CN109517367A - A kind of conductive thermoplastic dynamic vulcanization silicon rubber and preparation method thereof - Google Patents
A kind of conductive thermoplastic dynamic vulcanization silicon rubber and preparation method thereof Download PDFInfo
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- C08L2312/00—Crosslinking
Abstract
The invention discloses a kind of conductive thermoplastic dynamic vulcanization silicon rubber and preparation method thereof.This conductive thermoplastic dynamic vulcanization silicon rubber is made of raw material below: thermoplastic polyurethane elastomer, silicon rubber gross rubber, conductive filler, crosslinking agent, compatilizer, catalyst.The dynamic vulcanization preparation method of this conductive thermoplastic dynamic vulcanization silicon rubber is also disclosed simultaneously.The characteristics such as the conductive good, comfortable feel of the preparation-obtained conductive thermoplastic dynamic vulcanization silicon rubber of the present invention, recyclable, excellent in mechanical performance, are widely portable to the fields such as electric, automobile, military project, communication.
Description
Technical field
The present invention relates to a kind of conductive thermoplastic dynamic vulcanization silicon rubber and preparation method thereof.
Background technique
Dynamic vulcanization is a kind of emerging rubber curing techniques, be by unvulcanized rubber under high shear forces with thermoplastic
Property the common melt blending of material, while be added vulcanizing agent make its vulcanize process.In this process, heat cured rubber phase
(dispersed phase) is evenly dispersed in thermoplastic material (continuous phase) with a certain particle size range, while rubber phase particles are completed to hand over
Connection, finally obtains thermoplastic dynamic perduren (TPV).The maximum feature of dynamic vulcanization is by this as heat cured rubber phase
It is carried in thermoplastic material, to thermoset rubber and thermoplastic plastic properties be combined, while convenient for material
Processing and recycling.
Thermoplastic polyurethane elastomer (TPU) is a kind of thermoplastic elastomer (TPE) haveing excellent performance, by isocyanates and polynary
Alcohol is polymerized, and has excellent mechanical property, oil resistivity, wearability, but its weatherability and processing performance are poor.
Silicon rubber refers to that main chain is alternately made of silicon and oxygen atom, and the rubber there are two organic group, silicon are connected on silicon atom
Rubber comfortable feel, good weatherability can keep stable mechanical property between -40-200 DEG C, and keep certain toughness, return
Elasticity and hardness.
Conductive polymer material refers to conductive high molecular material, compared with traditional conductive metal material, leads
Electric high molecular material has many advantages, such as that density is small, conductivity is controllable, easy processing, low in cost, can be used for sensor, electromagnetic shielding
Equal fields.Meanwhile conductive polymer material also has the shortcomings that coarse feel, poor mechanical property, unstable quality.
TPU is combined to silicon rubber thus and assigned its conductive characteristic, can be effectively solved the above problem.It is existing
Have in document, US4500688, CN106751736A are prepared for TPU/ silicon rubber thermoplasticity by different dynamic vulcanization systems
Elastomer, but there is no the preparations for further studying the thermoplastic dynamic vulcanized silicon rubber of conductivity type.CN104098795A is logical
It crosses and thermoplastic, rubber particles, conductive filler progress simple blend has been obtained into a kind of conductive thermoplastic elastomer, but its
There is no this advanced technologies of dynamic vulcanization are used, each performance of obtained product not yet can preferably meet actual use and want
It asks.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the invention to use dynamic vulcanization method, provides a kind of with conduction
Good, recyclable, excellent in mechanical performance conductive thermoplastic dynamic vulcanization silicon rubber of property and preparation method thereof.The present invention passes through dynamic
Vulcanize the thermoplastic dynamic vulcanized silicon rubber that step preparation has conductive characteristic, obtained product has the feel of silk cunning, together
When with excellent mechanical property and electric conductivity.
