CN112876781A - Conductive polystyrene composite material and preparation method and application thereof - Google Patents
Conductive polystyrene composite material and preparation method and application thereof Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 121
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 38
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- -1 phenol amine modified graphene Chemical class 0.000 claims description 49
- 235000013824 polyphenols Nutrition 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005669 high impact polystyrene Polymers 0.000 claims description 4
- 239000004797 high-impact polystyrene Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000012628 flowing agent Substances 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229920006248 expandable polystyrene Polymers 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 14
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- 230000000052 comparative effect Effects 0.000 description 10
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- 239000011347 resin Substances 0.000 description 6
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- 239000002699 waste material Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229940079877 pyrogallol Drugs 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 244000208060 Lawsonia inermis Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a conductive polystyrene composite material and a preparation method and application thereof, wherein the conductive polystyrene composite material comprises the combination of polystyrene, graphene, carbon nano tubes, a toughening agent, an antioxidant and a silane coupling agent; according to the conductive polystyrene composite material, a specific part of graphene and carbon nano tubes are added into a polystyrene matrix to serve as a conductive agent, three-dimensional graphene and two-dimensional carbon nano tubes can generate a synergistic effect, and a conductive network is formed in the polystyrene matrix, so that the conductive polystyrene composite material has low resistivity; and by adding the toughening agent, the silane coupling agent and the antioxidant, the conductive polystyrene composite material also has excellent mechanical properties, and can meet the requirements on electrical properties and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a conductive polystyrene composite material as well as a preparation method and application thereof.
Background
Polystyrene (PS) is one of five general-purpose resins, and the demand of the PS is continuously increased along with the development of science and technology and the continuous progress of society; the traditional application field is nearly saturated, so the application range of the polystyrene is greatly expanded by a modification technology, and the conductive polystyrene is gradually and widely applied to the fields of plastic chips, portable power supplies, displays, robots, life sciences, solar energy and the like.
Conventional conductive polystyrenes achieve lower electrical resistance by incorporating high loadings of conventional conductive fillers and a series of more complex processing procedures. Due to the fact that the conductive material with high filling amount has a series of production problems of poor mechanical property, poor flowability, high processing difficulty and the like, the cost of a manufacturer is increased, profits are reduced, and the continuous development of the conductive material is not facilitated. The appearance of the graphene perfectly solves the problems brought by the traditional conductive filler. The graphene has excellent mechanical properties, electrical properties and self-structure. The high-fluidity graphene modified conductive polystyrene utilizes the ultrahigh electrical property of graphene to replace the traditional conductive filler, achieves the same conductive property, reduces the addition of carbon, and avoids the defect of material mechanics caused by overhigh carbon content. CN109280285A discloses a method for preparing core-shell-structured conductive polystyrene particles by using waste polystyrene, which is to add polystyrene particles prepared by using a waste polystyrene functional remodeling method into a mixed solvent containing a conductive material, stir the mixture to swell the surface of the polystyrene particles, allow the conductive material to enter a swelling network space on the surface of the polystyrene particles, and remove the mixed solvent to obtain the polystyrene particles with conductive shells. The shell conductive polystyrene prepared by the preparation method of the core-shell structure conductive polystyrene particles has the advantages of simple process, small conductive material consumption, high conductivity and low cost, and can effectively solve the problems of complex preparation process, poor mechanical property of the material and overhigh preparation cost of the conductive polystyrene. Meanwhile, the waste polystyrene is effectively utilized, and the problem of environmental pollution caused by the waste polystyrene is solved. However, the conductive particles with the core-shell structure are obtained by the technology, the conductive particles are really the outer shell, and the polystyrene at the central part still has no conductivity, which increases the application limitation; the core and the shell in the core-shell structure are two different materials, and the two materials have different mechanical properties, so that the phenomenon that the appearance is complete but the internal material is broken or the internal material is intact and the single-surface structure is damaged to lose conductivity can be generated, thereby affecting the quality of the final product.
