CN114149666A - PBT composite material and preparation method thereof - Google Patents
PBT composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PBT composite material and a preparation method thereof, wherein the PBT composite material is synthesized by the following raw materials: PBT resin, modified carbon nano tubes, modified carbon fibers, basic copper phosphate, tin oxide, spherical calcium carbonate, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, a main antioxidant and an auxiliary antioxidant. The PBT composite material has excellent mechanical property and wave-absorbing property, can be directly formed by laser, and is applied to the field of electronic and electrical equipment affected by electromagnetic interference.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a PBT composite material and a preparation method thereof.
Background
Microwave absorbing materials have received increased attention in recent years and have become an important component of civilian, commercial and military stealth defense systems. Microwave absorbing materials are used primarily to destroy electromagnetic interference to reduce environmental pollution caused by industrial and commercial use of electrical and electronic equipment, absorb microwaves incident on the surface of the material, and convert electromagnetic energy into internal energy or other forms of energy through loss mechanisms within the material. Carbon-based materials such as carbon black, graphite, carbon fiber, carbon nanotube, and the like have been widely studied. Compared with a Carbon Nano Tube (CNTs) reinforced resin matrix composite material and a carbon fiber reinforced resin matrix composite material, the CNTs/carbon fibers jointly reinforce the resin matrix composite material, and fully utilize mutual interaction and synergistic action, so that the defect of performance improvement of a single reinforced relative composite material is overcome, the performance of the composite material is qualitatively changed, for example, the crack resistance of a matrix is improved, and the wave absorbing performance, the interlayer fracture toughness, the impact resistance, the wear resistance and the like of the composite material are improved.
The interconnection communication industry developing at a high speed requires flexible signal frequency band configuration, narrow frequency receiving and transmitting, miniaturization of components and three-dimensional integration design, the traditional processing mode cannot meet the industrial development requirements, and the Laser Direct Structuring (LDS) technology has obvious technical and performance advantages in the production of electronic devices with integrated circuit carriers and shells due to the fact that the miniaturization, circuit design flexibility and environment-friendly processing process of electronic circuits can be realized. The laser direct forming material is suitable for preparing high-frequency and ultrahigh-frequency information antenna transceiving devices, can replace the traditional plastic material and metal patch process and the functional high-dielectric ceramic sintering technology, improves the system integration design redundancy and the production and manufacturing efficiency, is used for the field of signal receiving devices such as mobile communication and intelligent Internet of things, and has wide market prospect.
At present, some researches are made on a PBT composite material with wave-absorbing performance and an LDS technology in the prior art, such as: chinese patent CN 110205096A discloses a preparation method and application of an adjustable microporous wave-absorbing metamaterial, which is prepared from the following components in parts by weight: 3080 parts of metal framework material, 2070 parts of polymer resin powder, 2050 parts of wave-absorbing and heat-dissipating material, 2050 parts of carbon fiber, 13 parts of polyol, 0.20.5 parts of zinc sulfide and 0.21 parts of lubricant; chinese patent CN 103467937A discloses a master batch with wave-absorbing and radiation-proof functions, which is prepared by a resin matrix and functional additives through a blending and extrusion mode; the raw material of the resin matrix is resin powder obtained by shunting polyester chips step by step through a water milling method; the functional additives are conductive microfibers, whiskers and conductive powder subjected to surface modification treatment, and are uniformly dispersed in the resin matrix; chinese patent CN 109627712A discloses a PBT composition and a preparation method and application thereof. The PBT composition comprises PBT, glass fibers, and hollow metal oxide particles; the hollow metal oxide particles comprise hollow microspheres and metal oxide coated on the surfaces of the hollow microspheres, wherein the metal oxide can be activated by laser to form metal cores. The PBT composition is prepared by a method of melt extruding PBT, glass fiber and hollow metal oxide particles by using an extruder; chinese patent CN 110317437A discloses a laser direct forming resin and a preparation method thereof, which is prepared by high-speed mixing, mixing and extruding of 4070 parts of PBT resin, 5 parts of LDS additive, 2030 parts of ABS resin, 515 parts of aluminum titanate, 510 parts of flexibilizer and 0.4 part of antioxidant.
