CN110577701A

CN110577701A - permanent antistatic material and preparation method thereof

Info

Publication number: CN110577701A
Application number: CN201910904269.5A
Authority: CN
Inventors: 吴南松; 魏彬; 邹克兵; 梁晓玉; 赵庭国; 易华; 李绪军; 郑卫; 陈志豪
Original assignee: Chongqing Aocai New Material Corp Ltd
Current assignee: Chongqing Aocai New Material Corp Ltd
Priority date: 2019-09-24
Filing date: 2019-09-24
Publication date: 2019-12-17

Abstract

the invention provides a permanent antistatic material which is prepared from the following raw materials: 67 wt% -88 wt% of polymer matrix material; 0-10 wt% of a toughening agent; 1 wt% -11 wt% of styrene-butadiene-styrene block copolymer; 5 wt% -21 wt% of conductive master batch; 0.3 wt% -0.5 wt% of lubricant; 0.5 to 0.7 weight percent of antioxidant; the conductive master batch is an ethylene-vinyl acetate copolymer, a conductive carbon black grafted glycidyl methacrylate copolymer and/or an ethylene-vinyl acetate copolymer, and a single-walled carbon nanotube grafted glycidyl methacrylate copolymer. Compared with the prior art, the permanent antistatic material provided by the invention adopts specific content components to realize good interaction, so that the product has excellent physical properties and forming processing properties while meeting excellent antistatic properties, and is low in cost; the antistatic functional polymer material is suitable for further application in the fields of aerospace aviation, electronic packaging, petrochemical industry, electronic industry, coal mine and mine gas safety, fire protection, fire prevention, explosion prevention and the like.

Description

permanent antistatic material and preparation method thereof

Technical Field

the invention relates to the technical field of functionalized high polymer materials, in particular to a permanent antistatic material and a preparation method thereof.

background

the research and development background of the antistatic material is that countless major safety accidents occur due to static factors in the fields of military industry, aircraft manufacturing industry, petrochemical industry, electronic industry, coal mine and mine gas safety, fire protection, fire prevention, explosion prevention and the like, and major product quality accidents and equipment safety accidents are frequent in production and manufacturing processes of various industries due to the static factors. In order to eliminate the hidden trouble of the malignant electrostatic effect, the application of the antistatic material is an option of an effective measure for preventing static leakage, so that the development of the antistatic material becomes the most shortcut and scientific method for preventing the hidden trouble of electrostatic safety.

At present, the antistatic technology of the high polymer materials at home and abroad mainly comprises the following three types:

(1) additive type antistatic agent: the main types are cationic, anionic, nonionic and zwitterionic; however, the above materials are only suitable for short-term and common requirements, can pollute electronic components with fine and high-level requirements, and are only suitable for low-end products and short-term packaging applications.

(2) Antistatic inorganic additive filler: the main components comprise conductive carbon black, graphite, carbon fiber, carbon nanotube, metal fiber, metal powder, conductive mica powder, semiconductor oxide and compounds thereof, the materials are conductive materials, a conductive network can be generated by adding a certain amount of the materials, the materials belong to the category of permanent antistatic, and the conductive carbon black, graphite, carbon fiber and carbon nanotube are simple to use; however, the above materials have the disadvantages of difficult interface compatibility with high molecular polymer and difficult uniform dispersion, and greatly influence the physical index and antistatic effect of the antistatic high molecular polymer.

(3) Conductive polymer material: is a high molecular material with conductivity, belonging to the category of permanent antistatic; however, the current pure structure conductive high molecular polymer only contains poly (sulfur nitride), and although there is a great development space, the application requirement and the quality requirement of the permanent antistatic high molecular polymer in China are far from being met.

disclosure of Invention

in view of the above, the present invention provides a permanent antistatic material and a preparation method thereof, and the permanent antistatic material provided by the present invention has excellent physical properties and molding processability while satisfying excellent antistatic properties, and is low in cost.

the invention provides a permanent antistatic material which is prepared from the following raw materials:

67 wt% -88 wt% of polymer matrix material;

0-10 wt% of a toughening agent;

1 wt% -11 wt% of styrene-butadiene-styrene block copolymer;

5 wt% -21 wt% of conductive master batch;

0.3 wt% -0.5 wt% of lubricant;

