CN111825962A - PBT composite material with strength and thermal conductivity enhanced by modified composite carbon material and preparation method thereof - Google Patents
PBT composite material with strength and thermal conductivity enhanced by modified composite carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a PBT composite material with strength and thermal conductivity enhanced by a modified composite carbon material and a preparation method thereof, wherein the preparation method comprises the following steps: putting 70-80 parts by weight of dried PBT, 20-30 parts by weight of POE, 2-10 parts by weight of compatilizer, 5-15 parts by weight of carbon fiber/graphene modified composite carbon material, antioxidant and lubricant into a high-speed mixer, uniformly mixing to obtain a mixture, adding the mixture into a torque rheometer, melting and mixing, and then carrying out hot press molding by using a flat vulcanizing machine to obtain the PBT composite material. The preparation process of the carbon fiber/graphene modified composite carbon material comprises the following steps: firstly, oxidizing the carbon fiber subjected to degumming pretreatment by using a strong oxidant to obtain oxidized carbon fiber; secondly, grafting the oxidation-treated carbon fiber by POE-g-MAH to obtain a grafted carbon fiber; and finally, carrying out secondary grafting on the carbon fiber on the graphene oxide by adopting the grafting carbon fiber and an initiator.
Description
Technical Field
The invention relates to a PBT composite material with strength and thermal conductivity enhanced by a modified composite carbon material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is a polycondensate of terephthalic acid and 1, 4-butanediol, is a semi-crystalline thermoplastic resin, has excellent mechanical property, electrical property, heat resistance and processability, is widely applied to the industrial fields of electronic and electric products, mechanical equipment, automobile parts, precision instruments and the like, and is the fastest one of five engineering plastics. However, the PBT has the defects of low notch impact strength, poor high-temperature dimensional stability, high surface resistivity of products, easy electrostatic enrichment and the like, and the application of the PBT in some fields is limited.
POE is a block copolymer of ethylene and octene, is easy to process, and is a thermoplastic elastomer with excellent performance. The POE main chain is saturated, and has good elasticity, high strength and excellent ageing resistance and ultraviolet resistance. The POE is added to not only toughen the PBT, but also improve the weather resistance of the PBT composite material, but due to the structural relationship, the nonpolarity of a POE molecular chain causes the POE molecular chain to be incompatible with the PBT, and a compatilizer is required to be added to improve the compatibility of a system. In addition, the PBT composite material is applied to the industries of electronics, electric appliances, automobiles and the like, and the problems of insufficient rigidity, insufficient thermal conductivity and the like of the material are also needed to be solved.
The graphene is a novel quasi-two-dimensional carbon nanomaterial, has extremely high modulus and breaking strength, has good improvement effect on mechanical property, electrical property, heat conductivity and the like of a composite material, and is often used for preparing a high-performance polymer composite material by compounding with a polymer matrix. The carbon fiber is a high-strength and high-modulus fiber, has excellent mechanical properties, has the characteristics of light weight, high specific strength and specific modulus, good overall design and the like, and is often applied as a reinforcement of a composite material. The carbon fiber and the heat-conducting filler (such as graphene) are jointly filled in the matrix to form a three-dimensional heat-conducting network more easily, and the heat-conducting network has more excellent heat-conducting property and mechanical property compared with the single material filling.
In conclusion, the POE toughened PBT has limited improvement on mechanical properties, and the application of PBT engineering materials in certain fields is limited. But untreated carbon fibers and graphene have low surface energy and poor compatibility with a PBT blending system, so that the functional carbon fibers and graphene are added to prepare the reinforced and heat-conducting PBT blending material with better performance and wider application range.
