CN117659601A - Polystyrene composite material and preparation method thereof - Google Patents
Polystyrene composite material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of polymer materials, and provides a polystyrene composite material and a preparation method thereof. The polystyrene composite material provided by the application comprises the following components in parts by weight: 80 to 95 parts of high impact polystyrene, 5 to 10 parts of modified carbon nano tube conductive particles, 0.1 to 1 part of lubricant and 0.1 to 1 part of antioxidant; the modified carbon nanotube conductive particles are obtained through ball milling and drying of carbon nanotubes and polystyrene carboxyl latex. In the present application, chemical bonding occurs between the carbon nanotubes and the polystyrene resin, and chemical crosslinking is formed through ester bond connection. Meanwhile, the polystyrene resin itself has high compatibility with high impact polystyrene. Therefore, the modified carbon nanotube conductive particles have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed, i.e. the carbon nanotubes have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed.
Description
Technical Field
The application belongs to the technical field of polymer materials, and particularly relates to a polystyrene composite material and a preparation method thereof.
Background
Carbon nanotubes are new materials of interest in recent years, which have many excellent properties and are applicable in many fields. The carbon nano tube is a seamless hollow tube body rolled by graphite sheets, and the electrons can only move in the graphite sheets along the axial direction of the carbon nano tube due to the quantum confinement effect of the electrons in the carbon nano tube, so that the carbon nano tube has unique electrical property and thermal property. The research and test results show that the average conductivity of the carbon nano tube can reach 1000-2000S/m (Siemens/m), and the heat conductivity coefficient at room temperature can reach 6600W/mk (watts/min Kelvin). In addition, the carbon nanotubes have excellent mechanical properties, such as higher strength and modulus.
The composite material of the carbon nano tube and the polymer can realize the advantage complementation of the two materials, thereby maximally utilizing the excellent properties of the two materials. In the carbon nano tube/polymer composite material, the carbon nano tube can be used as an electric conduction heat conductor and a reinforcing body, so that the composite material has antistatic property, heat conductivity, electromagnetic shielding property and higher structural strength, and has wide application prospect.
Compared with the traditional fillers (such as carbon black and nano clay), the Carbon Nano Tube (CNT) with high specific surface area can obviously improve the properties of the material, such as mechanical property, conductive property, thermal stability and the like, with only a small addition amount. However, based on the high length-diameter ratio of the carbon nano tube, the carbon nano tube is very easy to wind to form an aggregate, and is very easy to aggregate to form small particles in the preparation process of the composite material, so that the performance of the product is influenced. The dispersibility of carbon nanotubes in composites has therefore been a bottleneck affecting the application of carbon nanotubes. The preparation of the resin composition containing the carbon nano tubes belongs to the combination of two technical fields, including plastic processing and organic combination of carbon nano tube modification, and has great difficulty. In particular, in order to satisfy the conventional extrusion process for preparing plastics, carbon nanotubes are required to be uniformly dispersed within several minutes to more than ten minutes of extrusion of plastics, so that the carbon nanotubes are required to be rapidly dispersed in an extruder, and the extrusion shearing dispersion by a screw is far from sufficient.
In order not to affect the existing production process of plastic processing and solve the problem of the dispersion property of the carbon nanotubes, many researchers have made efforts mainly including physical modification and chemical modification of the carbon nanotubes. The physical modification comprises the physical coating of small molecules such as a surfactant, a dispersing agent, a modifying agent and the like on the carbon nano tube; the chemical modification comprises chemical grafting of the carbon nanotubes, and the compatibility with the resin composition is improved through grafted functional groups or polymers, so that the dispersion performance of the carbon nanotubes is improved. However, the chemical grafting modification treatment based on the carbon nanotubes has high cost, complex operation and very little effect, and in order to improve the application of the carbon nanotubes in the plastic field, especially the application of conductive antistatic plastics, a method capable of solving the dispersion performance of the carbon nanotubes is needed, and the cost is reduced as much as possible, so that the maximum dispersion effect is obtained by using a simple method.
Disclosure of Invention
The invention aims to provide a polystyrene composite material and a preparation method thereof, and aims to solve the problem of poor dispersibility of carbon nanotubes in the composite material.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a polystyrene composite comprising the following components in parts by weight:
the modified carbon nanotube conductive particles comprise carbon nanotubes and polystyrene resin coated on the surfaces of the carbon nanotubes; the modified carbon nanotube conductive particles are obtained by ball milling and drying carbon nanotubes and polystyrene carboxyl latex, and the carbon nanotubes comprise acidified single-wall carbon nanotubes and acidified array multi-wall carbon nanotubes.