The technical solution used in the present invention is:
A kind of conductive thermoplastic dynamic vulcanization silicon rubber, is made of the raw material of following mass parts: thermoplastic polyurethane bullet
30~70 parts of body of property, 30~70 parts of silicon rubber gross rubber, 1~30 part of conductive filler, 1~5 part of crosslinking agent, 5~20 parts of compatilizer,
0.01~0.5 part of catalyst.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, thermoplastic polyurethane elastomer be polyether-type TPU,
At least one of polyester-type TPU.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, the shore hardness of thermoplastic polyurethane elastomer is
60A~95A.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, silicon rubber gross rubber is by white carbon black reinforcement
Methyl vinyl silicone rubber (or being Methyl-ethylenvinyl gum)；It is further preferred that methyl vinyl silicon kautschuk is through white
The method of black-reinforced is vapor phase method or the precipitation method.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, the vinyl molar content in silicon rubber gross rubber
It is 0.04%~0.5%.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, conductive filler is carbon black, carbon fiber, graphite powder, stone
At least one of black alkene, carbon nanotube, hard carbon, carbosphere, silver powder, nickel powder, copper powder；It is further preferred that conductive filler is
At least one of carbon black, carbon fiber, graphite powder, silver powder, nickel powder, copper powder.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, the partial size of conductive filler is 0.1 μm~40 μm.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, crosslinking agent is the siloxanes containing Si -- H bond；Into one
Step is preferred, and crosslinking agent is containing hydrogen silicone oil, and the molar content of Si -- H bond is 0.4%~2% in crosslinking agent.
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, compatilizer be ethylene acrylic acid co polymer (EAA),
At least one of ethylene methyl acrylate copolymer (EMA), ethylene-vinyl acetate copolymer (EVA).
Preferably, in this conductive thermoplastic dynamic vulcanization silicon rubber, catalyst is platinum-type catalyst；Further, platinum
Class catalyst is selected from metal platinum, platinum black, platinum loaded catalyst or contains platinum alloy.
The preparation method of this conductive thermoplastic dynamic vulcanization silicon rubber, comprising the following steps:
1) in mixer or extruder, by thermoplastic polyurethane elastomer, silicon rubber gross rubber, conductive filler, crosslinking
Agent and compatilizer melt blending squeeze out, and are granulated, obtain pre-composition；
2) pre-composition is mixed with catalyst, adds twin-screw extrude and carries out dynamic vulcanization reaction, squeezed out, is granulated,
Obtain conductive thermoplastic dynamic vulcanization silicon rubber.
Preferably, in the preparation method step 1) of this conductive thermoplastic dynamic vulcanization silicon rubber, the technique of melt blending
Parameter is as follows: temperature is 160 DEG C~200 DEG C, and the time is 3min~10min, and revolving speed is 30r/min~100r/min.
Preferably, in the preparation method step 2) of this conductive thermoplastic dynamic vulcanization silicon rubber, double screw extruder
Technological parameter is as follows: processing temperature is 170 DEG C~210 DEG C, and screw speed is 200r/min~320r/min, dynamic vulcanization reaction
Time is 1min~4min.
The beneficial effects of the present invention are:
The conductive good, comfortable feel of the preparation-obtained conductive thermoplastic dynamic vulcanization silicon rubber of the present invention can return
The characteristics such as receipts, excellent in mechanical performance are widely portable to the fields such as electric, automobile, military project, communication.
Compared with prior art, advantages of the present invention is as follows:
1) present invention realizes silicon rubber in thermoplastic under the shear at high temperature effect of extrusion process by dynamic vulcanization technology
Property polyurethane elastomer melt in dynamic crosslinking, while realizing conductive filler in the polymer evenly dispersed, improve material
While expecting electric conductivity, avoids to realize functionalization and reprocessabilty and bring performance are carried out to dynamic vulcanization silicon rubber and damaged
It loses.
2) present invention realizes the biggish thermoplastic polyurethane elastomer of polarity spectrum and silicon rubber by the addition of compatilizer
The thermodynamic compatibility of glue, while the thermodynamic compatibility of organic high molecular material phase and inorganic conductive material phase is realized, thus
So that obtained conductive thermoplastic dynamic vulcanization silicon rubber has excellent mechanical property (tensile strength is up to 20MPa) and leads
Electrical property (volume resistivity is up to 0.1 Ω cm).
3) raw material used in the present invention and process equipment are all the common raw material of industry and equipment, easy to use, cost
It is cheap, it can be achieved that large-scale industrial production, and it is solvent-free, without toxic volatile gaseous contamination, meet environment protection requirement, it is great
Realistic meaning.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment, following embodiment cannot
It is not understood as limitation of the scope of the invention.Raw materials/equipment used in embodiment unless otherwise specified, can be from routine business
Approach obtains.The detection method of Silicone Rubber parameter is standard method of test well known in the art unless otherwise instructed.
