CN114478887A - High-performance polydicyclopentadiene and preparation method thereof - Google Patents
High-performance polydicyclopentadiene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-performance polydicyclopentadiene and a preparation method thereof, and relates to the technical field of high polymer materials. The method comprises the steps of firstly, preparing modified carbon fibers by using carbon fibers and 4- (4-aminophenyl) benzonitrile-triethanol siloxane through a supercritical auxiliary ultrasonic swelling process; preparing the post-treated modified carbon fiber by using a microwave coupling freeze drying process, and forming silicon dioxide gel with an interpenetrating network structure in the modified carbon fiber to enhance the flexural modulus of the post-treated modified carbon fiber; and then mixing the copper chloride solution, the formaldehyde solution and the dicyclopentadiene to form a dicyclopentadiene mixed solution, and performing a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using the dicyclopentadiene mixed solution to generate an imidazolium salt compound and a triazine ring structure compound to prepare the high-performance polydicyclopentadiene. The high-performance polydicyclopentadiene prepared by the method has high bending modulus and strong antistatic property and thermal stability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high-performance polydicyclopentadiene and a preparation method thereof.
Background
Polydicyclopentadiene is a thermosetting engineering plastic prepared by ring-opening metathesis polymerization of dicyclopentadiene, has high strength and toughness, and is mainly applied to the fields of automobile industry, office entertainment, electrical equipment, buildings and the like. Although polydicyclopentadiene is a material with excellent physical and mechanical properties, the impact strength is still excellent, but the problem of low flexural modulus is that the flexural modulus is only about 2GPa, while the traditional glass fiber reinforced plastics can reach about 9GPa, so that the market share of a large amount of polydicyclopentadiene is replaced by the traditional glass fiber reinforced plastics.
To solve this problem, glass fibers and carbon fibers having excellent properties of high specific strength and modulus, corrosion resistance, high temperature resistance, creep resistance, etc. are used to change the flexural modulus of polydicyclopentadiene. However, the interfacial bonding ability of carbon fibers and glass fibers with polydicyclopentadiene is poor, and the addition of a catalyst during polymerization greatly affects the flexural modulus and thermal stability of a composite material prepared from the carbon fibers and the glass fibers with polydicyclopentadiene, which makes it difficult to improve the flexural modulus of polydicyclopentadiene with the glass fibers and the carbon fibers.
The present invention addresses such problems by preparing high performance polydicyclopentadiene.
Disclosure of Invention
The invention aims to provide high-performance polydicyclopentadiene and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the high-performance polydicyclopentadiene is characterized in that the high-performance polydicyclopentadiene is prepared by carrying out a pulse electric field assisted reaction injection molding process on a mixed solution of post-treated modified carbon fiber and dicyclopentadiene, wherein the post-treated modified carbon fiber is prepared by firstly utilizing the carbon fiber and 4- (4-aminophenyl) benzonitrile triethanol siloxane to carry out a supercritical assisted ultrasonic swelling process to prepare modified carbon fiber, and then utilizing a microwave coupling freeze drying process to prepare the post-treated modified carbon fiber.
Furthermore, the dicyclopentadiene mixed solution is obtained by mixing a copper chloride solution, a formaldehyde solution and dicyclopentadiene.
Further, the dicyclopentadiene mixed liquor mainly comprises the following components in parts by weight: 10-20 parts of copper chloride solution, 8-24 parts of formaldehyde solution and 300-800 parts of dicyclopentadiene.
Further, the supercritical auxiliary ultrasonic swelling process comprises the steps of putting carbon fibers and dichloroethane into a reaction kettle under the protection of nitrogen, introducing nitrogen to discharge dichloroethane gas in the reaction kettle after reacting for a preset time at high temperature and high pressure, taking out, washing, drying, immersing into 4- (4-aminophenyl) benzonitrile triethanol siloxane, and performing ultrasonic treatment for a preset time to obtain the modified carbon fibers.
Further, the preparation method of the high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) preparing modified carbon fibers by using carbon fibers and 4- (4-aminophenyl) benzonitrile triethanolsiloxane through a supercritical assisted ultrasonic swelling process;
(2) treating the modified carbon fiber by using a microwave coupling freeze drying process to prepare a post-treated modified carbon fiber;
(3) and (3) carrying out a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using the dicyclopentadiene mixed solution to prepare the high-performance polydicyclopentadiene.