Disclosure of Invention
Therefore, aiming at the problems, the background and the problems, the invention aims to provide a PBT composite material with a modified composite carbon material for enhancing strength and thermal conductivity, which is prepared by carrying out melt blending on POE, a compatilizer and PBT and adding a treated carbon fiber/graphene modified composite carbon material.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: the PBT composite material is a carbon fiber/graphene modified composite carbon material which is reinforced in strength and thermal conductivity by a modified composite carbon material, and is prepared from the following materials in parts by weight:
on the basis of the technical scheme, the modification method of the carbon fiber/graphene modified composite carbon material comprises the following steps:
(1) pretreatment of carbon fibers: soaking carbon fiber in acetone at 35-40 deg.C for 20-24h, repeatedly washing with ionized water or distilled water, and drying in a 70 deg.C drying oven for 5h to obtain degumming carbon fiber to obtain pretreated carbon fiber;
(2) oxidation treatment of carbon fiber: reacting the pretreated carbon fiber in a strong oxidant at the temperature of 80-110 ℃ for 2-5h, repeatedly washing the carbon fiber with deionized water or distilled water for many times after the reaction is finished and cooled until the pH value is 6-7, and drying the carbon fiber in a drying box at the temperature of 70 ℃ for 5h to obtain the oxidized carbon fiber, wherein the oxidized carbon fiber is named as O-CF;
(3) primary grafting treatment of carbon fibers: placing 10g of oxidized carbon fiber and 300ml of 200-plus anhydrous ethanol into a 500ml round-bottom flask, placing the flask into an ultrasonic cleaner with the power of 100W, performing ultrasonic dispersion for 30-40min to obtain a carbon fiber suspension, then adding the suspension into a solution containing POE-g-MAH, adding 0.06-1 part of an initiator, performing reflux reaction for 2-3h at 40-50 ℃, repeatedly washing the suspension with anhydrous ethanol or distilled water or deionized water after treatment, and drying the suspension in a drying oven at 70 ℃ for 5h to obtain grafted carbon fiber, wherein the grafted carbon fiber is named PCF for standby;
(4) oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and then 4g of graphite powder and 2g of NaNO are put into the reaction bottle3Adding the mixture into concentrated sulfuric acid under the condition of intense stirring; then slowly adding a strong oxidant KMnO4Controlling the temperature of the system below 10 ℃, and continuously stirring for reaction for 1h to complete the low-temperature intercalation reaction; then the reaction bottle is moved to a constant temperature water bath kettle, the temperature of the system is raised to (36 +/-2) DEG C, and the system is continuously stirred for 30min at constant temperature to complete the medium temperature oxidation reaction; then slowly adding 400-500ml deionized water, and continuously stirring and reacting at (96 +/-2) DEG C for 20-30min to complete high-temperature hydrolysis; finally, adding 60-100ml of hydrogen peroxide (30%) to terminate the reaction, carrying out suction filtration while the reaction is hot, washing the suction filtration product by deionized water for three times until the product is neutral to obtain graphene oxide, wherein the graphene oxide is named as GO for later use;
(5) and (3) secondary grafting treatment of the carbon fiber: adding a proper amount of graphene oxide into an acetone solution, carrying out ultrasonic oscillation for 45-60min to obtain a uniformly dispersed GO suspension, then adding a proper amount of POE-g-MAH grafted carbon fiber PCF and an initiator into the GO suspension, carrying out suction filtration after reacting for 12-14h at 85-100 ℃, repeatedly washing and suction filtration the carbon fiber subjected to suction filtration with deionized water for many times, and drying for 5h at 60 ℃ under a vacuum condition to obtain graphene oxide secondary grafted carbon fiber (GO-g-PCF) for later use.
Further, the carbon fiber is polyacrylonitrile-based carbon fiber.
Further, the detergent is one of ionized water, distilled water and absolute ethyl alcohol.
Further, the strong oxidant is one or more of sulfuric acid, nitric acid, hypochlorous acid and potassium permanganate mixed in any mixing ratio.
Further, the solvent is one of acetone, toluene and xylene.
Further, the initiator is one or more of dicumyl peroxide, benzoyl tert-butyl peroxide and methyl ethyl ketone peroxide which are mixed in any mixing ratio.
The first graft is ethylene-octene grafted maleic anhydride copolymer, namely POE-g-MAH, and the second graft is graphene oxide, namely GO.
Further, the compatibilizer is at least one selected from ethylene octene-grafted maleic anhydride copolymer (POE-g-MAH), ethylene octene-grafted glycidyl methacrylate (POE-g-GMA), polyethylene-grafted maleic anhydride (PE-g-MAH), polyethylene-grafted glycidyl methacrylate (PE-g-GMA), styrene-maleic anhydride binary copolymer (SMA), and styrene-glycidyl methacrylate copolymer (SGMA).
Further, the antioxidant is at least one selected from the group consisting of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris (nonylphenyl) phosphite (TNPP), tris [2, 4-di-tert-butylphenyl ] phosphite (168), and 2, 5-di-tert-butylhydroquinone antioxidant DTBHQ.
Further, the lubricant is at least one selected from polyethylene wax and liquid paraffin (white oil).
Based on the same invention idea, the invention also provides a method for preparing the PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material, which comprises the following steps:
A. and (3) obtaining the carbon fiber/graphene modified composite carbon material according to the modification method of the carbon fiber/graphene modified composite carbon material.
B. Respectively drying PBT, POE, the compatilizer, the treated carbon fiber and graphene in vacuum, accurately weighing the dried PBT, POE, the treated carbon fiber/graphene modified composite carbon material, the compatilizer, the antioxidant and the lubricant according to the weight part ratio, and then placing the weighed components in a high-speed mixer to be uniformly mixed to obtain a mixture.