0.5 to 0.7 weight percent of antioxidant;

the conductive master batch is an ethylene-vinyl acetate copolymer, a conductive carbon black grafted glycidyl methacrylate copolymer and/or an ethylene-vinyl acetate copolymer, and a single-walled carbon nanotube grafted glycidyl methacrylate copolymer.

preferably, the polymer matrix material is selected from one or more of polypropylene, styrene-butadiene-acrylonitrile terpolymer and high impact polystyrene.

preferably, the toughening agent is selected from ethylene-octene copolymer and/or ABS high rubber powder.

preferably, the ethylene-vinyl acetate copolymer and the conductive carbon black grafted glycidyl methacrylate copolymer are prepared from the following raw materials:

40-60 wt% of conductive carbon black;

35 wt% -45 wt% of ethylene-vinyl acetate copolymer;

2.5 to 3 weight percent of glycidyl methacrylate;

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of dimethylformamide;

3 to 4 weight percent of dispersant;

10100.1 wt% -0.5 wt% of antioxidant.

Preferably, the ethylene-vinyl acetate copolymer and the single-wall carbon nanotube grafted glycidyl methacrylate copolymer are prepared from the following raw materials:

5-25 wt% of single-wall carbon nanotube;

72 wt% -82 wt% of ethylene-vinyl acetate copolymer;

1.5-2 wt% of glycidyl methacrylate;

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of dimethylformamide;

3 to 4 weight percent of dispersant;

10100.1 wt% -0.5 wt% of antioxidant.

preferably, the lubricant is zinc stearate.

preferably, the antioxidant is prepared from the following components in a mass ratio of 1: (1.5-2.5) antioxidant 1010 and antioxidant 168.

the invention also provides a preparation method of the permanent antistatic material, which comprises the following steps:

a) the polymer matrix material, the toughening agent, the styrene-butadiene-styrene segmented copolymer, the conductive master batch, the lubricant and the antioxidant are mixed to be uniform, and then extrusion granulation is carried out to obtain the permanent antistatic material.

Preferably, the mixing in step a) is performed by stirring; the stirring speed is 1000 r/min-1300 r/min, and the time is 3 min-7 min.

preferably, the temperature of the extrusion granulation in the step a) is 200 ℃ to 230 ℃.

The invention provides a permanent antistatic material which is prepared from the following raw materials: 67 wt% -88 wt% of polymer matrix material; 0-10 wt% of a toughening agent; 1 wt% -11 wt% of styrene-butadiene-styrene block copolymer; 5 wt% -21 wt% of conductive master batch; 0.3 wt% -0.5 wt% of lubricant; 0.5 to 0.7 weight percent of antioxidant; the conductive master batch is an ethylene-vinyl acetate copolymer, a conductive carbon black grafted glycidyl methacrylate copolymer and/or an ethylene-vinyl acetate copolymer, and a single-walled carbon nanotube grafted glycidyl methacrylate copolymer. Compared with the prior art, the permanent antistatic material provided by the invention adopts specific content components, realizes better interaction, ensures that the product has excellent physical properties and forming processing properties while meeting excellent antistatic properties, and has low cost; the antistatic functional polymer material is suitable for further application in the fields of aerospace aviation, electronic packaging, petrochemical industry, electronic industry, coal mine and mine gas safety, fire protection, fire prevention, explosion prevention and the like.

in addition, the preparation method provided by the invention does not need to modify forming processing equipment, has the advantages of simple process, mild conditions and low production cost, is suitable for large-scale industrial production, and has wide application prospect.

Detailed Description

the technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

67 wt% -88 wt% of polymer matrix material;

0-10 wt% of a toughening agent;

1 wt% -11 wt% of styrene-butadiene-styrene block copolymer;

5 wt% -21 wt% of conductive master batch;

0.3 wt% -0.5 wt% of lubricant;

0.5 to 0.7 weight percent of antioxidant;

in the present invention, the polymer matrix material is preferably selected from one or more of polypropylene (PP), styrene-butadiene-acrylonitrile terpolymer (ABS) and High Impact Polystyrene (HIPS), and more preferably from one or two of polypropylene (PP), styrene-butadiene-acrylonitrile terpolymer (ABS) and High Impact Polystyrene (HIPS). In a preferred embodiment of the invention, the polymer matrix material is polypropylene (PP); in another preferred embodiment of the present invention, the polymer matrix material is styrene-butadiene-acrylonitrile terpolymer (ABS); in another preferred embodiment of the present invention, the polymer matrix material is High Impact Polystyrene (HIPS); in another preferred embodiment of the invention, the polymer matrix material is polypropylene (PP) and High Impact Polystyrene (HIPS), and the mass ratio of the polypropylene (PP) to the High Impact Polystyrene (HIPS) is preferably (76-82): 5.