Therefore, the PBT composite material disclosed in the prior art only has single function and wave-absorbing performance or laser direct forming performance, and the PBT composite material which has the wave-absorbing performance and can be directly formed by laser has no related patent publication for a while.
Disclosure of Invention
Based on the above, one of the purposes of the invention is to provide a PBT composite material with wave-absorbing performance and capable of being directly formed by laser, which is applied to the field of electronic and electrical equipment affected by electromagnetic interference.
The specific technical scheme for realizing the aim of the invention is as follows:
the PBT composite material is prepared from the following raw materials in parts by weight:
the modified carbon nano tube (m-CNTs) is obtained by modifying Carbon Nano Tubes (CNTs) by 1,3, 5-benzenetricarboxylic acid;
the modified carbon fiber (m-CF) is obtained by modifying Carbon Fiber (CF) with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
In some embodiments, the PBT composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the PBT composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the method for preparing the modified carbon nanotube comprises the following steps: dispersing 100 parts by weight of carbon nano tubes in a polyphosphoric acid solution, adding 40-60 parts by weight of 1,3, 5-benzenetricarboxylic acid and 5-15 parts by weight of phosphorus pentoxide, heating to 90-110 ℃ under the protection of nitrogen, stirring for 1-3 hours, dripping 5-15 parts by weight of phosphoric acid, then continuously heating to 120-140 ℃, stirring for 10-16 hours, cooling to normal temperature, filtering the modified carbon nano tubes by using a microporous filter membrane and an acid-base-resistant funnel, washing for 1-3 times by using acetone, and then drying the obtained modified carbon nano tubes at 50-70 ℃.
In some embodiments, the method for preparing the modified carbon fiber comprises the following steps: putting 100 parts by weight of carbon fiber into a stirrer, atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1: 7-13 onto the carbon fiber at normal temperature, stirring and scattering at 1000-2000 r/min, and heating and drying to obtain modified carbon fiber; the amount of the mixed liquid is 2-4% of the mass of the carbon fiber.
In some of these embodiments, the primary antioxidant is 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
The invention also aims to provide a preparation method of the PBT composite material.
The specific technical scheme for realizing the aim of the invention is as follows:
a preparation method of a PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 100-120 ℃ for 2-4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 225-245 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 235-255 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 230-250 ℃, the temperature of the die head is 230-250 ℃, and the rotating speed of the screw is 200-600 rpm.
In some of these embodiments, a method of making the PBT composite includes the steps of:
(1) drying the PBT resin at the temperature of 105-115 ℃ for 2.5-3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone), and adding the modified carbon fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 225-235 ℃, the temperature of the second zone is 230-240 ℃, the temperature of the third zone is 235-245 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 240-250 ℃, the temperature of the sixth zone is 240-250 ℃, the temperature of the seventh zone is 235-245 ℃, the temperature of the eighth zone is 235-245 ℃, the temperature of the die head is 235-245 ℃, and the rotating speed of the screw is 300-500 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area.
In some of these embodiments, the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
In some embodiments, in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500-.
The PBT composite material has the following functions of raw materials:
the principle of the conductive loss type wave absorbing agent is that under the action of an electric field, conductive carriers do directional drift motion, so that conductive current can be formed in a wave absorbing material, the current is thermally lost, namely, the conductive loss is obtained, and the wave absorbing agent belonging to the conductive loss type comprises carbon nano tubes, carbon fibers and the like. Compared with a Carbon Nano Tube (CNTs) reinforced resin matrix composite material and a carbon fiber reinforced resin matrix composite material, the CNTs/carbon fibers jointly reinforce the resin matrix composite material, and fully utilize mutual interaction and synergistic action, so that the defect of performance improvement of a single reinforced relative composite material is overcome, the performance of the composite material is qualitatively changed, for example, the crack resistance of a matrix is improved, and the wave absorbing performance, the interlayer fracture toughness, the impact resistance, the wear resistance and the like of the composite material are improved. The conductivity loss influence factor is conductivity, and the larger the conductivity is, the larger the current caused by the change of the electric field and the eddy current caused by the change of the magnetic field are, the larger the loss of the electromagnetic energy is. Therefore, more effective conductive networks can be formed by compounding and using the modified carbon nano tubes and the modified carbon fibers, and the conductivity is increased, so that the conductivity loss is increased, and the wave-absorbing performance is improved.
