CN105820499A - Polyaniline composite conductive plastic - Google Patents
Polyaniline composite conductive plastic Download PDFInfo
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- CN105820499A CN105820499A CN201610354836.0A CN201610354836A CN105820499A CN 105820499 A CN105820499 A CN 105820499A CN 201610354836 A CN201610354836 A CN 201610354836A CN 105820499 A CN105820499 A CN 105820499A
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L27/00—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to the technical field of composite conductive materials, and particularly discloses a polyaniline composite conductive plastic and a preparation method thereof .The polyaniline composite conductive plastic is mainly prepared from, by weight, 90-100 parts of a plastic base material, 15-25 parts of polyaniline, 5-15 parts of dimethyl sulfoxide, 2-4 parts of graphene, 1-5 parts of nano-silver, 1-4 parts of a coupling agent, 15-20 parts of a plasticizer, 0.2-1 part of calcium stearate, 1-5 parts of maleic anhydride grafted polypropylene and 0.5-1.5 parts of a surfactant .Mechanical defects of polyaniline can be overcome by compositing polyaniline and other high polymer materials, the electrical properties of the common high polymer materials can be improved at the same time, and thus the polyaniline composite conductive plastic can be more widely applied and popularized.
Description
Technical field
The invention belongs to composite conducting material technical field, concretely relate to a kind of polyaniline composite conductive plastic and preparation method thereof.
Background technology
Polyaniline is the one of macromolecular compound, has special electricity, an optical property, doped after can have electric conductivity and chemical property.After certain process, the various equipment with specific function and material can be prepared, as having more excellent reversible electrode material, selective membrane material, antistatic and electromagnetic shielding material, conductive fiber, anti-corrosion material in charge and discharge process as the urease sensor of biological or chemical sensor, electronic field emission source, more traditional lithium electrode material, etc..Polyaniline because of its raw material having be easy to get, synthesis technique is simple, chemistry and the feature such as environmental stability is good and obtained studying widely and applying.But owing to intermolecular strong effect and high rigid chain cause the processing molten, difficult of its indissoluble, greatly limit application.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of polyaniline composite conductive plastic and preparation method thereof.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of polyaniline composite conductive plastic, mark meter by weight includes: plastic basis material 90-100 part, polyaniline 15-25 part, dimethyl sulfoxide 5-15 part, Graphene 2-4 part, nanometer silver 1-5 part, coupling agent 1-4 part, plasticizer 15-20 part, calcium stearate 0.2-1 part, maleic anhydride inoculated polypropylene 1-5 part, surfactant 0.5-1.5 part.
Preferably, in the preferred embodiment, the mixture of one or more during described plastic basis material is ABS resin, polythene PE, polypropylene PP, polyvinylchloride, polycarbonate, nylon PA etc..
Preferably, in the preferred embodiment, described polyaniline mark meter by weight is made up of following material, aniline 15-25 part, dioctyl phthalate 40-60 part, hydrochloric acid 10-20 part, p-methyl benzenesulfonic acid 15-25 part, potassium dichromate 1-5 part, sodium hydroxide 40-60 part, acetone 60-80 part.
Preferably, in the preferred embodiment, described coupling agent is silane coupler, and described silane coupler is titanate coupling agent or aluminate coupling agent one therein or mixture.
Preferably, in the preferred embodiment, at least one during described plasticizer is triacetyl glycerine or triethyl citrate.
The preparation method of a kind of polyaniline composite conductive plastic, comprises the following steps:
(1) described aniline, described dioctyl phthalate are joined in the mixed acid solution of described hydrochloric acid, described p-methyl benzenesulfonic acid, stir 0.5-2h with 300-500r/min, form emulsion;Then described potassium dichromate is added drop-wise in described emulsion, adds described sodium hydroxide after completion of dropwise addition and continue reaction 1-3h, whole during the temperature of reaction system maintain 0-20 DEG C；The washing of example water is gone not contain Cl to washing liquid-, then with described washing with acetone, filter, be dried, grind, obtain described polyaniline；
(2) described plastic substrate, described calcium stearate and described maleic anhydride inoculated polypropylene are placed in high-speed mixer, stir with 2000-3000r/min and be warming up to during 30-50 DEG C add described plasticizer, continue insulation 1-4h and obtain mixture；
(3) 50-60 DEG C of water-bath, described Graphene, described nanometer silver are added stirring mixing in described dimethyl sulfoxide, in point 3-5 the described mixture of addition, keep constant temperature 55-60 DEG C stirring 1.5-2.5h;Described polyaniline is added in above-mentioned solution, 15-20min is stirred under 35-40 DEG C of constant temperature, add described coupling agent, described surfactant adds stirring 1.5-2h in step (2) described mixture after continuing stirring 20-30min, after supersound process 25-35min, 90-100 DEG C of vacuum drying 20-24h i.e. obtains described polyaniline composite conductive plastic.