Further, the preparation method of the high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 20-1: 30 is put into a reaction kettle with the pressure of 1.8 to 2.2MPa, the temperature is raised to 99 to 101 ℃ at the rate of 1.9 to 2.1 ℃/min, then the temperature is raised to 198 to 202 ℃ at the rate of 3.9 to 4.1 ℃/min, the temperature is maintained for 28 to 32s, then the temperature is raised to 256 to 258 ℃ at the rate of 0.9 to 1.1 ℃/min, the temperature is maintained for 1.4 to 1.6h, then the gas is discharged to the pressure of 0.1 to 0.2MPa in the kettle at the rate of 0.1 to 0.2MPa, and then the pressure is 3 to 5m3Introducing nitrogen gas into the reactor to discharge dichloroethane gas in the reactor, taking out the dichloroethane gas, washing the dichloroethane gas with ethanol for 2-4 times, washing the dichloroethane gas with deionized water for 2-4 times, drying the dichloroethane gas in an oven at 30-40 ℃ for 0.8-1.2 h, naturally cooling the dichloroethane gas to room temperature, immersing the dichloroethane gas into 4- (4-aminophenyl) benzonitrile-based triethanol siloxane with the mass of carbon fibers being 3-5 times of that of the carbon fibers at 25-26 ℃ under the protection of nitrogen gas at 1.8-2.2 MPa, and performing ultrasonic treatment at 30-40 kHz for 20-30 min to obtain modified carbon fibers;
(2) placing the modified carbon fiber into a microwave device with the frequency of 2200-2400 MHz and the power of 600-800W under the nitrogen atmosphere for microwave treatment for 40-50 min, freezing at-8 to-4 ℃ for 11-13 h, freeze-drying at-56 to-54 ℃ for 46-50 h under the condition of 11-15 Pa, and continuing to perform microwave treatment for 20-30 min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 8-1: 12, stirring at 800-1000 r/min for 40-60 min, injecting the mixture into a mold at the pressure of 0.4-0.6 MPa at the volume of 10-20 mL/min, placing the mold into a high-pressure pulse device for 6-8 times, standing for 59-61 h at the temperature of 68-72 ℃ and under the pressure of 12-18 Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Further, the preparation method of the dicyclopentadiene mixed solution in the step (3) is as follows: at the temperature of 25-27 ℃, mixing a copper chloride solution, a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 0.8: 30-1: 1.2: 40, stirring for 40-60 min at 900-1100 r/min to obtain the dicyclopentadiene mixed solution.
Further, the preparation method of the copper chloride solution comprises the following steps: at the temperature of 25-27 ℃, copper chloride and ethanol are mixed according to the mass ratio of 1: 8-1: 10, and stirring for 20-30 min at 900-1100 r/min to obtain a copper chloride solution.
Further, the mass ratio of formaldehyde to ethanol in the formaldehyde solution is 3: 10-4: 10.
further, the pulse duration of the high-voltage pulse device in the step (3) is 1.8-2.2 mu s, the peak value of the output voltage is 8-12 kV, the peak value of the output current is 18-22A, the electric field intensity is 15-25 kV/cm, and the frequency is 2000-2500 Hz.
Compared with the prior art, the invention has the following beneficial effects:
when preparing high-performance polydicyclopentadiene, firstly, preparing modified carbon fiber by using 4- (4-aminophenyl) benzonitrile triethanol siloxane through a supercritical auxiliary ultrasonic swelling process; preparing the post-treated modified carbon fiber by using a microwave coupling freeze drying process; then mixing the copper chloride solution, the formaldehyde solution and the dicyclopentadiene to form a dicyclopentadiene mixed solution, and then carrying out a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using the dicyclopentadiene mixed solution to prepare the high-performance polydicyclopentadiene.
