CN109735047B - Low-filling antistatic ABS (acrylonitrile-butadiene-styrene) modified plastic and preparation method thereof - Google Patents
Low-filling antistatic ABS (acrylonitrile-butadiene-styrene) modified plastic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to low-filling antistatic ABS modified plastic and a preparation method thereof. The preparation method of the ABS modified plastic comprises the following steps: weighing common ABS plastic, styrene-maleic anhydride-phenyl maleimide copolymer and dicumyl peroxide in proportion, mixing the raw materials, and extruding and granulating at the temperature of 190 ℃ and 210 ℃ by using an extruder; then mixing the ABS particles subjected to the crosslinking reaction with carbon black particles; then, blending 50-80 parts by weight of common ABS plastic, 10-30 parts by weight of ethylene-acrylic acid copolymer, 15-20 parts by weight of the mixture obtained in the step 2, 0.1-2 parts by weight of coupling agent and 0.1-0.4 part by weight of antioxidant; finally, extruding the obtained blend at the temperature of 160-200 ℃ by using an extruder, and cooling to obtain the ABS modified plastic. The ABS modified plastic disclosed by the invention is low in filler, antistatic, easy to process and good in mechanical property.
Description
Technical Field
The invention belongs to the field of antistatic materials, and particularly relates to low-filling antistatic ABS modified plastic and a preparation method thereof.
Background
ABS plastic is a general plastic, has wide application in the field of electric appliances, and is commonly used for electric appliance shells and the like. In the field of electrical appliances, ABS is generally required to have good processability, mechanical properties and antistatic properties. However, ABS is a brittle and insulating plastic, and a common method for improving the antistatic property of ABS is to add a large amount of conductive particles. The addition of conductive particles deteriorates the processability and mechanical properties of the material. How to comprehensively realize the antistatic property of the low-filling ABS is an urgent problem to be solved.
The Chinese invention patent CN104693335B discloses an in-situ synthesis method for antistatic modification of ABS, which is mainly characterized in that an antistatic monomer hydroxybutyl vinyl ether is added in the synthesis process of ABS, and the method can realize good antistatic property of ABS. However, the method has the disadvantages of complicated process, non-durable antistatic effect and low efficiency.
Chinese invention patent CN201410847944.2 discloses an antistatic ABS modified plastic and a preparation method thereof, wherein 8-12 parts of carbon black is used as an antistatic agent, so that the surface resistivity of the modified ABS is reduced by 5-7 orders of magnitude; and 8-12 parts of toughening agent is independently added for improving the mechanical toughness of the composite material. However, the content of the toughening agent added by the method is higher, and although the toughness of the material is improved, the bending property and the heat resistance of the material are greatly reduced.
The invention patent CN101864141B discloses that the antistatic property of ABS is improved by using tetrapod-like zinc oxide whisker and adding compatilizer, coupling agent, etc. to inhibit the precipitation of electrostatic agent. However, the method adds 15 wt% of zinc oxide whiskers, and the content is too high, so that the mechanical property and the processability of the material are deteriorated.
In the above preparation methods, the procedure is complicated and the amount of the filler is high by an improved method of in-situ synthesis or a manner of adding a large amount of the conductive filler. Therefore, the development of an ABS plastic with low filler, antistatic property, easy processing and good mechanical property is a problem to be solved at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides low-filling antistatic ABS modified plastic and a preparation method thereof.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of low-filling antistatic ABS modified plastic comprises the following steps:
step 1, weighing common ABS plastic, a styrene-maleic anhydride-phenylmaleimide copolymer and dicumyl peroxide in proportion, mixing the raw materials, and extruding and granulating at the temperature of 190-; in which the styrene-maleic anhydride-phenylmaleimide copolymer is presentThe average molecular weight is (1 to 5) × 104The mass ratio of ABS to the styrene-maleic anhydride-phenylmaleimide copolymer is (1-5) to 1;
step 2, mixing the ABS particles subjected to the crosslinking reaction with carbon black particles, wherein the blending mass ratio of the ABS particles subjected to the crosslinking reaction to the carbon black particles is (1-2) to (0.5-1), and the particle size of the carbon black particles is 20-40 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials according to the blending formula:
50-80 parts of common ABS plastic, 10-30 parts of ethylene-acrylic acid copolymer, 15-20 parts of the mixture obtained in the step 2, 0.1-2 parts of coupling agent and 0.1-0.4 part of antioxidant;
and 4, extruding and cooling the blend obtained in the step 3 at the temperature of 160-200 ℃ by using an extruder to obtain the ABS modified plastic.
