CN110922666A - Dyeable permanent antistatic flame-retardant polyolefin material and preparation method and application thereof - Google Patents
Dyeable permanent antistatic flame-retardant polyolefin material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dyeable permanent antistatic flame-retardant polyolefin material and a preparation method thereof. The polyolefin material has the three performances of dyeability, permanent antistatic property and flame retardance, and can meet the requirements of MT181-1988 standard mine pipes and the requirements of standardized mines.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a dyeable permanent antistatic flame-retardant polyolefin material and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the advance of standardized mine construction, underground pipelines of coal mines (such as water supply pipes, water discharge pipes, positive pressure air pipes, guniting pipes and the like) are required to have antistatic performance and flame retardant performance, and the internal fluid conveying type of the underground pipelines can be intuitively distinguished according to the appearance color. The existing mining plastic and composite pipe thereof have the following defects: 1. polyolefin materials such as carbon black, graphene and carbon nanotubes which take carbon materials as antistatic agents are black, and only black pipes can be prepared by the materials, and the materials cannot be dyed, so that the requirements of current standardized mine construction on pipe color identification cannot be met; 2. the antistatic agent of the pipe prepared by the polyolefin material modified by the traditional migration type antistatic agent is easy to migrate, the antistatic effect is easy to attenuate along with the prolonging of time, the loss of the antistatic property is large, and the long-term safe use of the pipe is not facilitated; 3. the plastic pipe with color lines and the composite pipe have thin marked lines and are difficult to identify, and the pipeline of the paint mark is coated on the surface of a product by brushing, spraying or dip-coating and other methods, so that the paint is easy to fall off due to friction and washing, is difficult to mark for a long time, and only can provide temporary or short-term antistatic electricity.
When the permanent antistatic agent is used for modifying polyolefin, the doping amount is large, although the polyolefin can be permanently antistatic, the compatibility of the permanent antistatic agent and the polyolefin is poor, so that the mechanical property of the modified polyolefin material is obviously reduced, and the polyolefin material is difficult to apply to a mine environment. In addition, permanent antistatic agents are expensive and, when used in large amounts, can significantly increase pipeline costs.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a dyeable permanent antistatic flame-retardant polyolefin material and a preparation method thereof. The polyolefin material has the three performances of dyeability, permanent antistatic property and flame retardance, and can meet the requirements of MT181-1988 standard mine pipes and the requirements of standardized mines.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a dyeable permanent antistatic flame-retardant polyolefin material comprises a polyolefin substrate, a flame retardant, a compatilizer and an antistatic agent, wherein the antistatic agent comprises a permanent antistatic agent and a non-ionic antistatic agent.
The inventor finds that when the nonionic antistatic agent and the permanent antistatic agent are simultaneously applied to the polyolefin material, a better synergistic effect can be generated, and on the basis of achieving the same antistatic effect, the addition amount of the antistatic agent can be effectively reduced, so that the processing cost of the polyolefin material is effectively reduced.
Meanwhile, what is more important is that the polyolefin material modified by the nonionic antistatic agent and the permanent antistatic agent is light white, and the polyolefin material can be dyed into different colors by adding color master batches with different colors in the extrusion processing process of the pipe so as to distinguish the appearance colors of the pipe. Through the observation to different tubular product outward appearance colours, can distinguish the type of tubular product internal fluid fast.
In some embodiments, the compatibilizer is a mixture of one or more of ethylene vinyl acetate, POE (high polymer of ethylene octene), maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene. After a certain amount of compatilizer is added into the polyolefin, the compatibility of the permanent antistatic agent and the polyolefin can be improved, and further, the mechanical property of the polyolefin material using the permanent antistatic agent can be improved, so that the mechanical property requirement of the pipeline used under the coal mine can be met. In addition, the compatilizer can also improve the dispersion degree of the flame retardant so as to improve the flame retardant property of the polyolefin.
In some embodiments, the compatibilizer is present in the polyolefin material in an amount of 10 to 15 percent by weight.
