CN106009449A - High temperature-resistant oil-resistant thermoplastic vulcanizate and preparation method thereof - Google Patents
High temperature-resistant oil-resistant thermoplastic vulcanizate and preparation method thereof Download PDFInfo
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- CN106009449A CN106009449A CN201610356615.7A CN201610356615A CN106009449A CN 106009449 A CN106009449 A CN 106009449A CN 201610356615 A CN201610356615 A CN 201610356615A CN 106009449 A CN106009449 A CN 106009449A
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
- C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
Abstract
The invention discloses a high temperature-resistant oil-resistant thermoplastic vulcanizate and a preparation method thereof. The high temperature-resistant oil-resistant thermoplastic vulcanizate is prepared from the following main raw materials in parts by mass: 100 parts of rubber, 20 to 90 parts of fluoroplastics, 5 to 20 parts of an anti-hydrolysis agent, 0.5 to 5 parts of a vulcanizing agent and 0.5 to 5 parts of a vulcanizing auxiliary. The preparation method comprises the following steps: uniformly mixing rubber and the anti-hydrolysis agent at room temperature; blending the mixture and the fluoroplastics at 180 to 300 DEG C under mechanical shear conditions; after the mixture and the fluoroplastics are mixed uniformly, cooling a discharged material to the room temperature, and uniformly mixing the discharged material with the vulcanizing agent and the vulcanizing auxiliary; finally, performing dynamic vulcanization on the mixture through a twin-screw extruder to obtain the thermoplastic vulcanizate. The thermoplastic vulcanizate disclosed by the invention has the characteristics that the preparation process is simple; a compatibilizer is not required; the phase state structure is exquisite; the mechanical property is excellent; the hardness is relatively low; the high temperature resistance and the oil resistance are excellent; the high temperature-resistant oil-resistant thermoplastic vulcanizate is recyclable. The high temperature-resistant oil-resistant thermoplastic vulcanizate can be applied to a rubber hose of an automobile, an insulating layer of a wire or a cable, a tool handle and the like instead of conventional thermoplastic rubber.
Description
Technical field
High temperature resistant oil resistant thermoplastic sulfurized rubber that the present invention relates to a kind of dynamic vulcanization and preparation method thereof, belongs to macromolecule
Material processing field.
Background technology
Thermoplastic sulfurized rubber is a kind of special thermoplastic elastomer (TPE) obtained by dynamic vulcanization reacting processing technology.When
When a small amount of plastics phase and substantial amounts of rubber melt blending, rubber issues biochemical crosslinking in cross-linking agent effect, and viscosity increases, therefore
And under the effect that high-temperature machinery is sheared, rubber thermoplastic blend generation phase reversal, substantial amounts of rubber is broken into micron mutually and (or receives
Rice) granule and be scattered in uniformly a small amount of plastics mutually in, form special sea-island structure after rubber cross.This special knot
Structure makes thermoplastic sulfurized rubber have high resiliency and the flexibility of traditional rubber concurrently, also has can processing and can return by thermoplastic of plastics
Receive the performance utilized, the most progressively replace traditional thermoset rubber.