Relative to prior art, beneficial effects of the present invention: owing to ABS resin, polythene PE, polypropylene PP, polyvinylchloride, polycarbonate, nylon PA etc. are the plastics that combination property is the most excellent, there is excellent chemical stability, and there is preferable mechanical property, polyaniline is combined with it, the machinability of polyaniline can be improved to a certain extent.The mechanics that compensate for polyaniline is not enough, improves the electric property of common high molecular materials simultaneously.Add nanometer silver and also improve electric conductivity and the heat conductivility of material equally.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Embodiment 1:
A kind of polyaniline composite conductive plastic, mark meter by weight includes: plastic basis material 90 parts, polyaniline 15 parts, dimethyl sulfoxide 5 parts, Graphene 2 parts, nanometer silver 1 part, coupling agent 1 part, plasticizer 15 parts, calcium stearate 0.2 part, maleic anhydride inoculated polypropylene 1 part, 0.5 part of surfactant.
Plastic basis material is the mixture of ABS resin and polycarbonate.
Polyaniline mark meter by weight is made up of following material, aniline 15 parts, dioctyl phthalate 40 parts, hydrochloric acid 10 parts, p-methyl benzenesulfonic acid 15 parts, potassium dichromate 1 part, sodium hydroxide 40 parts, 60 parts of acetone.
Coupling agent is silane coupler, and silane coupler is titanate coupling agent.
Plasticizer is triacetyl glycerine.
The preparation method of a kind of polyaniline composite conductive plastic, comprises the following steps:
(1) aniline, dioctyl phthalate are joined in the mixed acid solution of hydrochloric acid, p-methyl benzenesulfonic acid, stir 0.5h with 300r/min, form emulsion;Then potassium dichromate is added drop-wise in emulsion, adds sodium hydroxide after completion of dropwise addition and continue reaction 1h, whole during the temperature of reaction system maintain 0 DEG C；The washing of example water is gone not contain Cl to washing liquid-, then with washing with acetone, filter, be dried, grind, obtain polyaniline；
(2) plastic substrate, calcium stearate and maleic anhydride inoculated polypropylene are placed in high-speed mixer, stir with 2000r/min and be warming up to when 30 DEG C add plasticizer, continue insulation 1h and obtain mixture；
(3) 50 DEG C of water-baths, Graphene, nanometer silver are added stirring mixing in dimethyl sulfoxide, in point 3 addition mixture, keep constant temperature 55 DEG C stirring 1.5h;Polyaniline is added in above-mentioned solution, 15min is stirred under 35 DEG C of constant temperature, add coupling agent, surfactant adds stirring 1.5h in step (2) mixture after continuing stirring 20min, and after supersound process 25min, 90 DEG C of vacuum drying 20h i.e. obtain institute's polyaniline composite conductive plastic.
Embodiment 2:
A kind of polyaniline composite conductive plastic, mark meter by weight includes: plastic basis material 100 parts, polyaniline 25 parts, dimethyl sulfoxide 15 parts, Graphene 4 parts, nanometer silver 5 parts, coupling agent 4 parts, plasticizer 20 parts, calcium stearate 1 part, maleic anhydride inoculated polypropylene 5 parts, 1.5 parts of surfactant.
Plastic basis material is the mixture of polythene PE and polyvinylchloride.
Polyaniline mark meter by weight is made up of following material, aniline 25 parts, dioctyl phthalate 60 parts, hydrochloric acid 20 parts, p-methyl benzenesulfonic acid 25 parts, potassium dichromate 5 parts, sodium hydroxide 60 parts, 80 parts of acetone.
Coupling agent is silane coupler, and silane coupler is aluminate coupling agent.
Plasticizer is triethyl citrate.