CN110698801A discloses a high-fluidity graphene modified polystyrene composite material and a preparation method thereof. The composite material is composed of the following components: polystyrene, a conductive material, a toughening agent, an antioxidant, a flow modifier, a coupling agent and other auxiliary agents. The high-fluidity graphene modified polystyrene composite material and the preparation method thereof provide a polystyrene composite material for improving the processing performance and the electrical conductivity, and the fully-peeled and uniformly-dispersed graphene nanosheets are prepared in situ in the solution by combining the moderate oxidation technology and the liquid phase peeling technology, so that the production process is simple, convenient and easy to implement, and has the effects of safety, environmental protection and low production cost. CN110305416A discloses a graphene/polymer conductive composite material and a preparation method thereof. The method for preparing the graphene/macromolecule electric conduction comprises the following steps: dispersing graphene in an anti-solvent to obtain a graphene dispersion liquid; mixing the graphene dispersion liquid with the resin solution to precipitate resin microspheres so as to obtain a solid-liquid mixture; filtering and drying the solid-liquid mixture to obtain a compound; and preparing the graphene/polymer conductive composite material by using the compound. Therefore, the resin microspheres are uniformly adhered to the surface of the graphene, so that good dispersion between the graphene and the resin is realized, and the phenomenon of graphene agglomeration in the conventional processing process is avoided, so that the capability of the graphene for constructing a conductive network in a resin matrix is exerted to the greatest extent, and the graphene/polymer composite material with excellent performance is finally obtained. However, the polystyrene conductive materials obtained by the two methods only pursue the conductivity, but neglect the mechanical properties of the final product, and the addition of a large amount of conductive agent has a large influence on the mechanical properties of the product, particularly on the tensile strength and the breaking strength of the material, so that the wide-range application of the polystyrene conductive materials is limited.
Therefore, the development of a polystyrene composite material having high conductivity, high toughness and high impact strength is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a conductive polystyrene composite material and a preparation method and application thereof, wherein the conductive polystyrene composite material has lower resistivity by adding a certain part of graphene and carbon nano tubes as conductive agents into a polystyrene matrix; and the toughening agent, the silane coupling agent and the antioxidant are added, so that the conductive polystyrene composite material also has excellent mechanical properties, can meet the requirements on electrical properties and mechanical properties, and is wide in application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a conductive polystyrene composite material, which comprises the following components in parts by weight:
the conductive polystyrene provided by the invention comprises the combination of polystyrene, graphene, carbon nano tubes, an antioxidant, a silane coupling agent and a toughening agent; the graphene and the carbon nano tube have good conductivity by adding the specific parts of the graphene and the carbon nano tube into the polystyrene matrix, the graphene is of a three-dimensional sheet structure, and the carbon nano tube is of a two-dimensional tubular structure; the conductive polystyrene composite material and the conductive polystyrene composite material are jointly used as a conductive agent to be added into a polystyrene matrix, so that a three-dimensional net structure with a large specific surface area can be formed, the three-dimensional net structure is more beneficial to electron transfer, and the seepage threshold of the conductive polystyrene composite material is effectively reduced, so that the effect of effectively reducing the resistivity of the material can be achieved under the condition of less adding parts, and the influence on the mechanical property of the conductive polystyrene composite material is small; secondly, a toughening agent and an antioxidant are added, so that the conductive polystyrene composite material has more excellent mechanical properties; and moreover, the silane coupling agent is added, so that the polystyrene matrix and the auxiliary agent have better compatibility, and the conductive polystyrene composite material with excellent mechanical property and mechanical property is prepared.
The polystyrene may be 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, or the like.
The graphene may be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9 parts by weight, or the like.
The carbon nanotubes may be 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, or the like.
The toughening agent may be 4.3 parts by weight, 4.6 parts by weight, 4.9 parts by weight, 5.2 parts by weight, 5.5 parts by weight, 5.8 parts by weight, 6.1 parts by weight, 5.6 parts by weight, 5.9 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, or the like.
The antioxidant may be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight, etc.
The silane coupling agent may be 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, or the like.
Preferably, the polystyrene comprises any one of general purpose polystyrene, high impact polystyrene, or expandable polystyrene, or a combination of at least two thereof.
