CN109370189B - Antistatic polyester alloy material and preparation method thereof - Google Patents
Antistatic polyester alloy material and preparation method thereof Download PDFInfo
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The antistatic polyester alloy material comprises the following components in parts by weight: 30-50 parts of polybutylene terephthalate, 50-70 parts of polycarbonate, 2.1-11 parts of conductive particles, 3-15 parts of a toughening agent, 0.1-1 part of an antioxidant and 0.2-1 part of a lubricant, wherein the conductive particles are granular conductive particles formed by banburying 2-10 parts of conductive carbon black and 0.1-1 part of silicone oil.
Description
Technical Field
The invention relates to the technical field of high polymer material processing, in particular to an antistatic polyester alloy material and a preparation method thereof.
Background
At present, in the scenes of household appliances and industrial application, dust absorption is easy to happen when equipment such as fan blades and electric appliances are placed and operated, dust is accumulated for a long time, the appearance is accumulated, the appearance is attractive, the equipment is not easy to clean, the operation is poor, the service life of the electric appliance is damaged, and the surface resistance of the material is required to reach 10^ 8-9 to effectively prevent dust.
The conductive carbon black is used as a high-quality conductive filler and can change the surface resistance of a base material. However, the conductive carbon black has a large difference with the powder and the granules, and processing defects such as material layering, bridging, floating and the like are easy to occur, so that the problem that the conductive carbon black is difficult to be fed into the material for blending and modification is caused.
The prior patent No. CN104961975A discloses a conductive carbon black modified regenerated polypropylene composite material and a preparation method thereof, which improve the conductivity by adding higher conductive carbon black dosage, so that the surface resistance of the composite material is improved, but the problems of carbon black loss and equipment environmental pollution are caused by excessive conductive carbon black dosage. In addition, the polycarbonate resin with reduced conductive carbon black addition amount disclosed in patent No. CN104004336B and the preparation method thereof can obtain a polycarbonate material with good impact and low surface resistance by optimizing the processing temperature, but the processing difficulty that blanking is difficult is still not solved due to the small particle size and fluffy limitation of the conductive carbon black, thereby affecting the application of the conductive carbon black in polyester alloy.
Disclosure of Invention
The invention aims to provide an antistatic polyester alloy material, which has uniform and stable surface resistance.
The invention also aims to provide a preparation method of the antistatic polyester alloy material, which can overcome the problems of layering, bridging and the like in the blanking process of the conductive carbon black and greatly reduce the addition amount of the conductive carbon black.
In order to achieve the purpose, the invention adopts the following technical scheme:
the antistatic polyester alloy material comprises the following components in parts by weight:
the conductive particles are granular conductive particles formed by banburying 2-10 parts of conductive carbon black and 0.1-1 part of silicone oil. The invention provides an antistatic polyester alloy material, which is prepared by firstly adopting special silicone oil and conductive carbon black to carry out meshing and mixing to obtain granular conductive particles, the silicon oil not only effectively increases the granularity of the conductive carbon black, but also forms a compact conductive particulate matter structure, then the conductive particles are compounded with the polybutylene terephthalate, the polycarbonate, the toughening agent, the antioxidant and the lubricant according to a certain weight part, so that the blanking stability of the conductive carbon black is effectively ensured in the mixed blanking process, the conductive carbon black is stably and effectively fed into the material, thereby solving the problems of bridging and layering of the blanking of the conductive carbon black, greatly reducing the addition of the conductive carbon black, avoiding the loss and waste of the conductive carbon black, improving the processing environment, and the conductive particles are distributed more uniformly in the components, so that the surface resistance of the obtained antistatic polyester alloy material is uniform and stable.
Further, the polyester alloy material is a mixed composition formed by mixing the components, and is melted and extruded in a double-screw extruder with a telescopic steel ball arranged at a main feed opening and the vacuum degree of less than 0.09MPa, and is granulated to form the antistatic polyester alloy material.