The preparation method of a kind of polyaniline composite conductive plastic, comprises the following steps:
(1) aniline, dioctyl phthalate are joined in the mixed acid solution of hydrochloric acid, p-methyl benzenesulfonic acid, stir 2h with 500r/min, form emulsion;Then potassium dichromate is added drop-wise in emulsion, adds sodium hydroxide after completion of dropwise addition and continue reaction 3h, whole during the temperature of reaction system maintain 20 DEG C；The washing of example water is gone not contain Cl to washing liquid-, then with washing with acetone, filter, be dried, grind, obtain polyaniline；
(2) plastic substrate, calcium stearate and maleic anhydride inoculated polypropylene are placed in high-speed mixer, stir with 3000r/min and be warming up to when 50 DEG C add plasticizer, continue insulation 4h and obtain mixture；
(3) 60 DEG C of water-baths, Graphene, nanometer silver are added stirring mixing in dimethyl sulfoxide, in point 5 addition mixture, keep constant temperature 60 DEG C stirring 2.5h;Polyaniline is added in above-mentioned solution, 20min is stirred under 40 DEG C of constant temperature, add coupling agent, surfactant adds stirring 2h in step (2) mixture after continuing stirring 30min, and after supersound process 35min, 100 DEG C of vacuum drying 24h i.e. obtain institute's polyaniline composite conductive plastic.
Embodiment 3:
A kind of polyaniline composite conductive plastic, mark meter by weight includes: plastic basis material 95 parts, polyaniline 20 parts, dimethyl sulfoxide 10 parts, Graphene 3 parts, nanometer silver 3 parts, coupling agent 2 parts, plasticizer 17 parts, calcium stearate 0.6 part, maleic anhydride inoculated polypropylene 3 parts, 1.0 parts of surfactant.
Plastic basis material is polypropylene PP, the mixture of polyvinylchloride and polycarbonate.
Polyaniline mark meter by weight is made up of following material, aniline 20 parts, dioctyl phthalate 50 parts, hydrochloric acid 15 parts, p-methyl benzenesulfonic acid 20 parts, potassium dichromate 3 parts, sodium hydroxide 50 parts, 70 parts of acetone.
Coupling agent is silane coupler, and silane coupler is the mixture of titanate coupling agent and aluminate coupling agent.
Plasticizer is the mixture of triacetyl glycerine and triethyl citrate.
The preparation method of a kind of polyaniline composite conductive plastic, comprises the following steps:
(1) aniline, dioctyl phthalate are joined in the mixed acid solution of hydrochloric acid, p-methyl benzenesulfonic acid, stir 1.2h with 400r/min, form emulsion;Then potassium dichromate is added drop-wise in emulsion, adds sodium hydroxide after completion of dropwise addition and continue reaction 2h, whole during the temperature of reaction system maintain 10 DEG C；The washing of example water is gone not contain Cl to washing liquid-, then with washing with acetone, filter, be dried, grind, obtain polyaniline；
(2) plastic substrate, calcium stearate and maleic anhydride inoculated polypropylene are placed in high-speed mixer, stir with 2500r/min and be warming up to when 40 DEG C add plasticizer, continue insulation 2.5h and obtain mixture；
(3) 55 DEG C of water-baths, Graphene, nanometer silver are added stirring mixing in dimethyl sulfoxide, in point 4 addition mixture, keep constant temperature 57 DEG C stirring 2.0h;Polyaniline is added in above-mentioned solution, 17min is stirred under 37 DEG C of constant temperature, add coupling agent, surfactant adds stirring 1.7h in step (2) mixture after continuing stirring 25min, and after supersound process 30min, 95 DEG C of vacuum drying 22h i.e. obtain institute's polyaniline composite conductive plastic.
Polyaniline composite conductive plastic obtained by embodiment 1-3 has carried out conductivity and 30-3000Hz, and shield effectiveness is tested, and finds that the product conductivity prepared by embodiment 3 is higher, shield effectiveness is more preferable.
| Embodiment | Conductivity s/cm | Shielding efficiency (dB) |
| Embodiment 1 | 1.5×10-2 | 25-50 |
| Embodiment 2 | 1.5×10-2 | 25-45 |
| Embodiment 3 | 1.6×10-2 | 30-55 |
Claims (6)
1. a polyaniline composite conductive plastic, it is characterized in that, mark meter by weight includes: plastic basis material 90-100 part, polyaniline 15-25 part, dimethyl sulfoxide 5-15 part, Graphene 2-4 part, nanometer silver 1-5 part, coupling agent 1-4 part, plasticizer 15-20 part, calcium stearate 0.2-1 part, maleic anhydride inoculated polypropylene 1-5 part, surfactant 0.5-1.5 part.
A kind of polyaniline composite conductive plastic the most according to claim 1, it is characterised in that: described plastic basis material is the mixture of one or more in ABS resin, polythene PE, polypropylene PP, polyvinylchloride, polycarbonate, nylon PA etc..