C. And adding the prepared mixture into a torque rheometer, wherein the melting and mixing temperature is 230 ℃, the rotor speed is 50r/min, the melting and mixing time is about 10min, carrying out hot press molding on the PBT/POE/treated carbon fiber/graphene modified composite carbon material obtained after blending by using a flat vulcanizing machine, wherein the hot press temperature is 235 ℃, melting is 5-7 min, carrying out hot press for 10min, and carrying out heat preservation for 15min to obtain the PBT/composite material.
And finally cutting the sample to obtain a dumbbell-shaped tensile sample and a strip-shaped impact sample for later use.
By adopting the technical scheme, the invention has the beneficial effects that:
firstly, the mechanical property of the PBT blending material is improved to a certain extent by adding the POE with the toughening agent and the compatilizer.
And secondly, by adding the carbon fiber/graphene modified composite carbon material, the incompatible state of a carbon fiber, graphene and PBT blending system is solved, the mechanical property of the PBT blending material is further improved, the problems of compatibility, strength, thermal conductivity and the like of the blending system are solved, and the application of the PBT blending material in certain fields, such as electronic appliances, automobiles and the like, is expanded.
Thirdly, the PBT composite material prepared by the invention not only has good impact resistance, but also has strong strength, thermal conductivity and weather resistance, the prepared blending material is light, meets the requirements of some higher use conditions, and the preparation method is simple and convenient, is easy to realize and has important practical application value.
Detailed Description
The invention will now be further illustrated with reference to specific examples.
Example 1
In the embodiment, the PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material is prepared by the following components in parts by weight: 70 parts of PBT; 30 parts of POE; 5 parts of carbon fiber/graphene modified composite carbon material; 5 parts of POE-g-MAH; 10100.2 parts of an antioxidant; 0.2 part of white oil.
This example was prepared as follows:
the preparation process of the carbon fiber/graphene modified composite carbon material comprises the following steps:
step 1, pretreatment of carbon fibers: soaking the carbon fiber in acetone at 35 ℃ for 24h, repeatedly washing the carbon fiber with deionized water for many times, and drying the carbon fiber in a drying oven at 70 ℃ for 5h to obtain the pretreated carbon fiber without the photoresist.
Step 2, oxidation treatment of carbon fibers: and (2) reacting the pretreated carbon fiber in a strong oxidant at 80 ℃ for 3h, repeatedly washing the carbon fiber with deionized water for many times until the pH value is 7 after the reaction is finished and the carbon fiber is cooled, and drying the carbon fiber in a drying oven at 70 ℃ for 5h to obtain the oxidized carbon fiber O-CF.
Step 3, primary grafting treatment of the carbon fibers: placing 10g of oxidized carbon fiber and 300mL of absolute ethyl alcohol into a 500mL round-bottom flask, placing the flask into an ultrasonic cleaner with the power of 100W, performing ultrasonic dispersion for 30min to obtain a carbon fiber suspension, then adding the suspension into an acetone solution of POE-g-MAH, adding 0.06 part of BPO, performing reflux reaction at 40 ℃ for 3h, repeatedly washing the suspension with deionized water for multiple times after treatment, and drying the suspension in a drying oven at 70 ℃ for 5h to obtain the grafted carbon fiber PCF for later use.
Step 4, oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and then 4g of graphite powder and 2g of NaNO are put into the reaction bottle3Adding the mixture into concentrated sulfuric acid under the condition of intense stirring; then slowly adding a strong oxidant KMnO4Controlling the temperature of the system below 10 ℃, and continuously stirring for reaction for 1h to complete the low-temperature intercalation reaction. Then moving the reaction bottle to a constant-temperature water bath kettle, raising the temperature of the system to 36 ℃, and continuously stirring for 30min at constant temperature to finish the medium-temperature oxidation reaction; then 400ml of deionized water was slowly added and the reaction was continued with stirring at 96 ℃ for 25min to complete the hydrolysis at high temperature; and finally, adding 60ml of hydrogen peroxide (30%) to terminate the reaction, carrying out suction filtration while the reaction is hot, washing the suction filtration product by using deionized water for three times until the product is neutral, and obtaining the graphene oxide GO for later use.
Step 5, secondary grafting treatment of carbon fibers: adding a proper amount of graphene oxide into an acetone solution, and performing ultrasonic oscillation for 60min to obtain a uniformly dispersed GO suspension. And then adding a proper amount of carbon-containing fiber PCF, BPO and acetone solution into the suspension, performing suction filtration after reacting for 12h at 100 ℃, repeatedly washing and suction filtering the carbon fiber subjected to suction filtration for many times by deionized water, and drying for 5h at 60 ℃ under a vacuum condition to obtain the graphene oxide secondary grafted carbon fiber (GO-g-PCF).
