CN105255026B - A kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof - Google Patents
A kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof Download PDFInfo
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- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- B29C2948/92704—Temperature
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- C08L2205/00—Polymer mixtures characterised by other features
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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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Abstract
The present invention relates to a kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof.Method by the way that butyl rubber, bifunctional compound, radical initiator are mixed at high temperature, prepare the butyl rubber of bifunctional compound graft modification, then by the use of the butyl rubber of graft modification as bulking agent, premixed using rubber and plastic, the butyl rubber with excellent physical mechanical property, air-tightness, hardness etc./polyamide thermoplastic vulcanizate is prepared in the technology of dynamic vulcanization.
Description
Technical field：
The present invention relates to a kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof.Belong to
Polymeric material 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 is with substantial amounts of rubber melt blending, rubber issues biochemical crosslinking in crosslinking agent effect, and viscosity increases, therefore
And be broken into micron-sized rubber grain under strong mechanical shearing effect, ultimately form using rubber as dispersed phase and using plastics as
The special Phase stracture of continuous phase.This special construction causes thermoplastic sulfurized rubber to have the high resiliency and softness of traditional rubber concurrently
Property, also with plastics can thermoplastic processing and recoverable performance.
Can not be too high it is necessary to have certain mechanical property, hardness as tyre airtight layer material, it is most important that to have
Excellent gas barrier property.Butyl rubber and polyamide are all the very excellent materials of air-tightness, and both pass through dynamic vulcanization
The thermoplastic sulfurized rubber that technique is prepared has excellent air-tightness, can be applied to tyre airtight layer, refrigeration hoses or resistance
Gas material lining etc..Compared with traditional thermosetting tyre airtight layer, its quality is lighter, and air-tightness is more preferable.But butyl rubber
It is poor with polyamide-compatible, therefore, for butyl rubber/polyamide system, improve the compatibility of the two and reduce hard
Degree is difficult point place.Generally in butyl rubber/polyamide TPV preparation process, we can add bulking agent to improve both
Compatibility, to obtain product of good performance.The A of patent CN 102964702 disclose a kind of polyamide/brombutyl heat
Thermoplastic elastic and its production and use, it is by brombutyl and ternary polymerization polyamide dynamic sulphur in banbury
Change, respectively using the pungent dilute copolymer (POE-g-MAH) of haloflex (CPE) and maleic anhydride grafted polyethylene as bulking agent,
But gained thermoplastic sulfurized rubber Dispersed Phase Size is larger, and Phase stracture is not fine.The A of patent CN 103030895 disclose one kind
Thermoplastic sulfurized rubber of high gas-obstructing character energy and preparation method thereof, is added in the system of chlorinated scoline/polyamide 12
Make bulking agent (chlorinated scoline, polyisobutene, " pre-composition " of maleic anhydride) by oneself, power is made in dynamic vulcanization in twin-screw
Learn performance and the more excellent thermoplastic sulfurized rubber of gas barrier property.Above patent of invention by add the method for compatilizer come
TPV performance is improved, but compatibilization effect can't reach industrial high request.The present invention is by using difunctionality dough
Compound graft modification butyl rubber is as bulking agent, and by dynamic vulcanization technology, physical and mechanical property, airtight has been prepared
Property, hardness etc. are superior to the thermoplastic sulfurized rubber of prior art.
The content of the invention：
It is an object of the invention to provide a kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and its preparation side
Method.Method by the way that butyl rubber, bifunctional compound, radical initiator are mixed at high temperature, prepares difunctionality
The butyl rubber of dough compound graft modification, then by the use of the butyl rubber of graft modification as bulking agent, premixed, moved using rubber and plastic
Butyl rubber/polyamide thermoplastic with physical and mechanical properties such as excellent air-tightness, hardness is prepared in the technology of state vulcanization
Vulcanizate.
A kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate provided by the invention, it is formed substantially and matter
It is as follows to measure number：
Wherein make the butyl rubber that bulking agent is bifunctional compound graft modification under radical initiator effect by oneself,
The mass ratio of butyl rubber, bifunctional compound and radical initiator is 100：0.01-20：0.01-5.