Preferably, the mass ratio of the graphene to the carbon nanotubes is 1 (1.5-2), such as 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75, 1:1.8, 1:1.85, 1:1.9, or 1: 1.95.
As a preferred technical scheme, when the mass ratio of the added graphene to the carbon nano tube is 1 (1.5-2), better synergistic effect can be generated, and more excellent conductive effect can be achieved under the state of the least adding parts; on one hand, if the addition amount of the graphene is too much, the graphene is easy to agglomerate, and the mechanical property of the material is influenced, so that waste is generated; on the other hand, if the addition amount of the graphene is too small, a complete three-dimensional network structure cannot be formed, and the conductivity of the material is affected.
Preferably, the graphene is phenol amine modified graphene.
Preferably, the phenolic amine modified graphene is prepared by a method comprising:
(1) adding graphene into a polyphenol aqueous solution to obtain a polyphenol-graphene mixed solution;
(2) and (2) adding polyamine into the polyphenol-graphene mixed solution obtained in the step (1), adjusting the pH value, and stirring to obtain the phenolic amine modified graphene.
As a preferred technical scheme, the graphene provided by the invention is phenol amine modified graphene, the graphene material has high surface energy and good chemical stability, and further has low compatibility with a high-molecular matrix material, so that the mechanical property of the material is influenced; the phenolic amine modified graphene material has more phenolic hydroxyl groups on the surface, so that the compatibility of the phenolic amine modified graphene material with a polystyrene matrix can be improved, and the mechanical property of the conductive graphene composite material is further improved.
Preferably, the polyphenol comprises catechol and/or pyrogallol.
Preferably, the polyamine comprises any one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or hexaethylene heptamine or a combination of at least two of the foregoing.
Preferably, the concentration of polyphenol in the aqueous polyphenol solution is 5 to 25mM, such as 7mM, 9mM, 11mM, 13mM, 15mM, 17mM, 19mM, 21mM or 23mM, and the specific points therebetween, are not exhaustive and are included for brevity.
Preferably, the mass ratio of the graphene to the polyphenol is 1 (1-3), such as 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6 or 1: 2.8.
Preferably, the molar ratio of the polyphenol to the polyamine is 1 (0.3-3), such as 1:05, 1:1, 1:1.3, 1:1.6, 1:1.9, 1:2.2, 1:2.4, 1:2.6, or 1: 2.8.
Preferably, the pH of the system after pH adjustment is 7-9, such as 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4, 8.6 or 8.8, and the specific values therebetween are not exhaustive, and for brevity and clarity.
Preferably, the rotation speed of the stirring is 30-100 r/min, such as 35r/min, 40r/min, 45r/min, 50r/min, 55r/min, 60r/min, 65r/min, 70r/min, 75r/min, 80r/min, 85r/min, 90r/min or 95r/min, and the specific values therebetween are limited to the space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the stirring time is 5-60 min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the toughening agent comprises any one of or a combination of at least two of a styrene-butadiene-styrene copolymer, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, or a hydrogenated styrene-butadiene block copolymer.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite.
Preferably, the silane coupling agent includes any one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or gamma-methacryloxypropyltrimethoxysilane, or a combination of at least two thereof.
Preferably, the conductive polystyrene composite further comprises a flowing agent.
Preferably, the content of the flowing agent in the conductive polystyrene composite is 1-5%, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, and specific values therebetween, which are limited by space and for brevity, are not exhaustive, and the specific values included in the range are not included in the present invention.
Preferably, the flow agent comprises any one of or a combination of at least two of polyethylene wax, paraffin wax or white oil.
In a second aspect, the present invention provides a method for preparing the conductive polystyrene composite material according to the first aspect, the method comprising the steps of:
(A1) mixing a toughening agent, a coupling agent, an antioxidant, polystyrene and optionally a flow agent to obtain a mixture;
(A2) mixing graphene, carbon nanotubes and the mixture obtained in the step (A1), and extruding to obtain the conductive polystyrene composite material.
