CN114369352B - High-toughness heat-conducting PC composite material and preparation method thereof - Google Patents
High-toughness heat-conducting PC composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-toughness heat-conducting PC composite material and a preparation method thereof, belonging to the field of polymer composite materials. The high-toughness heat-conducting PC composite material is prepared from the following raw materials in parts by weight: 100 parts of PC, 5-20 parts of a toughening agent, 1-8 parts of a heat conduction auxiliary agent and 0.5 part of dioctyl phthalate, wherein the toughening agent is GF-g-PMMA, and the heat conduction agent is BM-TA. The high-toughness heat-conducting PC composite material prepared by the invention has a scientific and reasonable formula and a simple and practical process flow, the toughening agent mainly takes glass fiber as a main component, the surface of the toughening agent is modified by KH560, and PMMA is further grafted on the surface of the toughening agent; according to the invention, the tannin modified boehmite is used as the heat conducting agent to enhance the compatibility with the matrix material, and GF-g-PMMA is used as the toughening agent, BM-TA is used as the heat conducting agent, so that the mechanical property and the heat conductivity of PC can be effectively increased, and the PC composite material with excellent performance is prepared.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a high-toughness heat-conducting PC composite material and a preparation method thereof.
Background
Polycarbonate (PC) is one of five major engineering plastics in widespread use. The PC has good mechanical properties, particularly excellent impact strength, and can keep the shape unchanged in a wider temperature range. PC is an amorphous transparent material, has good heat resistance, has a heat distortion temperature of 135-145 ℃, and can improve the bending strength, the elastic modulus and the like by heat treatment for a long time above 100 ℃. Since the market was entered in the sixties of the last century, PCs have been widely used in the fields of electric appliances, machinery, electronics, automobiles, instruments, aviation, and home life. However, PC has significant disadvantages, such as high melt viscosity, difficulty in processing, high internal stress, susceptibility to stress cracking of the finished product, and resistance to chemical agents, particularly swelling, cracking, and degradation in alkaline and organic solvents. The main chain of the PC structural unit is connected with two benzene rings, so that the PC structural unit has high rigidity and cannot bend. The ester group has larger polarity, strong intermolecular force, difficult movement of polymer molecular chain segments and higher Tg of PC.
The glass fiber is an inorganic non-metallic reinforcing material with excellent performance, has the characteristics of good heat resistance, high mechanical strength and the like, can effectively enhance various performances of the glass fiber by modifying the surface of the glass fiber by using the silane coupling agent, and can enhance the compatibility of PC and the heat-conducting filler added in experiments by grafting the polymethyl methacrylate, thereby enhancing the performances of the glass fiber.
Boehmite (BM) is a fine white crystal, has complete crystallization, fine crystal grains and few crystal structure defects, so the thermal conductivity is higher. However, at present, reliable data of boehmite thermal conductivity coefficient do not exist, but the thermal conductivity of the room temperature vulcanized silicone rubber filled with boehmite is between that of zinc oxide and silicon nitride, and compared with other heat conduction materials, boehmite has unique advantages, smaller hardness and density, proper price, smaller abrasion to a screw rod in the processing process, smaller product density and competitiveness, and has very strong practical value by using boehmite as a heat conduction filler.
According to the invention, the high-toughness heat-conducting PC composite material is prepared by a melt blending method of the toughening agent and the heat conducting agent, the surface of the glass fiber is modified by the toughening agent through KH560, and then PMMA is grafted, so that the compatibility and mechanical property of the matrix material are improved, and agglomeration is prevented. Secondly, the heat conducting agent is based on boehmite, the boehmite has good heat conductivity, the surface of the boehmite is coated with tannic acid, and the tannic acid has a unique molecular structure, good biocompatibility and high chemical activity, and contains a large amount of phenolic hydroxyl on the surface, so that strong van der Waals force and hydrogen bonds can be formed when the tannin is compounded with the boehmite, and the heat conductivity and the mechanical property of the composite material are further improved.
Disclosure of Invention
The invention aims to provide a high-toughness heat-conducting PC composite material and a preparation method thereof. The invention has scientific and reasonable formula and simple and practical process flow, and the produced PC composite material has excellent mechanical property and heat-conducting property by adding the toughening agent and the heat-conducting agent, and can generate great social and economic benefits.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the high-toughness heat-conducting PC composite material comprises the following raw materials in parts by weight: 100 parts of PC, 5-20 parts of a toughening agent, 1-8 parts of a heat conducting agent and 0.5 part of dioctyl phthalate, wherein the toughening agent is GF-g-PMMA, and the heat conducting agent is BM-TA.