Examples 1 to 3 and comparative example 1
The silicon rubber of Examples 1 to 3 and comparative example 1 composition is shown in Table 1, and composition described in table 1 is mass parts.
The silicon rubber of 1 Examples 1 to 3 of table and comparative example 1 composition
The conductive thermoplastic dynamic vulcanization silicon rubber of Examples 1 to 3 the preparation method is as follows:
Step 1) by shown in table 1 formula in thermoplastic polyurethane elastomer (TPU), silicon rubber gross rubber, compatilizer,
Crosslinking agent, conductive filler are added in mixer, and temperature is set as 170 DEG C, revolving speed 40rpm, mixing time 5min, and extrusion is made
Grain obtains pre-composition.Thermoplastic polyurethane elastomer used in Examples 1 to 3 is that the WHT-8285 of Wan Hua chemical company is (poly-
Ether), silicon rubber gross rubber is the EN-5150A of Dong Jue organosilicon company, and compatilizer EVA, crosslinking agent is containing for Dow Corning Corporation
Hydrogen silicone oil, model JHF-901, platinum catalyst are the RD7 platinum catalyst of Dow Corning Corporation, and the conductive filler partial size of selection is
40μm。
Step 2) by the catalyst platinum in formula shown in the resulting pre-composition addition table 1 of step 1, it is added after mixing
Double screw extruder, 190 DEG C, screw speed 250rpm of temperature setting, progress dynamic vulcanization reaction, reaction time 2min,
Extruding pelletization obtains conductive thermoplastic dynamic vulcanization silicon rubber.Obtained conductive thermoplastic dynamic vulcanization silicon rubber appearance is equal
It is even, comfortable feel.
The silicon rubber of comparative example 1 the preparation method is as follows:
According to the technological parameter of Examples 1 to 3, but there is no crosslinking agent and catalyst is added, using non-dynamic vulcanization
Method prepares formula in table 1, obtains sample.
The performance parameter of Examples 1 to 3 and comparative example 1 is shown in Table 2.
The Silicone Rubber parameter of 2 Examples 1 to 3 of table and comparative example 1
By comparison it is found that prepared by the electric conductivity of the Examples 1 to 3 prepared by dynamic vulcanization and non-dynamic vulcanization
Comparative example 1 be not much different, but its mechanical property will be substantially better than comparative example 1.
Embodiment 4~6 and comparative example 2
The silicon rubber of embodiment 4~6 and comparative example 2 composition is shown in Table 3, and composition described in table 3 is mass parts.
The silicon rubber of 3 embodiment 4~6 of table and comparative example 2 composition
The conductive thermoplastic dynamic vulcanization silicon rubber of embodiment 4~6 the preparation method is as follows:
Step 1) by shown in table 3 formula in thermoplastic polyurethane elastomer (TPU), silicon rubber gross rubber, compatilizer,
Crosslinking agent, conductive filler are added in mixer, and temperature is set as 180 DEG C, revolving speed 60rpm, mixing time 7min, and extrusion is made
Grain obtains pre-composition.Thermoplastic polyurethane elastomer used in embodiment 4~6 is that the S-185ALL of Taiwan brothers company is (poly-
Ester), silicon rubber gross rubber is the EN-8151 of Dong Jue organosilicon company, and compatilizer is ethylene acrylic acid co polymer (EAA), crosslinking
Agent is the containing hydrogen silicone oil of Dow Corning Corporation, and model JHF-901, platinum catalyst is the RD7 platinum catalyst of Dow Corning Corporation, institute
The conductive filler partial size of selection is 30 μm.
Step 2) by the catalyst platinum in formula shown in the resulting pre-composition addition table 3 of step 1, it is added after mixing
Double screw extruder, 200 DEG C, screw speed 300rpm of temperature setting, progress dynamic vulcanization reaction, reaction time 3min,
Extruding pelletization obtains conductive thermoplastic dynamic vulcanization silicon rubber.Obtained conductive thermoplastic dynamic vulcanization silicon rubber appearance is equal
It is even, comfortable feel.
The silicon rubber of comparative example 2 the preparation method is as follows:
According to the technological parameter of embodiment 4~6, but there is no compatilizer is added, prepared by formula in table 3, obtained
To sample.