The sources of the polypropylene (PP), the styrene-butadiene-acrylonitrile terpolymer (ABS) and the High Impact Polystyrene (HIPS) are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the present invention, the permanent antistatic material comprises 67 to 88 wt% of a polymer base material; in a preferred embodiment, the specific values are respectively: 67 wt%, 77 wt%, 81 wt%, 82 wt%, 87 wt%, 88 wt%.

in the present invention, the toughening agent is preferably selected from ethylene-octene copolymer (POE) and/or ABS high rubber powder; in a preferred embodiment of the present invention, when the polymer matrix material comprises polypropylene (PP), ethylene-octene copolymer (POE) is used as the toughening agent; when the polymer matrix material comprises styrene-butadiene-acrylonitrile terpolymer (ABS), ABS high rubber powder is used as a toughening agent. The source of the toughening agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the permanent antistatic material comprises 0-10 wt% of a toughening agent; in a preferred embodiment, the specific values are respectively: 0 wt%, 6 wt%, 8 wt%, 10 wt%.

In the invention, the styrene-butadiene-styrene block copolymer (SBS) has the function of improving the interfacial compatibility and the dispersibility of the conductive master batch and the polymer matrix material, and simultaneously has the function of toughening High Impact Polystyrene (HIPS). The source of the styrene-butadiene-styrene block copolymer (SBS) according to the present invention is not particularly limited, and commercially available products well known to those skilled in the art may be used. In the present invention, the permanent antistatic material includes 1 to 11 wt% of styrene-butadiene-styrene block copolymer (SBS); in a preferred embodiment, the specific values are respectively: 1 wt%, 2 wt%, 6 wt%, 7 wt%, 11 wt%.

In the invention, the conductive master batch is ethylene-vinyl acetate copolymer (EVA), conductive carbon black grafted Glycidyl Methacrylate (GMA) copolymer (hereinafter expressed as (conductive carbon black + EVA) -g-GMA conductive master batch) and/or ethylene-vinyl acetate copolymer (EVA), single-walled carbon nanotube grafted Glycidyl Methacrylate (GMA) copolymer (hereinafter expressed as (single-walled carbon nanotube + EVA) -g-GMA conductive master batch) and is preferably (conductive carbon black + EVA) -g-GMA conductive master batch and (single-walled carbon nanotube + EVA) -g-GMA conductive master batch, or (single-walled carbon nanotube + EVA) -g-GMA conductive master batch; in a preferred embodiment of the present invention, the conductive masterbatch is (conductive carbon black + EVA) -g-GMA conductive masterbatch and (single-walled carbon nanotube + EVA) -g-GMA conductive masterbatch, and the mass ratio of the (conductive carbon black + EVA) -g-GMA conductive masterbatch to the (single-walled carbon nanotube + EVA) -g-GMA conductive masterbatch is preferably 14: 1 or 20: 1.

in the invention, the (conductive carbon black + EVA) -g-GMA conductive master batch is conductive carbon black and an EVA grafted GMA copolymer, and the conductive carbon black and the EVA can have GMA polar functional groups; the (conductive carbon black + EVA) -g-GMA conductive master batch is preferably prepared from the following raw materials:

40-60 wt% of conductive carbon black;

35 wt% -45 wt% of ethylene-vinyl acetate copolymer (EVA);

2.5-3 wt% of Glycidyl Methacrylate (GMA);

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of Dimethylformamide (DMF);

3 to 4 weight percent of dispersant;

10100.1-0.5 wt% of antioxidant;

More preferably:

50 wt% of conductive carbon black;

Ethylene-vinyl acetate copolymer (EVA)40 wt%;

2.5 wt% of Glycidyl Methacrylate (GMA);

0.1 wt% of an initiator;

dimethylformamide (DMF)3.5 wt%;

3.6 wt% of a dispersant;

10100.3 wt% of antioxidant.

the sources of the conductive carbon black, ethylene-vinyl acetate copolymer (EVA), Glycidyl Methacrylate (GMA), dimethyl formamide (DMF) (mainly used for controlling the crosslinking reaction in the grafting reaction process) and the antioxidant 1010 (mainly used for preventing the oxidative degradation of the main body material in the high-temperature extrusion process) are not particularly limited, and commercial products well known to those skilled in the art can be adopted.

