CN110724340B - Permanent antistatic polypropylene composite material and preparation method thereof - Google Patents
Permanent antistatic polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a permanent antistatic polypropylene composite material and a preparation method thereof, wherein the permanent antistatic polypropylene composite material is prepared from the following raw materials: 75-91 parts of polypropylene, 5-15 parts of carbon/wollastonite composite material, 4-10 parts of oxidized superconducting carbon black, 1-2 parts of silane coupling agent and 0.1-0.5 part of antioxidant. According to the invention, by adopting the compounding and implementation scheme of the superconducting carbon black and the carbon/wollastonite composite material, the polypropylene is subjected to antistatic modification, so that the addition amount of the superconducting carbon black can be reduced, and the influence of the carbon black on the mechanical property of the material is reduced. The composite material prepared by the method has permanent antistatic performance, and can be applied to a plurality of fields such as electronic and electric appliance turnover boxes, new energy vehicles and the like.
Description
Technical Field
The invention relates to a polypropylene composite material, in particular to a permanent antistatic polypropylene composite material and a preparation method thereof, belonging to the technical field of polypropylene modification.
Background
As a general plastic, polypropylene has the advantages of low price, good heat resistance and the like, and is widely applied to the fields of automobiles, household appliances, office supplies and various electronic and electrical appliances. However, polypropylene is used as a high-insulation material, and the surface resistivity of the polypropylene is as high as 1016-1017Omega. The high resistance causes the accumulation of static charges on the surface of the material, and the polypropylene part can cause the accumulation of dust on the surface of the part in the processes of injection molding, transportation and assembly, so that the appearance and the assembly efficiency of the part are influenced; and can cause electrical breakdown, spark discharge, and even serious consequences of combustion or explosion. This limits the application of polypropylene materials in the field of daily production and life, especially in the field of electronic and electrical appliances. In recent years, with the increasing safety awareness, the surface resistivity of polypropylene materials is reduced, and the development of antistatic polypropylene materials is a research and development direction with great attention. The preparation method of the antistatic polypropylene material at present is to carry out blending modification on an antistatic agent and the polypropylene material so as to reduce the surface resistivity of the material. The following are commonly used antistatic agents: (1) the antistatic effect of the material is large in dependence on the humidity of the environment, and the material loses the antistatic effect in a dry or low-humidity working condition; (2) the macromolecular permanent/semi-permanent antistatic agent has high addition amount (more than 10 percent), low antistatic efficiency and high material cost, and the antistatic agent has obvious influence on the mechanical property of the material, so the material has no great practicability; and (3) conductive fillers such as carbon fibers, carbon nanotubes, graphene, metal sheets and the like are added, and the antistatic agent can endow polypropylene with permanent antistatic performance, but is high in price and not practical. The superconducting carbon black is used as a conductive filler with low price, can endow polypropylene with permanent antistatic performance, but the mechanical property of the material can be obviously reduced when the addition amount is high (more than 15 percent); meanwhile, the relationship between the addition amount of the carbon black and the surface resistivity of the material is nonlinear, and the surface resistivity of the material can be broken as long as the addition amount reaches a percolation threshold valueThe critical value can be reached only by adding 15-25 parts of the conventional commercially available superconducting carbon black, and the addition of a large amount of carbon black greatly reduces the fluidity, strength and modulus of the material, increases the cost of the material and finally leads the material to fail to meet the use requirements of a finished piece.
Chinese patent publication CN 105924663a provides an antistatic polypropylene foam material, which is prepared by mixing and reacting conductive carbon black and acrylamide in advance, and then coating antistatic adhesive on the surface of a foamed polypropylene sheet, thereby achieving the antistatic effect. Although the method can realize the foaming material with better antistatic effect, the process is complex, and the method is only suitable for extruding sheets and is not suitable for injection molding parts.