In recent years, along with the development of the industries such as Aero-Space, automobile, machinery, higher wanting is proposed the performance of rubber
Ask, and along with the minimizing of the non-renewable resources such as oil, it is desirable to material is towards environmental protection, and callable direction is developed.Tradition
Oil resistant rubber goods generally use nitrile rubber, neoprene etc., goods not recoverable, and oil resistivity especially high temperature
Under oil resistivity be increasingly difficult to meet the requirement of industry development.Ethylene vinyl acetate rubber, ethylene-acrylate rubber, third
Olefin(e) acid ester rubber has the feature of high temperature resistant oil resistant, and the existence of side base ester group also improves the fire resistance of material.Fluoroplastics
Not only there are high high temperature resistant, oil resistant, insulating properties, and be natural fire proofing, there is the wearability of excellence simultaneously
Energy.Therefore, by the method for dynamic vulcanization, both being prepared as the rubber disperse thermoplastic sulfurized rubber at fluoroplastics matrix, it has
There are the high temperature resistant oil resistant of excellence, insulation, the performance such as wear-resisting.Patent CN 102690479A discloses the polyamides of a kind of dynamic crosslinking
Amine/Ethylene-vinyl acetate rubber thermoplastic elastomer and preparation method thereof, in banbury, mill or screw extruder,
Control blending temperature and be 170-240 DEG C, add polyamide, ethylene vinyl acetate rubber, compatilizer and peroxide cross-linking agent,
It is blended 8-15 minute, the Polyamide/ethylene-vacetate acetate thermoplastic elastomer of dynamic vulcanization can be accessed.Due to poly-
Amide is poor with the compatibility of ethylene vinyl acetate rubber, it is therefore desirable to adds bulking agent, this not only adds cost and make
Preparation technology is more complicated, and prepared thermoplastic elastomer (TPE) is difficulty with fine microstructure；And polyamide facile hydrolysis,
Also limit the application of prepared material.Patent CN 103059401A disclose a kind of Oil resistance thermoplastic elastomer and
Preparation method, is first 1000:0.1～5 by ethylene vinyl acetate (EVM) and vulcanizing agent according to mass ratio, 30 DEG C～200 DEG C
Lower blended, prepare rubber master batch；It is down to room temperature after rubber master batch discharging and pulverizes；Rubber master batch after pulverizing and ethylene vinyl acetate (EVA)
After mix homogeneously, dynamic vulcanization 1～5 minutes at 140～250 DEG C, discharging prepares Oil resistance thermoplastic elastomer.Due to EVA itself
High temperature resistant oil resistance poor, the high temperature resistant oil resistance of therefore prepared thermoplastic elastomer (TPE) is poor, can not meet
Actual use requirement.Patent CN 103396639A discloses a kind of dynamic vulcanization fluoroplastics/fluorubber/silicone rubber thermoplasticity
Elastomer and preparation method thereof, by fluoroplastics, fluorubber, acid-acceptor, silicone rubber and interface modifier the temperature of 175～330 DEG C
After the lower mix homogeneously of degree, under high speed shear, add cross-linking agent with crosslinking coagent, rubber is carried out dynamic vulcanization mutually and obtain product.Fluorine
The compatibility extreme difference of plastics and silicone rubber, therefore to add expensive fluorubber as bulking agent, and silicone rubber itself
Oil resistivity is very poor, and it is not fine that therefore prepared thermoplastic sulfurized rubber exists microstructure, and performance is undesirable, and relatively costly asks
Topic.
Summary of the invention
Present invention aims to prior art and the defect of product existence, it is provided that a kind of high temperature resistant oil resistant thermoplasticity
Vulcanizate and preparation method thereof.Rubber (ethylene vinyl acetate rubber, ethylene-acrylate rubber or the propylene that the present invention selects
Acid esters rubber) and fluoroplastics the most all there is the feature of high temperature resistant oil resistant, and both is compatible preferable, it is not necessary to add increase-volume
Agent.The present invention uses rubber plastic blend, the technology of dynamic vulcanization is prepared into thermoplastic sulfurized rubber and has preparation technology simply, and phase is tied
Structure is fine, excellent in mechanical performance, and hardness is relatively low, high temperature resistant, oil resistance is excellent, the feature of recoverable.
The technical scheme is that a kind of high temperature resistant oil resistant thermoplastic sulfurized rubber of offer, according to the mass fraction, it is main
Composition includes:
Described rubber is ethylene vinyl acetate rubber (vinyl acetate content 40%～80%), ethylene-acrylate
One in rubber (methyl acrylate content 8%～40%) or acrylate rubber.
Described fluoroplastics are polyvinyl fluoride, Kynoar, ethylene-tetrafluoroethylene copolymer, ethylene-chlorinated
One in copolymer, polytrifluorochloroethylene or perfluoroethylene-propylene.
Described hydrolysis-resisting agent is conventional hydrolysis-resisting agent, such as polycarbodiimide (being called for short PCD-50).