In order to ensure the rapid and stable blanking of conductive particles, the telescopic motion of a telescopic steel ball at a main material port of a double-screw extruder is mechanically utilized in the material mixing process to provide uniform physical acting force for the conductive particles, so that the blanking of conductive carbon black is further accelerated, the situations of excessive blanking or blockage cannot occur, and the blanking is more uniform and stable; meanwhile, the vacuum degree of the double-screw extruder is improved to be more than 0.09MPa, so that the problem of bridging of the conductive carbon black during blanking can be completely avoided, and the conductive particles are more fully and uniformly mixed and melted with other components such as polybutylene terephthalate, polycarbonate and the like under higher vacuum degree, so that a stable melt is formed, and the surface resistance of the antistatic polyester alloy material obtained through melt extrusion and granulation is uniform and stable.
Further, the viscosity of the polybutylene terephthalate is 0.45-1.2 dl/gr. Among them, the polybutylene terephthalate preferably has a viscosity of 0.8 dl/gr.
Further, the weight average molecular weight of the polycarbonate is 25000-40000; the polycarbonate is powder synthesized by a phosgene method. Because the stability of the polycarbonate is low, the powder is synthesized by adopting a phosgene method, the stability of the polycarbonate is improved, and the polycarbonate is more fully mixed and reacted with the polybutylene terephthalate and the conductive particles.
Further, the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96.
Further, the toughening agent is MBS resin, and the particle size of the MBS resin is 300-600 nm. The MBS resin refers to a terpolymer of methyl methacrylate, butadiene and styrene.
Further, the lubricant comprises one or more of silicone powder, pentaerythritol ester and ethylene bisstearylamide. Wherein the antioxidant comprises one or more of commercially available antioxidant 264, antioxidant 1076 and antioxidant 168.
The preparation method of the antistatic polyester alloy material comprises the following steps:
(1) and preparing conductive particles, and mixing and banburying the conductive carbon black and the silicone oil for 20-30 min to obtain granular conductive particles.
(2) Adding polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant into a high-speed stirrer together for mixing to obtain a mixed composition;
(3) and (3) feeding the mixed composition obtained in the step (2) into a double-screw extruder, utilizing a telescopic steel ball with the diameter of 30cm arranged at a main feed opening of the double-screw extruder to vertically stretch at the speed of 5mm/s to accelerate feeding of conductive particles, setting the vacuum degree of the double-screw extruder to be less than 0.09MPa, carrying out melt extrusion on the mixed composition through the double-screw extruder, and granulating to obtain the antistatic polyester alloy material.
Compared with the prior art, the preparation method of the antistatic polyester alloy material provided by the invention has the advantages that conductive carbon black is engaged and kneaded into small granular conductive particles by using special silicon oil, the conductive particles, polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant are stirred and mixed at a high speed, a mixed composition of the conductive particles, the polybutylene terephthalate, the polycarbonate, the conductive particles, the toughening agent, the antioxidant and the lubricant is blended and granulated by using a double-screw extruder, meanwhile, on machinery, the stretching ball with the diameter of 30cm performs further auxiliary blanking at the speed of 5mm/s by stretching up and down, the vacuum degree of the true double-screw extruder is increased to be more than 0.09MPa, so that the problem that the conductive carbon black is difficult to stably feed into the material for blending and modification due to the processing defects of layering, bridging, floating and the like in the blanking process can be effectively solved, the addition amount of the conductive carbon black is greatly reduced, the loss and waste of the conductive carbon black are avoided, the surface resistance of the antistatic polyester alloy material obtained through melting, extruding and granulating is uniform and stable, and the polyester material is widely applied to stable antistatic household appliance materials.
Further, the mixed composition is melted and extruded at the temperature of 200-280 ℃, the extrusion pressure is 2MPa, the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, and the length-diameter ratio is 32-44. The stability of the melt is ensured by controlling the temperature and pressure of the melt extrusion, so that the components are more fully melted and mixed.