Preferably, the carbon black particles are one of acetylene black, channel black and furnace black;
preferably, the ethylene-acrylic acid copolymer is one of an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer and an ethylene-acrylic ester-maleic anhydride graft copolymer.
Preferably, the coupling agent is one of gamma- (methacryloyloxy) propyl trimethoxy silane, 3-glycidyl ether oxypropyl trimethoxy silane and gamma-mercaptopropyl triethoxy silane.
Preferably, the antioxidant is one or more of antioxidant 1076, antioxidant 168 and antioxidant 330.
The ABS modified plastic is obtained by the preparation method of the low-filling antistatic ABS modified plastic.
The invention has the beneficial effects that:
(1) the styrene-maleic anhydride-phenyl maleimide copolymer and the common ABS plastic are subjected to chemical reaction in the extrusion blending process to form a partially crosslinked network structure on the common ABS plastic, so that the viscosity and the heat resistance of the common ABS plastic are improved.
(2) ABS particles containing a partial cross-linked structure are used as a modifier and are added into common ABS plastic together with carbon black particles, so that the volume exclusion effect is caused, and the carbon black particles are induced to be mainly distributed in the common ABS plastic, so that a more effective conductive path is formed.
(3) The invention well reduces the consumption of carbon black particles, maintains the mechanical property of the ABS modified plastic, and has the advantages of simple preparation method, convenient operation, low cost and easy industrialization.
Detailed Description
The technical scheme of the invention is more specifically explained by combining the following embodiments:
the common ABS plastic is a terpolymer of acrylonitrile-butadiene-styrene polymerized by adopting an emulsion method. The starting materials used in the following examples are all derived from common commercial products.
Example one
Step 1, weighing 50 parts by weight of common ABS plastic and 10 parts by weight of common ABS plastic with the molecular weight of 5 multiplied by 104Mixing the raw materials and adopting a double-screw extruder to extrude and granulate at 200 ℃ to obtain ABS particles which are subjected to crosslinking reaction with the styrene-maleic anhydride-phenylmaleimide copolymer;
step 2, mixing 10 parts by weight of the ABS particles subjected to the crosslinking reaction with 5 parts by weight of carbon black particles with the particle size of 20 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials in a mixer, wherein the rotating speed of the mixer is 500 r/min, the blending time is 3 minutes, and the blending formula is as follows:
60 parts by weight of common ABS plastic, 20 parts by weight of ethylene-methyl acrylate copolymer, 15 parts by weight of the mixture obtained in the step 2, 0.6 part by weight of coupling agent gamma- (methacryloyloxy) propyl trimethoxy silane and 0.3 part by weight of antioxidant 1076;
and 4, finally adding the blend obtained in the step 3 into a double-screw extruder, wherein the length-diameter ratio of the extruder is 40:1, the diameter of a screw is 65mm, and extruding by using the double screwsThe rotating speed of the extruder is 300 r/min, the temperature of the double-screw extruder from the conveying section to the discharge port is 190-
3 x 3mm ABS modified plastic particles.
Example two
Step 1, weighing 50 parts by weight of common ABS plastic and 30 parts by weight of common ABS plastic with the molecular weight of 3 multiplied by 104Mixing the raw materials and adopting a double-screw extruder to extrude and granulate at 200 ℃ to obtain ABS particles which are subjected to crosslinking reaction with the styrene-maleic anhydride-phenylmaleimide copolymer;
step 2, mixing 20 parts by weight of the ABS particles subjected to the crosslinking reaction with 8 parts by weight of carbon black particles with the particle size of 30 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials in a mixer, wherein the rotating speed of the mixer is 500 r/min, the blending time is 3 minutes, and the blending formula is as follows:
50 parts by weight of common ABS plastic, 30 parts by weight of ethylene-acrylate-maleic anhydride graft copolymer, 28 parts by weight of the mixture obtained in the step 2, 0.8 part by weight of coupling agent 3-glycidyl ether oxypropyltrimethoxysilane, 0.2 part by weight of antioxidant 168 and 0.2 part by weight of antioxidant 1076;
and 4, finally adding the blend obtained in the step 3 into a double-screw extruder, wherein the length-diameter ratio of the extruder is 40:1, the diameter of a screw is 65mm, the rotating speed of the double-screw extruder is 300 r/min, the temperature from the conveying section to the discharge port of the double-screw extruder is 160-
3 x 3mm ABS modified plastic particles.
