble cross-linkable ketimine polyether ether ketone (the number average molecular weight is 4000 g/mol);
adding 10g of phenyl maleimide into 100mL of aqueous solution containing 15g of sodium nitrite and 0.1mol of hydrochloric acid at zero degree, and recrystallizing to obtain the phenyl maleimide diazonium salt. Drawing the carbon fiber into acetonitrile solution added with 1mmol/L phenyl maleimide diazonium salt, and introducing 0.5A current by using an electric brush to carry out grafting reaction so as to graft a crosslinking group onto the surface of the carbon fiber and provide an active reaction group; the carbon fiber drawing rate was 50 mm/min. Then the carbon fiber is pulled into acetonitrile to be washed and dried by an infrared heater.
Dissolving 25g of soluble phenylmaleimide terminated ketimine polyether-ether-ketone in 997.5mL of THF (tetrahydrofuran), and obtaining a 10% phenylmaleimide terminated ketimine polyether-ether-ketone sizing agent after complete dissolution; placing the sizing agent in a sizing tank with an effective stroke of 1m, and drawing the carbon fiber with the surface grafted with the crosslinking group into the sizing tank at the speed of 100mm/min to perform sizing treatment on the carbon fiber;
the sized carbon fibers are drawn through an infrared heater and the solvent is dried at 100 ℃.
And (3) introducing the fiber bundle from which the solvent is removed into a hydrolysis tank of benzenesulfonic acid with the mass fraction of 5%, and performing acidification treatment for 5h to obtain the crystal type cross-linkable polyether-ether-ketone sized carbon fiber bundle after hydrolysis.
And (3) drawing the acidified and hydrolyzed sized carbon fiber through a deionized water tank, washing off micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, and then drying to obtain the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber.
The carbon fibers are pulled by acetone solution suspended by polyether-ether-ketone powder at the speed of 50mm/min, then the fibers are arranged in order, the carbon fiber unidirectional tape is obtained by hot pressing at 5MPa and 350 ℃ for 30min, the multi-layer unidirectional tape is subjected to mould pressing at 360 ℃ and 10MPa to obtain a polyether-ether-ketone carbon fiber composite material plate, then the pressure is kept, the temperature is continuously increased to 380 ℃, and the heat treatment is carried out for 30min, so that the crystallized polyether-ether-ketone sizing carbon fiber composite material is obtained.
After the treatment by the method, the interface shear strength of the carbon fiber in the composite material and the pure polyether-ether-ketone resin matrix is 108MPa, and is increased by 170 percent compared with the interface shear strength (40MPa) of the carbon fiber without sizing and the pure polyether-ether-ketone (the test curve of the interface shear strength is shown in figure 2).
Example 3:
and (3) adding 20mmol of ketimine fluoroketone and 20mmol of biphenol into sulfolane, polymerizing for 24 hours at the reflux temperature, reducing the temperature of the polymer solution to 120 ℃ after the polymerization is finished, and directly adding 1mmol of phenylethynyl fluoroketone for end capping. Discharging the reaction product into methanol after the reaction is finished, and washing the reaction product for three times to obtain phenylacetylene-terminated soluble crosslinkable ketimine polyether-ether-ketone (the number average molecular weight is 20000 g/mol);
adding 10g of phenylethynylaniline into 100mL of aqueous solution containing 15g of sodium nitrite and 1mol of hydrochloric acid at zero degree, and recrystallizing to obtain phenylethynyl diazonium salt. The carbon fiber is pulled into acetonitrile solution added with phenylethynyl diazonium salt with the concentration of 1mmol/L, and 0.5A current is introduced by using an electric brush to carry out grafting reaction, so that a crosslinking group is grafted to the surface of the carbon fiber, and an active reaction group is provided; the carbon fiber drawing rate was 50 mm/min. Then the carbon fiber is pulled into acetonitrile to be washed and dried by an infrared heater.