Firstly, 4- (4-aminophenyl) benzonitrile triethanol siloxane is subjected to a supercritical auxiliary ultrasonic swelling process to prepare modified carbon fibers, a sizing agent in the carbon fibers is removed, so that the surfaces of the carbon fibers are provided with a large number of active groups such as hydroxyl groups, the 4- (4-aminophenyl) benzonitrile triethanol siloxane reacts with the hydroxyl groups on the surfaces of the carbon fibers, a silica bond is broken and condensed to form a stable covalent bond, the 4- (4-aminophenyl) benzonitrile triethanol siloxane is stably grafted on the surfaces of the carbon fibers to generate glycol, the silica bond is continuously broken and polymerized to form silica sol with a three-dimensional network structure under the combined action of the glycol, meanwhile, part of the glycol is oxidized to form glyoxal, and the bending modulus of the modified carbon fibers is enhanced; and then preparing the post-treated modified carbon fiber by using a microwave coupling freeze drying process to form silicon dioxide gel with a three-dimensional network structure, reacting the dialdehyde of glyoxal with the amino of 4- (4-aminophenyl) benzonitrile triethanol siloxane to generate cyano, connecting the 4- (4-aminophenyl) benzonitrile triethanol siloxane with the silicon dioxide gel through the two cyano to form an interpenetrating network structure compound with the silicon dioxide gel, increasing the crosslinking density in the modified carbon fiber, and further enhancing the flexural modulus of the modified carbon fiber, thereby enhancing the flexural modulus of the high-performance polydicyclopentadiene.
Secondly, mixing a copper chloride solution, a formaldehyde solution, dicyclopentadiene and the like to form a dicyclopentadiene mixed solution, then carrying out a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using the dicyclopentadiene mixed solution to prepare high-performance polydicyclopentadiene, wherein two cyano groups connected with 4- (4-aminophenyl) benzonitrile triethanolsiloxane in the post-treated modified carbon fiber are unstable and react with formaldehyde to form an imidazolium salt compound with a conjugated structure, so that the high-performance polydicyclopentadiene has good antistatic property; copper chloride is ionized to form free copper ions and chloride ions, an imidazolium compound in the modified carbon fiber quickly captures the copper ions to form coordinate bond crosslinking to generate an N-heterocyclic carbene copper complex, dicyclopentadiene is subjected to ring opening ectopic polymerization to form polydicyclopentadiene under the combined action of catalysis of the N-heterocyclic carbene copper complex, and cyano groups in the post-treated modified carbon fiber are polymerized to form a triazine ring structure compound, so that the thermal stability of the high-performance polydicyclopentadiene is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing the indexes of the high-performance polydicyclopentadiene prepared in the following examples as follows:
flexural modulus: the high-performance polydicyclopentadiene prepared in the same mass of the examples and comparative examples was tested for flexural modulus according to the GB/T2570 standard method.
Thermal stability: the thermal stability was determined by measuring the glass transition temperature of high performance polydicyclopentadiene prepared in the same mass examples and comparative examples according to the GB/T19466 standard method.
Antistatic property: the antistatic properties of high-performance polydicyclopentadiene prepared in the same quality examples and comparative examples were measured by measuring the electrical resistance according to the GB/T15738 standard method.
Example 1
The high-performance polydicyclopentadiene mainly comprises 10 parts of modified carbon fiber and 80 parts of dicyclopentadiene mixed liquor in parts by weight.
