CN111286150A - Graphene modified ABS antistatic plastic for electric appliance shell and preparation method thereof - Google Patents
Graphene modified ABS antistatic plastic for electric appliance shell and preparation method thereof Download PDFInfo
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- CN111286150A CN111286150A CN201810810962.1A CN201810810962A CN111286150A CN 111286150 A CN111286150 A CN 111286150A CN 201810810962 A CN201810810962 A CN 201810810962A CN 111286150 A CN111286150 A CN 111286150A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention relates to the field of antistatic plastics, and discloses graphene modified ABS antistatic plastic for an electric appliance shell and a preparation method thereof. The preparation method comprises the following preparation processes: (1) mixing a silane coupling agent, graphene oxide and a styrene monomer, and then carrying out a grafting reaction to obtain graphene oxide graft modified styrene; (2) mixing graft modified styrene and acrylonitrile monomer for copolymerization to obtain modified styrene-acrylonitrile copolymer; (3) and after reduction reaction, blending the obtained product with ABS powder and an auxiliary agent, extruding and granulating to obtain the graphene modified ABS antistatic plastic. According to the antistatic plastic prepared by the invention, graphene is uniformly dispersed in matrix resin, the obtained plastic has high conductivity, good antistatic performance and excellent electrostatic shielding effect, and the defect that the surface of an electric appliance shell is difficult to clean due to static electricity is avoided.
Description
Technical Field
The invention relates to the field of antistatic plastics, and discloses graphene modified ABS antistatic plastic for an electric appliance shell and a preparation method thereof.
Background
With the development of society, electrical appliances become a necessity in daily life of people at present. The electric appliance shell is used as an important component of an electric appliance and must meet the requirements of heat resistance, flame retardance, voltage resistance, corona resistance and mechanical property. In the 21 st century, various materials with high cost performance are continuously developed, and the material selection of the electric appliance shell gradually shifts to low cost, light weight and higher cost performance. Research and development of electrical appliance housing materials are important issues for the development of the television industry.
At present, the shell material of the electric appliance is mostly made of ABS engineering plastics, and the ABS plastics are styrene-butadiene-acrylonitrile terpolymers and belong to modified polystyrene plastics. It has the properties of toughness, hardness and rigidity. The product is used for manufacturing electric appliance shells, instrument shells, refrigerator linings, textile parts and the like in industry. However, such materials are electrical insulating materials, lack of conductivity, and are used in electronic products such as electric appliances, refrigerators and the like, which are prone to generate static electricity, so that plastic shells can adsorb dust or other impurities in the air, the appearance is affected, and the cleaning is difficult, so that antistatic modification is often needed.
In the modified material of the ABS engineering plastic, due to the excellent heat conduction, radiation protection, static prevention and other performances of the graphene, the application of the graphene can practically improve the anti-electronic interference and static prevention capability of the product, and meanwhile, the light weight of the product is realized. The most important thing of the graphene for electrostatic shielding is to ensure that the graphene can be uniformly dispersed and form an interconnected intercommunicating structure so as to improve the conductivity of the graphene, and the graphene has a conductive network which is mutually overlapped, so that the electron transmission efficiency is higher, and the electrostatic shielding effect is more excellent. Therefore, the graphene is increasingly used for modifying the ABS television shell material.
Chinese patent application No. 200810089428.2 discloses a method for manufacturing a modified PC/ABS alloy material, belonging to the technical field of plastic alloy material production. The manufacturing method of the modified PC/ABS alloy material comprises the following steps: adding PC/ABS alloy granules, a heat-resistant auxiliary agent and a toughening auxiliary agent into a plastic extruder in proportion; and adjusting the temperature of the plastic extruder to 220-250 ℃, and extruding the modified PC/ABS alloy material. Meanwhile, the invention also provides an electric appliance front shell which is made of the modified PC/ABS alloy material. By modifying the PC/ABS alloy material, the heat resistance and the strength are improved on the premise of ensuring that the injection molding fluidity of the PC/ABS alloy material is not reduced, and the cost of the front shell material of the plasma electric appliance is greatly reduced.
Chinese patent application No. 201511013528.3 discloses an antistatic plastic, which comprises the following components in parts by weight: 50 parts of ABS, 5 parts of silane coupling agent, 10 parts of toughening agent, 1 part of dispersing agent and 12 parts of antistatic agent, wherein the weight ratio of the antistatic agent is 1: 1 with titanium dioxide. The antistatic property of the ABS plastic is greatly improved by adding the antistatic agent.