According to the mechanism that the superconducting carbon black reduces the surface resistivity of the material: the superconducting carbon black is a conductive material, and in an insulating system such as polypropylene and the like, the addition amount of the superconducting carbon black is high enough to obviously reduce the resistivity of the material and improve the conductivity of the material after a conductive network is formed. Therefore, in order to obtain a modified polypropylene material with a low addition amount of superconducting carbon black, the formation of a conductive network in the material is firstly ensured.
Disclosure of Invention
The invention aims to solve the technical problem of providing a permanent antistatic polypropylene composite material and a preparation method thereof, and solves the problems of environmental dependence, timeliness, poor mechanical properties and high cost of the antistatic property of the existing polypropylene material. The finally prepared antistatic polypropylene material can obtain permanent antistatic performance by adding a small amount of superconducting carbon black, and the mechanical property of the material is obviously improved, so that the material can be applied to a plurality of fields such as electronic and electric appliance transfer boxes, new energy automobiles and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a permanent antistatic polypropylene composite material is prepared from the following raw materials:
75-91 parts of polypropylene, preferably 80-86 parts;
5-15 parts of carbon/wollastonite composite material, preferably 8-12 parts;
4-10 parts of oxidized superconducting carbon black, preferably 6-8 parts;
1-2 parts of silane coupling agent, preferably 1.3-1.7 parts;
0.1-0.5 part of antioxidant; preferably 0.2 to 0.4 parts.
In the invention, the carbon/wollastonite composite material is prepared by the following method:
(1) mixing wollastonite, water and polyethylene glycol, preferably mixing the wollastonite, 3-4 parts of deionized water and 0.01-0.02 part of polyethylene glycol based on the mass of the wollastonite, and uniformly stirring at the temperature of 80-100 ℃ to obtain a wollastonite suspension;
(2) adding 20wt% hydrochloric acid solution into the wollastonite suspension, controlling pH to 2-3, reacting for 3-5h, washing with water, and drying to obtain acid-treated wollastonite;
(3) dissolving epoxy resin in acetone, adding acid-treated wollastonite, preferably 30-40 parts of acid-treated wollastonite based on the mass of the epoxy resin, reacting for 2-4h, drying, carbonizing, preferably carbonizing in a tubular furnace at 500-700 ℃ for 3-5h in a nitrogen atmosphere to obtain the carbon/wollastonite composite material.
As a preferred scheme, the carbon/wollastonite composite material is prepared by the following method:
(1) mixing wollastonite, 3-4 parts of deionized water based on the mass of the wollastonite and 0.01-0.02 part of polyethylene glycol, and uniformly stirring in a water bath kettle at the constant temperature of 80-100 ℃ to obtain wollastonite suspension for later use;
(2) slowly dripping 20% hydrochloric acid solution into the wollastonite suspension, controlling the pH value to be 2-3, reacting for 3-5h, washing for 3-5 times, and drying at the temperature of 100-120 ℃ to obtain acid-treated wollastonite;
(3) placing epoxy resin and 30-40 parts of acetone based on the epoxy resin in a 50-80 ℃ constant-temperature water bath kettle, uniformly stirring, pouring into a wollastonite beaker containing 30-40 parts of acid-treated wollastonite based on the mass of the epoxy resin, covering wollastonite powder, standing, reacting for 2-4h, drying at 100-120 ℃, and carbonizing for 3-5h in a 500-700 ℃ tube furnace under the nitrogen atmosphere to obtain the carbon/wollastonite composite material.
In the invention, the wollastonite is commercially available wollastonite capable of being used for plastic modification, the shape is fibrous, and the length-diameter ratio is 10-20: 1. Suitable examples include, but are not limited to, Haichard mining W625, Xinda H-1250F, and the like.
In the invention, the oxidized superconducting carbon black is prepared by the following method: mixing and reacting the superconducting carbon black with 5-8 parts of nitric acid based on the mass of the superconducting carbon black for 2-5h, washing and drying to obtain the product, preferably drying in a vacuum oven with the temperature of 100-120 ℃ and the pressure of 0.3-0.5 KPa.