Described vulcanizing agent is dual-tert-butyl dicumyl peroxide, cumyl peroxide or dibenzoyl peroxide
In one；Described vulcanization aid is Triallyl isocyanurate (being called for short TAIC) or triallyl cyanurate (abbreviation
TAC) one in.
Described high temperature resistant oil resistant thermoplastic sulfurized rubber, in parts by weight, its composition also includes:
Oxidant 0.5-5；
Plasticizer 5-20；
Age resistor 1-5；
Described antioxidant is conventional antioxidant, such as Hinered phenols antioxidant 1010；Described age resistor is conventional anti-old
Agent, such as 2,2,4-trimethyl-1,2-dihyaroquinoline polymer (RD)；Described plasticizer is Conventional plasticizers, such as paraffin oil.
Present invention also offers the preparation method of a kind of high temperature resistant oil resistant thermoplastic sulfurized rubber, it is characterised in that include with
Lower step:
(1) rubber and plastic premix: under room temperature, by rubber, hydrolysis-resisting agent mix homogeneously；Mix at 180 DEG C～300 DEG C with fluoroplastics
After closing uniformly, discharging is cooled to room temperature；Under room temperature, mix homogeneously with vulcanizing agent and auxiliary curing agent and obtain rubber and plastic pre-composition；
(2) dynamic vulcanization: the rubber and plastic pre-composition of step (1) gained is placed in double screw extruder, temperature 200 DEG C～
330 DEG C, under the conditions of rotating speed 300～700rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
Rubber (ethylene vinyl acetate rubber, ethylene-acrylate rubber or acrylate rubber) selected by the present invention
Not only there is high high temperature resistant, oil resistance with fluoroplastics, between the fluorine atom that carbonyl contained by rubber and fluoroplastics contain simultaneously
Having stronger dipole-dipole interaction, the compatibility making both is preferable, it is not necessary to add bulking agent.The present invention uses rubber and plastic
The thermoplastic sulfurized rubber that premix, dynamic vulcanization technology prepare, not only has the feature that oil resistance is excellent, and still has under high temperature
Having the oil resistivity of excellence, on the one hand, the fluoroplastics strand main chain as matrix is carbon-carbon single bond structure, side base is containing polarized
Fluorine atom, and fluoroplastics have crystallinity, when temperature is less than its fusing point, its lattice is not destroyed, and solvent is difficult to penetrate into densification
Lattice in；On the other hand, the rubber molecule main chain as dispersion phase contains the ester group of polarity without double bond, side base.Additionally, this
It is simple that bright thermoplastic sulfurized rubber also has preparation technology, and Phase stracture is fine, and excellent in mechanical performance, hardness is relatively low, recyclable
The features such as utilization.It is exhausted that the alternative traditional thermoplastic elastomer of thermoplastic sulfurized rubber of the present invention is applied to automotive hose, electric wire
Edge layer, handle for tool etc., have novelty, creativeness and practicality.
Accompanying drawing explanation
Fig. 1. mechanical property change before and after embodiment 2 oil resistant test, wherein 1 is stress strain curve before oil resistant test, and 2 is oil resistant
Test after-drawing curve.Test shows, temperature is at 125 DEG C, after soaking 72h in IRM903 standard oil, thermoplastic sulfurized rubber
Hot strength and elongation at break
Change, less than 10%, illustrates that thermoplastic sulfurized rubber at high temperature has the oil resistivity of excellence.
Fig. 2. the Phase stracture figure of embodiment 2, show that prepared thermoplastic sulfurized rubber has fine microstructure.
Below in conjunction with embodiment, the present invention will be further described:
Detailed description of the invention
Hot strength, elongation at break in embodiment are measured by standard GB/T528-2009, GB/T528-2009 respectively.
High temperature resistant, oil resistance is measured by standard GB/T1690-2010.