in the present invention, the initiator is preferably dicumyl peroxide (DCP); the source of the initiator is not particularly limited in the present invention, and a commercially available product of the above-mentioned dicumyl peroxide (DCP) known to those skilled in the art may be used.

in the invention, the dispersant is preferably a maleic acid acrylic acid copolymer sodium salt dispersant, which can ensure that the (conductive carbon black + EVA) -g-GMA conductive master batch has good interfacial compatibility with other components (mainly high molecular polymers) and the whole conductive master batch has perfect conductivity. The source of the dispersant in the present invention is not particularly limited, and a commercially available product of the above-mentioned maleic acid acrylic acid copolymer sodium salt dispersant known to those skilled in the art may be used.

In the present invention, the preparation method of the (conductive carbon black + EVA) -g-GMA conductive masterbatch is preferably specifically:

uniformly mixing GMA, DMF, an initiator, an antioxidant 1010 and a dispersant to obtain a raw material mixed solution; putting conductive carbon black into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (300 r/min-600 r/min) stirring for 2 min-4 min, then switching to high-speed (1000 r/min-1300 r/min) stirring for 5 min-6 min, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (300 r/min-600 r/min) stirring for 1 min-2 min, then switching to high-speed (1000 r/min-1300 r/min) stirring for 3 min-4 min, then discharging the materials into a double-screw extruder for melt mixing (175 ℃ -210 ℃) to realize grafting, and finally carrying out granulation to obtain (conductive carbon black + EVA) -g-GMA conductive master batch;

More preferably:

Uniformly mixing GMA, DMF, an initiator, an antioxidant 1010 and a dispersant to obtain a raw material mixed solution; putting conductive carbon black into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (450r/min) stirring for 3min, then switching to high-speed (1150r/min) stirring for 5min, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (450r/min) stirring for 2min, switching to high-speed (1150r/min) stirring for 3min, then discharging into a double-screw extruder for melt mixing (185-195 ℃) to realize grafting, and finally granulating to obtain (conductive carbon black + EVA) -g-GMA conductive master batch.

in the invention, the (single-walled carbon nanotube + EVA) -g-GMA conductive master batch is a single-walled carbon nanotube and an EVA grafted GMA copolymer, and can enable the single-walled carbon nanotube and the EVA to have GMA polar functional groups; the (single-walled carbon nanotube + EVA) -g-GMA conductive master batch is preferably prepared from the following raw materials:

5-25 wt% of single-wall carbon nanotube;

72 wt% -82 wt% of ethylene-vinyl acetate copolymer (EVA);

1.5-2 wt% of Glycidyl Methacrylate (GMA);

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of Dimethylformamide (DMF);

3 to 4 weight percent of dispersant;

10100.1-0.5 wt% of antioxidant;

more preferably:

15 wt% of single-wall carbon nanotube;

77 wt% of ethylene-vinyl acetate copolymer (EVA);

1.5 wt% of Glycidyl Methacrylate (GMA);

0.1 wt% of an initiator;

dimethylformamide (DMF)2.5 wt%;

3.6 wt% of a dispersant;

10100.3 wt% of antioxidant.

The sources of the single-walled carbon nanotube, the ethylene-vinyl acetate copolymer (EVA), the Glycidyl Methacrylate (GMA), the Dimethylformamide (DMF) (mainly used for controlling the crosslinking reaction in the grafting reaction process) and the antioxidant 1010 (mainly used for preventing the oxidative degradation of the main body material in the high-temperature extrusion process) are not particularly limited, and the single-walled carbon nanotube, the ethylene-vinyl acetate copolymer (EVA), the Glycidyl Methacrylate (GMA), the antioxidant 1010 and the antioxidant can be commercially available products well known to those skilled in the art.

in the invention, the dispersant is preferably maleic acid acrylic acid copolymer sodium salt dispersant, which can ensure that the (single-walled carbon nanotube + EVA) -g-GMA conductive master batch has good interfacial compatibility with other components (mainly high molecular polymers) and the whole conductive master batch has perfect conductivity. The source of the dispersant in the present invention is not particularly limited, and a commercially available product of the above-mentioned maleic acid acrylic acid copolymer sodium salt dispersant known to those skilled in the art may be used.

in the present invention, the preferable preparation method of the (single-walled carbon nanotube + EVA) -g-GMA conductive masterbatch is specifically:

Uniformly mixing GMA, DMF, an initiator, an antioxidant 1010 and a dispersant to obtain a raw material mixed solution; putting a single-walled carbon nanotube into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (300 r/min-600 r/min) stirring for 2 min-4 min, then switching to high-speed (1000 r/min-1300 r/min) stirring for 5 min-6 min, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (300 r/min-600 r/min) stirring for 1 min-2 min, then switching to high-speed (1000 r/min-1300 r/min) stirring for 3 min-4 min, then discharging the materials into a double-screw extruder for melt mixing (175 ℃ -210 ℃) to realize grafting, and finally carrying out granulation to obtain (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

More preferably:

uniformly mixing GMA, DMF, an initiator, an antioxidant 1010 and a dispersant to obtain a raw material mixed solution; putting the single-walled carbon nanotubes into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (450r/min) stirring for 3min, then switching to high-speed (1150r/min) stirring for 5min, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (450r/min) stirring for 2min, then switching to high-speed (1150r/min) stirring for 3min, then discharging the materials into a double-screw extruder for melt mixing (185-195 ℃) to realize grafting, and finally granulating to obtain the (single-walled carbon nanotubes + EVA) -g-GMA conductive master batch.

Compared with the traditional conductive carbon black and single-wall carbon nanotubes (the surface treatment of the conductive carbon black and the carbon nanotubes at home and abroad is basically carried out by adopting coupling agent surface treatment and core-shell treatment at present, the treatment methods can influence the conductivity of the conductive carbon black and the carbon nanotubes, and particularly, the conductive carbon black and the single-wall carbon nanotubes have the characteristics of difficult interfacial compatibility and difficult uniform dispersion with high molecular polymers due to inertia, and influence on the conductivity by dispersing agents and coupling agents with different molecular structures), have the stability of the interfacial compatibility and the conductivity with the high molecular polymers, meet the application requirements and the quality requirements (mainly applying the permanent antistatic function and the interfacial compatibility dispersion effect of PP, ABS and HIPS polymers) on the permanent antistatic high molecular polymers at home, thereby being beneficial to ensuring the permanent antistatic effect, excellent physical property and excellent processing formability of the whole material in the market application process.

in the present invention, the lubricant is preferably zinc stearate; the lubricating function is realized in the extrusion granulation process. The source of the lubricant is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the permanent antistatic material includes 0.3 wt% to 0.5 wt% of a lubricant, preferably 0.4 wt%.

In the present invention, the antioxidant is preferably prepared from a mixture of 1: (1.5-2.5) an antioxidant 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ] and an antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), more preferably a mixture of (1, 5-di-tert-butyl-4-hydroxyphenyl) propionate and (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 1: 2, an antioxidant 1010 and an antioxidant 168; wherein, the antioxidant 1010 plays a role of a primary antioxidant, the antioxidant 168 plays a role of assisting the primary antioxidant in antioxidation, and particularly realizes corresponding functions in the extrusion granulation process. The source of the antioxidant 1010 and the antioxidant 168 is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the permanent antistatic material comprises 0.5-0.7 wt% of antioxidant, preferably 0.6 wt%.

the permanent antistatic material provided by the invention adopts components with specific contents, realizes better interaction, ensures that the product has excellent physical properties and forming processability while meeting excellent antistatic properties, and has low cost; the antistatic functional polymer material is suitable for further application in the fields of aerospace aviation, electronic packaging, petrochemical industry, electronic industry, coal mine and mine gas safety, fire protection, fire prevention, explosion prevention and the like.

firstly, mixing a polymer matrix material, a toughening agent, a styrene-butadiene-styrene block copolymer, a conductive master batch, a lubricant and an antioxidant uniformly; the polymer matrix material, the toughening agent, the styrene-butadiene-styrene block copolymer, the conductive master batch, the lubricant and the antioxidant are the same as those in the technical scheme, and are not repeated herein.

the mixing apparatus of the present invention is not particularly limited, and a high-speed mixer known to those skilled in the art may be used. In the present invention, the mixing is preferably performed by stirring; the rotating speed of the stirring is preferably 1000 r/min-1300 r/min, and more preferably 1100 r/min-1200 r/min; the stirring time is preferably 3 to 7min, and more preferably 5 min.