As a preferred scheme, the oxidized superconducting carbon black is prepared by the following method: placing the superconducting carbon black and 5-8 parts of nitric acid with the mass fraction of 35% based on the mass of the superconducting carbon black in a beaker, stirring at room temperature, reacting for 2-5h, and then washing the carbon black with deionized water until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 100-120 ℃ and the pressure of 0.3-0.5KPa until the quality is constant.
The superconducting carbon black is commercially available nano-scale superconducting carbon black which can be used for plastic modification, and the average particle size is less than 100 nm. Suitable examples include, but are not limited to, ASAHI superconducting carbon black AX-015, BIRLACARBON superconducting carbon black 7093, and the like.
In the invention, the polypropylene is one or a mixture of two of commercially available injection molding grade homopolymerized polypropylene and copolymerization polypropylene, the melt index is 10-100g/10min, and the shrinkage rate is 1.5-2.0%. Suitable examples include, but are not limited to, luoyang petrochemical MN15, korean dadall HJ730, and the like.
In the present invention, the silane coupling agent is a silane coupling agent product that can be used for plastic modification, and suitable examples include, but are not limited to, KH550, KH560, KH570 and the like, which are national medicines.
In the present invention, the antioxidant is an antioxidant product which can be used for plastic modification, and suitable examples include but are not limited to basf 1010, 168, etc., and the preferred weight ratio is 1:2-2:1 antioxidant 1010 and antioxidant 168.
A preparation method of a permanent antistatic polypropylene composite material comprises the following steps:
(1) adding the carbon/wollastonite composite material into ethanol and stirring to obtain carbon/wollastonite turbid liquid, adding a silane coupling agent into the turbid liquid and fully stirring, reacting at the temperature of 60-80 ℃ for 0.5-2h, adding oxidized superconducting carbon black into the system, fully stirring, further reacting at the temperature of 60-80 ℃ for 1-3h, and drying at the temperature of 100-120 ℃ to obtain a superconducting carbon black/wollastonite composite material mixture;
(2) placing the raw materials of polypropylene, superconducting carbon black-carbon/wollastonite composite material and antioxidant in a high-speed stirrer to be mixed for 3-5 minutes at the rotation speed of 500-1500rpm to obtain premix, and adding the premix through a main feeding port of a double-screw extruder;
(3) and melting, extruding, cooling, granulating and drying the premixed raw materials in an extruder to obtain the polypropylene composite material. Preferably, the parameters of the twin screws are set as follows: the temperature of the first zone is 185-plus-195 ℃, the temperature of the second zone is 190-plus-200 ℃, the temperature of the third zone is 190-plus-200 ℃, the temperature of the fourth zone is 185-plus-195 ℃, and the rotation speed of the screw is 300-plus-500 r/min; generally, the product is extruded from a double screw, cooled by cooling water, granulated by a granulator and dried in an oven at 90 ℃ for 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with granular superconducting carbon black, the fibrous carbon/wollastonite composite material has larger length-diameter ratio and is easier to be connected with each other in the material to form a conductive network.
(2) Compared with the carbon/wollastonite composite material, the superconducting carbon black has excellent conductive performance, and is used as a charge transmission pivot in a conductive network to ensure that charges are smooth and unimpeded in the conductive network.
(3) The polypropylene is subjected to antistatic modification by compounding the superconducting carbon black and the carbon/wollastonite composite material, wherein the addition amount of the superconducting carbon black can be reduced by the synergistic effect of the granular superconducting carbon black and the fibrous carbon/wollastonite, so that the influence of the carbon black on the mechanical property of the material is reduced. The carbon/wollastonite composite material is carbonized only on the surface layer of the wollastonite, the crystal structure and the performance of the wollastonite are still kept inside the carbon/wollastonite composite material, and the tensile strength and the flexural modulus of the carbon/wollastonite composite material can be obviously improved in a polypropylene system, so that the mechanical property of the carbon/wollastonite composite material meets the requirements of actual use.