A preparation method of high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) Under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 20 is put into a reaction kettle with the pressure of 1.8MPa, the temperature is raised to 99 ℃ at the speed of 1.9 ℃/min, then the temperature is raised to 198 ℃ at the speed of 3.9 ℃/min, the temperature is maintained for 28s, then the temperature is raised to 256 ℃ at the speed of 0.9 ℃/min, the temperature is maintained for 1.4h, then the gas is discharged to the pressure of 0.1MPa in the kettle at the speed of 0.1MPa/min, and then the gas is discharged at the speed of 3m3Introducing nitrogen gas into the reactor per min to discharge dichloroethane gas in the reactor, taking out the dichloroethane gas, washing the dichloroethane gas with ethanol for 2 times, washing the dichloroethane gas with deionized water for 2 times, placing the dichloroethane gas into a drying oven at the temperature of 30 ℃ to dry for 0.8 hour, then naturally cooling the dichloroethane gas to the room temperature, immersing the dichloroethane gas into 4- (4-aminophenyl) benzonitrile triethanol siloxane with the mass of carbon fibers being 3 times of that of the carbon fibers at the temperature of 25 ℃ and under the protection of nitrogen gas at the pressure of 1.8MPa, and performing ultrasonic treatment at the frequency of 30kHz for 20min to obtain modified carbon fibers;
(2) placing the modified carbon fiber in a microwave device with the frequency of 2200MHz and the power of 600W for microwave treatment for 40min under the nitrogen atmosphere, freezing for 11h at the temperature of minus 8 ℃, freezing and drying for 46h under the conditions of minus 56 ℃ and 11Pa, and continuing to perform microwave treatment for 20min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) at 25 ℃, copper chloride and ethanol are mixed according to a mass ratio of 1: 8, mixing, and stirring at 900r/min for 20min to obtain a copper chloride solution; at 25 ℃, mixing a copper chloride solution, formaldehyde and ethanol in a mass ratio of 3: 10, mixing the formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 0.8: 30, stirring for 40min at 900r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to a mass ratio of 1: 8, stirring for 40min at 800r/min, injecting the mixture into a mold at the speed of 10mL/min under the condition of 0.4MPa, putting the mold into a high-voltage pulse device with the pulse duration of 1.8 mu s, the output voltage peak value of 8kV, the output current peak value of 18A, the electric field intensity of 15kV/cm and the frequency of 2000Hz, pulsing for 6 times, standing for 59 hours under the conditions of 68 ℃ and 12Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Example 2
The high-performance polydicyclopentadiene mainly comprises 15 parts of modified carbon fiber and 150 parts of dicyclopentadiene mixed liquor in parts by weight.
A preparation method of high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 25 is put into a reaction kettle with the pressure of 2MPa, the temperature is raised to 100 ℃ at the speed of 2 ℃/min, then raised to 200 ℃ at the speed of 4 ℃/min, the temperature is kept for 30s, the temperature is raised to 257 ℃ at the speed of 1 ℃/min, the temperature is kept for 1.5h, then the gas is discharged until the pressure in the kettle is 0.15MPa at the speed of 0.15MPa, and then the pressure is 4m3Introducing nitrogen gas into the reactor per min, discharging dichloroethane gas in the reactor, taking out, washing for 3 times by using ethanol, washing for 3 times by using deionized water, placing the reactor into a drying oven at 35 ℃ for drying for 1h, naturally cooling to room temperature, immersing the reactor into 4- (4-aminophenyl) benzonitrile-triethanolamine-based siloxane with the mass of carbon fiber being 4 times that of the carbon fiber at 25.5 ℃ under the protection of 2MPa and nitrogen gas, and performing ultrasonic treatment for 25min at 35kHz to obtain modified carbon fiber;
(2) placing the modified carbon fiber in a 2300MHz and 700W microwave device for microwave treatment for 45min under the nitrogen atmosphere, freezing at-6 ℃ for 12h, then freeze-drying at-55 ℃ under 13Pa for 48h, and continuing to perform microwave treatment for 25min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) at 26 ℃, copper chloride and ethanol are mixed according to a mass ratio of 1: 9, mixing, and stirring at 1000r/min for 25min to obtain a copper chloride solution; at 26 ℃, mixing a copper chloride solution, formaldehyde and ethanol in a mass ratio of 3.5: 10, mixing a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 1: 35, mixing, and stirring for 50min at the speed of 1000r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 10, stirring for 50min at 900r/min, injecting the mixture into a mold at 15mL/min under the condition of 0.5MPa, putting the mold into a high-voltage pulse device with the pulse duration of 2 mus, the output voltage peak value of 10kV, the output current peak value of 20A, the electric field intensity of 20kV/cm and the frequency of 2250Hz, pulsing for 7 times, standing for 60h under the conditions of 70 ℃ and 15Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Example 3
The high-performance polydicyclopentadiene mainly comprises 20 parts of modified carbon fiber and 240 parts of dicyclopentadiene mixed liquor in parts by weight.