Dissolving 2.5g of soluble phenylacetylene-terminated ketimine biphenyl type polyether-ether-ketone in 997.5mL of THF, and obtaining a phenylacetylene-terminated ketimine biphenyl type polyether-ether-ketone sizing agent with the mass fraction of 1% after complete dissolution; placing the sizing agent in a sizing tank with an effective stroke of 1m, and drawing the carbon fiber with the surface grafted with the crosslinking group into the sizing tank at the speed of 50mm/min to perform sizing treatment on the carbon fiber;
the sized carbon fibers are drawn through an infrared heater and the solvent is dried at 100 ℃.
And (3) introducing the fiber bundle with the solvent removed into a hydrolysis tank of dilute sulfuric acid with the mass fraction of 5%, and carrying out acidification treatment for 2h to obtain the crystal type cross-linkable biphenyl type polyetheretherketone sized carbon fiber bundle after hydrolysis.
And (3) drawing the acidified and hydrolyzed sized carbon fiber through a deionized water tank, washing off micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, and then drying to obtain the crystalline crosslinkable biphenyl polyaryletherketone sizing agent modified carbon fiber.
The carbon fibers are pulled by acetone solution suspended by polyether-ether-ketone powder at the speed of 50mm/min, then the fibers are arranged in order, hot pressing is carried out for 30min at the temperature of 360 ℃ under the pressure of 5MPa to obtain carbon fiber unidirectional tapes, the multi-layer unidirectional tapes are subjected to mould pressing processing at the temperature of 380 ℃ under the pressure of 10MPa to obtain polyether-ether-ketone carbon fiber composite material plates, then the pressure is kept to be continuously increased to 390 ℃ for heat treatment for 30min, and the crystalline cross-linkable biphenyl type polyether-ether-ketone sized carbon fiber composite material is obtained.
After the treatment by the method, the interface shear strength of the carbon fiber in the composite material and the pure polyether-ether-ketone resin matrix is 102MPa, and is increased by 155 percent compared with the interface shear strength (40MPa) of the carbon fiber without sizing and the pure polyether-ether-ketone (the test curve of the interface shear strength is shown in figure 2).
Example 4:
dissolving polyether-ether-ketone-1, 3-dioxolane (with the number average molecular weight of 15000g/mol) in 500mL of sulfolane, adding 1mmol of phenylacetylene fluorone end capping agent after complete dissolution, and heating the system to 120 ℃ for reaction and end capping. And after the reaction is finished, discharging the material into methanol, and washing the material for three times to obtain the phenylacetylene-terminated soluble crosslinkable ketimine polyether-ether-ketone.
Adding 10g of p-phenylaminophenylacetylene into 100mL of aqueous solution containing 15g of sodium nitrite and 1mol of hydrochloric acid at zero degree, and recrystallizing to obtain phenylacetylene diazonium salt. The carbon fiber is pulled into acetonitrile solution added with phenylacetylene diazonium salt with the concentration of 1mmol/L, and 0.5A current is introduced by an electric brush for grafting reaction, so that a crosslinking group is grafted on the surface of the carbon fiber to provide an active reaction group; the carbon fiber drawing rate was 50 mm/min. Then the carbon fiber is pulled into acetonitrile to be washed and dried by an infrared heater.
2.5g of soluble phenylacetylene-terminated polyether-ether-ketone-1, 3-dioxolane is dissolved in 997.5mL of THF, and the phenylacetylene-terminated polyether-ether-ketone-1, 3-dioxolane sizing agent with the mass fraction of 1% is obtained after complete dissolution; placing the sizing agent in a sizing tank with an effective stroke of 1m, and drawing the carbon fiber with the surface grafted with the crosslinking group into the sizing tank at the speed of 50mm/min to perform sizing treatment on the carbon fiber.
The sized carbon fibers are drawn through an infrared heater and the solvent is dried at 100 ℃.
And (3) introducing the fiber bundle from which the solvent is removed into a hydrolysis tank of 10 mass percent benzenesulfonic acid for acidification treatment for 1h, and hydrolyzing to obtain the crystal type cross-linkable polyether-ether-ketone sized carbon fiber bundle.
And (3) drawing the acidified and hydrolyzed sized carbon fiber through a deionized water tank, washing off micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, and then drying to obtain the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber.