Preferably, the temperature of the mixing in the step (a1) is 90-170 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃, and the specific values therebetween are limited by the space and the conciseness, and the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing time in step (a1) is 10-60 min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, and the specific points between the above points are limited by space and for brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the temperature of the mixing in the step (a2) is 150 to 190 ℃, for example 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃ or 185 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing in the step (a2) is performed under stirring conditions, and more preferably under stirring conditions at a rotation speed of 800 to 1500rpm (e.g., 900rpm, 950rpm, 1000rpm, 1050rpm, 1100rpm, 1150 rpm, 1200rpm, 1250rpm, 1300rpm, 1400rpm, etc.).
Preferably, the mixing time in step (a2) is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28min, and the specific points between the above points are limited by space and for brevity, the invention is not exhaustive of the specific points included in the range.
Preferably, the extruding of step (a2) is performed by a twin screw extruder.
As a preferred technical scheme, the preparation method comprises the following steps:
(A1) mixing a toughening agent, a coupling agent, an antioxidant, polystyrene and an optional flow agent at 90-170 ℃ for 10-60 min to obtain a mixture;
(A2) and (C) mixing the graphene, the carbon nano tube and the mixture obtained in the step (A1) at the temperature of 150-190 ℃ for 10-30 min, and extruding the mixture through a double-screw extruder to obtain the conductive polystyrene composite material.
In a third aspect, the present invention provides a use of the conductive polystyrene composite of the first aspect in a plastic chip, a power supply or a display.
Compared with the prior art, the invention has the following beneficial effects:
the conductive polystyrene composite material provided by the invention adopts polystyrene as a matrix, and graphene and carbon nano tubes in characteristic parts are added as conductive agents, so that the polystyrene matrix and the graphene can form a complete three-dimensional network structure, and the resistivity of the polystyrene is greatly reduced; meanwhile, the toughening agent, the silane coupling agent and the antioxidant are added, so that the conductive polystyrene composite material has excellent mechanical properties and can meet the requirements on electrical properties and mechanical properties; the surface resistance of the conductive polystyrene composite material is 1.0 multiplied by 103～1.27×103Omega, the notched impact strength is 11.3 to 13.1kJ/m2The tensile strength can reach32.2-38.6 MPa, and can meet the requirements on the electrical and mechanical properties of the material when applied to electronic products.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The preparation method of the phenolic amine modified graphene comprises the following steps:
(1) adding graphene (Henan Taiji chemical products Co., Ltd.) into 10mM polyphenol (pyrogallol) aqueous solution, wherein the mass ratio of the graphene to the polyphenol is 1:2, so as to obtain polyphenol-graphene mixed solution;
(2) adding polyamine (diethylenetriamine) into the polyphenol-graphene mixed solution obtained in the step (1), adjusting the pH value to be 8, stirring for 30min at the rotating speed of 50r/min, and obtaining the phenolic amine modified graphene, wherein the molar ratio of the polyphenol to the polyamine is 1: 1.5.
Preparation example 2
The preparation method of the phenolic amine modified graphene comprises the following steps:
(1) adding graphene (Henan Taiji chemical products Co., Ltd.) into 5mM polyphenol (pyrogallol) water solution, wherein the mass ratio of the graphene to the polyphenol is 1:1, so as to obtain polyphenol-graphene mixed solution;
(2) adding diethylenetriamine into the polyphenol-graphene mixed solution obtained in the step (1), adjusting the pH value to 7, and stirring for 60min at the rotating speed of 30r/min, wherein the molar ratio of polyphenol to polyamine is 1:0.3, so as to obtain the phenolic amine modified graphene.
Preparation example 3
The preparation method of the phenolic amine modified graphene comprises the following steps:
(1) adding graphene (Henan Taiji chemical products Co., Ltd.) into a 25mM polyphenol (pyrogallol) aqueous solution, wherein the mass ratio of the graphene to the polyphenol is 1:3, so as to obtain a polyphenol-graphene mixed solution;
(2) adding diethylenetriamine into the polyphenol-graphene mixed solution obtained in the step (1), adjusting the pH value to 9, and stirring for 5min at the rotating speed of 100r/min, wherein the molar ratio of polyphenol to polyamine is 1:3, so as to obtain the phenolic amine modified graphene.