A kind of polyaniline composite conductive plastic the most according to claim 1, it is characterized in that: described polyaniline mark meter by weight is made up of following material, aniline 15-25 part, dioctyl phthalate 40-60 part, hydrochloric acid 10-20 part, p-methyl benzenesulfonic acid 15-25 part, potassium dichromate 1-5 part, sodium hydroxide 40-60 part, acetone 60-80 part.
A kind of polyaniline composite conductive plastic the most according to claim 1, it is characterised in that: described coupling agent is silane coupler, and described silane coupler is titanate coupling agent or aluminate coupling agent one therein or mixture.
A kind of polyaniline composite conductive plastic the most according to claim 1, it is characterised in that: described plasticizer is at least one in triacetyl glycerine or triethyl citrate.
6. the preparation method of the polyaniline composite conductive plastic as described in any one of claim 1-5, it is characterised in that comprise the following steps:
(1) described aniline, described dioctyl phthalate are joined in the mixed acid solution of described hydrochloric acid, described p-methyl benzenesulfonic acid, stir 0.5-2h with 300-500r/min, form emulsion;Then described potassium dichromate is added drop-wise in described emulsion, adds described sodium hydroxide after completion of dropwise addition and continue reaction 1-3h, whole during the temperature of reaction system maintain 0-20 DEG C；The washing of example water is gone not contain Cl to washing liquid-, then with described washing with acetone, filter, be dried, grind, obtain described polyaniline；
(2) described plastic substrate, described calcium stearate and described maleic anhydride inoculated polypropylene are placed in high-speed mixer, stir with 2000-3000r/min and be warming up to during 30-50 DEG C add described plasticizer, continue insulation 1-4h and obtain mixture；
(3) 50-60 DEG C of water-bath, described Graphene, described nanometer silver are added stirring mixing in described dimethyl sulfoxide, in point 3-5 the described mixture of addition, keep constant temperature 55-60 DEG C stirring 1.5-2.5h;Described polyaniline is added in above-mentioned solution, 15-20min is stirred under 35-40 DEG C of constant temperature, add described coupling agent, described surfactant adds stirring 1.5-2h in step (2) described mixture after continuing stirring 20-30min, after supersound process 25-35min, 90-100 DEG C of vacuum drying 20-24h i.e. obtains described polyaniline composite conductive plastic.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519414A (en) * | 2016-11-15 | 2017-03-22 | 山东中塑泰富科技有限公司 | Environmentally friendly antistatic film material and preparation method thereof |
| CN109486091A (en) * | 2018-11-08 | 2019-03-19 | 浙江祥盛汽车科技有限公司 | A kind of antistatic automobile grid and preparation method thereof |
| CN111002674A (en) * | 2019-12-19 | 2020-04-14 | 横店集团东磁股份有限公司 | Composite electromagnetic shielding material and preparation method thereof |
| CN111073250A (en) * | 2019-12-20 | 2020-04-28 | 无锡若祎新材料科技有限公司 | Novel reinforced stable plastic material |
| CN114015173A (en) * | 2021-11-19 | 2022-02-08 | 广东腐蚀科学与技术创新研究院 | Modified polyaniline/polyamide filler doped composite conductive blend and preparation method thereof |
| CN116554573A (en) * | 2023-04-27 | 2023-08-08 | 山东金沅金新材料科技有限公司 | Composite conductive plastic and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519414A (en) * | 2016-11-15 | 2017-03-22 | 山东中塑泰富科技有限公司 | Environmentally friendly antistatic film material and preparation method thereof |
| CN109486091A (en) * | 2018-11-08 | 2019-03-19 | 浙江祥盛汽车科技有限公司 | A kind of antistatic automobile grid and preparation method thereof |
| CN111002674A (en) * | 2019-12-19 | 2020-04-14 | 横店集团东磁股份有限公司 | Composite electromagnetic shielding material and preparation method thereof |
| CN111002674B (en) * | 2019-12-19 | 2021-06-25 | 横店集团东磁股份有限公司 | Composite electromagnetic shielding material and preparation method thereof |
| CN111073250A (en) * | 2019-12-20 | 2020-04-28 | 无锡若祎新材料科技有限公司 | Novel reinforced stable plastic material |
| CN114015173A (en) * | 2021-11-19 | 2022-02-08 | 广东腐蚀科学与技术创新研究院 | Modified polyaniline/polyamide filler doped composite conductive blend and preparation method thereof |
| CN116554573A (en) * | 2023-04-27 | 2023-08-08 | 山东金沅金新材料科技有限公司 | Composite conductive plastic and preparation method thereof |
| CN116554573B (en) * | 2023-04-27 | 2024-04-26 | 河南海瑞祥科技有限公司 | Composite conductive plastic and preparation method thereof |
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