In some embodiments, the permanent antistatic agent is a polyether-polyamide type permanent antistatic agent or a polyamide-polyether hindered amine type permanent antistatic agent.
Further, the permanent antistatic agent accounts for 10-20% of the polyolefin material by mass.
In some embodiments, the weight percentage of the nonionic antistatic agent in the polyolefin material is 0.5 to 2%.
In some embodiments, the flame retardant in the polyolefin material is an organic nitrogen phosphorus flame retardant.
The organic nitrogen-phosphorus flame retardant is white, does not influence the dyeability of the polyolefin material, has good flame retardant effect, has small influence on the conductive efficiency of the material, and further has small influence on the antistatic property of the polyolefin material. In addition, the amount of harmful gas generated after the organic nitrogen-phosphorus flame retardant is combusted is relatively small, and the environment-friendly requirement is met.
Further, the organic nitrogen-phosphorus flame retardant is a pentaerythritol, phosphorus oxychloride and melamine synthetic product.
In some embodiments, the polyolefin material further comprises a lubricant.
Further, the lubricant is polyethylene wax, polypropylene wax, EBS, oxidized polyethylene wax or silicone powder, and the mass percentage of the lubricant in the polyolefin material is 2-5%.
In tests, it was found that when the permanent antistatic agent system is dominant, the surface of the extruded product is not smooth, affecting the product quality. When a certain amount of lubricant is added, the surface of the extrusion molded product is smooth. And the addition of the lubricant does not influence the antistatic performance of the material, so that the quality of the product is effectively improved.
In some embodiments, the polyolefin material further comprises an antioxidant.
Further, the antioxidant is one or a compound of more of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, phosphite antioxidant, octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate and octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
In some embodiments, the matrix material of the polyolefin material is a composite of one or more of polyethylene, polybutylene, homo-polypropylene or random co-polypropylene.
The preparation method of the dyeable permanent antistatic flame-retardant polyolefin material comprises the following steps:
grinding the granular permanent antistatic agent into powder, mixing with the compatilizer until the compatilizer is completely melted, and granulating;
uniformly mixing the granulated permanent antistatic agent, the non-ionic antistatic master batch, the polyolefin and other auxiliaries, heating, melting and extruding to obtain the antistatic agent;
the nonionic antistatic master batch is prepared by extruding and granulating polyethylene, a compatilizer, a nonionic antistatic agent and a dispersing agent.
After the permanent antistatic agent is ground, mixed with the compatilizer and granulated, the compatibility with the polyolefin can be effectively improved.
Because the addition amount of the nonionic antistatic master batch is less, the nonionic antistatic master batch can be effectively improved to have good dispersibility and compatibility in polyolefin materials after being prepared into the master batch and then being mixed with other components for granulation.
In some embodiments, the nonionic antistatic master batch comprises 50-60 parts of carrier resin, 10-20 parts of compatilizer, 15-25 parts of nonionic antistatic agent and 5-10 parts of dispersing agent;
the carrier resin is polyethylene, the compatilizer is ethylene-vinyl acetate copolymer, and the dispersant is polyethylene wax.
In some embodiments, the method of making further comprises the steps of qualifying, slitting, and drying the extruded mass.
In some embodiments, the permanent electrostatic agent has a milled particle size of less than 300 mesh. So as to improve the uniform mixing degree of the permanent electrostatic agent and the polyolefin material.
The dyeable permanent antistatic flame-retardant polyolefin material is applied to the preparation of mining pipes, automobile parts, precision machinery, electronic and electric products and permanent antistatic films.
The invention has the beneficial effects that:
the permanent antistatic agent and the nonionic antistatic agent are used for synergism, and the polyolefin material is modified by the organic nitrogen phosphorus flame retardant and other additives to prepare the permanent antistatic flame-retardant polyolefin composite material. The polyolefin composite material is light white, and the color permanent antistatic flame-retardant polyolefin composite material with mechanical properties not reduced can be prepared by adding color master batches or toner. The composite material can be used for producing mining pipes by extrusion, is applied to preparing permanent antistatic flame-retardant electronic and electrical products, automobile parts and precision machinery by injection molding, or can be used for permanent antistatic films by replacing polyolefin substrates with film blowing-level polyolefin matrix resin.