According to the above, in the existing scheme, the antistatic modified graphene for the ABS plastic is easy to agglomerate in resin and difficult to disperse, so that the conductivity of the material is poor, the antistatic performance is affected, and the application of the antistatic modified graphene in the housing of an electric appliance is restricted. The invention provides a graphene modified ABS antistatic plastic for an electric appliance shell and a preparation method thereof, which can effectively solve the technical problems.
Disclosure of Invention
In the prior art of widely applying the technology for carrying out antistatic modification on the ABS plastic of the electric appliance shell by using the graphene, the problems that the graphene is easy to agglomerate in resin and is difficult to disperse, so that the conductivity of the material is poor, and the antistatic performance is influenced exist.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of graphene modified ABS antistatic plastic for an electric appliance shell comprises the following specific steps:
(1) uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer;
(3) and adding a reducing agent, reducing oxygen-containing groups remained on the surface of the graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic.
Preferably, in the grafting reaction system in the step (1), the following components are calculated according to parts by weight: 1-2 parts of silane coupling agent, 5-8 parts of graphene oxide and 90-94 parts of styrene monomer.
Preferably, the silane coupling agent in the step (1) is at least one of kh550, kh560, kh570, kh540 and kh 590.
Preferably, the irradiation in the step (1) is ultraviolet irradiation, and the intensity is 180-200 muW/cm3The time is 12-15 h.
Preferably, in the copolymerization reaction system in the step (2), the weight portions are as follows: 30-60 parts of graft modified styrene and 40-70 parts of acrylonitrile monomer.
Preferably, the temperature of the copolymerization reaction in the step (2) is 60-65 ℃, and the time is 100-120 min.
Preferably, the reducing agent in step (3) is one of hydrazine hydrate and phenylhydrazine.
Preferably, the auxiliary agent in step (3) includes, but is not limited to, one or more of an antioxidant, a flame retardant, a plasticizer, a lubricant, and a heat stabilizer.
Preferably, in the blending system in the step (3), the weight parts are as follows: 20-30 parts of modified styrene-acrylonitrile copolymer, 60-78 parts of ABS powder and 2-10 parts of auxiliary agent.
According to the graphene modified ABS antistatic plastic for the electric appliance shell, the modified SAN resin obtained by grafting activated graphene oxide and styrene and then copolymerizing is used as an antistatic agent, and the modified SAN resin is matched with ABS powder to extrude to obtain the antistatic modified ABS resin, so that the defects that the existing graphene is easy to agglomerate and disperse unevenly in the resin are overcome, the antistatic property of the master batch is greatly improved, and the problem that the ABS composite material is low in conductivity is solved.
The graphene distribution characteristics and the volume resistance of the graphene modified ABS antistatic plastic prepared by the invention are tested, and compared with the common graphene modified ABS plastic and the common ABS plastic, the method disclosed by the invention has obvious advantages.
The invention provides a graphene modified ABS antistatic plastic for an electric appliance shell and a preparation method thereof, and compared with the prior art, the graphene modified ABS antistatic plastic has the outstanding characteristics and excellent effects that:
1. a method for preparing graphene modified ABS antistatic plastic for an electric appliance shell by using graphene oxide modified styrene-acrylonitrile copolymer is provided.
2. The modified ABS plastic is prepared by preparing the antistatic agent by grafting the activated graphene oxide and the modified styrene, so that the dispersibility of the graphene in matrix resin is obviously improved.
3. The graphene modified ABS antistatic plastic prepared by the invention has high conductivity, good antistatic property and excellent electrostatic shielding effect, and avoids the defect that the surface of an electric appliance shell is difficult to clean due to static electricity.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene; the silane coupling agent is kh 550; the irradiation is ultraviolet irradiation with intensity of 195 μ W/cm3The time is 14 h;
in the grafting reaction system, by weight, the following components are added: 1 part by weight of silane coupling agent, 7 parts by weight of graphene oxide and 92 parts by weight of styrene monomer;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer; the temperature of the copolymerization reaction is 63 ℃ and the time is 112 min;
in the copolymerization reaction system, by weight, the following components are added: 50 parts of graft modified styrene and 50 parts of acrylonitrile monomer;
(3) adding a reducing agent, reducing oxygen-containing groups remained on the surface of graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic; the reducing agent is hydrazine hydrate; the auxiliary agent comprises 2 parts by weight of antioxidant 1010, 2 parts by weight of flame retardant magnesium hydroxide, 2 parts by weight of plasticizer white oil and 1 part by weight of heat stabilizer zinc stearate;
in the blending system, by weight, the following components are added: 26 parts of modified styrene-acrylonitrile copolymer, 67 parts of ABS powder and 7 parts of auxiliary agent.