The basic copper phosphate can be used as a laser sensitive additive, and after laser irradiation, the basic copper phosphate can release metal copper atoms with reducibility, so that a catalytic activation center is provided for subsequent chemical plating, metal ions in chemical plating solution are promoted to be deposited in a laser region to form a conductive pattern, and the metal copper atoms also have the effect of increasing the bonding strength of a plating layer and a resin matrix. The Cu and Sn have high absorptivity to near infrared laser, based on the interaction theory of the Cu and Sn and laser and the rutile structure of tin oxide, when the near infrared laser irradiates the surface of a material, the laser energy initiates the physical and chemical reaction in the material, the valence bond of the tin oxide is broken, tin particles are exposed and deposited on the surface of the material, the relative density of tin atoms is higher, more catalytic activation seeds can be provided for chemical copper plating, and because the number of atoms on the surface of a nanoparticle is more, the coordination number of surface atoms is insufficient and the combination energy is different from that of internal atoms, the nanoparticle has high surface energy and high surface activity, and in the chemical copper plating process, the tin atoms on the surface of the material are more likely to react with other atoms in a chemical plating solution, so that the catalytic activity of the tin atoms as the activation seeds is improved. In addition, the spherical calcium carbonate is beneficial to improving the roughness of the surface of the LDS part, thereby being beneficial to copper deposition in the chemical copper plating process. Therefore, when the basic copper phosphate, the tin oxide and the spherical calcium carbonate are used as the laser sensitive additive in a compounding way, more activated seeds and catalytic activity can be provided, the chemical plating time of a sample is shorter, the speed is higher, the plating layer is finer and smoother, and the binding force between the plating layer and a matrix resin material is better.
The main antioxidant 1,3, 5-tri (4-tertiary butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the auxiliary antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite have high heat resistance, are suitable for being used in blending preparation and have good compatibility with PBT materials.
Compared with the prior art, the PBT composite material and the preparation method thereof provided by the invention have the following beneficial effects:
1. the modified carbon nano tube and the modified carbon fiber are compounded to form more effective conductive networks, so that the conductivity is increased, the conductivity loss is increased, and the wave-absorbing performance of the PBT composite material is improved.
2. When the basic copper phosphate, the tin oxide and the spherical calcium carbonate are used as the laser sensitive additive in a compounding way, more activated seeds and catalytic activity can be provided, the chemical plating time of a sample is shorter, the speed is higher, the plating layer is finer and smoother, and the binding force between the plating layer and a matrix resin material is better.
3. The preparation method of the PBT composite material provided by the invention has the advantages of simple process, easiness in control and low requirements on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the preparation method is favorable for industrial production.
Drawings
FIG. 1 is a flow chart of a preparation process of the PBT composite material.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The reaction mechanism of the PBT composite material is as follows (see a preparation process flow chart in figure 1):
wherein R is modified carbon fiber, basic copper phosphate, tin oxide and spherical calcium carbonate.
Mechanism of reaction
As can be seen from the above reaction formula, (1) grafting 1,3, 5-benzenetricarboxylic acid on Carbon Nanotubes (CNTs) under the catalysis of polyphosphoric acid and phosphorus pentoxide to obtain modified carbon nanotubes (m-CNTs); (2) the terminal carboxyl of the modified carbon nano tube can react with the terminal hydroxyl of the PBT to obtain m-CNTs-g-PBT; (3) epoxy groups in the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate coated with the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane can react with terminal hydroxyl groups of the PBT, so that the compatibility and the interface cohesiveness of the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate with the PBT base material resin are improved.
The raw materials used in the embodiment of the invention are as follows:
PBT resin, available from Changchun plastics, Inc., Taiwan, China.
Carbon nanotubes, purchased from Shenzhen nanogang GmbH.
Carbon fibers, available from Shenzhou carbon fibers, Inc. of Jilin.