In a second aspect, the present application provides a method for preparing a polystyrene composite, comprising the steps of: mixing high impact polystyrene, carbon nano tube conductive particles, a lubricant and an antioxidant to obtain a first mixture; or mixing high impact polystyrene, carbon nano tube conductive particles, a lubricant, an antioxidant and a compatilizer to obtain a second mixture;
and carrying out melt extrusion granulation treatment on the first mixture or the second mixture to obtain the polystyrene composite material.
The first aspect of the application provides a polystyrene composite, which comprises modified carbon nanotube conductive particles, wherein the modified carbon nanotube conductive particles comprise carbon nanotubes and polystyrene resin, the polystyrene resin is coated on the surfaces of the carbon nanotubes, and chemical bonding is performed between the carbon nanotubes and the polystyrene resin, and chemical crosslinking is formed through ester bond connection. Meanwhile, the polystyrene resin itself has high compatibility with high impact polystyrene. Therefore, the carbon nano tube conductive particles have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed, namely, the carbon nano tubes have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed.
According to the preparation method of the polystyrene composite material containing carbon nanotubes, which is provided by the second aspect of the application, the acidified carbon nanotubes and the polystyrene carboxyl latex are mixed to prepare carbon nanotube conductive particles, chemical bonding reaction can be carried out on carboxyl groups on the acidified carbon nanotubes and the polystyrene to form chemical crosslinking, and meanwhile, the polystyrene has high compatibility with high-impact polystyrene. Therefore, the carbon nano tube has good interfacial compatibility and uniform dispersion in the high impact polystyrene substrate.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the present application more clear, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the embodiments of the present application may refer not only to specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, any ratio of the contents of the relevant components according to the embodiments of the present application may be enlarged or reduced within the scope disclosed in the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical industry such as μ g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a polystyrene composite material, which comprises the following components in parts by weight:
the modified carbon nanotube conductive particles comprise carbon nanotubes and polystyrene resin coated on the surfaces of the carbon nanotubes; the modified carbon nanotube conductive particles are obtained by ball milling and drying carbon nanotubes and polystyrene carboxyl latex, and the carbon nanotubes comprise acidified single-wall carbon nanotubes and acidified array multi-wall carbon nanotubes.
The first aspect of the application provides a polystyrene composite, which comprises modified carbon nanotube conductive particles, wherein the modified carbon nanotube conductive particles comprise carbon nanotubes and polystyrene resin, the polystyrene resin is coated on the surfaces of the carbon nanotubes, and chemical bonding is performed between the carbon nanotubes and the polystyrene resin, and chemical crosslinking is formed through ester bond connection. Meanwhile, the polystyrene resin itself has high compatibility with high impact polystyrene. Therefore, the carbon nano tube conductive particles have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed, namely, the carbon nano tubes have good interfacial compatibility in the high impact polystyrene substrate and are uniformly dispersed.
In some embodiments, the carbon nanotubes include acidified single-walled carbon nanotubes and acidified array multi-walled carbon nanotubes, which may be obtained commercially or prepared by conventional acidification methods. The application selects the combination of the single-wall carbon nano tube and the array multi-wall carbon nano tube, and the combination is characterized in that the disorder degree is not high, and the combination can be better dispersed and wrapped by high polymer substances, so that the surface is uniformly wrapped.
In some embodiments, the mass ratio of carbon nanotubes to polystyrene resin in the modified carbon nanotube conductive particles is 1: (0.1-10).
In some embodiments, the weight ratio of acidified single-walled carbon nanotubes to acidified array multi-walled carbon nanotubes is (10-30): (70-90). The application combines a small amount of single-wall carbon nanotubes and array multi-wall carbon nanotubes, so that the longer single-wall carbon nanotubes can further lap the cross-linked network formed by the shorter array multi-wall carbon nanotubes, and the conductive network path is longer and more stable.
Further, the specification of the acidified single-walled carbon nanotubes is: the pipe diameter is 0.7-2.0 nm, the length is 10-100 mu m, the length-diameter ratio is 5000:1-120000:1, and the specific surface area is 800-1200 m 2 The resistivity of the powder is 0.1-5 mΩ cm, and the Raman ID/IG is 0.3-0.7; the specification of the acidification array multiwall carbon nano tube is as follows: the pipe diameter is 5-20 nm, the length is 0.5-8 mu m, the length-diameter ratio is 5:1-2500:1, and the specific surface area is 150-250 m 2 And/g, wherein the powder resistivity is 60-70 mΩ & cm, and the Raman ID/IG is 0.5-1.0. According to the method, the specification of the carbon nano tube is selected according to the conductivity of the carbon nano tube, so that the formed conductive network path is more stable.