The plastic pipe and the composite pipe produced by adding the color master batches with different colors into the polyolefin material have bright appearance color, and the types of the fluid inside the pipe can be distinguished by observing the appearance color of the pipe. In addition, the surface resistance of the prepared pipe reaches 5 multiplied by 107～1×107Omega (excellent antistatic effect) completely meets the requirements of MT181-1988 standard mine pipes. Meanwhile, the nitrogen-phosphorus flame retardant is added, the flame retardant property also reaches the standard of MT181-1988, and the harmful gas generated after combustion is less than that of bromine-antimony flame retardant. The composite material can simultaneously meet the triple requirements of permanent antistatic property, flame retardance and easy color identification of the mining pipe.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
According to the formula: 50 parts of HDPE (high-density polyethylene), 10 parts of compatilizer (EVA resin and maleic anhydride grafted polyethylene in a mass ratio of 1:1), 15 parts of permanent antistatic agent-polyoxyethylene-polyamide compound, 5 parts of nonionic antistatic master batch, 2.5 parts of lubricant (polyethylene wax and oxidized polyethylene wax in a mass ratio of 1:1), 0.5 part of antioxidant (168+1010+1076) and 17 parts of organic NP flame retardant-melamine polyphosphate flame retardant. After being uniformly mixed at a high speed, the mixture is granulated by a double-screw extruder by a set production process to produce the dyeable permanent antistatic flame-retardant polyethylene material.
In the nonionic antistatic master batch, 60 parts of polyethylene, 10 parts of EVA (ethylene-vinyl acetate), 25 parts of nonionic antistatic agent-polyethylene glycol amide and 5 parts of dispersing agent-polyethylene wax are added.
The antioxidant 168 is a phosphite antioxidant, the antioxidant 1010 is tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, the antioxidant 1076 is octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate or octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, the antioxidant of the embodiment is a compound of three antioxidants, and the mass ratio of the three antioxidants is 1:1: 1.
The specific production process comprises the following steps:
1) grinding the granular permanent antistatic agent on a grinding mill to obtain powder with the grain diameter of less than 300 meshes;
2) the powdery permanent antistatic agent and EVA resin are mixed and refined in an internal mixer for 15 minutes until the EVA is completely melted, and a single-screw extruder is used for granulation, so that the effect of high compatibility of the antistatic agent and polyolefin and good compatibility in mixing and granulating is achieved.
3) According to the formula proportion, all the materials are weighed, uniformly dispersed in a high-speed mixer and then added into a hopper of a double-screw extruder, a heater is arranged outside an extruded machine barrel, and the materials in the machine barrel are heated to the melting temperature through heat conduction. When the machine is operated, the screw rod in the machine barrel conveys the materials forwards. The materials are rubbed and sheared with the machine barrel, the screw and the materials in the moving process to generate a large amount of heat, and the added materials are continuously melted under the action of the heat and the heat conduction. The molten material is continuously and stably fed into a shaped head (or die). After passing through the neck mold, the material in the flowing state takes an approximate shape of the neck mold, and then enters a cooling and shaping device to ensure that the material keeps a set shape and is solidified, and then the extruded and shaped material is input into a granulator to cut the round strip plastic into particles, and the particles are dried and packaged.
The parameters of the twin-screw extruder are as follows:
1. parameters of the double-screw extruder: screw diameter: 75 mm; length-diameter ratio: 40; screw rotation speed: 600 rpm; power of the main motor: 132 kW;
2. screw combination: in order to achieve uniform dispersion and distribution mixing, a screw combination with medium shear strength is adopted;
3. setting the temperature to be 150, 160, 170, 175, 180, 185 and 170 ℃;
4. the rotating speed of the main machine is 300 rpm;
5. the feeding rotating speed is 10 Hz.