(4) In order to facilitate the compounding effect of the superconducting carbon black and the carbon/wollastonite composite material, the carbon/wollastonite composite material is subjected to surface modification by using a silane coupling agent, and two hydroxyl groups connected with a silicon element in the modified silane coupling agent are exposed in the air without further reaction. By adding the super-conductive carbon black subjected to the oxidation treatment into the system, the carboxyl on the surface of the carbon black is further reacted with the hydroxyl in the silane coupling agent, and finally one end of a silicon element in the silane coupling agent is connected with the carbon/wollastonite composite material, and the other two ends of the silicon element are connected with the super-conductive carbon black. The processing method enables the superconducting carbon black and carbon/wollastonite composite material to have better compounding effect in a final material system, and simultaneously can greatly improve the compatibility of the inorganic filler and the polypropylene matrix and ensure the formation of a final conductive network.
The antistatic polypropylene material finally obtained is added with a small amount of superconducting carbon black, so that the permanent antistatic performance can be obtained, the mechanical property of the material is improved, the material can be recycled, and the environment-friendly property is realized. The finally prepared material can be applied to a plurality of fields such as electronic and electric appliance turnover boxes, new energy automobiles and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.
The polypropylene is Loyang petrochemical homopolymerized polypropylene MN15, the material melt index is 15g/10min, and the shrinkage rate is 1.8%.
The superconducting carbon black is ASAHI superconducting carbon black AX-015, and the average grain diameter of the product is 19 nm.
The length-diameter ratio of the adopted wollastonite is Haicheng mining wollastonite W625, and is 11: 1.
The antioxidant is Pasteur antioxidant 1010, 168, and the product ratio is 1: 1. (ii) a
The silane coupling agent is a Chinese medicament KH 560;
example 1
(1) Mixing 150g of wollastonite W625 with 450mL of deionized water, adding 3.0g of polyethylene glycol, and uniformly stirring in a water bath kettle at the constant temperature of 90 ℃ for later use; slowly dripping 20% hydrochloric acid solution into wollastonite suspension, controlling pH value to 2, standing, reacting for 5h, washing with water for 3 times, and drying at 120 deg.C to obtain acid-treated wollastonite. Dissolving 5.0g of epoxy resin in 200mL of acetone, pouring the mixture into a wollastonite beaker filled with 150g of acid treatment, covering wollastonite powder, standing, reacting for 4 hours, drying at 120 ℃, carbonizing for 5 hours in a 700 ℃ tube furnace in nitrogen atmosphere, and thus obtaining the carbon/wollastonite composite material.
(2) 100g of superconducting carbon black AX-015 and 500mL of nitric acid with the mass fraction of 0.35 are taken to be put in a beaker, stirred at room temperature, and after 5 hours of reaction, the carbon black is washed by deionized water until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 120 ℃ and the pressure of 0.5KPa until the quality is constant.
(3) Taking 150g of carbon/wollastonite composite material, stirring in 500mL of ethanol to obtain carbon/wollastonite suspension, adding 20g of silane coupling agent into the obtained suspension, fully stirring, reacting at 70 ℃ for 0.5h, adding 100g of oxidized superconducting carbon black into the system, fully stirring, keeping the reaction temperature of 70 ℃, further reacting for 2h, and drying at 100 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material.