In some embodiments, the high impact polystyrene has a weight average molecular weight of 150000 ～ 300000; the melt index of the high impact polystyrene is 9-13 g/10min under the test condition of 5kg at 230 ℃. The particle size of the carbon nano tube conductive particles is 0.1-1 mm. The lubricant includes at least one of calcium stearate, talc, and polyethylene wax. The antioxidant comprises at least one of 1010, 168, 1076, 1330, 1035, 3144, 1024, 126.
In some embodiments, the polystyrene composite further comprises 0.5 to 2 parts by weight of a compatibilizer. The compatibilizer comprises maleic anhydride grafted methyl methacrylate. According to the preparation method, the compatilizer is added, so that the dispersibility of the carbon nanotube conductive particles in the high-impact polystyrene is further improved, the carbon nanotube conductive particles are thinned, and the dispersion in the high-impact polystyrene is more uniform, so that the structure of the carbon nanotube-containing polystyrene composite is more stable, and the mechanical property of the carbon nanotube-containing polystyrene composite is further enhanced.
A second aspect of the embodiments of the present application provides a method for preparing a polystyrene composite material, including the following steps:
s1: mixing high impact polystyrene, modified carbon nanotube conductive particles, a lubricant and an antioxidant to obtain a first mixture; or mixing high impact polystyrene, modified carbon nano tube conductive particles, a lubricant, an antioxidant and a compatilizer to obtain a second mixture;
s2: and carrying out melt extrusion granulation treatment on the first mixture or the second mixture to obtain the polystyrene composite material.
Further, the preparation method of the modified carbon nanotube conductive particles comprises the following steps: dispersing the acidified single-wall carbon nano tube and the acidified array multi-wall carbon nano tube in polystyrene carboxyl latex, performing ball milling treatment to obtain ball milling slurry, and drying the ball milling slurry to obtain the modified carbon nano tube conductive particles.
The modified carbon nanotube conductive particles are prepared by ball milling of the acidified carbon nanotube and the polystyrene carboxyl latex, the acidified carbon nanotube and carboxyl on the polystyrene can undergo chemical bonding reaction to form chemical crosslinking, and meanwhile, the polystyrene has high compatibility with high-impact polystyrene. Therefore, the carbon nano tube has good interfacial compatibility and uniform dispersion in the high impact polystyrene substrate.
The polystyrene carboxyl latex is selected, on one hand, the polystyrene carboxyl latex has good wettability to the carbon nano tube, and on the other hand, the substances cannot influence the performance of the subsequent resin material, so the polystyrene carboxyl latex is selected. In addition, the polystyrene carboxyl latex has good mixing effect on the acidified carbon nano tube, and is better than the mixing effect of the carbon nano tube master batch prepared by the melting granulation process.
In some embodiments, the ratio of the total weight of the acidified single-walled carbon nanotubes and the acidified array multi-walled carbon nanotubes to the weight of the polystyrene carboxyl latex is (5-10): (50-100). Further preferably, the solid content of the polystyrene carboxyl latex is 5% -15%, the particle size of the polystyrene carboxyl latex is 100-500 nm, and the carboxyl content of the polystyrene carboxyl latex is 60-100 mu mol/g. The inventor finds that the dispersibility of the obtained carbon nanotube conductive particles is best and the mechanical property of the obtained carbon nanotube-containing polystyrene composite material is excellent in the weight ratio defined by the invention and the performance parameter range of the polystyrene carboxyl latex by adjusting the weight ratio range of the carbon nanotube and the polystyrene carboxyl latex and the specification of the polystyrene carboxyl latex.
In some embodiments, the ball milling process step comprises: dispersing the acidified single-wall carbon nano tube and the acidified array multi-wall carbon nano tube in polystyrene carboxyl latex, and adopting a high-energy ball milling method, wherein the ball milling treatment conditions comprise: the grinding medium is zirconia balls and/or agate balls; the size of the grinding medium is 0.5-1.0 mm; the filling rate of the grinding medium is 60% -85%; the stirring speed is 500-900 r/min. After the ball milling treatment is completed, ball milling slurry is obtained, and the ball milling slurry is subjected to spray drying to obtain carbon nanotube conductive particles, wherein the particle size of the carbon nanotube conductive particles is 0.1-1 mm.