The performance test results of the dyeable permanent antistatic flame-retardant polyethylene material prepared are as follows:
melt index: 1.4g/10min (190 ℃ C.. times.5 Kg);
oxidation induction period 47min (oxidation induction temperature 230 ℃);
yield strength: 13.8 MPa;
breaking strength: 19.1 MPa;
elongation at break: 660%;
flame retardancy: 2.7s (mean burning time);
surface resistance: 5X 107Ω。
Example 2
According to the formula: 50 parts of HDPE, 12 parts of compatilizer (a mixture of EVA and POE in a mass ratio of 1:1), 12 parts of permanent antistatic agent-polyoxyethylene-polyamide composite, 8 parts of nonionic antistatic master batch, 2.5 parts of lubricant (polyethylene wax and EBS in a mass ratio of 1:1), 0.5 part of antioxidant (antioxidant 1010+168 in a mass ratio of 1:1) and 15 parts of organic NP flame retardant-melamine polyphosphate flame retardant. After being uniformly mixed at a high speed, the mixture is granulated by a double-screw extruder by a given production process (same as the example 1) to produce the dyeable permanent antistatic flame-retardant polyethylene material.
In the nonionic antistatic master batch, 60 parts of polyethylene, 10 parts of EVA (ethylene-vinyl acetate), 25 parts of nonionic antistatic agent-polyethylene glycol amide and 5 parts of dispersing agent-polyethylene wax are added.
The performance test results of the dyeable permanent antistatic flame-retardant polyethylene material prepared are as follows:
melt index: 1.2g/10min (190 ℃ C.. times.5 Kg);
oxidation induction period: 33min (oxidation induction temperature 230 ℃);
yield strength: 11.9 MPa;
breaking strength: 17.3 MPa;
elongation at break: 510%;
flame retardancy: 7.9s (average burning time)
Surface resistance: 7X 108Ω。
Example 3
According to the formula: 50 parts of HDPE (high-density polyethylene), 10 parts of compatilizer (a mixture of EVA and POE in a mass ratio of 1:2), 18 parts of permanent antistatic agent-polyoxyethylene-polyamide compound, 2 parts of nonionic antistatic master batch, 2.5 parts of lubricant (polyethylene wax and EBS in a mass ratio of 1:1), 0.5 part of antioxidant (antioxidant 1076+16 in a mass ratio of 1:1), and 20 parts of organic NP flame retardant-melamine polyphosphate flame retardant. After being uniformly mixed at a high speed, the mixture is granulated by a double-screw extruder by a set production process to produce the dyeable permanent antistatic flame-retardant polyethylene material.
In the nonionic antistatic master batch, 60 parts of polyethylene, 10 parts of EVA (ethylene-vinyl acetate), 25 parts of nonionic antistatic agent-polyethylene glycol amide and 5 parts of dispersing agent-polyethylene wax are added.
The performance test results of the dyeable permanent antistatic flame-retardant polyethylene material prepared are as follows:
melt index: 1.5g/10min (190 ℃ C.. times.5 Kg);
oxidation induction period: 68min (oxidation induction temperature 230 ℃);
yield strength: 12.9 MPa;
breaking strength: 17.8 MPa;
elongation at break: 510%;
flame retardancy: 1.9s (mean burning time);
surface resistance: 4X 108Ω。
Example 4
The formula of the permanent antistatic flame-retardant polyethylene material comprises the following components: 50 parts of HDPE, 10 parts of compatilizer-EVA, 2 parts of lubricant-polyethylene wax, 1680.8 parts of antioxidant, 17 parts of organic NP flame retardant-melamine polyphosphate flame retardant, and the permanent antistatic agent is a polyoxyethylene-polyether antistatic agent.
In the nonionic antistatic master batch (DHM-101), 60 parts of polyethylene, 10 parts of EVA (ethylene-vinyl acetate), 25 parts of nonionic antistatic agent-polyethylene glycol amide and 5 parts of dispersing agent-polyethylene wax are added.
The surface resistance of the polyethylene material prepared by changing the mixture ratio of the permanent antistatic agent and the DHM-101 according to the production process of the example 1 is shown in Table 1, and the unit of the addition amount in the Table 1 is as follows: and (4) parts by mass.