Example 1
The conductive polystyrene composite material comprises the following components in parts by weight:
wherein the polystyrene is high impact polystyrene (Taiwan Chimei, PH-88); the toughening agent is ethylene-vinyl acetate copolymer (Beijing organic EVA-14-2-made by China); carbon nanotubes (Shenzhen, Guangdong evolutionary technology Limited, Multi-walled carbon nanotubes); polyethylene wax (Chengdusan Boyu plastics Co., Ltd.); the mass ratio of the phenolic amine modified graphene to the carbon nano tube is 1: 1.67.
The preparation method of the conductive polystyrene composite material comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer, tris (2, 4-di-tert-butylphenyl) phosphite, gamma-aminopropyltriethoxysilane, high impact polystyrene and polyethylene wax at 100 ℃ for 30min to obtain a mixture;
(2) and (2) mixing the phenolic amine modified graphene, the carbon nano tube and the mixture obtained in the step (1) at 160 ℃ and at the rotating speed of 800rpm for 20min, and extruding the mixture through a double-screw extruder to obtain the conductive polystyrene composite material.
Example 2
The conductive polystyrene composite material comprises the following components in parts by weight:
wherein, the polystyrene is general polystyrene (GPPS-501 of a new material for Zhongxing Guo' an in Jiangsu); the toughening agent is ethylene-vinyl acetate copolymer (Beijing organic EVA-14-2-made by China); carbon nanotubes (Shenzhen, Guangdong evolutionary technology Limited, Multi-walled carbon nanotubes); polyethylene wax (Chengdusan Boyu plastics Co., Ltd.); the mass ratio of the phenolic amine modified graphene to the carbon nano tube is 1:2.
The preparation method of the conductive polystyrene composite material comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer, tris (2, 4-di-tert-butylphenyl) phosphite, gamma-aminopropyltriethoxysilane, general polystyrene and polyethylene wax at 90 ℃ for 10min to obtain a mixture;
(2) and (2) mixing the phenolic amine modified graphene, the carbon nano tube and the mixture obtained in the step (1) for 10min at the temperature of 150 ℃ and the rotating speed of 800rpm, and extruding the mixture by using a double-screw extruder to obtain the conductive polystyrene composite material.
Example 3
The conductive polystyrene composite material comprises the following components in parts by weight:
wherein, the polystyrene is general polystyrene (GPPS-501 of a new material for Zhongxing Guo' an in Jiangsu); the toughening agent is ethylene-vinyl acetate copolymer (Beijing organic EVA-14-2-made by China); carbon nanotubes (Shenzhen, Guangdong evolutionary technology Limited, Multi-walled carbon nanotubes); polyethylene wax (Chengdusan Boyu plastics Co., Ltd.); the mass ratio of the phenolic amine modified graphene to the carbon nano tube is 1: 1.5.
The preparation method of the conductive polystyrene composite material comprises the following steps:
(1) mixing ethylene-vinyl acetate copolymer, tris (2, 4-di-tert-butylphenyl) phosphite, gamma-aminopropyltriethoxysilane, general polystyrene and polyethylene wax at 170 ℃ for 60min to obtain a mixture;
(2) and (2) mixing the phenolic amine modified graphene, the carbon nano tube and the mixture obtained in the step (1) at 190 ℃ and at the rotating speed of 1500rpm for 30min, and extruding the mixture by using a double-screw extruder to obtain the conductive polystyrene composite material.
Example 4
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 1.6 parts by weight, the carbon nanotubes are added in an amount of 2.4 parts by weight, and other components, amounts and preparation methods are the same as those of example 1.
Example 5
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 1.3 parts by weight, the carbon nanotubes are added in an amount of 2.7 parts by weight, and other components, amounts and preparation methods are the same as those of example 1.
Example 6
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 1 part by weight, the carbon nanotubes are added in an amount of 3 parts by weight, and other components, use amounts and preparation methods are the same as those of example 1.
Example 7
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 2 parts by weight, the carbon nanotubes are added in an amount of 2 parts by weight, and other components, amounts and preparation methods are the same as those of example 1.