Example 2
(1) Uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene; the silane coupling agent is kh 560; the irradiation is ultraviolet irradiation with intensity of 190 μ W/cm3The time is 14.5 h;
in the grafting reaction system, by weight, the following components are added: 1 part by weight of silane coupling agent, 6 parts by weight of graphene oxide and 93 parts by weight of styrene monomer;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer; the temperature of the copolymerization reaction is 64 ℃, and the time is 105 min;
in the copolymerization reaction system, by weight, the following components are added: 40 parts of graft modified styrene and 60 parts of acrylonitrile monomer;
(3) adding a reducing agent, reducing oxygen-containing groups remained on the surface of graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic; the reducing agent is phenylhydrazine; the auxiliary agent comprises 1 part by weight of antioxidant 1010, 1 part by weight of flame retardant magnesium hydroxide, 1 part by weight of plasticizer white oil and 1 part by weight of heat stabilizer zinc stearate;
in the blending system, by weight, the following components are added: 22 parts of modified styrene-acrylonitrile copolymer, 74 parts of ABS powder and 4 parts of auxiliary agent.
Example 3
(1) Uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and the graphene oxide with a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare the graphene oxide graft modified styrene(ii) a The silane coupling agent is kh 570; the irradiation is ultraviolet irradiation with intensity of 198 μ W/cm3The time is 13 h;
in the grafting reaction system, by weight, the following components are added: 2 parts of silane coupling agent, 7 parts of graphene oxide and 91 parts of styrene monomer;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer; the temperature of the copolymerization reaction is 64 ℃ and the time is 112 min;
in the copolymerization reaction system, by weight, the following components are added: 55 parts of graft modified styrene and 45 parts of acrylonitrile monomer;
(3) adding a reducing agent, reducing oxygen-containing groups remained on the surface of graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic; the reducing agent is hydrazine hydrate; the auxiliary agent comprises 2 parts by weight of antioxidant 1010, 2 parts by weight of flame retardant magnesium hydroxide, 2 parts by weight of plasticizer white oil and 2 parts by weight of heat stabilizer zinc stearate;
in the blending system, by weight, the following components are added: 28 parts of modified styrene-acrylonitrile copolymer, 64 parts of ABS powder and 8 parts of auxiliary agent.
Example 4
(1) Uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene; the silane coupling agent is kh 540; the irradiation is ultraviolet irradiation with intensity of 180 μ W/cm3The time is 15 h;
in the grafting reaction system, by weight, the following components are added: 1 part by weight of silane coupling agent, 5 parts by weight of graphene oxide and 94 parts by weight of styrene monomer;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer; the temperature of the copolymerization reaction is 60 ℃, and the time is 120 min;
in the copolymerization reaction system, by weight, the following components are added: 30 parts of graft modified styrene and 70 parts of acrylonitrile monomer;
(3) adding a reducing agent, reducing oxygen-containing groups remained on the surface of graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic; the reducing agent is phenylhydrazine; the auxiliary agent comprises 0.5 part by weight of antioxidant 1010, 0.5 part by weight of flame retardant magnesium hydroxide, 0.5 part by weight of plasticizer white oil and 0.5 part by weight of heat stabilizer zinc stearate;
in the blending system, by weight, the following components are added: 20 parts of modified styrene-acrylonitrile copolymer, 78 parts of ABS powder and 2 parts of auxiliary agent.
Example 5
(1) Uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene; the silane coupling agent is kh 590; the irradiation is ultraviolet irradiation with intensity of 200 μ W/cm3The time is 12 hours;
in the grafting reaction system, by weight, the following components are added: 2 parts of silane coupling agent, 8 parts of graphene oxide and 90 parts of styrene monomer;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer; the temperature of the copolymerization reaction is 65 ℃ and the time is 100 min;
in the copolymerization reaction system, by weight, the following components are added: 60 parts of graft modified styrene and 40 parts of acrylonitrile monomer;
(3) adding a reducing agent, reducing oxygen-containing groups remained on the surface of graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic; the reducing agent is hydrazine hydrate; the auxiliary agent comprises 2 parts by weight of antioxidant 1010, 3 parts by weight of flame retardant magnesium hydroxide, 3 parts by weight of plasticizer white oil and 2 parts by weight of heat stabilizer zinc stearate;
in the blending system, by weight, the following components are added: 30 parts of modified styrene-acrylonitrile copolymer, 60 parts of ABS powder and 10 parts of auxiliary agent.