TABLE 1
| Antistatic agent | Permanent + DHM-101 | Permanent + DHM-101 | Permanent + DHM-101 |
| Adding amount of | 15 parts and 5 parts of | 18 parts and 2 parts of | 12 parts and 8 parts |
| Surface resistance | 4×107Ω | 3×108Ω | 7×108Ω |
Example 5
The formula of the permanent antistatic flame-retardant polyethylene material comprises the following components: 50 parts of HDPE, 7.5 parts of compatilizer-EVA, 18 parts of permanent antistatic agent-polyoxyethylene-polyamide composite, 2 parts of nonionic antistatic master batch, 2 parts of lubricant-polyethylene wax, 0.5 part of antioxidant (168+1010+1076 in a mass ratio of 1:1:1), and 20 parts of organic NP flame retardant-melamine polyphosphate flame retardant. In the nonionic antistatic master batch (DHM-101), 60 parts of polyethylene, 10 parts of EVA (ethylene-vinyl acetate), 25 parts of nonionic antistatic agent-polyethylene glycol amide and 5 parts of dispersing agent-polyethylene wax are added. The preparation was carried out according to the production process of example 1.
As a comparative example, the organic NP flame retardant is replaced by an inorganic NP flame retardant (phosphate and melamine composition in a mass ratio of 2:1), and the formula of the polyethylene material is as follows: 40 parts of HDPE, 7.5 parts of compatilizer-EVA (ethylene vinyl acetate), 15 parts of permanent antistatic agent-polyoxyethylene-polyamide compound, 5 parts of nonionic antistatic master batch, 2 parts of lubricant-polyethylene wax, 0.5 part of antioxidant (168+1010+1076 in a mass ratio of 1:1:1) and 30 parts of inorganic NP flame retardant. The preparation was carried out according to the production process of example 1.
The prepared polyethylene material was subjected to the MT181-88 burning method and the resistance test, and the test results are shown in Table 2.
TABLE 2
| Type of material | Inorganic NP fire retardant | Organic NP flame retardant |
| Adding amount of | 30％ | 20％ |
| Average burning time | 2.7s | 2.4s |
| Surface resistance | 5×109Ω | 2×107Ω |
As can be seen from table 2, the inorganic NP flame retardant has poor flame retardant effect on the polyolefin composite material and also has a great influence on the conductive efficiency of the polyolefin composite material. The organic nitrogen-phosphorus flame retardant has good flame retardant effect, and can keep good conductive efficiency of the polyolefin composite material.
Example 6
The formula of the antistatic flame-retardant polyethylene material comprises the following components: 50 parts of random copolymer polypropylene, 10 parts of a compatilizer (POE + maleic anhydride grafted polypropylene in a mass ratio of 2:1), 15 parts of a permanent antistatic agent-polyoxyethylene-polyamide compound, 5 parts of a nonionic antistatic master batch, 2.5 parts of a lubricant- (polypropylene wax + EBS in a mass ratio of 1:1), 0.5 part of an antioxidant (168+1010+1076 in a mass ratio of 1:2:1), and 17 parts of an organic NP flame retardant-melamine polyphosphate flame retardant. The nonionic antistatic master batch was the same as in example 1.
The preparation method is as in example 1.
Example 7
The formula of the antistatic flame-retardant polyethylene material comprises the following components: 50 parts of homopolymerized polypropylene, 10 parts of compatilizer (POE + maleic anhydride grafted polypropylene with the mass ratio of 1:3), 5 parts of nonionic antistatic master batch, 15 parts of permanent antistatic agent, 2.5 parts of lubricant (polypropylene wax + EBS with the mass ratio of 1:1), 0.5 part of antioxidant (168+1010+1076) and 17 parts of organic NP flame retardant melamine polyphosphate flame retardant. The nonionic antistatic master batch was the same as in example 1. The preparation method is as in example 1.