The performance parameter of embodiment 4~6 and comparative example 2 is shown in Table 4.
The Silicone Rubber parameter of table 4 embodiment 4~6 and comparative example 2
By comparison it is found that the properties of the embodiment 4~6 prepared after compatilizer by dynamic vulcanization are added all
It is substantially better than comparative example 2.
Embodiment 7~10 and comparative example 3
The silicon rubber of embodiment 7~10 and comparative example 3 composition is shown in Table 5, and composition described in table 5 is mass parts.
The silicon rubber of 5 embodiment 7~10 of table and comparative example 3 composition
The conductive thermoplastic dynamic vulcanization silicon rubber of embodiment 7~10 the preparation method is as follows:
Step 1) by shown in table 5 formula in thermoplastic polyurethane elastomer (TPU), silicon rubber gross rubber, compatilizer,
Crosslinking agent, conductive filler are added in mixer, and temperature is set as 190 DEG C, revolving speed 80rpm, mixing time 4min, and extrusion is made
Grain obtains pre-composition.Thermoplastic polyurethane elastomer used in embodiment 7~10 is the WHT-8285 of Wan Hua chemical company, silicon
The rubber mixed EN-5150A for Dong Jue organosilicon company, crosslinking agent are the containing hydrogen silicone oil of Dow Corning Corporation, model JHF-
901, platinum catalyst is the RD7 platinum catalyst of Dow Corning Corporation, and selected conductive filler partial size is 10 μm.
Step 2) by the catalyst platinum in formula shown in the resulting pre-composition addition table 5 of step 1, it is added after mixing
Double screw extruder, 210 DEG C, screw speed 320rpm of temperature setting, progress dynamic vulcanization reaction, reaction time 1min,
Extruding pelletization obtains conductive thermoplastic dynamic vulcanization silicon rubber.Obtained conductive thermoplastic dynamic vulcanization silicon rubber appearance is equal
It is even, comfortable feel.
The silicon rubber of comparative example 3 the preparation method is as follows:
Step 1) according to embodiment 7~10 technological parameter, but there is no be added conductive filler, will be formulated in table 5 into
Row preparation, obtains pre-composition.
Step 2) by the conductive filler in formula shown in the pre-composition addition table 5 in step 1, in double screw extruder
It carries out blending extrusion temperature and sets 210 DEG C, screw speed 320rpm, extruding pelletization obtains sample.Due to the formula of comparative example 3
In there is no crosslinking agent and catalytic component, comparative example 3 can be regarded as to be prepared by non-dynamic vulcanization process.
The performance parameter of embodiment 7~10 and comparative example 3 is shown in Table 6.
The Silicone Rubber parameter of table 6 embodiment 7~10 and comparative example 3
By comparison it is found that the properties of the embodiment 7~10 prepared by dynamic vulcanization are all substantially better than pair
Ratio 3.
Embodiment 11~13 and comparative example 4
The silicon rubber of embodiment 11~13 and comparative example 4 composition is shown in Table 7, and composition described in table 7 is mass parts.
The silicon rubber of 7 embodiment 11~13 of table and comparative example 4 composition
The conductive thermoplastic dynamic vulcanization silicon rubber of embodiment 11~13 the preparation method is as follows:
Step 1) by shown in table 7 formula in thermoplastic polyurethane elastomer (TPU), silicon rubber gross rubber, compatilizer,
Crosslinking agent, conductive filler are added in mixer, and temperature is set as 160 DEG C, revolving speed 80rpm, mixing time 3min, and extrusion is made
Grain obtains pre-composition.Thermoplastic polyurethane elastomer used in embodiment 11~13 is the WHT-8285 of Wan Hua chemical company,
Silicon rubber gross rubber is the EN-5150A of Dong Jue organosilicon company, and compatilizer EMA, crosslinking agent is the Silicon Containing Hydrogen of Dow Corning Corporation
Oil, model JHF-901, platinum catalyst are the RD7 platinum catalyst of Dow Corning Corporation, and the partial size of selected conductive black is
0.1μm。
Step 2) by the catalyst platinum in formula shown in the resulting pre-composition addition table 7 of step 1, it is added after mixing
Double screw extruder, 170 DEG C, screw speed 200rpm of temperature setting, progress dynamic vulcanization reaction, reaction time 4min,
Extruding pelletization obtains conductive thermoplastic dynamic vulcanization silicon rubber.Obtained conductive thermoplastic dynamic vulcanization silicon rubber appearance is equal
Even, comfortable feel.