The carbon fibers are pulled by acetone solution suspended by polyether-ether-ketone powder at the speed of 50mm/min, then the fibers are arranged in order, the carbon fiber unidirectional tape is obtained by hot pressing at the temperature of 5MPa and 340 ℃ for 30min, the multi-layer unidirectional tape is subjected to mould pressing at the temperature of 350 ℃ and the pressure of 10MPa to obtain a polyether-ether-ketone carbon fiber composite material plate, then the pressure is kept to be continuously increased to 360 ℃ for heat treatment for 30min, and the crystalline cross-linkable polyether-ether-ketone sized carbon fiber composite material is obtained.
After the treatment by the method, the interface shear strength of the carbon fiber in the composite material and the pure polyether-ether-ketone resin matrix is 96MPa, and is increased by 140 percent compared with the interface shear strength (40MPa) of the carbon fiber without sizing and the pure polyether-ether-ketone (the test curve of the interface shear strength is shown in figure 2).
Example 5:
dissolving biphenyl polyether ether ketone-1, 3-dioxolane (with the number average molecular weight of 15000g/mol) in 500mL of sulfolane, adding 1mmol of phenylacetylene end capping agent after complete dissolution, and heating the system to 120 ℃ for reaction for end capping. And after the reaction is finished, discharging the material into methanol, and washing the material for three times to obtain the phenylacetylene-terminated soluble crosslinkable ketimine polyether-ether-ketone.
Adding 10g of p-phenylaminophenylacetylene into 100mL of aqueous solution containing 15g of sodium nitrate and 1mol of hydrochloric acid at zero degree, and recrystallizing to obtain phenylacetylene diazonium salt. The carbon fiber is pulled into acetonitrile solution added with phenylacetylene diazonium salt with the concentration of 1mmol/L, and 0.01A current is introduced by an electric brush for grafting reaction, so that a crosslinking group is grafted on the surface of the carbon fiber to provide an active reaction group; the carbon fiber drawing rate was 50 mm/min. Then the carbon fiber is pulled into acetonitrile to be washed and dried by an infrared heater.
Dissolving 2.5g of soluble phenylacetylene-terminated biphenyl polyether-ether-ketone-1, 3-dioxolane in 997.5mL of THF, and obtaining a phenylacetylene-terminated biphenyl polyether-ether-ketone-1, 3-dioxolane sizing agent with the mass fraction of 1 percent after complete dissolution; placing the sizing agent in a sizing tank with an effective stroke of 1m, and drawing the carbon fiber with the surface grafted with the crosslinking group into the sizing tank at the speed of 50mm/min to perform sizing treatment on the carbon fiber.
The sized carbon fibers are drawn through an infrared heater and the solvent is dried at 150 ℃.
And introducing the fiber bundle with the solvent removed into a hydrolysis tank with 30% of benzenesulfonic acid by mass percent for acidification treatment for 45min, and hydrolyzing to obtain the crystal type cross-linkable biphenyl type polyetheretherketone sized carbon fiber bundle.
And (3) drawing the acidified and hydrolyzed sized carbon fiber through a deionized water tank, washing off micromolecules and acid liquor remained on the surface of the carbon fiber after acidification, and then drying to obtain the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber.
The carbon fibers are pulled by acetone solution suspended by polyether-ether-ketone powder at the speed of 50mm/min, then the fibers are arranged in order, hot pressing is carried out for 30min at the temperature of 360 ℃ under the pressure of 5MPa to obtain carbon fiber unidirectional tapes, the multi-layer unidirectional tapes are subjected to mould pressing processing at the temperature of 380 ℃ under the pressure of 10MPa to obtain a polyether-ether-ketone carbon fiber composite material plate, then the pressure is kept to be continuously increased to 400 ℃ for heat treatment for 30min, and the crystalline cross-linkable biphenyl type polyether-ether-ketone sized carbon fiber composite material is obtained.