(II) blending type process:
the embodiment further provides a preparation method of the PBT composite material with the enhanced strength and thermal conductivity of the modified composite carbon material based on the implementation mode of the carbon fiber/graphene modified composite carbon material, and the preparation method comprises the following steps:
and 6, respectively vacuum-drying the PBT, POE, the ethylene-octene-grafted maleic anhydride copolymer (POE-g-MAH) and the carbon fiber/graphene modified composite carbon material, accurately weighing the dried PBT, POE, the treated carbon fiber, graphene, the ethylene-octene-grafted maleic anhydride copolymer (POE-g-MAH), the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and the polyethylene wax lubricant according to the weight part ratio, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture.
And 7, adding the prepared mixture into a torque rheometer, wherein the melt mixing temperature is 230 ℃, the rotor speed is 50r/min, and the melt mixing time is about 10 min. And (3) carrying out hot-press molding on the PBT/POE/treated graphene and the carbon fiber obtained after blending by using a flat vulcanizing machine, wherein the hot-press temperature is 235 ℃, melting is carried out for 6min, hot-pressing is carried out for 10min, and heat preservation is carried out for 15min, so as to obtain the composite material.
And cutting the sample to obtain a dumbbell-shaped tensile sample and a strip-shaped impact sample for later use.
The test bars of this example were subjected to tensile property test (GB/T1040.2-2006), impact property test (GB/T1043.1-2008), and heat distortion temperature and thermal conductivity test, respectively, and the test results are shown in Table 1.
Example 2
In the embodiment, the PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material is prepared by the following components in parts by weight: 80 parts of PBT; POE 20; 8 parts of carbon fiber/graphene modified composite carbon material; 5 parts of POE-g-GMA; 1680.3 parts of an antioxidant; 0.5 part of polyethylene wax.
This example was prepared as follows:
the preparation process of the carbon fiber/graphene modified composite carbon material comprises the following steps:
step 1, pretreatment of carbon fibers: soaking the carbon fiber in acetone at 40 ℃ for 20h, repeatedly washing the carbon fiber with distilled water for many times, and drying the carbon fiber in a drying oven at 70 ℃ for 5h to obtain the pretreated carbon fiber without the photoresist for later use.
Step 2, oxidation treatment of carbon fibers: and (2) reacting the pretreated carbon fiber in a strong oxidant at 100 ℃ for 2h, repeatedly washing the carbon fiber with distilled water for many times until the pH value is 6.5 after the reaction is finished and cooled, and drying the carbon fiber in a drying oven at 70 ℃ for 5h to obtain the oxidized carbon fiber O-CF for later use.
Step 3, primary grafting treatment of the carbon fibers: placing 10g of oxidized carbon fiber and 250mL of absolute ethyl alcohol into a 500mL round-bottom flask, placing the flask into an ultrasonic cleaner with the power of 100W, performing ultrasonic dispersion for 35min to obtain a carbon fiber suspension, then adding the suspension into a toluene solution of POE-g-MAH, adding 0.08 part of BPO initiator, performing reflux reaction for 3h at 40 ℃, repeatedly washing the suspension with distilled water for multiple times after treatment, and drying the suspension in a drying oven at 70 ℃ for 5h to obtain the grafted carbon fiber PCF for later use.
Step 4, oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and then 4g of graphite powder and 2g of NaNO are put into the reaction bottle3The mixture is added under vigorous stirring toIn concentrated sulfuric acid; then slowly adding a strong oxidant KMnO4And controlling the temperature of the system below 10 ℃, and continuously stirring for reacting for 1h to complete the low-temperature intercalation reaction. Then the reaction bottle is moved to a constant temperature water bath kettle, the temperature of the system is raised to 38 ℃, and the constant temperature is continuously stirred for 30min to complete the medium temperature oxidation reaction; then 500ml of deionized water is slowly added, and the reaction is continuously stirred at the temperature of 98 ℃ for 20min to complete the high-temperature hydrolysis; finally, 80ml of hydrogen peroxide (30%) is added to stop the reaction. And carrying out suction filtration while the product is hot, washing the suction filtration product for three times by using deionized water until the product is neutral, and then obtaining graphene oxide GO for later use.
Step 5, secondary grafting treatment of carbon fibers: adding a proper amount of graphene oxide into an acetone solution, and performing ultrasonic oscillation for 45min to obtain a uniformly dispersed GO suspension. And then adding carbon fiber PCF, BPO and acetone solution into the suspension, performing suction filtration after reacting for 14h at 85 ℃, repeatedly washing and suction filtering the carbon fiber deionized water subjected to suction filtration for many times, and drying for 5h at 60 ℃ under a vacuum condition to obtain the graphene oxide secondary grafted carbon fiber (GO-g-PCF) for later use.