A preparation method of high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 30 is put into a reaction kettle with the pressure of 2.2MPa, the temperature is raised to 101 ℃ at the speed of 2.1 ℃/min, then the temperature is raised to 202 ℃ at the speed of 4.1 ℃/min, the temperature is maintained for 32s, then the temperature is raised to 258 ℃ at the speed of 1.1 ℃/min, the temperature is maintained for 1.6h, then the gas is discharged to the pressure of 0.2MPa in the kettle at the speed of 0.2MPa/min, and then the gas is discharged at the speed of 5m3Introducing nitrogen gas into the reactor per min to discharge dichloroethane gas in the reactor, taking out the dichloroethane gas, washing the dichloroethane gas with ethanol for 4 times, washing the dichloroethane gas with deionized water for 4 times, drying the dichloroethane gas in an oven at 40 ℃ for 1.2 hours, naturally cooling the dichloroethane gas to room temperature, immersing the dichloroethane gas into 4- (4-aminophenyl) benzonitrile-triethanolamine-based siloxane with the mass of carbon fibers being 5 times of that of the carbon fibers at 26 ℃ under the protection of nitrogen gas at 2.2MPa, and performing ultrasonic treatment at 40kHz for 30min to obtain modified carbon fibers;
(2) placing the modified carbon fiber into a microwave device of 2400MHz and 800W for microwave treatment for 50min under the nitrogen atmosphere, freezing at-4 ℃ for 13h, then freezing and drying at-54 ℃ for 50h under the condition of 15Pa, and continuing to perform microwave treatment for 30min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) at the temperature of 27 ℃, copper chloride and ethanol are mixed according to the mass ratio of 1: 10, mixing, and stirring for 30min at 1100r/min to obtain a copper chloride solution; at the temperature of 27 ℃, the mass ratio of the copper chloride solution to formaldehyde to ethanol is 4: 10, mixing a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 1.2: 40, stirring for 60min at 1100r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 12, stirring for 60min at 1000r/min, injecting the mixture into a mold at 20mL/min under the condition of 0.6MPa, putting the mold into a high-voltage pulse device with the pulse duration of 2.2 mu s, the output voltage peak value of 12kV, the output current peak value of 22A, the electric field intensity of 25kV/cm and the frequency of 2500Hz, pulsing for 8 times, standing for 61h under the conditions of 72 ℃ and 18Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Comparative example 1
The high-performance polydicyclopentadiene mainly comprises 15 parts of modified carbon fiber and 150 parts of dicyclopentadiene mixed liquor in parts by weight.
A preparation method of high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) under the protection of nitrogen and the ultrasonic of 35kHz, mixing carbon fiber and dichloroethane according to the mass ratio of 1: 25 is put into a reaction kettle with the pressure of 2MPa, the temperature is raised to 100 ℃ at the speed of 2 ℃/min, then raised to 200 ℃ at the speed of 4 ℃/min, the temperature is kept for 30s, the temperature is raised to 257 ℃ at the speed of 1 ℃/min, the temperature is kept for 1.5h, then the gas is discharged until the pressure in the kettle is 0.15MPa at the speed of 0.15MPa, and then the pressure is 4m3Introducing nitrogen gas into the reaction kettle to discharge dichloroethane gas in the reaction kettle, taking out, washing with ethanol for 3 times, washing with deionized water for 3 times, placing the reaction kettle into a drying oven at 35 ℃ to dry for 1 hour, and naturally cooling to room temperature to obtain modified carbon fibers;
(2) placing the modified carbon fiber in a 2300MHz and 700W microwave device for microwave treatment for 45min under the nitrogen atmosphere, freezing at-6 ℃ for 12h, then freeze-drying at-55 ℃ under 13Pa for 48h, and continuing to perform microwave treatment for 25min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) at 26 ℃, copper chloride and ethanol are mixed according to a mass ratio of 1: 9, mixing, and stirring at 1000r/min for 25min to obtain a copper chloride solution; at 26 ℃, the mass ratio of the first generation of the glassine catalyst to the copper chloride solution to the formaldehyde to the ethanol is 3.5: 10, mixing a formaldehyde solution and dicyclopentadiene according to a mass ratio of 0.001: 1: 1: 35, mixing, and stirring for 50min at the speed of 1000r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 10, stirring for 50min at 900r/min, injecting the mixture into a mold at 15mL/min under the condition of 0.5MPa, putting the mold into a high-voltage pulse device with the pulse duration of 2 mus, the output voltage peak value of 10kV, the output current peak value of 20A, the electric field intensity of 20kV/cm and the frequency of 2250Hz, pulsing for 7 times, standing for 60h under the conditions of 70 ℃ and 15Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Comparative example 2