After the treatment by the method, the interface shear strength of the carbon fiber in the composite material and the pure polyether-ether-ketone resin matrix is 97MPa, which is increased by 145 percent compared with the interface shear strength (40MPa) of the carbon fiber without sizing and the pure polyether-ether-ketone.
Claims (5)
1. A preparation method of a carbon fiber modified by a crystalline crosslinkable polyaryletherketone sizing agent comprises the following steps:
(1) dissolving a difluoride monomer containing an aniline side group and a bisphenol monomer shown in a structural formula (II) in sulfolane for polymerization, or substituting carbonyl in crystalline polyaryletherketone shown in a structural formula (III) into 1, 4-dioxolane to obtain a soluble polyaryletherketone polymer; then adding a crosslinking group end-capping agent with a structural formula shown in one of (IV) into the cooled soluble polyaryletherketone for end-capping to obtain crosslinking group end-capped soluble crosslinkable polyaryletherketone, and dissolving the crosslinking group end-capped soluble crosslinkable polyaryletherketone in acetone to prepare a solution with the mass fraction of 1-10 wt% to obtain a crosslinking group end-capped soluble crosslinkable polyaryletherketone sizing agent;
(2) dissolving 0.1-10 mmol of diazonium salt containing a crosslinking group and shown in one of the structures (V) and 15-30 mmol of tetrabutyl tetrafluoroborate in 1L of acetonitrile to prepare an electrolyte; then, drawing the carbon fiber with the drawing speed of 15-50 mm/min into the electrolyte, and simultaneously introducing 0.01-0.5A of current into the carbon fiber at room temperature to carry out electrochemical reduction grafting on the surface of the carbon fiber so as to graft a crosslinking group onto the surface of the carbon fiber; finally, the carbon fiber is pulled into acetonitrile to wash away the attached unreacted diazonium salt, and the carbon fiber grafted by the crosslinking group is obtained after drying; the diazonium salt has the same crosslinking group as the capping agent used in step (1);
(3) sizing the carbon fiber grafted by the crosslinking group obtained in the step (2) by using the crosslinking group-terminated soluble crosslinkable polyaryletherketone sizing agent obtained in the step (1), wherein the traction rate of the carbon fiber is 1-100 mm/min;
(4) evaporating the solvent of the carbon fiber subjected to sizing treatment obtained in the step (3);
(5) introducing the sizing carbon fiber of which the solvent is evaporated to dryness obtained in the step (4) into a hydrolysis tank, and carrying out acidification hydrolysis treatment to convert soluble crosslinkable polyaryletherketone into insoluble crystalline crosslinkable polyaryletherketone;
(6) and (4) pulling the sized carbon fiber subjected to the acidification and hydrolysis treatment in the step (5) to be washed by deionized water, and then drying the carbon fiber by an infrared heater to obtain the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber.
2. The method for preparing a crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber according to claim 1, wherein the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber comprises the following steps: the obtained soluble polyaryletherketone is ketimine polyetheretherketone, ketimine polyetherketone, ketimine biphenyl polyetheretherketone, ketimine polydiphenyl polyetheretherketone, polyetheretherketone-1, 3-dioxolane, polyetherketone-1, 3-dioxolane, biphenyl polyetheretherketone-1, 3-dioxolane or biphenyl polyetheretherketone-1, 3-dioxolane, the structural formula of which is shown in the specification,
3. the method for preparing a crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber according to claim 1, wherein the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber comprises the following steps: the number average molecular weight of the crosslinking group end-capped soluble crosslinkable polyaryletherketone prepared in the step (1) is 4000-20000 g/mol.
4. The method for preparing a crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber according to claim 1, wherein the crystalline crosslinkable polyaryletherketone sizing agent modified carbon fiber comprises the following steps: the reagent for acidification and hydrolysis treatment in the step (5) is a sulfuric acid solution with the mass concentration of 5-30% or a benzenesulfonic acid aqueous solution with the mass concentration of 5-30%, and the acidification treatment time is 1-5 h.
5. A carbon fiber modified by a crystalline crosslinkable polyaryletherketone sizing agent is characterized in that: is prepared by the method of any one of claims 1 to 4.
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