(4) Placing 750g of homopolymerized polypropylene MN15, 250g of superconducting carbon black-carbon/wollastonite composite material and 1.0g of antioxidant in a high-speed stirrer to be mixed for 5 minutes at the rotating speed of 1500rpm to obtain premix, and adding the premix through a main feeding port of a double-screw extruder;
(5) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 195 ℃, the temperature of the third zone is 195 ℃, the temperature of the fourth zone is 190 ℃ and the rotation speed of the screw is 500 r/min; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Example 2
(1) Mixing 120g of wollastonite W625 with 400mL of deionized water, adding 2.0g of polyethylene glycol, and uniformly stirring in a constant-temperature water bath kettle at 100 ℃ for later use; slowly dripping 20% hydrochloric acid solution into wollastonite suspension, controlling pH value to 3, standing, reacting for 4h, washing with water for 3 times, and drying at 100 deg.C to obtain acid-treated wollastonite. Dissolving 4.0g of epoxy resin in 160mL of acetone, pouring the mixture into a wollastonite beaker filled with 120g of acid treatment, covering wollastonite powder, standing, reacting for 3 hours, drying at 120 ℃, carbonizing for 4 hours in a 600 ℃ tube furnace in nitrogen atmosphere to obtain the carbon/wollastonite composite material.
(2) 80g of superconducting carbon black AX-015 and 480mL of nitric acid with the mass fraction of 0.35 are taken to be put in a beaker, stirred at room temperature and reacted for 4 hours, and then deionized water is used for washing the carbon black until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 110 ℃ and the pressure of 0.4KPa until the quality is constant.
(3) Stirring 120 carbon/wollastonite composite material in 400mL of ethanol to obtain carbon/wollastonite suspension, adding 17g of silane coupling agent into the obtained suspension, fully stirring, reacting at 70 ℃ for 1.25h, adding 80g of oxidized superconducting carbon black into the system, fully stirring, keeping the reaction temperature of 70 ℃, further reacting for 3h, and drying at 120 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material.
(4) Placing 800g of homo-polypropylene MN15, 200g of superconducting carbon black-carbon/wollastonite composite material and 2.0g of antioxidant in a high-speed stirrer to be mixed for 3 minutes at the rotating speed of 1000rpm to obtain premix, and adding the premix through a main feeding port of a double-screw extruder;
(5) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 195 ℃, the temperature of the third zone is 190 ℃, the temperature of the fourth zone is 190 ℃ and the rotation speed of the screw is 400 r/min; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Example 3
(1) Mixing 100g of wollastonite W625 with 350mL of deionized water, adding 1.5g of polyethylene glycol, and uniformly stirring in a water bath kettle at the constant temperature of 80 ℃ for later use; slowly dripping 20% hydrochloric acid solution into wollastonite suspension, controlling pH value to 2, standing, reacting for 3h, washing with water for 3 times, and drying at 120 deg.C to obtain acid-treated wollastonite. 2.5g of epoxy resin is dissolved in 120mL of acetone, poured into a wollastonite beaker filled with 100g of acid treatment, covered with wollastonite powder, kept stand, reacted for 2 hours, dried at 120 ℃, carbonized for 3 hours in a 500 ℃ tube furnace in nitrogen atmosphere, and the carbon/wollastonite composite material is obtained.
(2) 70g of superconducting carbon black AX-015 and 450mL of nitric acid with the mass fraction of 0.35 are taken out of a beaker, stirred at room temperature, and after reaction for 3 hours, the carbon black is washed by deionized water until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 100 ℃ and the pressure of 0.3KPa until the quality is constant.
(3) Stirring 100g of carbon/wollastonite composite material in 350mL of ethanol to obtain carbon/wollastonite suspension, adding 15g of silane coupling agent into the obtained suspension, fully stirring, reacting at 60 ℃ for 2h, adding 70g of oxidized superconducting carbon black into the system, fully stirring, keeping the reaction temperature of 60 ℃, further reacting for 1h, and drying at 110 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material.