(II) blending type process:
the embodiment further provides a preparation method of the PBT composite material with the enhanced strength and thermal conductivity of the modified composite carbon material based on the implementation mode of the carbon fiber/graphene modified composite carbon material, and the preparation method comprises the following steps:
and 6, respectively vacuum-drying the PBT, the POE, the ethylene octene grafted glycidyl methacrylate (POE-g-GMA), the treated carbon fiber and the graphene, accurately weighing the dried PBT, the POE, the treated carbon fiber and the treated graphene, the ethylene octene grafted glycidyl methacrylate (POE-g-GMA), the tris [ 2.4-di-tert-butylphenyl ] phosphite (168) and the liquid paraffin (white oil) lubricant according to the weight part ratio, and then placing the weighed components into a high-speed mixer to be uniformly mixed to obtain a mixture.
And 7, adding the prepared mixture into a torque rheometer, wherein the melt mixing temperature is 230 ℃, the rotor speed is 50r/min, and the melt mixing time is about 10 min. And (3) carrying out hot-press molding on the PBT/POE/treated graphene and the carbon fiber obtained after blending by using a flat vulcanizing machine, wherein the hot-press temperature is 235 ℃, melting is carried out for 5min, hot-pressing is carried out for 10min, and heat preservation is carried out for 15min, so as to obtain the composite material.
And cutting the sample to obtain a dumbbell-shaped tensile sample and a strip-shaped impact sample for later use.
The test bars of this example were subjected to tensile property test (GB/T1040.2-2006), impact property test (GB/T1043.1-2008), and heat distortion temperature and thermal conductivity test, respectively, and the test results are shown in Table 1.
Example 3
In the embodiment, the PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material is prepared by the following components in parts by weight: 75 parts of PBT; 25 parts of POE; 6 parts of carbon fiber/graphene modified composite carbon material; 6 parts of PE-g-MAH; 0.25 part of DTBHQ; 0.4 part of white oil.
The preparation process of the carbon fiber/graphene modified composite carbon material comprises the following steps:
step 1, pretreatment of carbon fibers: soaking the carbon fiber in acetone at 38 ℃ for 22h, repeatedly washing with ionized water or distilled water for many times, and drying in a drying oven at 70 ℃ for 5h to obtain the degumming carbon fiber for later use.
Step 2, oxidation treatment of carbon fibers: and (2) reacting the pretreated carbon fiber in a strong oxidant at 85 ℃ for 5h, repeatedly washing the carbon fiber with deionized water or distilled water for many times until the pH value is 7 after the reaction is finished and cooled, and drying the carbon fiber in a drying oven at 70 ℃ for 5h to obtain the oxidized carbon fiber O-CF for later use.
Step 3, primary grafting treatment of the carbon fibers: placing 10g of oxidized carbon fiber and 200mL of absolute ethyl alcohol into a 500mL round-bottom flask, placing the flask into an ultrasonic cleaner with the power of 100W, performing ultrasonic dispersion for 40min to obtain a carbon fiber suspension, then adding the suspension into an acetone solution of POE-g-MAH, adding 0.07 part of BPO initiator, performing reflux reaction at 50 ℃ for 2h, repeatedly washing the suspension with absolute ethyl alcohol or distilled water or deionized water after treatment, and drying the suspension in a drying oven at 70 ℃ for 5h to obtain the grafted carbon fiber PCF for later use.
Step 4, oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and thenThen 4g of graphite powder and 2g of NaNO are added3Adding the mixture into concentrated sulfuric acid under the condition of intense stirring; then slowly adding a strong oxidant KMnO4And controlling the temperature of the system below 10 ℃, and continuously stirring for reacting for 1h to complete the low-temperature intercalation reaction. Then moving the reaction bottle to a constant-temperature water bath kettle, raising the temperature of the system to 36 ℃, and continuously stirring for 30min at constant temperature to finish the medium-temperature oxidation reaction; then slowly adding 450ml of deionized water, and continuously stirring at 98 ℃ for reaction for 25min to complete high-temperature hydrolysis; finally, 80ml of hydrogen peroxide (30%) is added to stop the reaction. And carrying out suction filtration while the product is hot, washing the suction filtration product for three times by using deionized water until the product is neutral, and then obtaining graphene oxide GO for later use.