In some embodiments, the step of melt granulation processing comprises:
(1) In a high-speed mixer, firstly adding high-impact polystyrene, then adding carbon nano tube conductive particles, mixing for 5-10 min, then continuously adding a lubricant and an antioxidant, mixing for 5-10 min, and further, continuously adding a compatilizer, mixing to obtain a mixture.
(2) And (3) melting and mixing the mixture in a double-screw extruder, wherein the extrusion temperature is 210-240 ℃, the rotation speed of a host machine is 500-1000 rpm/min, and melting and extruding the mixture through the double-screw extruder.
(3) And drawing the melt obtained by melt mixing at a constant moving speed through a shaping die, cooling through a water tank, and air-drying and granulating to obtain the antistatic polystyrene composite material containing carbon nano tubes, wherein the particle diameter of the composite material is 1-3 mm.
Further, the twin-screw extruder sequentially includes a zone 1 (melting section), a zone 2 (extrusion section), a zone 3 (shearing section), a zone 4 (pressurizing section), a zone 5 (melt venting section), a zone 6 (extrusion section), a zone 7 (shearing section), a zone 8 (pressurizing section), a zone 9 (melt venting section), and a head. The set process conditions of the twin-screw extruder are as follows: zone 1: 210-220 ℃; zone 2: 220-230 ℃; zone 3: 220-230 ℃; zone 4: 225-235 ℃; zone 5: 220-230 ℃; region 6: 230-240 ℃;7 region: 230-240 ℃;8 region: 225-235 ℃; zone 9: 220-230 ℃; temperature of the machine head: 220-235 ℃; the rotation speed of the host machine is 500-1000 rpm/min, and the vacuum degree is less than or equal to-0.05 MPa.
The invention further optimizes the process of double-screw melt extrusion granulation, and enables the carbon nano tube to be uniformly dispersed in the resin base material by adjusting the parameter setting of the extrusion process.
The following description is made with reference to specific embodiments.
Example 1
The embodiment 1 of the invention provides a polystyrene composite material and a preparation method thereof.
A method for preparing a polystyrene composite of example 1, comprising the steps of:
s1: according to parts by weight, dispersing 1 part of acidified single-wall carbon nano tube and 4 parts of acidified array multi-wall carbon nano tube in 50 parts of polystyrene carboxyl latex, dispersing by adopting a high-energy ball milling method, wherein a grinding medium adopts 0.5mm zirconia balls, the filling rate of the grinding medium is 85%, the stirring speed is 500r/min, obtaining ball milling slurry, and carrying out spray drying on the ball milling slurry to obtain modified carbon nano tube conductive particles with the particle size of 0.4 mm. Wherein, polystyrene carboxyl latex is selected from the specification as follows: the solid content was 10% and the carboxyl content was 100. Mu. Mol/g. The specification of the acidulated single-wall carbon nano tube is as follows: the pipe diameter is 0.7-2nm, the length is 10-20 mu m, and the specific surface area is 800-1000 m 2 And/g, wherein the powder resistivity is 0.1-5 mΩ cm; the specification of the acidification array multiwall carbon nano tube is as follows: the pipe diameter is 8-18nm, the length is 2-8 mu m, and the specific surface area is 150-200 m 2 And/g, the powder resistivity is 60-70 mΩ & cm.
S2: adding 80 parts of high impact polystyrene into a high-speed mixer, adding 5 parts of modified carbon nanotube conductive particles, mixing for 5min, and then continuously adding 0.3 part of lubricant and 0.3 part of antioxidant, mixing for 5min to obtain a mixture, wherein the weight average molecular weight of the high impact polystyrene is 300000, and the melt index under the test condition of 5kg at 230 ℃ is 9g/10min; the lubricant is calcium stearate; 1010 is used as the antioxidant.
S3: the mixture is melted and mixed in a double-screw extruder, and the sectional extrusion temperature of the double-screw extruder is as follows: zone 1 (melt section): 210 ℃; zone 2 (extrusion section): 220 ℃; zone 3 (shear section): 220 ℃; zone 4 (boost section): 225 ℃; zone 5 (melt exhaust section): 220 ℃; zone 6 (extrusion section): 230 ℃; zone 7 (shear section): 230 ℃; zone 8 (boost section): 225 ℃; zone 9 (melt exhaust section): 220 ℃; temperature of the machine head: 220 ℃; the vacuum degree is less than or equal to-0.05 MPa.