(4) Placing 830g of homo-polypropylene MN15, 170g of superconducting carbon black-carbon/wollastonite composite material and 3.0g of antioxidant in a high-speed stirrer for mixing for 4 minutes at the rotating speed of 500rpm to obtain premix, and adding the premix through a main feeding port of a double-screw extruder;
(5) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 185 ℃, and the rotating speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Example 4
(1) Mixing 80g of wollastonite W625 with 300mL of deionized water, adding 0.9g of polyethylene glycol, and uniformly stirring in a water bath kettle at the constant temperature of 90 ℃ for later use; slowly dripping 20% hydrochloric acid solution into the wollastonite suspension, controlling the pH value to be 3, standing, reacting for 3h, washing with water for 3 times, and drying at 120 ℃ to obtain the acid-treated wollastonite. 2.0g of epoxy resin is dissolved in 90mL of acetone, poured into a wollastonite beaker filled with 80g of acid treatment, covered with wollastonite powder, kept stand, reacted for 3 hours, dried at 120 ℃, carbonized for 3 hours in a 500 ℃ tube furnace in nitrogen atmosphere, and the carbon/wollastonite composite material is obtained.
(2) 60g of superconducting carbon black AX-015 and 360mL of nitric acid with the mass fraction of 0.35 are taken out of a beaker, stirred at room temperature, and after 2 hours of reaction, the carbon black is washed by deionized water until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 110 ℃ and the pressure of 0.4KPa until the quality is constant.
(3) Stirring 80g of carbon/wollastonite composite material in 300mL of ethanol to obtain a carbon/wollastonite suspension, adding 13g of silane coupling agent into the obtained suspension, fully stirring, reacting at 80 ℃ for 1h, adding 60g of oxidized superconducting carbon black into the system, fully stirring, keeping the reaction temperature of 80 ℃, further reacting for 1h, and drying at 110 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material.
(4) 860g of homo-polypropylene MN15, 140g of superconducting carbon black-carbon/wollastonite composite material and 4.0g of antioxidant are placed in a high-speed stirrer to be mixed for 3 minutes at the rotating speed of 1000rpm to obtain premix, and then the premix is added through a main feeding port of a double-screw extruder;
(5) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 185 ℃, the temperature of the second zone is 195 ℃, the temperature of the third zone is 195 ℃, the temperature of the fourth zone is 195 ℃, and the rotation speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Example 5
(1) Mixing 50g of wollastonite W625 with 200mL of deionized water, adding 0.5g of polyethylene glycol, and uniformly stirring in a water bath kettle at the constant temperature of 80 ℃ for later use; slowly dripping 20% hydrochloric acid solution into wollastonite suspension, controlling pH value to 2, standing, reacting for 5h, washing with water for 3 times, and drying at 120 deg.C to obtain acid-treated wollastonite. Dissolving 1.25g of epoxy resin in 60mL of acetone, pouring into a wollastonite beaker filled with 50g of acid treatment, covering wollastonite powder, standing, reacting for 3 hours, drying at 120 ℃, carbonizing for 3 hours in a 600 ℃ tube furnace in nitrogen atmosphere to obtain the carbon/wollastonite composite material.
(2) And (3) taking 40g of superconducting carbon black AX-015 and 320mL of nitric acid with the mass fraction of 0.35 in a beaker, stirring at room temperature, reacting for 2 hours, and then washing the carbon black with deionized water until the pH value of a washing solution is constant. The carbon black after oxidation treatment is dried in a vacuum oven with the temperature of 100 ℃ and the pressure of 0.4KPa until the quality is constant.
(3) Taking 50g of carbon/wollastonite composite material, stirring in 200mL of ethanol to obtain carbon/wollastonite suspension, adding 10g of silane coupling agent into the obtained suspension, fully stirring, reacting at 80 ℃ for 1h, adding 40g of oxidized superconducting carbon black into the system, fully stirring, keeping the reaction temperature of 80 ℃, further reacting for 1h, and drying at 100 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material.