Step 5, secondary grafting treatment of carbon fibers: adding a proper amount of graphene oxide into an acetone solution, and performing ultrasonic oscillation for 50min to obtain a uniformly dispersed GO suspension. And then adding carbon fiber PCF, BPO and acetone solution into the suspension, performing suction filtration after reacting for 12h at 85 ℃, repeatedly washing and suction filtering the carbon fiber deionized water subjected to suction filtration for many times, and drying for 5h at 60 ℃ under a vacuum condition to obtain the graphene oxide secondary grafted carbon fiber (GO-g-PCF) for later use.
(II) blending type process:
the embodiment further provides a preparation method of the PBT composite material with the enhanced strength and thermal conductivity of the modified composite carbon material based on the implementation mode of the carbon fiber/graphene modified composite carbon material, and the preparation method comprises the following steps:
and step 6, respectively drying PBT, POE, a styrene-glycidyl methacrylate copolymer (SGMA), the treated carbon fiber and graphene in vacuum, accurately weighing the dried PBT, POE, the treated carbon fiber and graphene, the styrene-glycidyl methacrylate copolymer (SGMA), the 2, 5-di-tert-butylhydroquinone antioxidant DTBHQ and the polyethylene wax lubricant according to the weight part ratio, and then placing the weighed components in a high-speed mixer to be uniformly mixed to obtain a mixture.
And 7, adding the prepared mixture into a torque rheometer, wherein the melt mixing temperature is 230 ℃, the rotor speed is 50r/min, and the melt mixing time is about 10 min. And (3) carrying out hot-press molding on the PBT/POE/treated graphene and the carbon fiber obtained after blending by using a flat vulcanizing machine, wherein the hot-press temperature is 235 ℃, melting is carried out for 5min, hot-pressing is carried out for 10min, and heat preservation is carried out for 15min, so as to obtain the composite material. And finally cutting the sample to obtain a dumbbell-shaped tensile sample and a strip-shaped impact sample for later use.
And cutting the sample to obtain a dumbbell-shaped tensile sample and a strip-shaped impact sample for later use.
The test bars of this example were subjected to tensile property test (GB/T1040.2-2006), impact property test (GB/T1043.1-2008), and heat distortion temperature and thermal conductivity test, respectively, and the test results are shown in Table 1.
Performance testing
TABLE 1 test results of Material Properties
Claims (9)
1. The PBT composite material with the strength and the heat conductivity enhanced by the modified composite carbon material is characterized in that: the modified composite carbon material is a carbon fiber/graphene modified composite carbon material, and the composite material is prepared from the following materials in parts by weight:
2. the PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material according to claim 1, wherein: the preparation process of the carbon fiber/graphene modified composite carbon material is as follows:
firstly, oxidizing the carbon fiber subjected to photoresist removal pretreatment by using a strong oxidant to obtain oxidized carbon fiber;
secondly, placing the oxidized carbon fibers in absolute ethyl alcohol for ultrasonic dispersion to obtain a carbon fiber suspension, adding the carbon fiber suspension into a POE-g-MAH solution, simultaneously adding an initiator, carrying out reflux reaction for 2-3h, washing and drying to obtain grafted carbon fibers;
and finally, adding a proper amount of graphene oxide into a solvent to obtain a uniformly dispersed graphene suspension, and adding a proper amount of grafting carbon fibers and an initiator to perform secondary grafting of the graphene oxide on the carbon fibers to obtain the carbon fiber/graphene modified composite carbon material.
3. The PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material according to claim 2, wherein: the specific steps for preparing the carbon fiber/graphene modified composite carbon material are as follows:
step 1, pretreatment of carbon fibers: soaking carbon fibers in acetone at 35-40 ℃ for 20-24h, washing, and drying in a drying oven at 70 ℃ for 5h to obtain the degumming carbon fibers and obtain the pretreated carbon fibers;
step 2, oxidation treatment of carbon fibers: reacting the pretreated carbon fiber in a strong oxidant at 80-110 ℃ for 2-5h, cooling after the reaction is finished, washing until the pH value is 6-7, and drying in a drying oven at 70 ℃ for 5h to obtain oxidized carbon fiber;
step 3, primary grafting treatment of the carbon fibers: placing 10g of oxidation-treated carbon fiber and 300ml of 200-ml of anhydrous ethanol into a 500ml round-bottom flask, performing ultrasonic dispersion for 30-40min to obtain a carbon fiber suspension, then adding the carbon fiber suspension into a solution containing POE-g-MAH, adding 0.06-1 part of initiator, performing reflux reaction at 40-50 ℃ for 2-3h, washing, and drying to obtain grafting-treated carbon fiber for later use;
step 4, oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and then 4g of graphite powder and 2g of NaNO are put into the reaction bottle3Adding the mixture into concentrated sulfuric acid under the condition of intense stirring; then slowly adding a strong oxidant KMnO4Controlling the temperature of the system below 10 ℃, and continuously stirring for reaction for 1h to complete the low-temperature intercalation reaction; then the reaction bottle is moved to a constant temperature water bath kettle, the temperature of the system is raised to (36 +/-2) DEG C, and the system is continuously stirred for 30min at constant temperature to complete the medium temperature oxidation reaction; then slowly adding 400-500ml deionized water, and continuously stirring and reacting at (96 +/-2) DEG C for 20-30min to complete high-temperature hydrolysis; finally adding 60-100ml hydrogen peroxide (30%) to stop reaction, filtering and removingWashing the graphene oxide with ionized water to neutrality to obtain graphene oxide;
step 5, secondary grafting treatment of carbon fibers: adding a proper amount of graphene oxide into an acetone solution, carrying out ultrasonic oscillation for 45-60min to obtain a uniformly dispersed graphene suspension, then adding a proper amount of grafting carbon fiber and an initiator into the graphene suspension, carrying out suction filtration after reacting for 12-14h at 85-100 ℃, washing and carrying out suction filtration on the carbon fiber after suction filtration, and drying for 5h at 60 ℃ under a vacuum condition to obtain a graphene oxide secondary grafting carbon fiber, namely a carbon fiber/graphene modified composite carbon material.