Example 8
A conductive polystyrene composite material, which is different from the conductive polystyrene composite material in example 1 in that graphene (henna taiji chemical products limited) is used to replace phenolamine modified graphene, and other components, use amounts and preparation methods are the same as those in example 1.
Comparative example 1
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 0.5 parts by weight, the carbon nanotubes are added in an amount of 3.5 parts by weight, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 2
A conductive polystyrene composite material, which is different from the conductive polystyrene composite material in example 1 in that the phenolic amine modified graphene is added in an amount of 4 parts by weight, no carbon nanotube is added, and other components, the use amounts and the preparation method are the same as those of example 1.
Comparative example 3
A conductive polystyrene composite material, which is different from example 1 in that the phenolic amine modified graphene is added in an amount of 3 parts by weight, the carbon nanotube is added in an amount of 1 part by weight, and other components, amounts and preparation methods are the same as those of example 1.
Comparative example 4
A conductive polystyrene composite material, which is different from example 1 in that phenolic amine modified graphene is not added, the addition amount of carbon nanotubes is 4 parts by weight, and other components, the use amount and the preparation method are the same as those of example 1.
And (3) performance testing:
the conductive polystyrene composite materials provided in the examples 1 to 8 and the comparative examples 1 to 4 are subjected to injection molding to prepare standard sample bars, and the mechanical property and the electrical property are tested by the following specific method:
(1) surface resistance: testing by adopting a surface resistance tester SIMCO ST-4; the testing steps comprise: the tester is flatly placed on the tested sample strip, the rubber rod at the bottom of the tester is required to be in complete contact with the tested sample strip, the red square button is pressed, the test result is waited for, and if the test result shows 10.7, the surface resistance of the object is 1010.7Ω；
(2) Impact strength of the simply supported beam notch: testing according to the method recorded in the national standard GB/T1043-;
(3) tensile strength: the test was carried out according to the method described in the test Standard for tensile Properties of plastics in the national Standard GB/T16421-1996, using a universal drawing machine from the Zhuhai three-Si test Equipment Co., Ltd.
The standard sample strips obtained in examples 1 to 8 and comparative examples 1 to 4 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the surface resistance of the conductive styrene composite material provided by the invention is 1.0 multiplied by 103～1.27×103Omega, the notched impact strength is 11.3 to 13.1kJ/m2The tensile strength can reach 32.2-38.6 MPa, and the requirements of electronic products on the electrical and mechanical properties of the material can be met.
Specifically, the conductive styrene composite material provided in embodiments 1 to 8 is prepared by adding a specific part of phenol amine modified graphene and carbon nanotubes to a polystyrene matrix, and coordinating the phenol amine modified graphene and the carbon nanotubes to construct a three-dimensional conductive network favorable for electron transmission in polystyrene; on one hand, the conductivity of the conductive polystyrene composite material obtained by only adding the phenol amine modified graphene (comparative example 2) or adding too much phenol amine modified graphene (comparative example 3) is reduced, and the phenol amine modified graphene is easy to agglomerate in a polystyrene matrix due to too high addition part of the phenol amine modified graphene, so that the tensile strength and the notch impact strength of the finally obtained conductive polystyrene composite material are reduced; on the other hand, if the addition amount of the phenol amine modified graphene is too low (comparative example 1) or the addition amount of the phenol amine modified graphene is not too low (comparative example 4), the surface resistance of the conductive polyaniline composite material obtained is greatly improved, because only the two-dimensional carbon nanotubes are added or the addition amount of the three-dimensional phenol amine modified graphene is too low, a complete conductive network cannot be formed inside the polystyrene, and the conductivity is affected.
Further, it can be found by comparing examples 1 and 4 to 7 that the surface resistance of the conductive polyaniline composite materials obtained in examples 1, 4 and 5 is lower, while the surface resistance of the conductive polyaniline composite materials obtained in examples 6 and 7 is slightly improved, because a more complete to three-dimensional network can be formed only when the amounts of the graphene and the carbon nanotube are within a specific ratio range, and the effect of reducing the conductive percolation threshold of the materials is more obvious.