Further, in the step (1), the mixing and banburying time of the conductive carbon black and the silicone oil is 20 min. By controlling the sufficient mixing and banburying time of the conductive carbon black and the silicone oil, the particle structure of the formed conductive particles is more stable, the particle size is more uniform,
the invention has the beneficial effects that: the invention carries out meshing and mulling on the conductive carbon black by using special silicon oil to obtain small granular conductive particles, and after the conductive particles are stirred and mixed with polybutylene terephthalate, polycarbonate, the conductive particles, a toughening agent, an antioxidant and a lubricant at a high speed, the mixed composition is blended and granulated by using a double-screw extruder, meanwhile, on machinery, the telescopic ball with the diameter of 30cm carries out further auxiliary blanking at the speed of 5mm/s by virtue of up-and-down telescopic motion, and the vacuum degree of the true double-screw extruder is improved to more than 0.09MPa, so that the problem that the conductive carbon black is difficult to stably feed into a material for blending and modification due to the processing defects of layering, bridging, floating and the like in the blanking process of the conductive carbon black is effectively solved, the addition amount of the conductive carbon black is greatly reduced, the loss and waste of the conductive carbon black are avoided, and the conductive carbon, The antistatic polyester alloy material obtained by granulation has uniform and stable surface resistance, and the polyester material is widely applied to stable antistatic household appliance materials.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In the following examples and comparative examples, the polybutylene terephthalate was Mitsubishi G2815, and the polycarbonate was Dituer's L1225L; the conductive carbon black is Acksobel EC600 JD; the toughening agent is general MBS sold in the market; the silicone oil is prepared from 500ml of a traditional Chinese medicine reagent, and the antioxidants are Irganox 1076 and Irganox 168 of Ciba company, and the weight ratio of the components is 1: 1; the lubricant is commercially available LLDPE.
Example 1-a method for preparing an antistatic polyester alloy material, comprising the steps of:
(1) preparing conductive particles, and mixing and banburying conductive carbon black and silicone oil for 20min to obtain granular conductive particles; the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96;
(2) adding polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant into a high-speed stirrer together for mixing to obtain a mixed composition; wherein the viscosity of the polybutylene terephthalate is 0.45 dl/gr; the polycarbonate has a weight average molecular weight of 25000; the toughening agent is MBS resin with the grain diameter of 300 nm; the lubricant is silicone powder;
(3) and (3) feeding the mixed composition obtained in the step (2) into a double-screw extruder from a feeding port, utilizing a telescopic steel ball with the diameter of 30cm arranged at a main feed port of the double-screw extruder to vertically stretch at the speed of 5mm/s to accelerate feeding of conductive particles, setting the vacuum degree of the double-screw extruder to be less than 0.09MPa, carrying out melt extrusion on the mixed composition at the temperature of 200-280 ℃ through the double-screw extruder at the extrusion pressure of 2MPa, and carrying out granulation to obtain the polyester alloy material 1, wherein the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, and the length-diameter ratio is 32.
Example 2-a method for preparing an antistatic polyester alloy material, comprising the steps of:
(1) preparing conductive particles, and mixing and banburying conductive carbon black and silicone oil for 30min to obtain granular conductive particles; the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96;
(2) adding polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant into a high-speed stirrer together for mixing to obtain a mixed composition; wherein the viscosity of the polybutylene terephthalate is 1.2 dl/gr; the weight average molecular weight of the polycarbonate is 40000; the toughening agent is MBS resin with the grain diameter of 600 nm; the lubricant is pentaerythritol ester;
(3) and (3) feeding the mixed composition obtained in the step (2) into a double-screw extruder through a feeding material, utilizing a telescopic steel ball with the diameter of 30cm arranged at a main feed opening of the double-screw extruder to perform vertical telescopic motion at the speed of 5mm/s to accelerate feeding of conductive particles, setting the vacuum degree of the double-screw extruder to be less than 0.09MPa, performing melt extrusion on the mixed composition at the temperature of 200-280 ℃ through the double-screw extruder, wherein the extrusion pressure is 2MPa, and granulating the polyester alloy material 2, wherein the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, and the length-diameter ratio is 44.