EXAMPLE III
Step 1, weighing 50 parts by weight of common ABS plastic and 50 parts by weight of common ABS plastic with the molecular weight of 1 multiplied by 104Mixing the raw materials and adopting a double-screw extruder to extrude and granulate at 200 ℃ to obtain ABS particles which are subjected to crosslinking reaction with the styrene-maleic anhydride-phenylmaleimide copolymer;
step 2, mixing 20 parts by weight of the ABS particles subjected to the crosslinking reaction with 10 parts by weight of carbon black particles with the particle size of 40 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials in a mixer, wherein the rotating speed of the mixer is 500 r/min, the blending time is 3 minutes, and the blending formula is as follows:
80 parts by weight of common ABS plastic, 10 parts by weight of ethylene-acrylate-maleic anhydride graft copolymer, 30 parts by weight of the mixture obtained in the step 2, 1 part by weight of coupling agent gamma- (methacryloyloxy) propyl trimethoxy silane and 0.4 part by weight of antioxidant 168;
and 4, finally adding the blend obtained in the step 3 into a double-screw extruder, wherein the length-diameter ratio of the extruder is 40:1, the diameter of a screw is 65mm, the rotating speed of the double-screw extruder is 300 r/min, the temperature from the conveying section to the discharge port of the double-screw extruder is 160-
3 x 3mm ABS modified plastic particles.
Example four
Step 1, weighing 50 parts by weight of common ABS plastic and 20 parts by weight of common ABS plastic with the molecular weight of 2 multiplied by 104Mixing the raw materials and adopting a double-screw extruder to extrude and granulate at 200 ℃ to obtain ABS particles which are subjected to crosslinking reaction with the styrene-maleic anhydride-phenylmaleimide copolymer;
step 2, mixing 10 parts by weight of the ABS particles subjected to the crosslinking reaction with 10 parts by weight of carbon black particles with the particle size of 20 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials in a mixer, wherein the rotating speed of the mixer is 500 r/min, the blending time is 3 minutes, and the blending formula is as follows:
50 parts by weight of common ABS plastic, 20 parts by weight of ethylene-ethyl acrylate copolymer, 20 parts by weight of the mixture obtained in the step 2, 1 part by weight of coupling agent gamma-mercaptopropyltriethoxysilane and 0.3 part by weight of antioxidant 330;
and 4, finally adding the blend obtained in the step 3 into a double-screw extruder, wherein the length-diameter ratio of the extruder is 40:1, the diameter of a screw is 65mm, the rotating speed of the double-screw extruder is 300 r/min, the temperature from the conveying section to the discharge port of the double-screw extruder is 160-
3 x 3mm ABS modified plastic particles.
EXAMPLE five
Step 1, weighing 50 parts by weight of common ABS plastic and 10 parts by weight of common ABS plastic with the molecular weight of 4 multiplied by 104Mixing the raw materials and adopting a double-screw extruder to extrude and granulate at 200 ℃ to obtain ABS particles which are subjected to crosslinking reaction with the styrene-maleic anhydride-phenylmaleimide copolymer;
step 2, mixing 20 parts by weight of the ABS particles subjected to the crosslinking reaction with 8 parts by weight of carbon black particles with the particle size of 20 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials in a mixer, wherein the rotating speed of the mixer is 500 r/min, the blending time is 3 minutes, and the blending formula is as follows:
60 parts by weight of common ABS plastic, 25 parts by weight of ethylene-ethyl acrylate copolymer, 28 parts by weight of the mixture obtained in the step 2, 1 part by weight of coupling agent gamma-mercaptopropyltriethoxysilane and 0.3 part by weight of antioxidant 330;
step 4, finally adding the blend obtained in the step 3 into a double-screw extruder, wherein the length-diameter ratio of the extruder is 40:1, and the diameter of a screw is 65mmThe rotating speed of the double-screw extruder is 300 r/min, the temperature from the conveying section to the discharge port of the double-screw extruder is 160-
3 x 3mm ABS modified plastic particles.
The modified materials prepared according to the above examples were tested by compression molding or injection molding of corresponding sample specimens, and the results are shown in the following table.
