CN109021408A - A kind of preparation method and product of heat-conducting type thermoplastic vulcanised elastomer material - Google Patents
A kind of preparation method and product of heat-conducting type thermoplastic vulcanised elastomer material Download PDFInfo
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- CN109021408A CN109021408A CN201810879594.6A CN201810879594A CN109021408A CN 109021408 A CN109021408 A CN 109021408A CN 201810879594 A CN201810879594 A CN 201810879594A CN 109021408 A CN109021408 A CN 109021408A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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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
Abstract
The present invention relates to functionalized elastomers field of material technology, provide the preparation method and product of a kind of heat-conducting type thermoplastic vulcanizate material, which includes: (1) heat filling being surface modified and dried using coupling agent；(2) modified heat filling is mixed with matrix resin, through melt blending, extrusion, granulation and drying, obtains heat-conducting resin pellet；(3) heat-conducting resin pellet is mixed with rubber, vulcanizing system, carries out dynamic vulcanization reaction and extruding pelletization, obtains heat-conducting type thermoplastic vulcanised elastomer material.Thermoplastic vulcanised elastomer prepared by the present invention is other than excellent thermal conductivity few, material with heat filling dosage, also have machine-shaping property excellent, simple production process, high production efficiency and recyclable the advantages that recycling, it can be widely applied to electron and electrician, the numerous areas such as automobile, therefore have a vast market application prospect.
Description
[technical field]
The present invention relates to functionalized elastomers field of material technology, and in particular to a kind of heat-conducting type thermoplastic vulcanizates bullet
The preparation method and product of elastomer material.
[background technique]
With the development of electronic technology, electronics technology product is more inclined to lightweight and high performance.Electronic product makes
It will seriously affect electronic component if heat cannot be discharged in time with that can generate vibration in the process and discharge heat
Service life.
Although traditional heat conductive rubber material has many characteristics such as high resiliency, high-termal conductivity and insulating properties, due to rubber
Glue material processing molding method itself is single, and deposits and be difficult to the problems such as reusing after shaping, thus the largely upper limit
Its application on electronic product is made.
Heat-conducting type thermoplastic vulcanizate material, can keep thermal conductivity and it is elastomeric simultaneously, and have it is good
The characteristics such as machine-shaping property and repeatable processing, thus have broad application prospects and commercial value.
[summary of the invention]
The purpose of the present invention is to provide the preparation methods and product of a kind of heat-conducting type thermoplastic vulcanizate material, special
Point is not only to can be improved the heating conduction of elastomeric material, can also make it have good processing performance and reusable
Property.
The technical principle of invention is: being mutually continuous phase, rubber phase using resin in thermoplastic vulcanizates (TPV) elastomer
It is formed and is led in TPV elastomer by the way that a certain amount of modified heat filling is added in resin phase for the design feature of dispersed phase
Heat supply network chain, and then improve the heating conduction of TPV elastomer.
Based on above-mentioned technical principle, embodiments of the present invention provide a kind of heat-conducting type thermoplastic vulcanised elastomer
The preparation method of material, comprises the following steps:
(1) heat filling is surface modified and is dried using coupling agent, obtain modified heat filling；
(2) the modified heat filling is mixed with matrix resin, through melt blending, extrusion, granulation and drying, is led
Hot resin pellet；
(3) the heat-conducting resin pellet is mixed with rubber, vulcanizing system, carries out dynamic vulcanization reaction and extruding pelletization,
Obtain heat-conducting type thermoplastic vulcanised elastomer material.
Preferably, the heat filling be carbon nanotube, graphene, graphite, carbon black, silicon carbide, boron carbide, chromium carbide,
At least one of tungsten carbide, silicon nitride, boron nitride, aluminium nitride, beryllium oxide, aluminium oxide, zinc oxide, copper, silver, gold, al and ni.
Preferably, the coupling agent is at least one of silane coupling agent, aluminate coupling agent and titanate coupling agent.
Preferably, the dosage of the coupling agent is 1~3wt% of the heat filling.
Preferably, described matrix resin is in polypropylene, polyethylene, polystyrene, polyamide, polyvinyl chloride and polyurethane
At least one.