Embodiment 1:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by acrylate rubber, PCD-50 mix homogeneously；With the poly-fluorine dried
Ethylene and antioxidant 1010 mix at banbury 200 DEG C, and after mix homogeneously, discharging is cooled to room temperature；Under room temperature, with RD, paraffin
Oil, dual-tert-butyl dicumyl peroxide and triallyl cyanurate mix homogeneously in mill obtain rubber and plastic premix
Thing；
(2) dynamic vulcanization: rubber and plastic pre-composition is placed in double screw extruder (Nanjing Rubber & Plastics Machinery Plant Co., Ltd., HTS-
40, lower same) in, arranging extruder temperature is 220 DEG C, and rotating speed is 300rpm, and dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic vulcanizates
Glue.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
Embodiment 2:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by ethylene vinyl acetate rubber, PCD-50 mix homogeneously；With drying
Kynoar and antioxidant 1010 mix at banbury 180 DEG C, after mix homogeneously, discharging is cooled to room temperature；Under room temperature,
Mix homogeneously in mill with RD, paraffin oil, cumyl peroxide and Triallyl isocyanurate and obtain rubber and plastic premix
Thing；
(2) dynamic vulcanization: be placed in double screw extruder by rubber and plastic pre-composition, arranges extruder temperature 200 DEG C, rotating speed
700rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
Embodiment 3:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by ethylene vinyl acetate rubber, PCD-50 mix homogeneously；With second
Alkene-TFE copolymer and antioxidant 1010 mix at banbury 300 DEG C, and after mix homogeneously, discharging is cooled to room temperature；Room
Under temperature, mix homogeneously in mill with RD, paraffin oil, dual-tert-butyl dicumyl peroxide and triallyl cyanurate
Obtain rubber and plastic pre-composition；
(2) dynamic vulcanization: be placed in double screw extruder by rubber and plastic pre-composition, arranges extruder temperature 330 DEG C, rotating speed
500rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
Embodiment 4:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by ethylene vinyl acetate rubber (vinyl acetate content 60%),
PCD-50 mix homogeneously；Mix at banbury 260 DEG C with the ethylene-chlorotrifluoro-ethylene copolymer dried and antioxidant 1010,
After mix homogeneously, discharging is cooled to room temperature；Under room temperature, with RD, paraffin oil, cumyl peroxide and triallyl isocyanuric acid
Ester mix homogeneously in mill obtains rubber and plastic pre-composition；
(2) dynamic vulcanization: be placed in double screw extruder by rubber and plastic pre-composition, arranges extruder temperature 270 DEG C, rotating speed
400rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
Embodiment 5:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by ethylene-acrylate rubber (methyl acrylate content 35%),
PCD-50 mix homogeneously；Mix, after mix homogeneously at banbury 260 DEG C with the polytrifluorochloroethylene dried and antioxidant 1010
Discharging is cooled to room temperature；Under room temperature, with RD, paraffin oil, dibenzoyl peroxide and triallyl cyanurate in mill
Mix homogeneously obtains rubber and plastic pre-composition；
(2) dynamic vulcanization: be placed in double screw extruder by rubber and plastic pre-composition, arranges extruder temperature 240 DEG C, rotating speed
500rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
Embodiment 6:
The raw material composition selected and mass fraction are as follows:
The preparation technology of thermoplastic sulfurized rubber:
(1) rubber plastic blend: under room temperature, with mill by ethylene-acrylate rubber (methyl acrylate content 10%),
PCD-50 mix homogeneously；Mix at 280 DEG C in banbury with the perfluoroethylene-propylene dried and antioxidant 1010, mix homogeneously
Rear discharging is cooled to room temperature；Under room temperature, with RD, paraffin oil, dibenzoyl peroxide and Triallyl isocyanurate in mill
In machine, mix homogeneously obtains rubber and plastic pre-composition；
(2) dynamic vulcanization: be placed in double screw extruder by rubber and plastic pre-composition, arranges extruder temperature 300 DEG C, rotating speed
600rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
TPV becomes thin slice thick for 2mm test performance according to standard press, and performance is shown in Table 1.