The antistatic ABS modified plastic prepared by the invention has low carbon black content and good antistatic effect, the volume resistivity of the ABS modified material is reduced by 5-6 orders of magnitude, and meanwhile, the tensile property, the bending property and the heat resistance of the ABS modified material are almost unchanged from those of the common ABS material.
Claims (6)
1. A preparation method of low-filling antistatic ABS modified plastic is characterized by comprising the following steps: the method comprises the following steps:
step 1, weighing common ABS plastic, a styrene-maleic anhydride-phenylmaleimide copolymer and dicumyl peroxide in proportion, mixing the raw materials, and extruding and granulating at the temperature of 190-; wherein the average molecular weight of the styrene-maleic anhydride-phenylmaleimide copolymer is (1-5) x 104The mass ratio of ABS to the styrene-maleic anhydride-phenylmaleimide copolymer is (1-5) to 1;
step 2, mixing the ABS particles subjected to the crosslinking reaction with carbon black particles, wherein the blending mass ratio of the ABS particles subjected to the crosslinking reaction to the carbon black particles is (1-2) to (0.5-1), and the particle size of the carbon black particles is 20-40 nm;
and 3, blending the mixture obtained in the step 2 with the following raw materials according to the blending formula:
50-80 parts of common ABS plastic, 10-30 parts of ethylene-acrylic acid copolymer, 15-20 parts of the mixture obtained in the step 2, 0.1-2 parts of coupling agent and 0.1-0.4 part of antioxidant;
and 4, extruding and cooling the blend obtained in the step 3 at the temperature of 160-200 ℃ by using an extruder to obtain the ABS modified plastic.
2. The preparation method of the low-filling antistatic ABS modified plastic as claimed in claim 1, characterized in that: the carbon black particles are one of acetylene black, channel black and furnace black.
3. The preparation method of the low-filling antistatic ABS modified plastic as claimed in claim 1, characterized in that: the ethylene-acrylic acid copolymer is one of ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer and ethylene-acrylic ester-maleic anhydride graft copolymer.
4. The preparation method of the low-filling antistatic ABS modified plastic as claimed in claim 1, characterized in that: the coupling agent is one of gamma- (methacryloyloxy) propyl trimethoxy silane, 3-glycidyl ether oxypropyl trimethoxy silane and gamma-mercaptopropyl triethoxy silane.
5. The preparation method of the low-filling antistatic ABS modified plastic as claimed in claim 1, characterized in that: the antioxidant is one or more of antioxidant 1076, antioxidant 168 and antioxidant 330.
6. An ABS modified plastic obtained by the method for preparing a low-filled antistatic ABS modified plastic according to any one of claims 1 to 5.
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| CN101759974A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Low-odor antistatic and high tenacity polycarbonate composite |
| KR101301661B1 (en) * | 2012-11-13 | 2013-09-03 | 윤성윤 | Manufacturing method of plastic sheets preventing of static electricity with excellent durability |
| CN104693335A (en) * | 2013-12-10 | 2015-06-10 | 合肥杰事杰新材料股份有限公司 | Antistatic ABS composite material and preparation method thereof |
| CN107629385A (en) * | 2016-07-19 | 2018-01-26 | 大韩道恩高分子材料(上海)有限公司 | Low smell antistatic ABS composite of a kind of automobile using and preparation method thereof |
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- 2018-12-06 CN CN201811484454.5A patent/CN109735047B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101759974A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Low-odor antistatic and high tenacity polycarbonate composite |
| KR101301661B1 (en) * | 2012-11-13 | 2013-09-03 | 윤성윤 | Manufacturing method of plastic sheets preventing of static electricity with excellent durability |
| CN104693335A (en) * | 2013-12-10 | 2015-06-10 | 合肥杰事杰新材料股份有限公司 | Antistatic ABS composite material and preparation method thereof |
| CN107629385A (en) * | 2016-07-19 | 2018-01-26 | 大韩道恩高分子材料(上海)有限公司 | Low smell antistatic ABS composite of a kind of automobile using and preparation method thereof |
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| Modeling the electrical percolation of mixed carbon fillers in polymer blends;Zhuo-Yue Xiong等;《Carbon》;20140110(第70期);233-240 * |
| 聚合物/炭黑复合材料导电和增韧研究;景涛;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20131215;B020-62 * |
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