Comparative example 1
A permanent antistatic polyolefin resin material comprises the following components in parts by weight: 80 parts of polyethylene resin matrix and 20 parts of permanent antistatic agent.
The permanent antistatic agent is a compound of polyvinyl imidazole and octadecyl benzene sulfonic acid, and is prepared by dissolving two substances in DMF to obtain two solutions, mixing, stirring, heating to remove solvent, drying, and pulverizing.
The preparation method comprises the following steps: uniformly mixing the polyethylene resin matrix and the compound permanent antistatic agent according to the proportion, adding the mixture into a double-screw extruder through a weightless feeder at a certain speed, heating and plasticizing, cooling and granulating the extruded melt through a water tank to obtain the permanent antistatic olefin material with the surface resistance of 1 multiplied by 109Ω。
The process is complex, has solvent residue, certain flame retardant property and poor antistatic effect.
Comparative example 2
The formula of the antistatic flame-retardant polyethylene material comprises the following components: 50 parts of HDPE, 10 parts of compatilizer (EVA resin), 20 parts of permanent antistatic agent-polyoxyethylene-polyamide composite, 2.5 parts of lubricant-polyethylene wax, 1680.5 part of antioxidant and 17 parts of organic NP flame retardant-melamine polyphosphate flame retardant. After being uniformly mixed at a high speed, the mixture is granulated by a double-screw extruder by a set production process to produce the dyeable permanent antistatic flame-retardant polyethylene material. The production process was the same as in example 1.
The performance test results of the dyeable permanent antistatic flame-retardant polyethylene material prepared are as follows:
yield strength: 11.3 MPa;
breaking strength: 16.6 MPa;
elongation at break: 420%;
surface resistance: 3X 108Ω。
In the example, only the permanent antistatic agent is used, and the produced dyeable antistatic flame-retardant polyethylene material has large loss of mechanical property as seen from the elongation at break, and compared with the example 1, the dyeable antistatic flame-retardant polyethylene material has poor reprocessing performance and is inconvenient for processing pipes.
Comparative example 3
The formula of the antistatic flame-retardant polyethylene material comprises the following components: 50 parts of HDPE, 10 parts of compatilizer (mixture of EVA and POE), 20 parts of nonionic antistatic master batch, 2.5 parts of lubricant-polyethylene wax, 1680.5 part of antioxidant and 17 parts of organic NP flame retardant.
In the nonionic antistatic master batch, 60 parts of LDPE, 10 parts of EVA, 25 parts of nonionic antistatic agent and 5 parts of polyethylene wax. The preparation was carried out according to the production process of example 1.
The performance test results of the dyeable permanent antistatic flame-retardant polyethylene material prepared by only adding the nonionic antistatic agent are as follows:
yield strength: 12.1 MPa;
breaking strength: 17.7 MPa;
elongation at break: 540%;
surface resistance: 7X 108Ω。
Although the loss of mechanical properties is small by only adding the nonionic antistatic agent, the resistance value is larger, and the effect of the permanent long-acting antistatic agent cannot be ensured because the antistatic effect of the nonionic antistatic agent is influenced by the environmental humidity and the temperature. The surface of the produced material is greasy, so that the co-extruded material can not be bonded with polyethylene and can not be used for producing composite pipes.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A dyeable permanent antistatic flame retardant polyolefin material characterized by: polyolefin matrix, flame retardant, compatilizer and antistatic agent, wherein the antistatic agent comprises permanent antistatic agent and nonionic antistatic agent.
2. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the compatilizer is one or a mixture of more of ethylene-vinyl acetate polymer, POE, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene;
the mass percentage of the compatilizer in the polyolefin material is 10-15%.
3. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the permanent antistatic agent is a polyether-polyamide permanent antistatic agent or a polyamide-polyether hindered amine permanent antistatic agent;
further, the permanent antistatic agent accounts for 10-20% of the polyolefin material by mass.
4. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the mass percentage of the nonionic antistatic agent in the polyolefin material is 0.5-2%.
5. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the flame retardant in the polyolefin material is an organic nitrogen-phosphorus flame retardant;
further, the organic nitrogen-phosphorus flame retardant is a pentaerythritol, phosphorus oxychloride and melamine synthetic product.
Or, the polyolefin material further comprises a lubricant;
further, the lubricant is polyethylene wax, polypropylene wax, EBS, oxidized polyethylene wax or silicone powder, and the mass percentage of the lubricant in the polyolefin material is 2-5%.
6. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the polyolefin material further comprises an antioxidant;
further, the antioxidant is one or a compound of more of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, phosphite antioxidant, octadecyl-3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl propionate and octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
7. Dyeable, permanent antistatic flame retardant polyolefin material according to claim 1, characterized in that: the matrix material of the polyolefin material is one or a composite material of polyethylene, polybutylene, homo-polypropylene or random co-polypropylene.
8. Process for the preparation of dyeable, permanently antistatic flame-retardant polyolefin material according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
grinding the granular permanent antistatic agent into powder, mixing with the compatilizer until the compatilizer is completely melted, and granulating;
uniformly mixing the granulated permanent antistatic agent, the non-ionic antistatic master batch, the polyolefin and other auxiliaries, heating, melting and extruding to obtain the antistatic agent;
the nonionic antistatic master batch is prepared by extruding and granulating polyethylene, a compatilizer, a nonionic antistatic agent and a dispersing agent.
9. The method of claim 8, wherein: in the non-ionic antistatic master batch, 50-60 parts of carrier resin, 10-20 parts of compatible resin, 15-25 parts of antistatic agent and 5-10 parts of dispersing agent; the carrier resin is polyethylene, the compatilizer is ethylene-vinyl acetate copolymer, and the dispersant is polyethylene wax;
further, the preparation method also comprises the steps of carrying out qualitative, cutting and drying on the extruded material.
Furthermore, the particle size of the permanent electrostatic agent after being milled is less than 300 meshes.
10. Use of the dyeable permanent antistatic flame retardant polyolefin material according to any one of claims 1 to 7 for the production of mining pipes, automotive parts, precision machinery, electronic and electrical products and permanent antistatic films.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637003A (en) * | 2022-10-20 | 2023-01-24 | 苏州润佳工程塑料股份有限公司 | Permanent antistatic polypropylene composite material and preparation method thereof |
| CN115895234A (en) * | 2022-11-17 | 2023-04-04 | 聚力防静电科技(广东)有限公司 | High-rigidity low-warpage permanently antistatic reinforced PPO/LCP compound and preparation method thereof |
| CN115926314A (en) * | 2022-12-14 | 2023-04-07 | 广东道生科技股份有限公司 | Antistatic PP material and preparation method and application thereof |
| CN116041825A (en) * | 2022-12-30 | 2023-05-02 | 金发科技股份有限公司 | Polyethylene material and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427873A (en) * | 2000-04-12 | 2003-07-02 | 三光化学工业株式会社 | Antistatic composition |
| CN1742047A (en) * | 2003-01-24 | 2006-03-01 | 西巴特殊化学品控股有限公司 | Antistatic composition |
| CN101045804A (en) * | 2006-03-27 | 2007-10-03 | 东莞市问鼎静电科技有限公司 | Superclean permanent electrostatic screen package bag and composite |
| CN101805488A (en) * | 2010-04-16 | 2010-08-18 | 深圳市科聚新材料有限公司 | Transparent ABS material and preparation method thereof |
| CN102485786A (en) * | 2010-12-02 | 2012-06-06 | 辽宁杰事杰新材料有限公司 | High strength antistatic polypropylene structural sheet material and preparation method thereof |