After the mixing process is finished, the obtained mixture is extruded and granulated to obtain the permanent antistatic material. The extrusion granulation apparatus of the present invention is not particularly limited, and a twin-screw extruder known to those skilled in the art may be used. In the present invention, the temperature for the extrusion granulation is preferably 200 to 230 ℃, more preferably 210 to 220 ℃.

The preparation method provided by the invention does not need to transform forming processing equipment, has the advantages of simple process, mild conditions and low production cost, is suitable for large-scale industrial production, and has wide application prospect.

to further illustrate the present invention, the following examples are provided for illustration. The preparation method of the conductive masterbatch used in the following examples of the present invention is as follows:

(1) (conductive carbon black + EVA) -g-GMA conductive masterbatch:

The raw material ratio is as follows:

50 wt% of super conductive carbon black Nippon Ketjen black carbon black;

EVA (ethylene-vinyl acetate copolymer) 40 wt%;

2.5 wt% of GMA (glycidyl methacrylate);

Initiator DCP (dicumyl peroxide) 0.1 wt%;

DMF (dimethylformamide) 3.5 wt%;

3.6 wt% of maleic acid acrylic acid copolymer sodium salt dispersant;

antioxidant 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) 0.3 wt%.

the preparation process comprises the following steps:

pouring GMA, DMF, DCP, an antioxidant 1010 and a maleic acid acrylic acid copolymer sodium salt dispersing agent into a stainless steel container barrel, and uniformly stirring to obtain a raw material mixed solution; putting super conductive carbon black Nippon Ketjen black carbon black into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (450r/min) stirring for 3min, then switching to high-speed (1150r/min) stirring for 5min, fully and uniformly adsorbing GMA, DMF, DCP, maleic acid acrylic acid copolymer sodium salt dispersant and antioxidant 1010 with the carbon black, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (450r/min) stirring for 2min, then switching to high-speed (1150r/min) stirring for 3min, then discharging into a double-screw extruder for melt mixing (185-195 ℃) to realize grafting, and finally granulating to obtain (conductive carbon black + EVA) -g-GMA conductive master batch.

(2) (single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch:

The raw material ratio is as follows:

15 wt% of single-wall carbon nanotube;

77 wt% of EVA (ethylene-vinyl acetate copolymer);

GMA (glycidyl methacrylate) 1.5 wt%;

initiator DCP (dicumyl peroxide) 0.1 wt%;

DMF (dimethylformamide) 2.5 wt%;

3.6 wt% of maleic acid acrylic acid copolymer sodium salt dispersant;

The preparation process comprises the following steps:

Pouring GMA, DMF, DCP, an antioxidant 1010 and a maleic acid acrylic acid copolymer sodium salt dispersing agent into a stainless steel container barrel, and uniformly stirring to obtain a raw material mixed solution; putting a single-walled carbon nanotube into a high-speed stirrer, pouring the raw material mixed solution into the high-speed stirrer, closing a sealing cover of the high-speed stirrer, starting low-speed (450r/min) stirring for 3min, then turning to high-speed (1150r/min) stirring for 5min, fully and uniformly adsorbing GMA, DMF, DCP, maleic acid acrylic acid copolymer sodium salt dispersant and antioxidant 1010 with the single-walled carbon nanotube, stopping the rotation of the high-speed stirrer, opening the sealing cover, pouring EVA into the high-speed stirrer, closing the sealing cover, starting low-speed (450r/min) stirring for 2min, turning to high-speed (1150r/min) stirring for 3min, then discharging into an extruder for melt mixing (185-195 ℃) to realize grafting, and finally carrying out double-screw granulation to obtain the (single-walled carbon nanotube + EVA) -g-GMA conductive master batch.

Other raw materials are all commercially available.

example 1

(1) the raw material ratio is as follows:

PP 77wt％；

POE 6wt％；

SBS 1wt％；

(conductive carbon black + EVA) -g-GMA conductive masterbatch 14 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

Pouring all the raw materials into a high-speed stirrer, stirring at the rotating speed of 1100-1200 r/min for 5min until the raw materials are uniform, then directly discharging the materials into a double-screw extruder, and extruding and granulating at the temperature of 210-220 ℃ to obtain the permanent antistatic material.

through detection, the permanent antistatic material provided by the embodiment 1 of the invention has a melt index of 3.5g/10min, a tensile strength of not less than 26MPa, a notch impact strength of not less than 150J/m, a thermal deformation temperature of not less than 75 ℃, an elongation at break of not less than 40% and antistatic property of 10 to the power of 7-8.