S4: and drawing the melt obtained by melt mixing at a constant moving speed through a shaping die, cooling through a water tank, and air-drying and granulating to obtain the antistatic polystyrene composite material with the particle diameter of 1mm.
Example 2
The embodiment 2 of the invention provides a polystyrene composite material and a preparation method thereof.
A method for preparing a polystyrene composite of example 2, comprising the steps of:
s1: according to parts by weight, 3 parts of acidified single-wall carbon nanotubes and 7 parts of acidified array multi-wall carbon nanotubes are dispersed in 100 parts of polystyrene carboxyl latex, and the mixture is dispersed by a high-energy ball milling method, wherein a grinding medium adopts agate balls with the size of 1.0mm, the filling rate of the grinding medium is 60%, the stirring rate is 900r/min, ball milling slurry is obtained, and the ball milling slurry is subjected to spray drying to obtain modified carbon nanotube conductive particles with the particle size of 0.8 mm. Wherein, polystyrene carboxyl latex is selected from the specification as follows: the solids content was 15% and the carboxyl content was 100. Mu. Mol/g. The specification of the acidulated single-wall carbon nano tube is as follows: the pipe diameter is 0.7-2nm, the length is 10-20 mu m, and the specific surface area is 800-1000 m 2 And/g, wherein the powder resistivity is 0.1-5 mΩ cm; the specification of the acidification array multiwall carbon nano tube is as follows: the pipe diameter is 5-10nm, the length is 5-8 mu m, and the specific surface area is 200-250 m 2 And/g, the powder resistivity is 60-70 mΩ & cm.
S2: adding 95 parts of high impact polystyrene into a high-speed mixer, adding 10 parts of modified carbon nanotube conductive particles, mixing for 10min, and then continuously adding 0.6 part of lubricant and 0.7 part of antioxidant, mixing for 10min to obtain a mixture, wherein the weight average molecular weight of the high impact polystyrene is 150000, and the melt index under the test condition of 5kg at 230 ℃ is 13g/10min; the lubricant is talcum powder; the antioxidant is 168.
S3: the mixture is melted and mixed in a double-screw extruder, and the sectional extrusion temperature of the double-screw extruder is as follows: zone 1 (melt section): 220 ℃; zone 2 (extrusion section): 230 ℃; zone 3 (shear section): 230 ℃; zone 4 (boost section): 235 ℃; zone 5 (melt exhaust section): 230 ℃; zone 6 (extrusion section): 240 ℃; zone 7 (shear section): 240 ℃; zone 8 (boost section): 235 ℃; zone 9 (melt exhaust section): 230 ℃; temperature of the machine head: 235 ℃; the vacuum degree is less than or equal to-0.05 MPa.
S4: and drawing the melt obtained by melt mixing at a constant moving speed through a shaping die, cooling through a water tank, and air-drying and granulating to obtain the antistatic polystyrene composite material with the particle diameter of 1mm.
Example 3
The embodiment 3 of the invention provides a polystyrene composite material and a preparation method thereof.
A method for preparing a polystyrene composite of example 3, comprising the steps of:
s1: according to parts by weight, dispersing 2 parts of acidified single-wall carbon nano tubes and 6 parts of acidified array multi-wall carbon nano tubes in 80 parts of polystyrene carboxyl latex, dispersing by adopting a high-energy ball milling method, wherein a grinding medium adopts 0.8mm agate balls, the filling rate of the grinding medium is 70%, the stirring rate is 700r/min, obtaining ball milling slurry, and carrying out spray drying on the ball milling slurry to obtain modified carbon nano tube conductive particles with the particle size of 0.8 mm. Wherein, polystyrene carboxyl latex is selected from the specification as follows: the solid content was 10% and the carboxyl content was 100. Mu. Mol/g. The specification of the acidulated single-wall carbon nano tube is as follows: the pipe diameter is 0.7-2nm, the length is 40-70 mu m, and the specific surface area is 900-1100 m 2 And/g, wherein the powder resistivity is 0.1-5 mΩ cm; the specification of the acidification array multiwall carbon nano tube is as follows: the pipe diameter is 10-20nm, the length is 1-5 mu m, and the specific surface area is 150-200 m 2 And/g, the powder resistivity is 60-70 mΩ & cm.