Copper hydroxide phosphate, available from western Asia chemical technology (Shandong) Inc.
Tin oxide, available from new materials science and technology ltd, wanshan, fluvial.
Spherical calcium carbonate purchased from Shenzhen Jinhaohui industry development Limited.
3- (2, 3-glycidoxy) propyltrimethoxysilane, available from Shanghai Georgi Silicone science, Inc.
1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, available from Shih chemical Co., Ltd.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite available from Shanghai Ji to Biochemical technology, Inc.
Polyphosphoric acid, purchased from Chongqing Chundong chemical Co., Ltd.
1,3, 5-benzenetricarboxylic acid, available from Shandong Hao Shunhu chemical Co., Ltd.
Phosphorus pentoxide, available from cyclolee chemical ltd, Shandong.
Phosphoric acid, available from national pharmaceutical group chemical reagents, ltd.
Acetone, available from national pharmaceutical group chemical agents, ltd.
Ethanol, available from national pharmaceutical group chemical agents, ltd.
Modified carbon nanotubes (m-CNTs) used in the following examples, the preparation method of which comprises the following steps: dispersing 100g of carbon nano tube in a polyphosphoric acid solution, adding 50g of 1,3, 5-benzenetricarboxylic acid and 10g of phosphorus pentoxide, heating to 100 ℃ under the protection of nitrogen, stirring for 2 hours, then dripping 10g of phosphoric acid, continuing heating to 130 ℃, stirring for 13 hours, cooling to normal temperature, filtering the modified carbon nano tube by a microfiltration membrane and an acid-alkali resistant funnel, washing for 2 times by acetone, and then drying the obtained modified carbon nano tube at 60 ℃.
The modified carbon fibers (m-CF) used in the following examples were prepared by a method comprising the steps of: putting 100g of carbon fiber into a stirrer, then atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1:10 onto the carbon fiber at normal temperature, stirring and scattering at 1500r/min, and heating and drying to obtain modified carbon fiber; the dosage of the mixed liquid is 3% of the mass of the carbon fiber.
The present invention will be described in detail with reference to specific examples.
Example 1 PBT composite Material and Process for producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 120 ℃ for 2 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 240 ℃, the temperature in the second zone was 245 ℃, the temperature in the third zone was 250 ℃, the temperature in the fourth zone was 255 ℃, the temperature in the fifth zone was 255 ℃, the temperature in the sixth zone was 255 ℃, the temperature in the seventh zone was 250 ℃, the temperature in the eighth zone was 250 ℃, the temperature of the die head was 250 ℃ and the screw speed was 600 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 2 PBT composite Material and method for producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 100 ℃ for 4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 220 ℃, the temperature in the second zone was 225 ℃, the temperature in the third zone was 230 ℃, the temperature in the fourth zone was 235 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 230 ℃, the temperature in the seventh zone was 230 ℃, the temperature in the eighth zone was 230 ℃, the temperature in the die head was 230 ℃ and the screw speed was 200 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 3 PBT composite Material and method of producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 115 ℃ for 2.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 235 deg.C, the temperature in the second zone was 240 deg.C, the temperature in the third zone was 245 deg.C, the temperature in the fourth zone was 250 deg.C, the temperature in the fifth zone was 250 deg.C, the temperature in the sixth zone was 250 deg.C, the temperature in the seventh zone was 245 deg.C, the temperature in the eighth zone was 245 deg.C, the temperature in the die head was 245 deg.C, and the screw speed was 500 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 4 PBT composite Material and method of producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at 105 ℃ for 3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 225 ℃, the temperature in the second zone was 230 ℃, the temperature in the third zone was 235 ℃, the temperature in the fourth zone was 240 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 235 ℃, the temperature in the eighth zone was 235 ℃, the temperature in the die head was 235 ℃ and the screw speed was 300 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 5 PBT composite Material and method of making the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 6 PBT composite Material and method of producing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Example 7 PBT composite and Process for preparing the same
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 1
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the side direction (the fourth zone) of the parallel double-screw extruder (total eight zones) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 2
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 r/min;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 3
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, the spherical calcium carbonate and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 4
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, the tin oxide and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
Comparative example 5
The PBT composite material is prepared from the following raw materials in parts by weight:
the preparation method of the PBT composite material comprises the following steps:
(1) drying the PBT resin at the temperature of 110 ℃ for 3 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing at the rotating speed of 1000 revolutions per minute;
(2) adding the basic copper phosphate, the tin oxide and the spherical calcium carbonate into another stirrer for mixing, wherein the rotating speed is 1000 revolutions per minute;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), and adding the modified carbon fiber into the other lateral direction (a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 230 ℃, the temperature in the second zone was 235 ℃, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 245 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 240 ℃ and the screw speed was 400 rpm.