Preferably, the rubber is ethylene propylene diene rubber, butyl rubber, nitrile rubber, acrylic rubber, ethylene-the third
At least one of olefin(e) acid ester rubber, ethylene octane copolymer, silicon rubber and fluorubber.
Preferably, the mass ratio of the modified heat filling and matrix resin is (10~40): 100.
Preferably, the melt blending, extrusion, granulation process carry out in double screw extruder, double screw extruder
Melting extrusion temperature is 160~240 DEG C.
Preferably, the vulcanizing system is in sulphur, peroxide, sulfur donor, metal oxide and synthetic resin
At least one.
Preferably, the mass ratio of the heat-conducting resin pellet and rubber, vulcanizing system is (30~50): (70~50):
(1.75~1.25).
Preferably, dynamic vulcanization reaction carries out in double screw extruder, and the temperature of dynamic vulcanization is 180~220 DEG C, when
Between be 10~15min, extruder revolving speed be 50~80rpm.
Embodiments of the present invention also provide heat-conducting type thermoplastic vulcanised elastomer prepared by the above method
Material, comprising resin continuous phase and the rubber phase being dispersed in the resin continuous phase, the resin continuous phase includes to change
Property heat filling and matrix resin, the modified heat filling are connected with each other in the resin continuous phase and form thermally conductive network chain
Structure.
Compared with the existing technology, heat-conducting type thermoplastic vulcanised elastomer material prepared by embodiments of the present invention
Material, the heating conduction for not only having had Heat Conduction Material excellent, but also taken into account the excellent machine-shaping property of TPV elastomeric material and green
The feature of environmental protection improves the surcharge of heat-conducting elastomer material, has widened its application range, theoretical in heat-conducting type elastomeric material
Research and application and development etc. are of great significance.
[Detailed description of the invention]
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing, in which:
Fig. 1 is the preparation method flow diagram of heat-conducting type thermoplastic vulcanised elastomer material of the invention；
Wherein, the modified heat filling of 1-, 2- resin continuous phase, 3- vulcanized rubber phase.
[specific embodiment]
To make the object, technical solutions and advantages of the present invention clearer, below will to the embodiments of the present invention into
The detailed elaboration of row.However, it will be understood by those skilled in the art that in each embodiment of the present invention, in order to make to read
Person more fully understands the application and proposes many technical details.But even if without these technical details and based on following
The various changes and modifications of embodiment, each claim of the application technical solution claimed can also be realized.
In a specific embodiment of the invention, the preparation side of heat-conducting type thermoplastic vulcanised elastomer material is provided
Method comprises the following steps: (1) heat filling being surface modified and dried using coupling agent, obtain modified heat filling；
(2) the modified heat filling is mixed with matrix resin, through melt blending, extrusion, granulation and drying, obtains heat-conducting resin grain
Material；(3) the heat-conducting resin pellet is mixed with rubber, vulcanizing system, carries out dynamic vulcanization reaction and extruding pelletization, is led
Heat type thermoplastic vulcanised elastomer material.
In a specific embodiment of the invention, the heat filling is carbon nanotube, graphene, graphite, carbon black, carbonization
Silicon, boron carbide, chromium carbide, tungsten carbide, silicon nitride, boron nitride, aluminium nitride, beryllium oxide, aluminium oxide, zinc oxide, copper, silver, gold, aluminium
At least one of with nickel.
In a specific embodiment of the invention, the coupling agent is silane coupling agent, aluminate coupling agent and titanate esters
At least one of coupling agent.
In a specific embodiment of the invention, the dosage of the coupling agent is 1~3wt% of the heat filling.
In a specific embodiment of the invention, described matrix resin be polypropylene, polyethylene, polystyrene, polyamide,
At least one of polyvinyl chloride and polyurethane.
In a specific embodiment of the invention, the rubber is ethylene propylene diene rubber, butyl rubber, nitrile rubber, third
At least one of olefin(e) acid ester rubber, ethylene-acrylate rubber, ethylene octane copolymer, silicon rubber and fluorubber.
In a specific embodiment of the invention, the mass ratio of modified heat filling and matrix resin is (10~40):
100。
In a specific embodiment of the invention, the melt blending, extrusion, granulation process in double screw extruder into
Row, the melting extrusion temperature of double screw extruder are 160~240 DEG C.