Example 2

(1) The raw material ratio is as follows:

PP 67wt％；

POE 10wt％；

SBS 1wt％；

(conductive carbon black + EVA) -g-GMA conductive masterbatch 20 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 2 of the invention has a melt index of 3g/10min, a tensile strength of more than or equal to 22MPa, a notch impact strength of more than or equal to 200J/m, a thermal deformation temperature of more than or equal to 71 ℃, a breaking elongation of more than or equal to 88%, and antistatic property of 10 to the power of 3-4.

example 3

(1) the raw material ratio is as follows:

ABS 77wt％；

SBS 1wt％；

6 percent of ABS high rubber powder;

(conductive carbon black + EVA) -g-GMA conductive masterbatch 14 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 3 of the invention has a melt index of 2.5g/10min, a tensile strength of not less than 42MPa, a notch impact strength of not less than 140J/m, a thermal deformation temperature of not less than 85 ℃, a breaking elongation of not less than 30% and antistatic property of 10 to the power of 7-9.

example 4

(1) The raw material ratio is as follows:

ABS 67wt％；

SBS 1wt％；

10 percent of ABS high rubber powder;

(conductive carbon black + EVA) -g-GMA conductive masterbatch 20 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

Through detection, the permanent antistatic material provided by the embodiment 4 of the invention has a melt index of 2g/10min, a tensile strength of not less than 38MPa, a notch impact strength of not less than 180J/m, a thermal deformation temperature of not less than 81 ℃, an elongation at break of not less than 50% and an antistatic property of 10 to the power of 3-4.

example 5

(1) the raw material ratio is as follows:

HIPS 77wt％；

SBS 7wt％；

(conductive carbon black + EVA) -g-GMA conductive masterbatch 14 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

Through detection, the permanent antistatic material provided by the embodiment 5 of the invention has a melt index of 2.5g/10min, a tensile strength of not less than 32MPa, a notch impact strength of not less than 120J/m, a thermal deformation temperature of not less than 75 ℃, a breaking elongation of not less than 30% and antistatic property of 10 to the power of 7-9.

example 6

(1) The raw material ratio is as follows:

HIPS 67wt％；

SBS 11wt％；

(conductive carbon black + EVA) -g-GMA conductive masterbatch 20 wt%;

1 wt% of (single-walled carbon nanotube + EVA) -g-GMA conductive master batch;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

Through detection, the permanent antistatic material provided by the embodiment 6 of the invention has a melt index of 2.5g/10min, a tensile strength of more than or equal to 28MPa, a notch impact strength of more than or equal to 180J/m, a thermal deformation temperature of more than or equal to 71 ℃, an elongation at break of more than or equal to 50%, and antistatic property of 10 to the power of 3-4.

Example 7

(1) the raw material ratio is as follows:

PP 82wt％；

HIPS 5wt％；

POE 6wt％；

SBS 1wt％；

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 5 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 7 of the invention has a melt index of 2.5g/10min, a tensile strength of more than or equal to 28MPa, a notch impact strength of more than or equal to 120J/m, a thermal deformation temperature of more than or equal to 78 ℃, a breaking elongation of more than or equal to 45%, and antistatic property of 10 to the power of 7-9.

Example 8

(1) the raw material ratio is as follows:

PP 76wt％；

HIPS 5wt％；

POE 8wt％；

SBS 2wt％；

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 8 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

Through detection, the permanent antistatic material provided by the embodiment 8 of the invention has a melt index of 2g/10min, a tensile strength of more than or equal to 25MPa, a notch impact strength of more than or equal to 180J/m, a thermal deformation temperature of more than or equal to 75 ℃, an elongation at break of more than or equal to 60 percent and antistatic property of 10 to the power of 3-4.

Example 9

(1) the raw material ratio is as follows:

ABS 87wt％；

SBS 1wt％；

6 wt% of ABS high rubber powder;

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 5 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 9 of the invention has a melt index of 2.5g/10min, a tensile strength of not less than 48MPa, a notch impact strength of not less than 180J/m, a thermal deformation temperature of not less than 83 ℃, a breaking elongation of not less than 30% and antistatic property of 10 to the power of 7-8.

example 10

(1) The raw material ratio is as follows:

ABS 82wt％；

SBS 1wt％；

8 wt% of ABS high rubber powder;

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 8 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) The preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 10 of the invention has a melt index of 2.5g/10min, a tensile strength of more than or equal to 46MPa, a notch impact strength of more than or equal to 220J/m, a thermal deformation temperature of more than or equal to 81 ℃, an elongation at break of more than or equal to 50%, and antistatic property of 10 to the power of 3-4.

example 11

(1) the raw material ratio is as follows:

HIPS 88wt％；

SBS 6wt％；

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 5 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 11 of the invention has a melt index of 2.5g/10min, a tensile strength of more than or equal to 30MPa, a notch impact strength of more than or equal to 120J/m, a thermal deformation temperature of more than or equal to 78 ℃, an elongation at break of more than or equal to 35%, and antistatic property of 7-9 th power of 10.