The ratio L/D of the length L of the screw to the diameter D of the screw is 40; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
The following is a summary of the raw material compositions of examples 1-7 and comparative examples 1-5.
TABLE 1 summary of the raw material compositions of examples 1-7 and comparative examples 1-5
Wherein, the addition amounts of the primary antioxidant 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione and the secondary antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite of the above examples and comparative examples are 0.5 parts.
Examples 1 to 7 were conducted to prepare PBT composite materials by adjusting the addition amounts of modified carbon nanotubes, modified carbon fibers, basic copper phosphate, tin oxide, spherical calcium carbonate, and 3- (2, 3-glycidoxy) propyltrimethoxysilane, comparative examples 1 to 5 were conducted to prepare PBT composite materials on the basis of the raw materials of example 7, comparative example 1 was conducted without adding modified carbon fibers, comparative example 2 was conducted without adding modified carbon nanotubes, comparative example 3 was conducted without adding tin oxide, comparative example 4 was conducted without adding spherical calcium carbonate, and comparative example 5 was conducted without adding 3- (2, 3-glycidoxy) propyltrimethoxysilane. The PBT composite materials prepared by the above examples and comparative examples are subjected to the following performance tests:
tensile property: the tensile rate is 50mm/min according to the test of GB/T1040-2006 standard.
Wave-absorbing property: according to the GJB 5239-. The wider the width of the microwave frequency is, the better the coverage area is, and the higher the microwave frequency is, the better the coverage area is; the wave-absorbing performance reflects the wave-absorbing capacity of the material to electromagnetic waves, and the larger the absolute value of the wave-absorbing performance is, the more the electromagnetic waves passing through the material are attenuated, the better the wave-absorbing performance is.
Adhesion test of metal coating on plastic part surface (Baige test): testing according to ASTM D3359 standard, wherein under the conditions of room temperature 23 +/-2 ℃ and relative humidity 50 +/-5%, 10 multiplied by 10 small grids of 1 multiplied by 1mm are scribed on the surface of a test sample by a sharp blade (the blade angle is 15-30 ℃), and each scribing line is deep and a plating bottom layer is formed; the brush cleans the test area; firmly sticking the small tested grids by using a 3M600 adhesive tape, and forcibly wiping the adhesive tape by using an eraser to increase the contact area and force of the adhesive tape and the tested area; one end of the tape was grasped by hand and the scotch tape was quickly pulled off at an angle of 60 ° in the vertical direction and 2 identical tests were performed at the same location. And (4) judging a result: the adhesive force is qualified when the adhesive force is required to be more than or equal to 4B; 5B-the scribing edge is smooth, and no paint falls off at the scribing edge and the intersection; 4B-there are small pieces of paint falling off at the cross point of the line, and the total area of falling off is less than 5%; 3B-small pieces of paint fall off at the edge and the intersection of the scribing line, and the total falling area is between 5 and 15 percent; 2B-a piece of paint falls off at the edge and the intersection of the line, and the total area of the falling off is between 15 and 35 percent; 1B-a piece of paint falls off at the edge and the intersection of the line, and the total area of the falling off is between 35 and 65 percent; 0B-there is a patch of paint falling off at the edge and intersection of the score line, and the total area of falling off is greater than 65%.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of PBT composites of examples 1-7 and comparative examples 1-5
As can be seen from table 2:
with the reduction of the addition amount of the modified carbon fiber, the tensile strength of the PBT composite material shows a reduced variation trend. This is mainly because the modified carbon fiber has high strength and high rigidity, and has a strong reinforcing effect on the base resin.