Example 3-a method for preparing an antistatic polyester alloy material, comprising the steps of:
(1) preparing conductive particles, and mixing and banburying conductive carbon black and silicone oil for 25min to obtain granular conductive particles; the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96;
(2) adding polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant into a high-speed stirrer together for mixing to obtain a mixed composition; wherein the viscosity of the polybutylene terephthalate is 0.85 dl/gr; the weight average molecular weight of the polycarbonate is 35000; the toughening agent is MBS resin with the grain diameter of 500 nm; the lubricant is ethylene bisstearamide;
(3) and (3) feeding the mixed composition obtained in the step (2) into a double-screw extruder through a feeding material, utilizing a telescopic steel ball with the diameter of 30cm arranged at a main feed opening of the double-screw extruder to perform vertical telescopic motion at the speed of 5mm/s to accelerate feeding of conductive particles, setting the vacuum degree of the double-screw extruder to be less than 0.09MPa, performing melt extrusion on the mixed composition at the temperature of 200-280 ℃ through the double-screw extruder, wherein the extrusion pressure is 2MPa, and granulating to obtain the polyester alloy material 3, wherein the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, and the length-diameter ratio is 38.
Comparative example 1-a method for preparing an antistatic polyester alloy material, comprising the steps of: example 1 is based on changing the weight part ratio between the conductive carbon black and the silicone oil as follows: and (3) 11 parts of silicone oil: 1 part or electric carbon black: 1 part of silicone oil: 0.1 part by weight, and then carrying out mixing and banburying to obtain granular conductive particles, wherein the rest of the preparation steps and experimental parameter conditions are the same as those of the example 1, and thus a polyester alloy material 4 and a polyester alloy material 5 are obtained.
Comparative example 2-a method for preparing an antistatic polyester alloy material, comprising the steps of:
(1) respectively weighing polybutylene terephthalate, polycarbonate, conductive carbon black, silicone oil, a toughening agent, an antioxidant and a lubricant;
(2) directly feeding the raw materials into a double-screw extruder from a feeding port, performing melt extrusion at 200-280 ℃, wherein the extrusion pressure is 2MPa, the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, the length-diameter ratio is 32, and performing melt extrusion and granulation to obtain the polyester alloy material 6.
Comparative example 3-preparation of an antistatic polyester alloy material, comprising the steps of:
(1) preparing conductive particles, and mixing and banburying conductive carbon black and silicone oil for 20min to obtain granular conductive particles; the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96;
(2) adding polybutylene terephthalate, polycarbonate, conductive particles, a toughening agent, an antioxidant and a lubricant into a high-speed stirrer together for mixing to obtain a mixed composition; wherein the viscosity of the polybutylene terephthalate is 0.45 dl/gr; the polycarbonate has a weight average molecular weight of 25000; the toughening agent is MBS resin with the grain diameter of 300 nm; the lubricant is silicone powder;
(3) and directly feeding the mixed composition into a double-screw extruder from a feeding port, performing melt extrusion at 200-280 ℃, wherein the extrusion pressure is 2MPa, the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, the length-diameter ratio is 32, and performing melt extrusion and granulation to obtain the polyester alloy material 7.
Wherein the weight parts of each component in examples 1-3 and comparative examples 1-2 are as follows:
polyester alloy materials prepared in examples 1 to 3 and comparative examples 1 to 3 were used
The materials were tested and compared for their relevant properties, the results of which are shown in table 2 below:
according to the table above, the polyester alloy materials prepared in the embodiments 1 to 3 and the comparative embodiments 1 to 3 are compared, and it can be seen that the invention effectively solves the problem of bridging during the blanking of the conductive carbon black by meshing and mixing the conductive carbon black with special silicone oil into small particles, and using a telescopic ball to assist the blanking on a machine, and simultaneously improving the vacuum degree, and can effectively reduce the consumption of the conductive carbon black, and the surface resistance of the conductive carbon black can reach more than 10^9 omega/SQ, and is uniform and stable. In contrast example 1, the polyester alloy material prepared by the method can solve the problem of efficient bridging due to the change of the weight part ratio between the