The formulation of comparative example 2 was the same as example 2. The preparation method of the high-performance polydicyclopentadiene is different from the preparation method of the example 2 only in the difference of the step (1), and the step (1) is modified as follows: at 26 ℃, mixing carbon fiber and dichloroethane according to a mass ratio of 1: 25, stirring for 2.5h at 1000r/min, filtering, washing for 3 times by using ethanol, washing for 3 times by using deionized water, drying in an oven at 35 ℃ for 1h, naturally cooling to room temperature, immersing in 4- (4-aminophenyl) benzonitrile triethanol siloxane 4 times the mass of the carbon fiber under the protection of nitrogen at 25.5 ℃ and 2MPa, stirring for 5h at the same speed, filtering, washing for 3 times by using ethanol, washing for 3 times by using deionized water, and drying in an oven at 35 ℃ for 1h to obtain the modified carbon fiber. The rest of the preparation steps are the same as example 2.
Comparative example 3
The high-performance polydicyclopentadiene mainly comprises 15 parts of modified carbon fiber and 150 parts of dicyclopentadiene mixed liquor in parts by weight.
A preparation method of high-performance polydicyclopentadiene mainly comprises the following preparation steps:
(1) under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 25 is put into a reaction kettle with the pressure of 2MPa, the temperature is raised to 100 ℃ at the speed of 2 ℃/min, then raised to 200 ℃ at the speed of 4 ℃/min, the temperature is kept for 30s, the temperature is raised to 257 ℃ at the speed of 1 ℃/min, the temperature is kept for 1.5h, then the gas is discharged until the pressure in the kettle is 0.15MPa at the speed of 0.15MPa, and then the pressure is 4m3Introducing nitrogen gas into the reactor per min, discharging dichloroethane gas in the reactor, taking out, washing for 3 times by using ethanol, washing for 3 times by using deionized water, placing the reactor into a drying oven at 35 ℃ for drying for 1h, naturally cooling to room temperature, immersing the reactor into 4- (4-aminophenyl) benzonitrile-triethanolamine-based siloxane with the mass of carbon fiber being 4 times that of the carbon fiber at 25.5 ℃ under the protection of 2MPa and nitrogen gas, and performing ultrasonic treatment for 25min at 35kHz to obtain modified carbon fiber;
(2) at 26 ℃, copper chloride and ethanol are mixed according to a mass ratio of 1: 9, mixing, and stirring at 1000r/min for 25min to obtain a copper chloride solution; at 26 ℃, mixing a copper chloride solution, formaldehyde and ethanol in a mass ratio of 3.5: 10, mixing a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 1: 35, mixing, and stirring for 50min at the speed of 1000r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 10, stirring for 50min at 900r/min, injecting the mixture into a mold at 15mL/min under the condition of 0.5MPa, putting the mold into a high-voltage pulse device with the pulse duration of 2 mus, the output voltage peak value of 10kV, the output current peak value of 20A, the electric field intensity of 20kV/cm and the frequency of 2250Hz, pulsing for 7 times, standing for 60h under the conditions of 70 ℃ and 15Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
Comparative example 4
Comparative example 4 was formulated as in example 2. The preparation method of the high-performance polydicyclopentadiene is different from the preparation method of the example 2 only in the difference of the step (3), and the step (3) is modified as follows: at 26 ℃, copper chloride and ethanol are mixed according to a mass ratio of 1: 9, mixing, and stirring at 1000r/min for 25min to obtain a copper chloride solution; at 26 ℃, mixing a copper chloride solution, formaldehyde and ethanol in a mass ratio of 3.5: 10, mixing a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 1: 35, mixing, and stirring for 50min at the speed of 1000r/min to obtain a dicyclopentadiene mixed solution; under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 10, stirring at 900r/min for 50min, injecting into a mold at 15mL/min under the condition of 0.5MPa, standing for 60h at 70 ℃ under the condition of 15Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene. The rest of the preparation steps are the same as example 2.