S2: adding 90 parts of high impact polystyrene into a high-speed mixer, adding 8 parts of modified carbon nanotube conductive particles, mixing for 8min, and then continuously adding 0.5 part of lubricant and 0.4 part of antioxidant, mixing for 8min to obtain a mixture, wherein the weight average molecular weight of the high impact polystyrene is 200000, and the melt index under the test condition of 5kg at 230 ℃ is 12g/10min; the lubricant is polyethylene wax; 1076 is selected as the antioxidant.
S3: the mixture is melted and mixed in a double-screw extruder, and the sectional extrusion temperature of the double-screw extruder is as follows: zone 1 (melt section): 220 ℃; zone 2 (extrusion section): 230 ℃; zone 3 (shear section): 230 ℃; zone 4 (boost section): 235 ℃; zone 5 (melt exhaust section): 230 ℃; zone 6 (extrusion section): 240 ℃; zone 7 (shear section): 240 ℃; zone 8 (boost section): 235 ℃; zone 9 (melt exhaust section): 230 ℃; temperature of the machine head: 235 ℃; the vacuum degree is less than or equal to-0.05 MPa.
S4: and drawing the melt obtained by melt mixing at a constant moving speed through a shaping die, cooling through a water tank, and air-drying and granulating to obtain the antistatic polystyrene composite material with the particle diameter of 1mm.
Example 4
The embodiment 4 of the invention provides a polystyrene composite material and a preparation method thereof.
Example 4 was prepared essentially the same as the polystyrene composite of example 3, except that 1 part by weight of compatibilizer was added to the components of the composite. The different steps are as follows:
s2: adding 90 parts of high impact polystyrene into a high-speed mixer, adding 8 parts of modified carbon nanotube conductive particles, mixing for 8min, and then continuously adding 0.5 part of lubricant, 0.4 part of antioxidant and 1 part of compatilizer, mixing for 8min to obtain a mixture, wherein the weight average molecular weight of the high impact polystyrene is 200000, and the melt index under the test condition of 5kg at 230 ℃ is 12g/10min; the lubricant is polyethylene wax; 1076 is selected as an antioxidant; the compatilizer is maleic anhydride grafted methyl methacrylate.
Example 5
The embodiment 5 of the invention provides a polystyrene composite material and a preparation method thereof.
Example 5 was essentially the same as the polystyrene composite of example 3, except that: the feeding amount of the acidified single-wall carbon nano tube and the acidified array multi-wall carbon nano tube is 4 parts by weight.
Example 6
The embodiment 6 of the invention provides a polystyrene composite material and a preparation method thereof.
Example 6 was substantially identical to the polystyrene composite of example 3, except that: the feeding amounts of the acidified single-wall carbon nanotubes and the acidified array multi-wall carbon nanotubes are 6 parts by weight and 2 parts by weight respectively.
The components and parts by weight of examples 1 to 6 are shown in Table 1:
TABLE 1
| Component (A) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| High impact polystyrene | 80 | 95 | 90 | 90 | 90 | 90 |
| Modified carbon nanotube conductive particles | 5 | 10 | 8 | 8 | 8 | 8 |
| Lubricant | 0.3 | 0.6 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant | 0.3 | 0.7 | 0.4 | 0.4 | 0.4 | 0.4 |
| Compatibilizing agent | 0 | 0 | 0 | 1 | 0 | 0 |
| Acidified single-walled carbon nanotubes | 1 | 3 | 2 | 2 | 4 | 6 |
| Acidizing array multiwall carbon nanotube | 4 | 7 | 6 | 6 | 4 | 2 |
| Polystyrene carboxyl latex | 50 | 100 | 80 | 80 | 80 | 80 |
Comparative example 1
Comparative example 1 was substantially identical to the preparation method of example 3, except that the acidified single-walled carbon nanotubes and the acidified array multi-walled carbon nanotubes in comparative example 1 were not subjected to ball milling treatment with polystyrene carboxyl latex, i.e., the modified carbon nanotube conductive particles comprised only 2 parts by weight of the acidified single-walled carbon nanotubes and 6 parts by weight of the acidified array multi-walled carbon nanotubes.
Comparative example 2
Comparative example 2 was substantially the same as the preparation method of example 3, except that the polystyrene carboxyl latex in comparative example 2 was used in an amount of 40 parts by weight.
Comparative example 3
Comparative example 3 was substantially the same as the preparation method of example 3, except that the amount of the polystyrene carboxyl latex in comparative example 3 was 150 parts by weight.
Comparative example 4
Comparative example 4 was prepared in substantially the same manner as in example 3, except that the carbon nanotubes in comparative example 4 were only acidified array multiwall carbon nanotubes and did not contain acidified single wall carbon nanotubes.