With the reduction of the addition amount of the modified carbon nanotube and the modified carbon fiber, the wave absorbing capability of the PBT composite material is reduced. The carbon nanotube and the carbon fiber belong to a conductive loss type wave absorber, the conductive loss influence factor is conductivity, and the larger the conductivity is, the larger the current caused by the change of an electric field and the eddy current caused by the change of a magnetic field are, and the larger the loss of electromagnetic energy is. Because the addition amount of the modified carbon nano tube and the modified carbon fiber is reduced, the formed effective conductive network is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave absorbing performance is reduced.
With the reduction of the addition of the basic copper phosphate, the tin oxide and the spherical calcium carbonate, the adhesive force of the metal coating on the surface of the plastic part of the PBT composite material is not changed greatly. When the addition amount of the basic copper phosphate is 3 parts, the addition amount of the tin oxide is 0.5 part and the addition amount of the spherical calcium carbonate is 1 part, the adhesion force of the metal plating layer on the surface of the plastic part is reduced from 5B to 4B.
In conclusion, by adjusting the addition amounts of the modified carbon nanotube, the modified carbon fiber, the basic copper phosphate, the tin oxide, the spherical calcium carbonate and the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, the PBT composite material which has excellent mechanical properties and wave absorption properties and can be directly formed by laser can be obtained under the synergistic cooperation of all the additives.
Compared with the comparative example 1, the tensile strength and the wave absorbing performance of the comparative example 1 are lower than those of the example 7 without adding the modified carbon fiber. This is because the carbon fiber has high strength and high rigidity, and is higher than the carbon nanotube, so the tensile strength of example 7 is higher than that of comparative example 1; in addition, because the modified carbon nano tubes and the modified carbon fibers are not used in a compounding manner, an effective conductive network formed by the modified carbon nano tubes and the modified carbon fibers is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave-absorbing performance is reduced, so that the wave-absorbing performance of the embodiment 7 is higher than that of the comparative example 1.
Compared with the comparative example 2, the comparative example 2 does not add the modified carbon nano tube, and the wave absorbing performance of the modified carbon nano tube is lower than that of the example 7. Because the modified carbon nano tube and the modified carbon fiber are not used in a compounding way, an effective conductive network formed by the modified carbon nano tube and the modified carbon fiber is less, and the conductivity is reduced, so that the conductivity loss is reduced, and the wave absorbing performance is reduced.
Example 7 compared to comparative example 3, comparative example 3 was conducted without tin oxide and the adhesion of the metal coating on the surface of the plastic part was reduced from 5B to 4B. The absorption rate of Cu and Sn to near infrared laser is high, based on the interaction theory of Cu and Sn and laser and the rutile structure of tin oxide, when near infrared laser irradiates the surface of a material, laser energy initiates a physical and chemical reaction in the material, the valence bond of tin oxide is broken, tin particles are exposed and deposited on the surface of the material, the relative density of tin atoms is high, more catalytic activation seeds can be provided for chemical copper plating, and the surface of a nanoparticle has high surface energy and high surface activity because the number of atoms on the surface of the nanoparticle is large, the coordination number of surface atoms is insufficient and the binding energy is different from that of internal atoms, the tin atoms on the surface of the material are easy to react with other atoms in chemical plating solution in the chemical copper plating process, and the catalytic activity of the tin atoms as the activation seeds is improved. Thus, comparative example 3, which did not contain tin oxide, had a plastic part surface with a metallic coating with poorer adhesion than example 7.
Example 7 compared to comparative example 4, comparative example 4 had no spherical calcium carbonate added and the adhesion of the metal coating on the surface of the plastic part decreased from 5B to 4B. This is because spherical calcium carbonate is beneficial to improving the roughness of the surface of the LDS part, thereby being beneficial to copper deposition in the electroless copper plating process. Thus, comparative example 4, which did not contain spherical calcium carbonate, had a plastic part surface with a metal coating having a poorer adhesion than example 7.