Described bifunctional compound is a kind of small molecule monomer containing A and B Liang Zhong functional groups, and A functional groups are certainly
By can be reacted in the presence of base initiator with butyl rubber, B functional groups can occur anti-with the Amino End Group in polyamide
Should.Bifunctional compound is selected from GMA, 1,2- butadiene monoxides or acrylic anhydride.Described free radical draws
It is cumyl peroxide or dibenzoyl peroxide to send out agent.
Bulking agent is made by oneself to prepare using following method：Butyl rubber, bifunctional compound, radical initiator are existed
Melting mixing is reacted 3~20 minutes at 150 DEG C~230 DEG C, obtains the butyl rubber self-control bulking agent of graft modification.
Described butyl rubber is without one kind in haLobutyl rubbers, chlorinated scoline or brombutyl；It is described
Polyamide be polyamide 1010, polyamide 12 or polyamide 1212.
Described antioxidant is Hinered phenols antioxidant 1010；Age resistor is 2,2,4- trimethyl -1,2- dihyaroquinolines
Condensate (RD)；Vulcanizing agent is zinc oxide ZnO；Vulcanization aid is N, a N '-penylene BMI (HVA-2).
Present invention also offers the method that above-mentioned reactive compatibilization prepares butyl rubber/polyamide thermoplastic vulcanizate, its
Preparation method concretely comprises the following steps：
(1) by butyl rubber, bifunctional compound, radical initiator, melting mixing is reacted at 150 DEG C~230 DEG C
3~20 minutes, obtain the butyl rubber self-control bulking agent of graft modification；
(2) rubber and plastic premixes：The polyamide of drying is mixed at 180 DEG C~210 DEG C with butyl rubber first, in proportion plus
Enter the self-control bulking agent obtained in antioxidant and step (1), uniformly rear discharging to be mixed is cooled to room temperature；Then again at room temperature
It is well mixed to obtain rubber and plastic pre-composition with age resistor, plasticizer, vulcanizing agent and vulcanization aid；
(3) dynamic vulcanization：Rubber and plastic pre-composition obtained by step (2) is placed in screw extruder, 180 DEG C of extruder temperature is set
~210 DEG C, rotating speed is 300~700rpm, and dynamic vulcanization obtains butyl rubber/polyamide thermoplastic vulcanizate.
It is an advantage of the invention that bifunctional compound graft modification butyl rubber is employed as bulking agent, using rubber and plastic
The high gas that physical and mechanical property, air-tightness, hardness etc. are superior to existing patent has been prepared in premix, dynamic vulcanization technology
Body obstructs thermoplastic sulfurized rubber.
Nonpolar butyl rubber and the polyamide-compatible of polarity are poor, and how to improve both compatibilities is also to prepare height
The key technology of gas barrier thermoplastic sulfurized rubber.The bifunctional compound that the present invention uses is that one kind contains two kinds of officials of A and B
The small molecule monomer that can be rolled into a ball, A functional groups can react in the presence of radical initiator with butyl rubber to be graft-polymerized
Thing；B functional groups can react with the Amino End Group in polyamide, serve the effect of reactive compatibilization.It is and pre- using rubber and plastic
The high gas that physical and mechanical property, air-tightness, hardness etc. are superior to existing patent has been prepared in the mixed, technology of dynamic vulcanization
Body obstructs thermoplastic sulfurized rubber, has novelty and practicality.
Brief description of the drawings：
Accompanying drawing 1 is the back scattering scanning electron microscopic picture of embodiment 2.
Accompanying drawing 2 is the back scattering scanning electron microscopic picture of comparative example 2.