Comparative example 5
Comparative example 5 was prepared in substantially the same manner as in example 3, except that the carbon nanotubes in comparative example 5 were only acidified single-walled carbon nanotubes and did not contain an acid array of multi-walled carbon nanotubes.
The components and parts by weight of the polystyrene composite materials of comparative examples 1 to 5 are shown in Table 2:
TABLE 2
| Component (A) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| High impact polystyrene | 90 | 90 | 90 | 90 | 90 |
| Modified carbon nanotube conductive particles | 8 | 8 | 8 | 8 | 8 |
| Lubricant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Acidified single-walled carbon nanotubes | 2 | 2 | 2 | 0 | 8 |
| Acidizing array multiwall carbon nanotube | 6 | 6 | 6 | 8 | 0 |
| Polystyrene carboxyl latex | 0 | 40 | 150 | 80 | 80 |
Performance testing
The polystyrene composite samples prepared in examples 1 to 6 and comparative examples 1 to 5 were injection molded into test bars according to standard sizes, and surface resistivity was measured.
The surface resistivity test method comprises the following steps: the test method adopts a direct current comparison method, and the test equipment and the measurement error accord with the specification of GB/T3048.5. The surface resistivity in tables 3 and 4 refers to the resistivity of 10 positions on the front and back surfaces of the test bars.
Tensile strength: according to ISO 527:2010 (E), the test conditions are 5Kg,50 ℃/h;
flexural strength: the test speed is 2mm/min according to ISO 178:2010 (E);
impact strength: the impact energy was measured at 23℃at 4J according to ISO 179-1:2010 (E).
TABLE 3 results of test on spline Performance for examples 1-6
TABLE 4 test results of sample Performance for comparative examples 1-5
As can be seen from the composition table of table 1, example 4 is different from example 3 only in that the compatibilizing agent is added to the composition of the composite material, and as can be seen from the performance test results of table 3, the resistivity distribution of 10 positions on the front and back of example 4 is more concentrated, which indicates that the carbon nanotube conductive particles are more uniformly dispersed in the high impact polystyrene by adding the compatibilizing agent.
Examples 5 and 6, the weight ratio of acidified single-walled carbon nanotubes to acidified array multi-walled carbon nanotubes was 4:4 and 6:2, the conductivity was slightly lower than that of example 3, but still superior to that of comparative examples 1 to 4, and the sample surface was smooth and free of pitting.
As can be seen from the composition table of Table 2, the acidified single-walled carbon nanotubes and the acidified array multi-walled carbon nanotubes of comparative example 1 were not subjected to ball milling treatment with polystyrene carboxyl latex, and thus the resistivity distribution at 10 positions on the front and back sides of comparative example 1 was 4.1X10 4 To 9.8X10 9 And the surface of the sample is rough and has pits, which indicates that the acidified single-wall carbon nano tube and the acidified array multi-wall carbon nano tube which are not ball-milled with polystyrene carboxyl latex have poor dispersibility and very uneven distribution in polystyrene resin.
2 parts of the acidified single-walled carbon nanotubes and 6 parts of the acidified array multi-walled carbon nanotubes in comparative example 2 were dispersed in 40 parts of polystyrene carboxyl latex, and even though the carbon nanotubes were still difficult to disperse by high-energy ball milling, the carbon nanotubes in the prepared conductive particles were unevenly dispersed, and it was confirmed from the results of surface resistivity and surface roughness.
2 parts of the acidified single-walled carbon nanotubes and 6 parts of the acidified array multi-walled carbon nanotubes in comparative example 3 were dispersed in 150 parts of polystyrene carboxyl latex, and modified carbon nanotube conductive particles were prepared by high-energy ball milling, which were slightly inferior in conductivity to examples 1 to 6 in high impact polystyrene.
In comparative example 4, the carbon nanotubes were only acidified array multiwall carbon nanotubes, and the acidified single wall carbon nanotubes were not included, and the path of the conductive network was reduced, affecting the conductivity. In comparative example 5, the carbon nanotubes were only acidified single-walled carbon nanotubes, and the acidified array multi-walled carbon nanotubes were not contained, and the acidified single-walled carbon nanotubes were poor in dispersion and uneven in dispersion, resulting in particle agglomeration.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. The polystyrene composite material is characterized by comprising the following components in parts by weight:
the modified carbon nanotube conductive particles comprise carbon nanotubes and polystyrene resin coated on the surfaces of the carbon nanotubes;
the modified carbon nanotube conductive particles are obtained by ball milling and drying carbon nanotubes and polystyrene carboxyl latex, and the carbon nanotubes comprise acidified single-wall carbon nanotubes and acidified array multi-wall carbon nanotubes.