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The concrete preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat at 500 ℃ for 3h, adding 65wt% nitric acid, reacting at 70 ℃ for 5h, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =4-5, and then mechanically stirred at 80 ℃ for 1h, centrifuged, washed, and dried to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of Boehmite (BM) and adding the boehmite into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, suction filtering and drying to obtain a product BM-TA.
3) Adding GF-g-PMMA prepared in the step 1) and BM-TA prepared in the step 2) into dioctyl phthalate, uniformly mixing, then uniformly mixing with PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing in an oven at the temperature of 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
The invention has the beneficial effects that:
the high-toughness heat-conducting PC composite material prepared by the invention is scientific and reasonable in formula and simple and practical in process flow, the high-toughness heat-conducting PC composite material is prepared by a melt blending method of the toughening agent and the heat conducting agent, the surface of the glass fiber is modified by the toughening agent through KH560, and PMMA is grafted, so that the compatibility and mechanical property of a matrix material are improved, and agglomeration is prevented. Secondly, the heat conducting agent is based on boehmite, the boehmite has good heat conductivity, the surface of the boehmite is coated with tannic acid, and the tannic acid has a unique molecular structure, good biocompatibility and high chemical activity, and the surface of the tannin contains a large number of phenolic hydroxyl groups, so that strong van der Waals force and hydrogen bonds can be formed when the tannin is compounded with the boehmite, and the heat conductivity and the mechanical property of the composite material are further improved.
Drawings
FIG. 1 is an infrared image of GF-g-PMMA prepared in example 1. 2952 cm in the figure -1 And 2859 cm -1 Is the stretching vibration peak of methyl and methylene, 1650cm -1 Is the stretching vibration peak of the carbon-carbon double bond, and shows that KH560 has been successfully introduced to the surface of the glass fiber, 1728 cm -1 Being antisymmetric to carbon-oxygen double bondsAnd (4) stretching and vibrating peaks, which show that PMMA is successfully grafted on the surface of GF-KH 560.
FIG. 2 is an SEM image of BM-TA prepared in example 1, and it can be seen that the surface of BM is coated with tannin and the agglomeration phenomenon is not very obvious.
Detailed Description
The present invention will be further understood from the following examples, which are not intended to limit the scope of the invention.
Example 1
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The concrete preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the BM-TA product.
3) Adding 5 parts by weight of a toughening agent GF-g-PMMA and 6 parts by weight of a heat conducting agent BM-TA into 0.5 part by weight of dioctyl phthalate, uniformly mixing the materials, and then uniformly mixing the materials with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing the materials in an oven at the temperature of 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first-stage temperature: 300 ℃ and second stage temperature: 290 ℃ and third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Example 2
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat at 500 ℃ for 3h, adding 65wt% nitric acid, reacting at 70 ℃ for 5h, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the BM-TA product.
3) Adding 10 parts by weight of toughening agent GF-g-PMMA and 6 parts by weight of heat conducting agent BM-TA into 0.5 part by weight of dioctyl phthalate, uniformly mixing, then uniformly mixing with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing in an oven at 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first-stage temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining pressure: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Example 3
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The concrete preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat at 500 ℃ for 3h, adding 65wt% nitric acid, reacting at 70 ℃ for 5h, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the BM-TA product.
3) 15 parts by weight of a toughening agent GF-g-PMMA and 6 parts by weight of a heat conducting agent BM-TA are added into 0.5 part by weight of dioctyl phthalate and are uniformly mixed, and then the mixture is uniformly mixed with 100 parts by weight of PC particles in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 300 r/min, the temperature is 60 ℃, and then the mixture is placed in an oven at 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first-stage temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Example 4
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat at 500 ℃ for 3h, adding 65wt% nitric acid, reacting at 70 ℃ for 5h, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding the BM into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the product BM-TA.
3) 20 parts by weight of a toughening agent GF-g-PMMA and 6 parts by weight of a thermal conduction agent BM-TA are added into 0.5 part by weight of dioctyl phthalate and are uniformly mixed, and then the mixture is uniformly mixed with 100 parts by weight of PC particles in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 300 r/min, the temperature is 60 ℃, and then the mixture is placed in an oven at 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Performance testing
TABLE 1
Table 1 shows the results of the performance tests of each of examples 1 to 4. From the above performance test results, it is obvious that, on the basis of adding 6 parts by weight of the thermal conductive agent, as the addition amount of the toughening agent GF-g-PMMA is increased from 5 parts to 15 parts, the tensile strength, the notch impact strength and the bending strength of the PC composite material are increased, and the thermal conductivity is reduced. When the addition amount of the toughening agent is 20 parts by weight, the four performance improvement effects are not remarkable and even slightly reduced, and the toughening agent is likely to agglomerate in the matrix material to influence the performance. From the comprehensive performance, the effect is best when the addition amount of the toughening agent GF-g-PMMA is 15 parts by weight.