Comparative example 1
Comparative example 1 graphene oxide graft-modified styrene and acrylonitrile monomers were not copolymerized, graphene SAN was directly mixed, and the rest was the same as in example 5, and the graphene distribution characteristics and volume resistance of the prepared graphene-modified ABS antistatic plastic are shown in table 1.
Comparative example 2
Comparative example 2 is a normal ABS.
The graphene distribution characteristics and the volume resistance of the graphene modified ABS antistatic plastic prepared by the invention are tested, and compared with the common graphene modified ABS plastic and the common ABS plastic, the method disclosed by the invention has obvious advantages. As in table 1.
Table 2:
| performance index | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Distribution characteristics of graphene | Uniformly dispersed | Uniformly dispersed | Uniformly dispersed | Uniformly dispersed | Uniformly dispersed | Presence of agglomeration | -- |
| Volume resistance (omega. cm) | 0.7×106 | 0.6×106 | 1.0×106 | 1.3×106 | 1.1×106 | 5.3×107 | 1.6×109 |
Claims (10)
1. A preparation method of graphene modified ABS antistatic plastic for an electric appliance shell is characterized by comprising the following specific preparation processes:
(1) uniformly mixing a silane coupling agent and graphene oxide in a high-speed mixer, then mixing the silane coupling agent and a styrene monomer, and carrying out grafting reaction by adopting irradiation initiation to prepare graphene oxide graft modified styrene;
(2) fully mixing the graft modified styrene prepared in the step (1) with an acrylonitrile monomer, and performing one-step copolymerization to prepare a modified styrene-acrylonitrile copolymer;
(3) and adding a reducing agent, reducing oxygen-containing groups remained on the surface of the graphene oxide in the copolymer, blending with ABS powder and an auxiliary agent, and extruding and granulating by adopting a double-screw extruder to obtain the graphene modified ABS antistatic plastic.
2. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: in the grafting reaction system in the step (1), by weight, the method comprises the following steps: 1-2 parts of silane coupling agent, 5-8 parts of graphene oxide and 90-94 parts of styrene monomer.
3. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: the silane coupling agent in the step (1) is at least one of kh550, kh560, kh570, kh540 and kh 590.
4. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: the irradiation in the step (1) is ultraviolet irradiation, and the intensity is 180-200 mu W/cm3The time is 12-15 h.
5. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: in the copolymerization reaction system in the step (2), by weight, the following components are added: 30-60 parts of graft modified styrene and 40-70 parts of acrylonitrile monomer.
6. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: the temperature of the copolymerization reaction in the step (2) is 60-65 ℃, and the time is 100-120 min.
7. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: and (4) the reducing agent in the step (3) is one of hydrazine hydrate and phenylhydrazine.
8. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: the auxiliary agent in the step (3) comprises but is not limited to one or more of an antioxidant, a flame retardant, a plasticizer, a lubricant and a heat stabilizer.
9. The preparation method of the graphene modified ABS antistatic plastic for the electric appliance shell according to claim 1, characterized by comprising the following steps: in the blending system in the step (3), the weight portions are as follows: 20-30 parts of modified styrene-acrylonitrile copolymer, 60-78 parts of ABS powder and 2-10 parts of auxiliary agent.
10. The graphene modified ABS antistatic plastic for the electric appliance shell prepared by the method of any one of claims 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690245A (en) * | 2020-07-17 | 2020-09-22 | 合肥科拜耳材料科技有限公司 | Wear-resistant and damp-heat resistant PC/ABS material and preparation method thereof |
| CN116178914A (en) * | 2023-03-28 | 2023-05-30 | 东莞市金庆新材料有限公司 | Binary blending PBT master batch preparation method and blending master batch prepared by same |
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2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690245A (en) * | 2020-07-17 | 2020-09-22 | 合肥科拜耳材料科技有限公司 | Wear-resistant and damp-heat resistant PC/ABS material and preparation method thereof |
| CN111690245B (en) * | 2020-07-17 | 2022-04-01 | 合肥科拜尔新材料股份有限公司 | Wear-resistant and damp-heat resistant PC/ABS material and preparation method thereof |
| CN116178914A (en) * | 2023-03-28 | 2023-05-30 | 东莞市金庆新材料有限公司 | Binary blending PBT master batch preparation method and blending master batch prepared by same |
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Application publication date: 20200616 |