Example 7 in comparison to comparative example 5, which did not add 3- (2, 3-glycidoxy) propyltrimethoxysilane, had a poorer tensile strength than example 7. The epoxy groups in the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate coated with the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane can react with the terminal hydroxyl groups of the PBT, so that the compatibility and the interface cohesiveness of the modified carbon fiber, the basic copper phosphate, the tin oxide and the spherical calcium carbonate with the PBT base material resin are improved, and the tensile strength of the PBT composite material is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The PBT composite material is characterized by being prepared from the following raw materials in parts by weight:
the modified carbon nanotube is obtained by modifying a carbon nanotube by 1,3, 5-benzenetricarboxylic acid;
the modified carbon fiber is obtained by modifying carbon fiber with 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
2. The PBT composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
3. the PBT composite material according to claim 2, which is prepared from the following raw materials in parts by weight:
4. the PBT composite material according to any one of claims 1 to 3, wherein the preparation method of the modified carbon nanotubes comprises the following steps: dispersing 100 parts by weight of carbon nano tubes in a polyphosphoric acid solution, adding 40-60 parts by weight of 1,3, 5-benzenetricarboxylic acid and 5-15 parts by weight of phosphorus pentoxide, heating to 90-110 ℃ under the protection of nitrogen, stirring for 1-3 hours, dripping 5-15 parts by weight of phosphoric acid, then continuously heating to 120-140 ℃, stirring for 10-16 hours, cooling to normal temperature, filtering the modified carbon nano tubes by using a microporous filter membrane and an acid-base-resistant funnel, washing for 1-3 times by using acetone, and then drying the obtained modified carbon nano tubes at 50-70 ℃.
5. The PBT composite material according to any one of claims 1 to 3, wherein the preparation method of the modified carbon fiber comprises the following steps: putting 100 parts by weight of carbon fiber into a stirrer, atomizing and spraying a mixed solution of ethanol and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane with a mass ratio of 1: 7-13 onto the carbon fiber at normal temperature, stirring and scattering at 1000-2000 r/min, and heating and drying to obtain the modified carbon fiber; the amount of the mixed liquid is 2-4% of the mass of the carbon fiber.
6. The PBT composite material according to any one of claims 1 to 3, wherein the primary antioxidant is 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, and the secondary antioxidant is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
7. The preparation method of the PBT composite material according to any one of claims 1 to 6, which comprises the following steps:
(1) drying the PBT resin at the temperature of 100-120 ℃ for 2-4 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, adding the modified carbon fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 225-245 ℃, the temperature of the third zone is 230-250 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 235-255 ℃, the temperature of the seventh zone is 230-250 ℃, the temperature of the eighth zone is 230-250 ℃, the temperature of the die head is 230-250 ℃, and the rotating speed of the screw is 200-600 rpm.
8. The process for the preparation of a PBT composite according to claim 7, comprising the steps of:
(1) drying the PBT resin at the temperature of 105-115 ℃ for 2.5-3.5 hours, cooling, and adding the cooled PBT resin, the modified carbon nano tube, the main antioxidant and the auxiliary antioxidant into a stirrer for mixing;
(2) adding the basic copper phosphate, tin oxide, spherical calcium carbonate and 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into another stirrer for mixing;
(3) adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into the parallel double-screw extruder in the lateral direction, adding the modified carbon fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating, wherein the process parameters comprise: the temperature of the first zone is 225-235 ℃, the temperature of the second zone is 230-240 ℃, the temperature of the third zone is 235-245 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 240-250 ℃, the temperature of the sixth zone is 240-250 ℃, the temperature of the seventh zone is 235-245 ℃, the temperature of the eighth zone is 235-245 ℃, the temperature of the die head is 235-245 ℃, and the rotating speed of the screw is 300-500 rpm.
9. The process for preparing a PBT composite according to claim 7, wherein the screw shape of the parallel twin-screw extruder is a single-thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
10. The preparation method of the PBT composite material according to claim 9, wherein the ratio L/D of the screw length L and the diameter D is 35 to 45; 2 meshing block areas and 1 reverse thread area are arranged on the screw rod; in the step (1) and/or the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 500-.
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