The physical properties of table 1 thermoplastic sulfurized rubber
Above-mentioned table 1 data show, the high temperature resistant oil resistant thermoplastic sulfurized rubber prepared by the present invention at high temperature has excellence
Oil resistance, and hardness is relatively low, and expression surface is smooth, is the most excellent material of a kind of high temperature resistant oil resistance.
Claims (6)
1. a high temperature resistant oil resistant thermoplastic sulfurized rubber, it is characterised in that according to the mass fraction, it mainly comprises and includes:
Wherein, described rubber is the ethylene vinyl acetate rubber of vinyl acetate content 40%～80%, acrylic acid methyl ester.
One in the ethylene-acrylate rubber of content 8%～40% or acrylate rubber；
Described fluoroplastics are polyvinyl fluoride, Kynoar, ethylene-tetrafluoroethylene copolymer, ethylene-chlorinated copolymerization
One in thing, polytrifluorochloroethylene or perfluoroethylene-propylene.
High temperature resistant oil resistant thermoplastic sulfurized rubber the most according to claim 1, it is characterised in that described hydrolysis-resisting agent is poly-
Carbodiimides.
High temperature resistant oil resistant thermoplastic sulfurized rubber the most according to claim 1, it is characterised in that described vulcanizing agent is double uncles
One in butyl peroxy diisopropyl benzene, cumyl peroxide or dibenzoyl peroxide；Described vulcanization aid is
One in Triallyl isocyanurate or triallyl cyanurate.
High temperature resistant oil resistant thermoplastic sulfurized rubber the most according to claim 1, it is characterised in that described component also includes:
Oxidant 0.5-5；
Plasticizer 5-20；
Age resistor 1-5.
High temperature resistant oil resistant thermoplastic sulfurized rubber the most according to claim 4, it is characterised in that described antioxidant is hindered phenol
Kind antioxidant 1010；Described age resistor is 2,2,4-trimethyl-1,2-dihyaroquinoline polymer；Described plasticizer is stone
Wax oil.
The preparation method of high temperature resistant oil resistant thermoplastic sulfurized rubber the most according to claim 1, it is characterised in that include following
Step:
(1) rubber and plastic premix: at room temperature, by rubber, hydrolysis-resisting agent mix homogeneously；Mix at 180 DEG C～300 DEG C with fluoroplastics
After uniformly, discharging is cooled to room temperature；Under room temperature, mix homogeneously with vulcanizing agent and auxiliary curing agent and obtain rubber and plastic pre-composition；
(2) dynamic vulcanization: be placed in double screw extruder by the rubber and plastic pre-composition of step (1) gained, in temperature 200 DEG C～330
DEG C, under the conditions of rotating speed 300～700rpm, dynamic vulcanization obtains high temperature resistant oil resistant thermoplastic sulfurized rubber.
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| CN107446280A (en) * | 2017-08-09 | 2017-12-08 | 芜湖新农夫机械有限公司 | A kind of sulfuration type perfluoroethylene-propylene CABLE MATERIALS and its manufacturing process |
| CN107932609A (en) * | 2017-12-14 | 2018-04-20 | 维达纸业(浙江)有限公司 | A kind of wastepaper collecting device of papermaking cutting machine |
| CN108164897A (en) * | 2017-12-27 | 2018-06-15 | 安徽省二邦化工有限公司 | A kind of oil resistant synthetic resin and preparation method thereof |
| CN108752720A (en) * | 2018-05-02 | 2018-11-06 | 苏州耐思特塑胶有限公司 | A kind of soft coaxial cable sheath material of high flame retardant and preparation method thereof |
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| CN115260680A (en) * | 2022-08-05 | 2022-11-01 | 宁波博思特高分子材料科技有限公司 | High-weather-resistance TPV composite material and preparation method thereof |
| CN115304876A (en) * | 2022-08-05 | 2022-11-08 | 宁波博思特高分子材料科技有限公司 | High-elasticity TPV composite material and preparation method thereof |
| CN115490952A (en) * | 2022-10-09 | 2022-12-20 | 道恩高材(北京)科技有限公司 | Fluorine rubber/fluoroplastic thermoplastic vulcanized rubber and preparation method thereof |
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