4. The PBT composite material reinforced with the strength and the thermal conductivity by the modified composite carbon material according to any one of claims 1 to 3, wherein: the carbon fiber is polyacrylonitrile-based carbon fiber.
5. The PBT composite material reinforced with the strength and the thermal conductivity by the modified composite carbon material according to claim 2 or 3, wherein:
the strong oxidant is one or more of sulfuric acid, nitric acid, hypochlorous acid and potassium permanganate mixed in any mixing ratio;
the initiator is one or more of dicumyl peroxide, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide which are mixed in any mixing ratio.
6. The PBT composite material reinforced with the strength and the thermal conductivity by the modified composite carbon material according to any one of claims 1 to 3, wherein: the compatilizer is at least one selected from ethylene octene-grafted maleic anhydride copolymer (POE-g-MAH), ethylene octene-grafted glycidyl methacrylate (POE-g-GMA), polyethylene-grafted maleic anhydride (PE-g-MAH), polyethylene-grafted glycidyl methacrylate (PE-g-GMA), styrene-maleic anhydride binary copolymer (SMA) and styrene-glycidyl methacrylate copolymer (SGMA).
7. The PBT composite material reinforced with the strength and the thermal conductivity by the modified composite carbon material according to any one of claims 1 to 3, wherein: the antioxidant is at least one selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (nonylphenyl) phosphite (TNPP), tris [2, 4-di-tert-butylphenyl ] phosphite and 2, 5-di-tert-butylhydroquinone antioxidant DTBHQ.
8. The PBT composite material with the strength and the thermal conductivity enhanced by the modified composite carbon material according to claim 1, wherein: the lubricant is at least one selected from polyethylene wax and liquid paraffin.
9. The method for preparing the PBT composite material reinforced with strength and thermal conductivity by the modified composite carbon material according to any one of claims 1 to 8, is characterized by comprising the following steps:
the preparation process of the carbon fiber/graphene modified composite carbon material comprises the following steps:
step 1, pretreatment of carbon fibers: soaking carbon fibers in acetone at 35-40 ℃ for 20-24h, washing, and drying in a drying oven at 70 ℃ for 5h to obtain the degumming carbon fibers and obtain the pretreated carbon fibers;
step 2, oxidation treatment of carbon fibers: reacting the pretreated carbon fiber in a strong oxidant at 80-110 ℃ for 2-5h, cooling after the reaction is finished, washing until the pH value is 6-7, and drying in a drying oven at 70 ℃ for 5h to obtain oxidized carbon fiber;
step 3, primary grafting treatment of the carbon fibers: placing 10g of oxidation-treated carbon fiber and 300ml of 200-ml of anhydrous ethanol into a 500ml round-bottom flask, performing ultrasonic dispersion for 30-40min to obtain a carbon fiber suspension, then adding the carbon fiber suspension into a solution containing POE-g-MAH, adding 0.06-1 part of initiator, performing reflux reaction at 40-50 ℃ for 2-3h, washing, and drying to obtain grafting-treated carbon fiber for later use;
step 4, oxidation treatment of graphene: firstly, 100ml of concentrated sulfuric acid is put into a reaction bottle, the temperature in the reaction bottle is controlled within 4 ℃ by using an ice-water bath, and then 4g of graphite powder and 2g of NaNO are put into the reaction bottle3Adding the mixture into concentrated sulfuric acid under the condition of intense stirring; then slowly adding a strong oxidant KMnO4Controlling the temperature of the system below 10 ℃, and continuously stirring for reaction for 1h to complete the low-temperature intercalation reaction; then the reaction bottle is moved to a constant temperature water bath kettle, the temperature of the system is raised to (36 +/-2) DEG C, and the system is continuously stirred for 30min at constant temperature to complete the medium temperature oxidation reaction; then slowly adding 400-500ml deionized water, and continuously stirring and reacting at (96 +/-2) DEG C for 20-30min to complete high-temperature hydrolysis; finally, adding 60-100ml of hydrogen peroxide (30%) to terminate the reaction, carrying out suction filtration while the reaction is hot, and washing the reaction product with deionized water until the reaction product is neutral to obtain graphene oxide;
step 5, secondary grafting treatment of carbon fibers: adding a proper amount of graphene oxide into an acetone solution, carrying out ultrasonic oscillation for 45-60min to obtain a uniformly dispersed graphene suspension, then adding a proper amount of grafting carbon fiber and an initiator into the graphene suspension, carrying out suction filtration after reacting for 12-14h at 85-100 ℃, washing and carrying out suction filtration on the carbon fiber after suction filtration, and drying for 5h at 60 ℃ under a vacuum condition to obtain a graphene oxide secondary grafting carbon fiber, namely a carbon fiber/graphene modified composite carbon material.