Examples of effects
The following table 1 shows the results of analysis of flexural modulus, antistatic property and thermal stability of the high performance polydicyclopentadiene prepared by using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
From table 1, it can be seen that the high performance polydicyclopentadiene prepared in examples 1, 2, 3 has low absorption viscosity and good flexural modulus, antistatic property and thermal stability; from the comparison of experimental data of examples 1, 2 and 3 and comparative examples 1 and 2, it can be found that modified carbon fibers with high crosslinking density cannot be formed only by performing a supercritical assisted ultrasonic swelling process on carbon fibers, and an imidazolium salt compound cannot be formed after a microwave coupling freeze-drying process and a pulse electric field assisted reaction injection molding process are performed subsequently, so that the prepared high-performance polydicyclopentadiene has low flexural modulus and weak antistatic capability; only the 4- (4-aminophenyl) benzonitrile-triethanol siloxane is used for modifying the carbon fiber, the modified carbon fiber with high crosslinking density cannot be formed, and the prepared high-performance polydicyclopentadiene has low flexural modulus; experimental data of examples 1, 2 and 3 and comparative example 3 show that the modified carbon fiber is subjected to post-treatment by using a microwave coupling freeze drying process, so that the crosslinking density of the modified carbon fiber is enhanced, and the flexural modulus of the prepared high-performance polydicyclopentadiene is good; from the experimental data of examples 1, 2, 3 and comparative example 4, it can be found that the high-performance polydicyclopentadiene is prepared by performing a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using a dicyclopentadiene mixed solution to form an imidazolium salt compound and a triazine ring structure compound, and the prepared high-performance polydicyclopentadiene has strong antistatic property and thermal stability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The high-performance polydicyclopentadiene is characterized in that the high-performance polydicyclopentadiene is prepared by carrying out a pulse electric field assisted reaction injection molding process on a mixed solution of post-treated modified carbon fiber and dicyclopentadiene, wherein the post-treated modified carbon fiber is prepared by firstly utilizing the carbon fiber and 4- (4-aminophenyl) benzonitrile triethanol siloxane to carry out a supercritical assisted ultrasonic swelling process to prepare modified carbon fiber, and then utilizing a microwave coupling freeze drying process to prepare the post-treated modified carbon fiber.
2. The high-performance polydicyclopentadiene according to claim 1, wherein the dicyclopentadiene mixed solution is obtained by mixing a copper chloride solution, a formaldehyde solution and dicyclopentadiene.
3. The high-performance polydicyclopentadiene of claim 2, wherein the dicyclopentadiene mixed liquor comprises, by weight: 10-20 parts of copper chloride solution, 8-24 parts of formaldehyde solution and 300-800 parts of dicyclopentadiene.
4. The high-performance polydicyclopentadiene according to claim 3, wherein the supercritical assisted ultrasonic swelling process comprises placing carbon fibers and dichloroethane in a reaction kettle under the protection of nitrogen, reacting at high temperature and high pressure for a predetermined time, introducing nitrogen to discharge dichloroethane gas in the reaction kettle, taking out, washing, drying, immersing in 4- (4-aminophenyl) benzonitrile triethanol siloxane, and performing ultrasonic treatment for a predetermined time to obtain the modified carbon fibers.
5. The preparation method of the high-performance polydicyclopentadiene is characterized by mainly comprising the following preparation steps:
(1) preparing modified carbon fibers by using carbon fibers and 4- (4-aminophenyl) benzonitrile-triethanol siloxane through a supercritical auxiliary ultrasonic swelling process;
(2) treating the modified carbon fiber by using a microwave coupling freeze drying process to prepare a post-treated modified carbon fiber;
(3) and (3) carrying out a pulse electric field assisted reaction injection molding process on the post-treated modified carbon fiber by using the dicyclopentadiene mixed solution to prepare the high-performance polydicyclopentadiene.