2. The polystyrene composite of claim 1, wherein the acidified single wall carbon nanotubes have a specification of: the pipe diameter is 0.7-2.0 nm, the length is 10-100 mu m, the length-diameter ratio is 5000:1-120000:1, and the specific surface area is 800-1200 m 2 And/g, wherein the powder resistivity is 0.1-5 mΩ cm; and/or the number of the groups of groups,
the specification of the acidification array multiwall carbon nanotube is as follows: the pipe diameter is 5-20 nm, the length is 0.5-8 mu m, the length-diameter ratio is 5:1-2500:1, and the specific surface area is 150-250 m 2 And/g, the powder resistivity is 60-70 mΩ & cm.
3. The polystyrene composite of claim 2, wherein the weight ratio of the acidified single-walled carbon nanotubes to the acidified array of multi-walled carbon nanotubes is (10 to 30): (70-90); and/or the number of the groups of groups,
in the modified carbon nanotube conductive particles, the mass ratio of the carbon nanotubes to the polystyrene resin is 1: (0.1-10).
4. A polystyrene composite according to any one of claims 1 to 3 wherein said high impact polystyrene has a weight average molecular weight of 150000 ～ 300000; and/or the number of the groups of groups,
the melt index of the high impact polystyrene is 9-13 g/10min at 230 ℃ under 5kg test conditions; and/or the number of the groups of groups,
the particle size of the modified carbon nano tube conductive particles is 0.1-1 mm.
5. The polystyrene composite of claim 1, further comprising 0.5 to 2 parts by weight of a compatibilizer.
6. The method for preparing a polystyrene composite material according to any one of claims 1 to 5, comprising the steps of:
mixing the high impact polystyrene, the modified carbon nanotube conductive particles, the lubricant and the antioxidant to obtain a first mixture; or mixing the high impact polystyrene, the modified carbon nanotube conductive particles, the lubricant, the antioxidant and the compatilizer to obtain a second mixture;
and carrying out melt extrusion granulation treatment on the first mixture or the second mixture to obtain the polystyrene composite material.
7. The method for preparing polystyrene composite material according to claim 6, wherein the method for preparing the modified carbon nanotube conductive particles comprises the following steps:
dispersing the acidified single-wall carbon nanotubes and the acidified array multi-wall carbon nanotubes in polystyrene carboxyl latex, and performing ball milling treatment to obtain ball milling slurry;
and drying the ball milling slurry to obtain the modified carbon nanotube conductive particles.
8. The method of preparing a polystyrene composite according to claim 7, wherein the ratio of the total weight of said acidified single-walled carbon nanotubes and said acidified array multi-walled carbon nanotubes to the weight of said polystyrene carboxyl latex is (5-10): (50-100); and/or the number of the groups of groups,
the solid content of the polystyrene carboxyl latex is 5-15%, the particle size of the polystyrene carboxyl latex is 100-500 nm, and the carboxyl content of the polystyrene carboxyl latex is 60-100 mu mol/g; and/or the number of the groups of groups,
the ball milling treatment conditions include: the grinding medium is zirconia balls and/or agate balls; the size of the grinding medium is 0.5-1.0 mm; the filling rate of the grinding medium is 60% -85%; the stirring speed is 500-900 r/min.
9. The method of preparing a polystyrene composite according to claim 6, wherein said step of melt extrusion granulation comprises: and (3) carrying out melt extrusion granulation on the first mixture or the second mixture by a double-screw extruder, wherein the extrusion temperature is 210-240 ℃, the rotating speed of a host machine is 500-1000 rpm/min, and the vacuum degree is less than or equal to minus 0.05Mpa.
10. The method for preparing a polystyrene composite material according to claim 9, wherein the processing temperature of the twin-screw extruder is as follows in order: zone 1 temperature: 210-220 ℃; zone 2 temperature: 220-230 ℃; zone 3 temperature: 220-230 ℃; zone 4 temperature: 225-235 ℃; zone 5 temperature: 220-230 ℃; zone 6 temperature: 230-240 ℃;7 zone temperature: 230-240 ℃;8 zone temperature: 225-235 ℃;9 zone temperature: 220-230 ℃; temperature of the machine head: 220-235 ℃.
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