(II) blending type process:
step 6, accurately weighing the dried PBT, POE, carbon fiber/graphene modified composite carbon material, compatilizer, antioxidant and lubricant according to the weight part ratio, and then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture;
and 7, adding the prepared mixture into a torque rheometer, wherein the melt mixing temperature is 230 ℃, the rotor speed is 50r/min, and the melt mixing time is about 10min, hot-pressing and molding the composite material obtained after blending by using a flat vulcanizing machine, wherein the hot-pressing temperature is 235 ℃, the melting time is 5-7 min, the hot-pressing time is 10min, and the heat preservation time is 15min, so that the PBT composite material is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652018A (en) * | 2021-06-22 | 2021-11-16 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
| CN115522276A (en) * | 2022-09-28 | 2022-12-27 | 太仓荣文合成纤维有限公司 | Preparation method of conductive and reinforced PBT fiber |
| CN115534466A (en) * | 2021-06-30 | 2022-12-30 | 南亚塑胶工业股份有限公司 | Antibacterial and mildewproof polyester laminated structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199229A (en) * | 2015-10-27 | 2015-12-30 | 济南大学 | Graphene oxide-carbon fiber reinforced polypropylene composite and preparation method thereof |
| CN105239357A (en) * | 2015-08-24 | 2016-01-13 | 哈尔滨工业大学 | Method of chemically-grafting graphene oxide onto surface of carbon fiber |
| KR101597213B1 (en) * | 2014-11-25 | 2016-02-24 | 롯데케미칼 주식회사 | Dispersion for modifying carbon fiber surface, method of modifying carbon fiber surface, and preparation method of fibers reinforced composites |
| CN111205558A (en) * | 2020-02-28 | 2020-05-29 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene-reinforced heat-conducting polymer composite material, preparation method thereof and heat-conducting product |
-
2020
- 2020-06-28 CN CN202010597831.7A patent/CN111825962A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101597213B1 (en) * | 2014-11-25 | 2016-02-24 | 롯데케미칼 주식회사 | Dispersion for modifying carbon fiber surface, method of modifying carbon fiber surface, and preparation method of fibers reinforced composites |
| CN105239357A (en) * | 2015-08-24 | 2016-01-13 | 哈尔滨工业大学 | Method of chemically-grafting graphene oxide onto surface of carbon fiber |
| CN105199229A (en) * | 2015-10-27 | 2015-12-30 | 济南大学 | Graphene oxide-carbon fiber reinforced polypropylene composite and preparation method thereof |
| CN111205558A (en) * | 2020-02-28 | 2020-05-29 | 新奥（内蒙古）石墨烯材料有限公司 | Graphene-reinforced heat-conducting polymer composite material, preparation method thereof and heat-conducting product |
Non-Patent Citations (1)
| Title |
|---|
| 孔子明: "《最新新型工程材料生产新技术应用与新产品开发研制及行业技术标准实用大全》", 30 November 2004 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652018A (en) * | 2021-06-22 | 2021-11-16 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
| CN115534466A (en) * | 2021-06-30 | 2022-12-30 | 南亚塑胶工业股份有限公司 | Antibacterial and mildewproof polyester laminated structure |
| CN115522276A (en) * | 2022-09-28 | 2022-12-27 | 太仓荣文合成纤维有限公司 | Preparation method of conductive and reinforced PBT fiber |
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