6. The method for preparing high-performance polydicyclopentadiene according to claim 5, wherein the method for preparing high-performance polydicyclopentadiene mainly comprises the following steps:
(1) under the protection of nitrogen, carbon fibers and dichloroethane are mixed according to the mass ratio of 1: 20-1: 30 is put into a reaction kettle with the pressure of 1.8 to 2.2MPa, the temperature is raised to 99 to 101 ℃ at the rate of 1.9 to 2.1 ℃/min, then the temperature is raised to 198 to 202 ℃ at the rate of 3.9 to 4.1 ℃/min, the temperature is maintained for 28 to 32s, then the temperature is raised to 256 to 258 ℃ at the rate of 0.9 to 1.1 ℃/min, the temperature is maintained for 1.4 to 1.6h, then the gas is discharged to the pressure of 0.1 to 0.2MPa in the kettle at the rate of 0.1 to 0.2MPa, and then the pressure is 3 to 5m3Introducing nitrogen gas into the reactor to discharge dichloroethane gas in the reactor, taking out the dichloroethane gas, washing the dichloroethane gas with ethanol for 2-4 times, washing the dichloroethane gas with deionized water for 2-4 times, drying the dichloroethane gas in an oven at 30-40 ℃ for 0.8-1.2 h, naturally cooling the dichloroethane gas to room temperature, immersing the dichloroethane gas into 4- (4-aminophenyl) benzonitrile-based triethanol siloxane with the mass of carbon fibers being 3-5 times of that of the carbon fibers at 25-26 ℃ under the protection of nitrogen gas at 1.8-2.2 MPa, and performing ultrasonic treatment at 30-40 kHz for 20-30 min to obtain modified carbon fibers;
(2) placing the modified carbon fiber into a microwave device with the frequency of 2200-2400 MHz and the power of 600-800W under the nitrogen atmosphere for microwave treatment for 40-50 min, freezing at-8 to-4 ℃ for 11-13 h, freeze-drying at-56 to-54 ℃ for 46-50 h under the condition of 11-15 Pa, and continuing to perform microwave treatment for 20-30 min under the nitrogen atmosphere to obtain the post-treated modified carbon fiber;
(3) under the argon atmosphere, mixing the post-treated modified carbon fiber and dicyclopentadiene according to the mass ratio of 1: 8-1: 12, stirring at 800-1000 r/min for 40-60 min, injecting the mixture into a mold at the pressure of 0.4-0.6 MPa at the volume of 10-20 mL/min, placing the mold into a high-pressure pulse device for 6-8 times, standing for 59-61 h at the temperature of 68-72 ℃ and under the pressure of 12-18 Pa, naturally cooling to room temperature, and demolding to obtain the high-performance polydicyclopentadiene.
7. The method for preparing high-performance polydicyclopentadiene according to claim 6, wherein the method for preparing the dicyclopentadiene mixed liquor in step (3) is as follows: at the temperature of 25-27 ℃, mixing a copper chloride solution, a formaldehyde solution and dicyclopentadiene according to a mass ratio of 1: 0.8: 30-1: 1.2: 40, stirring for 40-60 min at 900-1100 r/min to obtain the dicyclopentadiene mixed solution.
8. The method for preparing high-performance polydicyclopentadiene according to claim 7, wherein the copper chloride solution is prepared by the following steps: at the temperature of 25-27 ℃, copper chloride and ethanol are mixed according to the mass ratio of 1: 8-1: 10, and stirring for 20-30 min at a speed of 900-1100 r/min to obtain a copper chloride solution.
9. The method for preparing high-performance polydicyclopentadiene according to claim 8, wherein the mass ratio of formaldehyde to ethanol in the formaldehyde solution is 3: 10-4: 10.
10. the method for preparing high-performance polydicyclopentadiene according to claim 9, wherein the high-voltage pulse device in step (3) has a pulse duration of 1.8-2.2 μ s, an output voltage peak of 8-12 kV, an output current peak of 18-22A, an electric field strength of 15-25 kV/cm and a frequency of 2000-2500 Hz.
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| CN102690486A (en) * | 2011-12-22 | 2012-09-26 | 河南科技大学 | Fiber-reinforced polydicyclopentadiene composite material and preparation method thereof |
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