In a specific embodiment of the invention, the vulcanizing system is sulphur, peroxide, sulfur donor, metal
At least one of oxide and synthetic resin.
In a specific embodiment of the invention, the matter of the heat-conducting resin pellet and the rubber, the vulcanizing system
Amount is than being (30~50): (70~50): (1.75~1.25).
In a specific embodiment of the invention, dynamic vulcanization reaction carries out in double screw extruder, dynamic vulcanization
Temperature is 180~220 DEG C, and the time is 10~15min, and extruder revolving speed is 50~80rpm.
In a specific embodiment of the invention, heat-conducting type thermoplastic vulcanizates elasticity prepared by the above method
Body material, comprising resin continuous phase and the rubber phase being dispersed in the resin continuous phase, the resin continuous phase includes
Modified heat filling and matrix resin, the modified heat filling are connected with each other in the resin continuous phase and form thermal conductive network
Chain structure.
It is some citings of a specific embodiment of the invention below:
Embodiment 1
The method that the present embodiment prepares heat-conducting type thermoplastic vulcanised elastomer material, selection polypropylene are resin phase,
Ethylene propylene diene rubber is rubber phase, and aluminium nitride is heat filling, comprising the following steps:
(1) aluminium nitride powder is calcined at 1600~1850 DEG C first in boron nitride crucible, is recycled after cooling
Butyl titanate coupling agent is surface-treated aluminium nitride powder, then dry 6 hours in 60 DEG C of convection oven；
(2) polypropylene granules and processed aluminium nitride powder are squeezed according to the ratio of 100:20 in 200 DEG C of twin-screw
Heat-conducting type polypropylene granules are finally prepared by melt blending, extrusion, water cooling, granulation under 60r/min revolving speed in machine out；
(3) thermally conductive polypropylene granules and EPDM raw rubber are then placed in convection oven drying 2 hours at 80 DEG C,
The 5min that plasticates under 80r/min revolving speed in the mixer that EPDM raw rubber is placed at 150 DEG C is taken out, EPDM is obtained and plasticates
Glue；
(4) by thermally conductive polypropylene granules, EPDM broken-down rubber and phenolic resin vulcanization system according to the ratio of 30:70:1.5
Example successively passes through dynamic vulcanization process, extruding pelletization in double screw extruder, finally obtains heat-conducting type thermoplastic vulcanizates
Elastomer particles, wherein the draw ratio of extruder screw is 40:1, revolving speed 70rpm, and each section of temperature is successively in process
It is 150 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C.
The preparation flow figure of the present embodiment is as shown in Fig. 1.As shown in Fig. 1, conductive hot obtained in the present embodiment
In plasticity vulcanised elastomer material, include resin continuous phase 2 and the vulcanized rubber phase being dispersed in resin continuous phase
3, the resin continuous phase 2 includes that modified heat filling 1 and matrix resin, the modified heat filling 1 are continuous in the resin
It is connected with each other in phase and forms thermally conductive supply chain network structure.
Embodiment 2
The method that the present embodiment prepares heat-conducting type thermoplastic vulcanised elastomer material, selection polypropylene are resin phase,
Ethylene propylene diene rubber is rubber phase, and graphite flake is heat filling, comprising the following steps:
(1) graphite flake is surface modified first with titanate coupling agent NDZ101, then the air blast at 60 DEG C is dried
Dry 6 hours in case；
(2) double screw extruder by the graphite flake of polypropylene granules and modified according to the ratio of 100:15 at 200 DEG C
It is middle finally to prepare heat-conducting type polypropylene granules by melt blending, extrusion, water cooling, granulation；
(3) thermally conductive polypropylene granules and EPDM raw rubber are then placed in convection oven drying 2 hours at 80 DEG C,
The 5min that plasticates under 80r/min revolving speed in the mixer that EPDM raw rubber is placed at 150 DEG C is taken out, EPDM is obtained and plasticates
Glue；
(4) by thermally conductive polypropylene granules, EPDM broken-down rubber and phenolic resin vulcanization system according to the ratio of 30:70:1.5
Example successively passes through dynamic vulcanization process, extruding pelletization in double screw extruder, finally obtains heat-conducting type thermoplastic vulcanizates
Elastomer particles, wherein the draw ratio of extruder screw is 40:1, revolving speed 50rpm, and each section of temperature is successively in process
It is 150 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C.