Comparing example 1 with example 8, it can be seen that the notched impact strength and tensile strength of the conductive polyaniline composite obtained in example 8 are slightly reduced compared to example 1, because the compatibility between graphene without phenol amine modification and polystyrene matrix is poor, and the mechanical properties of the finally obtained conductive polyaniline composite are affected.
The applicant states that the present invention is illustrated by the above examples to a conductive polyaniline composite material and a method for preparing the same and applications thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The conductive polystyrene composite material is characterized by comprising the following components in parts by weight:
2. the conductive polystyrene composite of claim 1, wherein the polystyrene comprises any one of general purpose polystyrene, high impact polystyrene, or expandable polystyrene, or a combination of at least two thereof.
3. The conductive polystyrene composite material as claimed in claim 1 or 2, wherein the mass ratio of the graphene to the carbon nanotubes is 1 (1.5-2);
preferably, the graphene is phenol amine modified graphene;
preferably, the phenolic amine modified graphene is prepared by a method comprising:
(1) adding graphene into a polyphenol aqueous solution to obtain a polyphenol-graphene mixed solution;
(2) adding polyamine into the polyphenol-graphene mixed solution obtained in the step (1), adjusting the pH value, and stirring to obtain the phenolic amine modified graphene;
preferably, the polyphenol comprises catechol and/or pyrogallol;
preferably, the polyamine comprises any one or a combination of at least two of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or hexaethylene heptamine;
preferably, the concentration of polyphenol in the polyphenol water solution is 5-25 mM;
preferably, the mass ratio of the graphene to the polyphenol is 1 (1-3);
preferably, the molar ratio of the polyphenol to the polyamine is 1 (0.3-3);
preferably, the pH value of the system after the pH value is adjusted is 7-9;
preferably, the rotating speed of the stirring is 30-100 r/min;
preferably, the stirring time is 5-60 min.
4. The conductive polystyrene composite of any one of claims 1 to 3, wherein the toughening agent comprises any one of or a combination of at least two of a styrene-butadiene-styrene copolymer, an ethylene-vinyl acetate copolymer, a polyolefin elastomer, or a hydrogenated styrene-butadiene block copolymer.
5. The conductive polystyrene composite of any one of claims 1 to 4, wherein the antioxidant comprises pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or tris (2, 4-di-tert-butylphenyl) phosphite;
preferably, the silane coupling agent includes any one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or gamma-methacryloxypropyltrimethoxysilane, or a combination of at least two thereof.
6. The conductive polystyrene composite material as claimed in any one of claims 1 to 5, further comprising a flow agent;
preferably, the content of the flowing agent in the conductive polystyrene composite material is 1-5 parts by weight;
preferably, the flow agent comprises any one of or a combination of at least two of polyethylene wax, paraffin wax or white oil.
7. A method for preparing the conductive polystyrene composite material as claimed in any one of claims 1 to 6, wherein the preparation method comprises the following steps:
(A1) mixing a toughening agent, a coupling agent, an antioxidant, polystyrene and optionally a flow agent to obtain a mixture;
(A2) mixing graphene, carbon nanotubes and the mixture obtained in the step (A1), and extruding to obtain the conductive polystyrene composite material.
8. The method according to claim 7, wherein the temperature of the mixing in the step (A1) is 90 to 170 ℃;
preferably, the mixing time of the step (A1) is 10-60 min;
preferably, the temperature of the mixing in the step (A2) is 150-190 ℃;
preferably, the mixing in the step (A2) is carried out under the condition of stirring, and more preferably under the condition of stirring at the rotating speed of 800-1500 rpm;
preferably, the mixing time of the step (A2) is 10-30 min;
preferably, the extruding of step (a2) is performed by a twin screw extruder.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(A1) mixing a toughening agent, a coupling agent, an antioxidant, polystyrene and an optional flow agent at 90-170 ℃ for 10-60 min to obtain a mixture;
(A2) and (C) mixing the graphene, the carbon nano tube and the mixture obtained in the step (A1) at the temperature of 150-190 ℃ for 10-30 min, and extruding the mixture through a double-screw extruder to obtain the conductive polystyrene composite material.
10. Use of the conductive polystyrene composite of any one of claims 1 to 6 in a plastic chip, a power supply or a display.
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