electrical carbon black and the silicone oil, but the surface resistance is low and not uniform and stable enough, while in contrast example 2, the electrical carbon black and the silicone oil are not banburied but directly melted and extruded, so that the phenomenon of bridging of electrical carbon black blanking occurs, the required conductive carbon black is excessively high in consumption, and the surface resistance is low; in comparative example 3, after the conductive particles are obtained by banburying the electrical carbon black and the silicone oil, the conductive particles are directly melt-extruded by a twin-screw extruder after being stirred and mixed with other components at a high speed, but a small amount of bridging phenomenon still exists in the process, and the stability of the surface resistance is low.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (8)
1. The preparation method of the antistatic polyester alloy material is characterized by comprising the following steps of: the method comprises the following steps:
(1) preparing conductive particles, mixing and banburying 2-10 parts of conductive carbon black and 0.1-1 part of silicone oil for 20-30 min according to the weight part ratio to obtain granular conductive particles;
(2) adding 30-50 parts of polybutylene terephthalate, 50-70 parts of polycarbonate, 2.1-11 parts of conductive particles, 3-15 parts of a toughening agent, 0.1-1 part of an antioxidant and 0.2-1 part of a lubricant into a high-speed stirrer together according to the parts by weight for mixing to obtain a mixed composition;
(3) and (3) feeding the mixed composition obtained in the step (2) into a double-screw extruder, utilizing a telescopic steel ball with the diameter of 30cm arranged at a main feed opening of the double-screw extruder to vertically stretch at the speed of 5mm/s to accelerate feeding of conductive particles, setting the vacuum degree of the double-screw extruder to be less than 0.09MPa, carrying out melt extrusion on the mixed composition through the double-screw extruder, and granulating to obtain the antistatic polyester alloy material.
2. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: the viscosity of the polybutylene terephthalate is 0.45-1.2 dl/gr.
3. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: the weight average molecular weight of the polycarbonate is 25000-40000; the polycarbonate is powder synthesized by a phosgene method.
4. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: the conductive carbon black is in a chain structure, and the average particle size is 150 nm; the silicone oil is methyl silicone oil with the density of 0.96.
5. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: the toughening agent is MBS resin, and the particle size of the MBS resin is 300-600 nm.
6. The antistatic polyester alloy material as claimed in claim 1, wherein: the lubricant comprises one or more of silicone powder, pentaerythritol ester and ethylene bisstearylamide.
7. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: the mixed composition is subjected to melt extrusion at the temperature of 200-280 ℃, the extrusion pressure is 2MPa, the rotating speed of the double-screw extruder is 500rpm, the diameter of a screw is 35mm, and the length-diameter ratio is 32-44.
8. The method for preparing the antistatic polyester alloy material according to claim 1, wherein the method comprises the following steps: in the step (1), the mixing and banburying time of the conductive carbon black and the silicone oil is 20 min.
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| CN101225217A (en) * | 2008-02-03 | 2008-07-23 | 博罗县长风电子有限公司 | Material for manufacturing computer fan |
| CN101591469A (en) * | 2009-06-15 | 2009-12-02 | 惠州市沃特新材料有限公司 | A kind of conductive polycarbonate moulding compound and preparation method thereof |
| CN101724241A (en) * | 2009-12-15 | 2010-06-09 | 上海新上化高分子材料有限公司 | Antistatic thermoplastic polycarbonate composition and preparation method thereof |
| CN102898806A (en) * | 2012-11-06 | 2013-01-30 | 上海冠旗电子新材料股份有限公司 | Antistatic polycarbonate/polyester alloy material and preparation method thereof |
| CN103013075A (en) * | 2012-11-16 | 2013-04-03 | 深圳市科聚新材料有限公司 | PET (polyethylene terephthalate) composite material as well as preparation method and application thereof |
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| CN101225217A (en) * | 2008-02-03 | 2008-07-23 | 博罗县长风电子有限公司 | Material for manufacturing computer fan |
| CN101591469A (en) * | 2009-06-15 | 2009-12-02 | 惠州市沃特新材料有限公司 | A kind of conductive polycarbonate moulding compound and preparation method thereof |
| CN101724241A (en) * | 2009-12-15 | 2010-06-09 | 上海新上化高分子材料有限公司 | Antistatic thermoplastic polycarbonate composition and preparation method thereof |
| CN102898806A (en) * | 2012-11-06 | 2013-01-30 | 上海冠旗电子新材料股份有限公司 | Antistatic polycarbonate/polyester alloy material and preparation method thereof |
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