| CN103131084A (en) * | 2011-11-25 | 2013-06-05 | 上海日之升新技术发展有限公司 | Halogen-free inflaming retarding permanent antistatic polypropylene composite material and preparation method |
| CN103665628A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Antistatic non-plasticized PVC composite |
| CN104277322A (en) * | 2013-07-03 | 2015-01-14 | 合肥杰事杰新材料股份有限公司 | Antistatic high-luster polypropylene composite material and preparation method thereof |
| CN104830043A (en) * | 2015-05-25 | 2015-08-12 | 上海跃贝塑化科技有限公司 | Antistatic PC/ASA (polycarbonate/acrylonitrile styrene acrylate copolymer) alloy plastic for automotive interior trim parts and method for manufacturing antistatic PC/ASA alloy plastic |
| CN106700270A (en) * | 2016-12-02 | 2017-05-24 | 广州科苑新型材料有限公司 | Polypropylene composite material and preparation method thereof |
| CN109370041A (en) * | 2018-08-09 | 2019-02-22 | 河南工程学院 | A kind of polypropylene modified material and preparation method thereof having both good rigidity and high elongation at tear |
| CN109593317A (en) * | 2018-11-02 | 2019-04-09 | 广东圆融新材料有限公司 | High fire-retardance antistatic ABS composite material and preparation method |
-
2019
- 2019-12-12 CN CN201911275479.9A patent/CN110922666A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427873A (en) * | 2000-04-12 | 2003-07-02 | 三光化学工业株式会社 | Antistatic composition |
| CN1742047A (en) * | 2003-01-24 | 2006-03-01 | 西巴特殊化学品控股有限公司 | Antistatic composition |
| CN101045804A (en) * | 2006-03-27 | 2007-10-03 | 东莞市问鼎静电科技有限公司 | Superclean permanent electrostatic screen package bag and composite |
| CN101805488A (en) * | 2010-04-16 | 2010-08-18 | 深圳市科聚新材料有限公司 | Transparent ABS material and preparation method thereof |
| CN102485786A (en) * | 2010-12-02 | 2012-06-06 | 辽宁杰事杰新材料有限公司 | High strength antistatic polypropylene structural sheet material and preparation method thereof |
| CN103131084A (en) * | 2011-11-25 | 2013-06-05 | 上海日之升新技术发展有限公司 | Halogen-free inflaming retarding permanent antistatic polypropylene composite material and preparation method |
| CN103665628A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Antistatic non-plasticized PVC composite |
| CN104277322A (en) * | 2013-07-03 | 2015-01-14 | 合肥杰事杰新材料股份有限公司 | Antistatic high-luster polypropylene composite material and preparation method thereof |
| CN104830043A (en) * | 2015-05-25 | 2015-08-12 | 上海跃贝塑化科技有限公司 | Antistatic PC/ASA (polycarbonate/acrylonitrile styrene acrylate copolymer) alloy plastic for automotive interior trim parts and method for manufacturing antistatic PC/ASA alloy plastic |
| CN106700270A (en) * | 2016-12-02 | 2017-05-24 | 广州科苑新型材料有限公司 | Polypropylene composite material and preparation method thereof |
| CN109370041A (en) * | 2018-08-09 | 2019-02-22 | 河南工程学院 | A kind of polypropylene modified material and preparation method thereof having both good rigidity and high elongation at tear |
| CN109593317A (en) * | 2018-11-02 | 2019-04-09 | 广东圆融新材料有限公司 | High fire-retardance antistatic ABS composite material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 刘慧珍等: "国内外高分子型抗静电剂的研究进展", 《杭州化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637003A (en) * | 2022-10-20 | 2023-01-24 | 苏州润佳工程塑料股份有限公司 | Permanent antistatic polypropylene composite material and preparation method thereof |
| CN115895234A (en) * | 2022-11-17 | 2023-04-04 | 聚力防静电科技(广东)有限公司 | High-rigidity low-warpage permanently antistatic reinforced PPO/LCP compound and preparation method thereof |
| CN115926314A (en) * | 2022-12-14 | 2023-04-07 | 广东道生科技股份有限公司 | Antistatic PP material and preparation method and application thereof |
| CN116041825A (en) * | 2022-12-30 | 2023-05-02 | 金发科技股份有限公司 | Polyethylene material and preparation method and application thereof |
| CN116041825B (en) * | 2022-12-30 | 2023-12-01 | 金发科技股份有限公司 | Polyethylene material and preparation method and application thereof |
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