Example 5
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The concrete preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding the BM into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the product BM-TA.
3) 15 parts by weight of a toughening agent GF-g-PMMA and 2 parts by weight of a heat conducting agent BM-TA are added into 0.5 part by weight of dioctyl phthalate and are uniformly mixed, and then the mixture is uniformly mixed with 100 parts by weight of PC particles in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 300 r/min, the temperature is 60 ℃, and then the mixture is placed in an oven at 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃ and third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Example 6
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a three-neck flask containing 50ml of absolute ethyl alcohol, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding the BM into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the product BM-TA.
3) Adding 15 parts by weight of a toughening agent GF-g-PMMA and 4 parts by weight of a heat conducting agent BM-TA into 0.5 part by weight of dioctyl phthalate, uniformly mixing the materials, and then uniformly mixing the materials with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing the materials in an oven at the temperature of 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first-stage temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Example 7
The preparation method of the high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding the BM into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the product BM-TA.
3) 15 parts by weight of a toughening agent GF-g-PMMA and 8 parts by weight of a heat conducting agent BM-TA are added into 0.5 part by weight of dioctyl phthalate and are uniformly mixed, and then the mixture is uniformly mixed with 100 parts by weight of PC particles in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 300 r/min, the temperature is 60 ℃, and then the mixture is placed in an oven at 100 ℃ for drying for 6 hours.
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining pressure: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Comparative example 1
A high-toughness PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) Adding 15 parts by weight of a toughening agent GF-g-PMMA to 0.5 part by weight of dioctyl phthalate, uniformly mixing with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing in an oven at the temperature of 100 ℃ for drying for 6 hours.
3) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
4) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness PC composite material.
Comparative example 2
A heat-conducting PC composite material comprises the following specific steps:
1) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of Tannic Acid (TA) and adding the Tannic Acid (TA) into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid, then weighing 0.5g of BM and adding the BM into the tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain the product BM-TA.
2) Adding 6 parts by weight of heat conducting agent BM-TA into 0.5 part by weight of dioctyl phthalate, uniformly mixing, then uniformly mixing with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing in an oven at the temperature of 100 ℃ for drying for 6 hours.
3) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
4) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: and (4) obtaining the heat-conducting PC composite material under 40 MPa.
Comparative example 3
A high-toughness heat-conducting PC composite material comprises the following specific steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat at 500 ℃ for 3h, adding 65wt% nitric acid, reacting at 70 ℃ for 5h, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution (volume ratio is 1), and placing the glass fiber in a vacuum drying oven at 80 ℃ for drying for 12h to obtain GF. 2g of dried GF is weighed and placed in a three-neck flask, and a deionized water-ethanol mixed solution (volume ratio is 1. Then, 2ml of KH560 was added dropwise, and the mixture was stirred at room temperature for 30min with glacial acetic acid to adjust pH =5, followed by mechanical stirring at 80 ℃ for 1h, centrifugal washing, and drying to obtain modified GF. And then weighing 1g of modified GF, adding the modified GF into a 50ml absolute ethyl alcohol three-neck flask, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA.
2) 15 parts by weight of a toughening agent GF-g-PMMA and 6 parts by weight of BM are added into 0.5 part by weight of dioctyl phthalate and uniformly mixed, and then the mixture is uniformly mixed with 100 parts by weight of PC particles in a high-speed mixer, wherein the rotating speed of the high-speed mixer is 300 r/min, the temperature is 60 ℃, and then the mixture is placed in an oven at 100 ℃ for drying for 6 hours.
3) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; and extruding and granulating to obtain the mixed master batch.
4) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
Performance testing
TABLE 2
Table 2 shows the results of the performance tests of examples 5, 6, 3, and 7 and comparative examples 1, 2, and 3. From the above performance test results, it is obvious that in examples 5, 6, 3 and 7, the tensile strength, the notch impact strength and the bending performance of the PC composite material gradually increase with the increase of the addition amount of the thermal conductive agent, but the increase tendency is small, and the thermal conductive performance is continuously improved. Comparing the comparative example 2 with the example 3, it can be seen that the addition of the toughening agent GF-g-PMMA can effectively improve the mechanical property of the PC composite material and simultaneously reduce the thermal conductivity, and as the glass fiber is a heat insulating material and has low thermal conductivity, the thermal conductivity of the composite material is continuously reduced along with the further increase of the addition amount. As can be seen by comparing example 3 with comparative example 3, whether or not TA is grafted on boehmite has an influence on both the mechanical properties and the thermal conductivity of the PC composite material. The tannic acid TA has good biocompatibility and high chemical activity, and the surface of the tannic acid TA contains a large amount of phenolic hydroxyl groups, so that strong van der Waals force and hydrogen bonds can be formed when the tannic acid TA is compounded with boehmite, the compatibility of the boehmite and a PC material can be improved, the agglomeration condition of the boehmite is improved, and the mechanical property and the thermal conductivity of the composite material are improved. In view of comprehensive performance, the PC composite material with excellent mechanical property and thermal conductivity can be prepared under the condition that 15 parts by weight of the toughening agent GF-g-PMMA and 8 parts by weight of the thermal conductive agent BM-TA are added.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (1)
1. A preparation method of a high-toughness heat-conducting PC composite material is characterized by comprising the following steps: the raw materials comprise the following components in parts by weight: 100 parts of PC, 15 parts of a toughening agent, 8 parts of a heat conducting agent and 0.5 part of dioctyl phthalate, wherein the toughening agent is GF-g-PMMA, and the heat conducting agent is BM-TA;
the preparation method of the high-toughness heat-conducting PC composite material comprises the following steps:
1) The specific preparation process of the toughening agent GF-g-PMMA comprises the following steps:
preparation of GF-g-PMMA: placing 5g of glass fiber in a muffle furnace, preserving heat for 3h at 500 ℃, adding 65wt% nitric acid, reacting for 5h at 70 ℃, washing the glass fiber to be neutral by using a deionized water-ethanol mixed solution with the volume ratio of 1; weighing 2g of dried GF, placing the dried GF in a three-neck flask, adding a deionized water-ethanol mixed solution with the volume ratio of 1; then weighing 1g of modified GF, adding the modified GF into a three-neck flask containing 50ml of absolute ethyl alcohol, adding 5 ml of methyl methacrylate, stirring for 10min, adding 0.1g of dibenzoyl peroxide, condensing and refluxing at 50 ℃ for 20min, heating to 85 ℃ after the dibenzoyl peroxide is completely dissolved, reacting at constant temperature for 6h, cooling to room temperature, and centrifugally drying to obtain GF-g-PMMA;
2) The preparation process of the heat conducting agent BM-TA comprises the following steps:
preparation of BM-TA: weighing 0.2g of tannic acid TA, adding the tannic acid TA into a beaker filled with 200ml of deionized water, stirring for 30min to fully dissolve the tannic acid TA, then weighing 0.5g of BM, adding the BM into a tannic acid aqueous solution, stirring for 2h at room temperature, and finally washing, filtering and drying to obtain a product BM-TA;
3) Adding 15 parts by weight of a toughening agent GF-g-PMMA and 8 parts by weight of a heat conducting agent BM-TA into 0.5 part by weight of dioctyl phthalate, uniformly mixing the mixture with 100 parts by weight of PC particles in a high-speed mixer at the rotating speed of 300 r/min and the temperature of 60 ℃, and then placing the mixture in an oven at the temperature of 100 ℃ for drying for 6 hours;
4) Adding the dried raw materials into a double-screw extruder, wherein the temperature of the first section of the double-screw extruder is 275 ℃, the temperature of the second section of the double-screw extruder is 270 ℃, the temperature of the third section of the double-screw extruder is 270 ℃, the temperature of the fourth section of the double-screw extruder is 260 ℃, and the temperature of the fifth section of the double-screw extruder is 255 ℃; the rotating speed of the screw is 10 r/min; extruding and granulating to obtain mixed master batches;
5) Drying the mixed master batch obtained by the double-screw extruder and the granulator in a drying oven at 100 ℃ for 6 hours, and performing injection molding by using an injection molding machine, wherein the temperatures from a feed inlet to a discharge outlet of the injection molding machine are respectively a first section temperature: 300 ℃ and second stage temperature: 290 ℃, third stage temperature: 285 ℃ and fourth stage temperature: 275 ℃ and temperature in the fifth stage: 265 ℃ of water; injection molding pressure: 135MPa; pressure maintaining pressure: 40MPa, and obtaining the high-toughness heat-conducting PC composite material.
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| CN113773458A (en) * | 2021-09-14 | 2021-12-10 | 安徽华超新材料科技有限公司 | Modification treatment method of chopped glass fibers |
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| CN109575551A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Modified resin and its preparation method and application for heat conduction and heat radiation |
| CN113773458A (en) * | 2021-09-14 | 2021-12-10 | 安徽华超新材料科技有限公司 | Modification treatment method of chopped glass fibers |
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