In the present embodiment in heat-conducting type thermoplastic vulcanised elastomer material obtained, comprising resin continuous phase and uniformly
The vulcanized rubber phase being dispersed in resin continuous phase, the resin continuous phase includes to be modified heat filling and matrix resin, described
Modified heat filling is connected with each other in the resin continuous phase and forms thermally conductive supply chain network structure.
Embodiment 3
The method that the present embodiment prepares heat-conducting type thermoplastic vulcanised elastomer material, selection polypropylene are resin phase,
Ethylene octane copolymer (POE) is rubber phase, and graphite flake is heat filling, comprising the following steps:
(1) graphite flake is surface modified first with titanate coupling agent NDZ101, then the air blast at 60 DEG C is dried
Dry 6 hours in case；
(2) double screw extruder by the graphite flake of polypropylene granules and modified according to the ratio of 100:15 at 200 DEG C
It is middle finally to prepare heat-conducting type polypropylene granules by melt blending, extrusion, water cooling, granulation；
(3) POE elastomeric pellets and thermally conductive polypropylene granules are placed in the convection oven at 80 DEG C 2 hours dry；
(4) by thermally conductive polypropylene granules, POE elastomeric pellets and peroxide vulcanizing system according to the ratio of 30:70:1
Successively pass through dynamic vulcanization process, extruding pelletization in double screw extruder, finally obtains heat-conducting type thermoplastic vulcanizates bullet
Elastomer particles, wherein the draw ratio of extruder screw is 40:1, revolving speed 50rpm, and each section of temperature is followed successively by process
150℃、200℃、200℃、200℃、200℃。
In the present embodiment in heat-conducting type thermoplastic vulcanised elastomer material obtained, comprising resin continuous phase and uniformly
The vulcanized rubber phase being dispersed in resin continuous phase, the resin continuous phase includes to be modified heat filling and matrix resin, described
Modified heat filling is connected with each other in the resin continuous phase and forms thermally conductive supply chain network structure.
Embodiment 4
The method that the present embodiment prepares heat-conducting type thermoplastic vulcanised elastomer material, selecting nylon 12 (PA12) is tree
Lipid phase, brombutyl (BIIR) are rubber phase, and graphite flake is heat filling, comprising the following steps:
(1) graphite flake is surface modified first with titanate coupling agent NDZ101, then the air blast at 60 DEG C is dried
Dry 6 hours in case；
(2) PA12 pellet is placed in in 80 DEG C of vacuum drying oven dry 12h, then by the PA12 pellet and modified after drying
Graphite flake prepare and lead by melt blending, extrusion, granulation in 200 DEG C of double screw extruder according to the ratio of 100:25
12 pellet of heat type nylon, the melting extrusion temperature of extruder are 200 DEG C；
(3) brombutyl and 12 pellet of heat-conducting type nylon are placed in the vacuum drying oven at 80 DEG C 2 hours dry；
(4) by brombutyl, 12 pellet of thermally conductive nylon and zinc oxide vulcanizing system according to the ratio of 100:54:1.2
Successively pass through dynamic vulcanization process, extruding pelletization in double screw extruder, finally obtains heat-conducting type thermoplastic vulcanizates bullet
Elastomer particles, wherein the draw ratio of extruder screw is 40:1, revolving speed 50rpm, and each section of temperature is followed successively by process
150℃、200℃、200℃、200℃、200℃。
In the present embodiment in heat-conducting type thermoplastic vulcanised elastomer material obtained, comprising resin continuous phase and uniformly
The vulcanized rubber phase being dispersed in resin continuous phase, the resin continuous phase includes to be modified heat filling and matrix resin, described
Modified heat filling is connected with each other in the resin continuous phase and forms thermally conductive supply chain network structure.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (12)
1. a kind of preparation method of heat-conducting type thermoplastic vulcanised elastomer material, which is characterized in that comprise the following steps:
(1) heat filling is surface modified and is dried using coupling agent, obtain modified heat filling；
(2) the modified heat filling is mixed with matrix resin, through melt blending, extrusion, granulation and drying, obtains thermally conductive tree
Fat granule material；
(3) the heat-conducting resin pellet is mixed with rubber, vulcanizing system, carries out dynamic vulcanization reaction and extruding pelletization, obtains
Heat-conducting type thermoplastic vulcanised elastomer material.
2. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The heat filling is carbon nanotube, graphene, graphite, carbon black, silicon carbide, boron carbide, chromium carbide, tungsten carbide, silicon nitride, nitrogen
Change at least one of boron, aluminium nitride, beryllium oxide, aluminium oxide, zinc oxide, copper, silver, gold, al and ni.
3. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The coupling agent is at least one of silane coupling agent, aluminate coupling agent and titanate coupling agent.
4. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 3, which is characterized in that
And the dosage of the coupling agent is 1~3wt% of the heat filling.
5. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
Described matrix resin is at least one of polypropylene, polyethylene, polystyrene, polyamide, polyvinyl chloride and polyurethane.
6. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The rubber is ethylene propylene diene rubber, butyl rubber, nitrile rubber, acrylic rubber, ethylene-acrylate rubber, polyene
At least one of hydrocarbon elastomer, silicon rubber and fluorubber.
7. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The mass ratio of the modified heat filling and matrix resin is (10~40): 100.
8. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The melt blending, extrusion, granulation process carry out in double screw extruder, and the melting extrusion temperature of double screw extruder is
160~240 DEG C.
9. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, which is characterized in that
The vulcanizing system is at least one of sulphur, peroxide, sulfur donor, metal oxide and synthetic resin.
10. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, feature exist
In the mass ratio of the heat-conducting resin pellet and the rubber, the vulcanizing system is (30~50): (70~50): (1.75~
1.25)。
11. the preparation method of heat-conducting type thermoplastic vulcanised elastomer material according to claim 1, feature exist
In, dynamic vulcanization reaction carries out in double screw extruder, and the temperature of dynamic vulcanization is 180~220 DEG C, and the time is 10~
15min, extruder revolving speed are 50~80rpm.
12. the heat-conducting type thermoplastic vulcanised elastomer material that method described in any one of claims 1 to 11 is prepared
Material, it includes resin continuous phases and the vulcanized rubber phase being dispersed in the resin continuous phase, which is characterized in that the tree
Rouge continuous phase includes that modified heat filling and matrix resin, the modified heat filling are connected with each other in the resin continuous phase
And form thermally conductive supply chain network structure.
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| CN110591234A (en) * | 2019-09-05 | 2019-12-20 | 上海阿莱德实业股份有限公司 | Rubber-based graphene heat-conducting interface material and preparation method thereof |
| CN110684285A (en) * | 2019-09-05 | 2020-01-14 | 上海阿莱德实业股份有限公司 | Rubber-based graphene heat conduction material |
| CN110684340A (en) * | 2019-09-05 | 2020-01-14 | 上海阿莱德实业股份有限公司 | Polyurethane-based graphite oriented heat-conducting interface material |
| CN111410792A (en) * | 2020-06-01 | 2020-07-14 | 天津美亚化工有限公司 | High-specific-strength modified polypropylene-based composite material and preparation method thereof |
| CN111635574A (en) * | 2020-06-19 | 2020-09-08 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
| CN112250943A (en) * | 2020-10-22 | 2021-01-22 | 安徽绿谷新材料有限公司 | Environment-friendly dynamic vulcanization thermoplastic elastomer and processing technology thereof |
| CN112341681A (en) * | 2020-11-26 | 2021-02-09 | 中国石油大学(北京) | Rubber-plastic blending modified hydrogenated nitrile rubber and preparation method and application thereof |
| CN113999517A (en) * | 2021-10-12 | 2022-02-01 | 中广核三角洲（江苏）塑化有限公司 | Antistatic dynamic vulcanized silicone rubber thermoplastic elastomer and preparation method thereof |
| CN114316477A (en) * | 2022-02-08 | 2022-04-12 | 广东大明弘成新能源科技有限公司 | Special TPE (thermoplastic elastomer) high-elasticity material for charging pile cables and preparation method thereof |
| CN116731432A (en) * | 2023-07-13 | 2023-09-12 | 深圳市好年璟科技有限公司 | Heat-conducting rubber-plastic composite material and preparation method thereof |
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