(4) 910g of homopolymerized polypropylene MN15, 90g of superconducting carbon black-carbon/wollastonite composite material and 5.0g of antioxidant are placed in a high-speed stirrer to be mixed for 3 minutes at the rotating speed of 1500rpm to obtain premix, and then the premix is added through a main feeding port of a double-screw extruder;
(5) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 190 ℃, the temperature of the second zone is 200 ℃, the temperature of the third zone is 195 ℃, the temperature of the fourth zone is 190 ℃ and the rotation speed of the screw is 400 r/min; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
TABLE 1 examples 1-5 product Properties
Comparative example 1
(1) Placing 830g of homo-polypropylene MN15 and 3.0g of antioxidant in a high-speed mixer for mixing for 4 minutes at the rotating speed of 500rpm to obtain a premix, and adding the premix through a main feeding port of a double-screw extruder;
(2) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 185 ℃, and the rotating speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Comparative example 2
(1) Placing 830g of homo-polypropylene MN15, 100g of wollastonite, 70g of superconducting carbon black and 3.0g of antioxidant in a high-speed stirrer, mixing for 4 minutes at the rotating speed of 500rpm to obtain a premix, and adding the premix through a main feeding port of a double-screw extruder;
(2) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 185 ℃, and the rotating speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Comparative example 3
(1) Placing 830g of homo-polypropylene MN15, 70g of superconducting carbon black AX-015 and 3.0g of antioxidant in a high-speed stirrer, mixing for 4 minutes at the rotating speed of 500rpm to obtain a premix, and adding the premix through a main feeding port of a double-screw extruder;
(2) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 185 ℃, and the rotating speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
Comparative example 4
(1) Placing 830g of homo-polypropylene MN15, 100g of wollastonite and 3.0g of antioxidant in a high-speed stirrer, mixing for 4 minutes at the rotating speed of 500rpm to obtain a premix, and adding the premix through a main feeding port of a double-screw extruder;
(2) the raw materials are melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material. The parameters of the twin-screw are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 190 ℃, the temperature of the third zone is 200 ℃, the temperature of the fourth zone is 185 ℃, and the rotating speed of the screw is 300 revolutions per minute; and extruding the product from a double screw, cooling by using cooling water, granulating by using a granulator, and finally drying in an oven at 90 ℃ for 2 hours.
TABLE 2 comparative examples 1-4 product Properties
Note:
1. according to the requirements of customers, the comprehensive evaluation criteria are as follows: the tensile strength of the material is more than or equal to 32MPa, and the flexural modulus of the material is as follows: more than or equal to 2500MPa, and the surface resistivity of the material is less than 1.0 x 1010Ω。
Referring to the performance requirements of the above aspects, the comprehensive evaluation method comprises the following steps:
all products meeting the requirements are qualified grade;
one of the products which does not meet the requirements is an unqualified grade;
according to the invention, the superconducting carbon black and the carbon/wollastonite composite material are compounded to carry out antistatic modification on the polypropylene, wherein the granular superconducting carbon black and the fibrous carbon/wollastonite have synergistic effect, so that the addition amount of the superconducting carbon black can be reduced, and the influence of the carbon black on the mechanical property of the material is reduced. The antistatic polypropylene material finally obtained is added with a small amount of superconducting carbon black, so that the permanent antistatic performance can be obtained, the mechanical property of the material is improved, the material can be repeatedly utilized, and the environment-friendly property is realized. The finally prepared material can be applied to a plurality of fields such as electronic and electric appliance turnover boxes, new energy automobiles and the like.
Claims (12)
1. A permanent antistatic polypropylene composite material is prepared from the following raw materials:
75-91 parts of polypropylene;
5-15 parts of carbon/wollastonite composite material;
4-10 parts of oxidized superconducting carbon black;
1-2 parts of a silane coupling agent;
0.1-0.5 part of antioxidant;
the carbon/wollastonite composite material is prepared by a method comprising the steps of:
dissolving epoxy resin in acetone, adding acid-treated wollastonite, reacting, drying, and carbonizing to obtain the carbon/wollastonite composite material.