The silicon rubber of comparative example 4 the preparation method is as follows:
Step 1) technological parameter according to embodiment 11~13, but there is no crosslinking agent and catalyst is added, by table 7
Prepared by middle formula, obtain pre-composition.
Step 2) pre-composition in step 1 is subjected to blending extrusion in double screw extruder, temperature sets 170 DEG C,
Screw speed is 200rpm, and extruding pelletization obtains sample.
The performance parameter of embodiment 11~13 and comparative example 4 is shown in Table 8.
The Silicone Rubber parameter of table 8 embodiment 11~13 and comparative example 4
By comparison it is found that carrying out the embodiment 11~13 of dynamic vulcanization preparation using different crosslinking agents and catalyst ratio
Properties be all substantially better than the comparative example 4 of non-dynamic vulcanization process preparation.
Claims (10)
1. a kind of conductive thermoplastic dynamic vulcanization silicon rubber, it is characterised in that: be made of the raw material of following mass parts: thermoplasticity
30~70 parts of polyurethane elastomer, 30~70 parts of silicon rubber gross rubber, 1~30 part of conductive filler, 1~5 part of crosslinking agent, compatilizer
5~20 parts, 0.01~0.5 part of catalyst.
2. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: thermoplastic polyurethane
The shore hardness of elastomer is 60A~95A.
3. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: silicon rubber gross rubber
For the methyl vinyl silicone rubber Jing Guo white carbon black reinforcement.
4. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: conductive filler is charcoal
At least one of black, carbon fiber, graphite powder, graphene, carbon nanotube, carbosphere, silver powder, nickel powder, copper powder.
5. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: crosslinking agent be containing
The siloxanes of Si -- H bond.
6. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: compatilizer is ethylene
At least one of acrylic copolymer, ethylene methyl acrylate copolymer, ethylene-vinyl acetate copolymer.
7. a kind of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 1, it is characterised in that: catalyst is platinum class
Catalyst.
8. a kind of any one of claim 1~7 preparation method of conductive thermoplastic dynamic vulcanization silicon rubber, feature exist
In: the following steps are included:
1) in mixer or extruder, by thermoplastic polyurethane elastomer, silicon rubber gross rubber, conductive filler, crosslinking agent and
Compatilizer melt blending squeezes out, and is granulated, obtains pre-composition；
2) pre-composition is mixed with catalyst, adds twin-screw extrude and carries out dynamic vulcanization reaction, squeezed out, be granulated, obtain
Conductive thermoplastic dynamic vulcanization silicon rubber.
9. a kind of preparation method of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 8, it is characterised in that: step
1) in, the technological parameter of melt blending is as follows: temperature is 160 DEG C~200 DEG C, and the time is 3min~10min, revolving speed 30r/
Min~100r/min.
10. a kind of preparation method of conductive thermoplastic dynamic vulcanization silicon rubber according to claim 8, it is characterised in that: step
It is rapid 2) in, the technological parameter of double screw extruder is as follows: processing temperature be 170 DEG C~210 DEG C, screw speed be 200r/min~
320r/min, dynamic vulcanization reaction time are 1min~4min.
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| CN110564042A (en) * | 2019-09-20 | 2019-12-13 | 深圳市宏商材料科技股份有限公司 | composition for preparing conductive heat-shrinkable composite material, conductive heat-shrinkable composite material and preparation method thereof |
| CN110885491A (en) * | 2019-12-20 | 2020-03-17 | 中南大学湘雅医院 | Conductive photosensitive resin for photocuring 3D printing and preparation method thereof |
| CN112143231A (en) * | 2020-08-21 | 2020-12-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized rubber and preparation method and application thereof |
| CN112143231B (en) * | 2020-08-21 | 2022-03-29 | 北京化工大学 | Silicone rubber/polyurethane thermoplastic vulcanized 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 |
| CN114058187A (en) * | 2021-12-03 | 2022-02-18 | 东莞市蔚美硅材料科技有限公司 | Silicone rubber with low permanent deformation at break and preparation method thereof |
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