Example 12

(1) the raw material ratio is as follows:

HIPS 82wt％；

SBS 9wt％；

(single-walled carbon nanotubes + EVA) -g-GMA conductive masterbatch 8 wt%;

0.4 wt% of zinc stearate;

10100.2 wt% of antioxidant;

1680.4 wt% of antioxidant.

(2) the preparation process comprises the following steps:

through detection, the permanent antistatic material provided by the embodiment 11 of the invention has a melt index of 2g/10min, a tensile strength of more than or equal to 28MPa, a notch impact strength of more than or equal to 220J/m, a thermal deformation temperature of more than or equal to 75 ℃, a breaking elongation of more than or equal to 50%, and antistatic property of 10 to the power of 3-4.

in conclusion, the permanent antistatic material provided by the invention is a novel polymer material with permanent antistatic function, is suitable for antistatic requirements of electronic industry, fire safety, military industry, aircraft manufacturing industry, chemical industry, automobile manufacturing industry, industrial films, plastic pipelines, electronic packaging and the like, and meets the antistatic requirements of domestic related high polymer antistatic application and quality standard; in addition, the preparation method provided by the invention does not need to modify forming processing equipment, has the advantages of simple process, mild conditions and low production cost, is suitable for large-scale industrial production, and has wide application prospect.

the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. a permanent antistatic material is prepared from the following raw materials:

67 wt% -88 wt% of polymer matrix material;

0-10 wt% of a toughening agent;

1 wt% -11 wt% of styrene-butadiene-styrene block copolymer;

5 wt% -21 wt% of conductive master batch;

0.3 wt% -0.5 wt% of lubricant;

0.5 to 0.7 weight percent of antioxidant;

2. The permanent antistatic material of claim 1 wherein the polymer matrix material is selected from one or more of polypropylene, styrene-butadiene-acrylonitrile terpolymer, and high impact polystyrene.

3. The permanent antistatic material of claim 1 wherein the toughening agent is selected from ethylene-octene copolymer and/or ABS high rubber powder.

4. the permanent antistatic material of claim 1, wherein the ethylene-vinyl acetate copolymer, the conductive carbon black grafted glycidyl methacrylate copolymer are prepared from the following raw materials:

40-60 wt% of conductive carbon black;

35 wt% -45 wt% of ethylene-vinyl acetate copolymer;

2.5 to 3 weight percent of glycidyl methacrylate;

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of dimethylformamide;

3 to 4 weight percent of dispersant;

10100.1 wt% -0.5 wt% of antioxidant.

5. The permanent antistatic material of claim 1, wherein the ethylene-vinyl acetate copolymer and the single-walled carbon nanotube-grafted glycidyl methacrylate copolymer are prepared from the following raw materials:

5-25 wt% of single-wall carbon nanotube;

72 wt% -82 wt% of ethylene-vinyl acetate copolymer;

1.5-2 wt% of glycidyl methacrylate;

0.05 wt% -0.15 wt% of initiator;

2.5 wt% -3.5 wt% of dimethylformamide;

3 to 4 weight percent of dispersant;

10100.1 wt% -0.5 wt% of antioxidant.

6. the permanent antistatic material of claim 1 wherein the lubricant is zinc stearate.

7. The permanent antistatic material as claimed in claim 1, wherein the antioxidant is prepared from the following components in a mass ratio of 1: (1.5-2.5) antioxidant 1010 and antioxidant 168.

8. a method for preparing the permanent antistatic material as claimed in any one of claims 1 to 7, comprising the following steps:

9. the method according to claim 8, wherein the mixing in step a) is performed by stirring; the stirring speed is 1000 r/min-1300 r/min, and the time is 3 min-7 min.

10. the method according to claim 8, wherein the temperature of the extrusion granulation in the step a) is 200 to 230 ℃.