2. The polypropylene composite according to claim 1, prepared from raw materials comprising:
80-86 parts of polypropylene;
8-12 parts of carbon/wollastonite composite material;
6-8 parts of oxidized superconducting carbon black;
1.3-1.7 parts of a silane coupling agent;
0.2 to 0.4 portion of antioxidant.
3. The polypropylene composite of claim 1, wherein the carbon/wollastonite composite is prepared by the following method:
(1) mixing wollastonite, water and polyethylene glycol, and stirring uniformly at the temperature of 80-100 ℃ to obtain wollastonite turbid liquid;
(2) adding acid solution into the wollastonite suspension, controlling the pH value to be 2-3, reacting for 3-5h, washing and drying to obtain acid-treated wollastonite;
(3) dissolving epoxy resin in acetone, adding acid-treated wollastonite, reacting for 2-4h, drying, and carbonizing to obtain the carbon/wollastonite composite material.
4. The polypropylene composite material as claimed in claim 3, wherein the mixing in the step (1) is mixing wollastonite and 3-4 parts of deionized water and 0.01-0.02 part of polyethylene glycol based on the mass of wollastonite; the acid solution in the step (2) is a 20wt% hydrochloric acid solution; the amount of the acid-treated wollastonite in the step (3) is 30 to 40 parts by mass based on the epoxy resin; the carbonization is carried out in a 500-700 ℃ tube furnace under the nitrogen atmosphere for 3-5 h.
5. The polypropylene composite material according to claim 3, wherein the wollastonite is commercially available wollastonite for modifying plastics, the shape of the wollastonite is fibrous, and the length-diameter ratio of the wollastonite is 10-20: 1.
6. The polypropylene composite according to any one of claims 1 to 5, wherein the oxidized superconducting carbon black is prepared by a method comprising: mixing and reacting the superconducting carbon black with 5-8 parts of nitric acid based on the mass of the superconducting carbon black for 2-5 hours, and then washing and drying to obtain the superconducting carbon black.
7. The polypropylene composite according to claim 6, wherein the superconducting carbon black is a commercially available nano-sized superconducting carbon black product having an average particle size of < 100 nm.
8. The polypropylene composite material according to any one of claims 1 to 5, wherein the polypropylene is one or a mixture of two of commercially available injection molding grade homo-polypropylene and co-polypropylene, and has a melt index of 10 to 100g/10min and a shrinkage of 1.5 to 2.0%.
9. Polypropylene composite according to any of claims 1-5, whereby the silane coupling agent is a mixture of one or more of the commercially available grades KH550, K H560, KH 570.
10. The polypropylene composite according to any one of claims 1 to 5, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:2 to 2: 1.
11. Process for the preparation of a permanently antistatic polypropylene composite according to any one of claims 1 to 10 comprising the steps of:
(1) adding the carbon/wollastonite composite material into ethanol and stirring to obtain carbon/wollastonite suspension, adding a silane coupling agent into the suspension and stirring, reacting at the temperature of 60-80 ℃ for 0.5-2h, adding oxidized superconducting carbon black into the system, reacting at the temperature of 60-80 ℃ for 1-3h, and drying at the temperature of 100-120 ℃ to obtain the superconducting carbon black-carbon/wollastonite composite material;
(2) placing the raw materials of polypropylene, superconducting carbon black-carbon/wollastonite composite material and antioxidant in a high-speed stirrer to be mixed for 3-5 minutes at the rotation speed of 500-1500rpm to obtain premix, and adding the premix through a main feeding port of a double-screw extruder;
(3) the premix is melted, extruded, cooled, granulated and dried in an extruder to obtain the polypropylene composite material.
12. The method for preparing according to claim 11, wherein the parameters of the twin-screw extruder are set as follows: the temperature of the first zone is 185-plus-195 ℃, the temperature of the second zone is 190-plus-200 ℃, the temperature of the third zone is 190-plus-200 ℃, the temperature of the fourth zone is 185-plus-195 ℃, and the rotation speed of the screw is 300-plus-500 r/min.
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