Dark parts are rubber phase in figure, and light-colored part is plastics phase.It can be seen that it is not added with graft modification chlorination
The microstructure for the TPV that polyamide obtains with chlorinated scoline dynamic vulcanization is more coarse during butyl rubber (bulking agent), rubber
Glue dispersed phase size is about 8 μm；And the TPV that polyamide obtains with chlorinated scoline dynamic vulcanization after addition self-control bulking agent
Phase stracture is more fine, and the size of dispersed phase is about 3 μm, illustrates that the butyl rubber of bifunctional compound graft modification can be with
The compatibilization of polyamide and chlorinated scoline system is functioned well as, it is fine, of good performance to be advantageous to preparation structure
TPV。
With reference to embodiment, the present invention will be further described：
Embodiment：
Tensile strength, elongation at break and Shao A hardness in embodiment press following standard GB/T528-2009, GB/ respectively
T528-2009 and GB/T531.1-2008 measure.Gas permeability coefficient is by ISO2782 standards (self-control automatic air tightness testing
Instrument) gas barrier property test is carried out, test condition is：40 DEG C, N2Atmosphere.
Embodiment 1：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Without haLobutyl rubbers 100；
GMA 0.01；
Cumyl peroxide 1
, first will be without haLobutyl rubbers, GMA, cumyl peroxide in Haake by above-mentioned formula
At 150 DEG C of banbury melting mixing react 5 minutes, obtain graft modification without haLobutyl rubbers；Then by the polyamide of drying
1010 mix with without haLobutyl rubbers at 190 DEG C, be proportionally added into graft modification without haLobutyl rubbers and antioxidant etc., treat
Discharging is cooled to room temperature after well mixed；Then mixed with age resistor, plasticizer, vulcanizing agent and vulcanization aid at normal temperatures again
It is even to obtain rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in screw extruder, it is 210 DEG C to set curing temperature, and rotating speed is
300rpm, dynamic vulcanization obtain butyl rubber/polyamide thermoplastic vulcanizate.TPV according to standard press into thin slice thick 2mm simultaneously
Test performance, performance are shown in Table 1.
Comparative example 1
By embodiment 1 formula but be added without bifunctional compound graft modification without haLobutyl rubbers (increase-volume
Agent), prepare TPV using same method dynamic vulcanization under the same conditions, according to standard press into thin slice thick 2mm simultaneously
Test performance, performance are shown in Table 1.
Embodiment 2：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Chlorinated scoline 100
1,2- butadiene monoxides 0.5
Cumyl peroxide 0.1
By above-mentioned formula, first by chlorinated scoline, 1,2- butadiene monoxides, cumyl peroxide in Haake banburies
Melting mixing is reacted 8 minutes at 170 DEG C, obtains the chlorinated scoline of graft modification；Then by the polyamide 1212 of drying with
Chlorinated scoline mixes at 200 DEG C, is proportionally added into chlorinated scoline and antioxidant of graft modification etc., to be mixed equal
Discharging is cooled to room temperature after even；Then it is well mixed to obtain with age resistor, plasticizer, vulcanizing agent and vulcanization aid at normal temperatures again
Rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in screw extruder, it is 200 DEG C, rotating speed 500rpm to set curing temperature, dynamic
Vulcanization obtains butyl rubber/polyamide thermoplastic vulcanizate.Thin slices and test performance of the TPV according to standard press into 2mm thickness, property
1 can be shown in Table.
Comparative example 2
By the formula of embodiment 2 but the chlorinated scoline of bifunctional compound graft modification is added without, identical
Under conditions of using same method dynamic vulcanization prepare TPV, according to standard press into thick 2mm thin slice and test performance,
Performance is shown in Table 1.
Embodiment 3：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Brombutyl 100
Acrylic anhydride 5
Cumyl peroxide 3
By above-mentioned formula, first by brombutyl, acrylic anhydride, cumyl peroxide in 190 DEG C of Haake banburies
Lower melting mixing is reacted 10 minutes, obtains the brombutyl of graft modification；Then by the polyamide 12 of drying and bromination fourth
Base rubber mixes at 210 DEG C, is proportionally added into brombutyl and antioxidant of graft modification etc., it is to be mixed uniformly after go out
Material is cooled to room temperature；Then it is well mixed with age resistor, plasticizer, vulcanizing agent and vulcanization aid to obtain rubber and plastic at normal temperatures again pre-
Mixed thing；Rubber and plastic pre-composition is placed in screw extruder, it is 190 DEG C to set curing temperature, and rotating speed 700rpm, dynamic vulcanization obtains
To butyl rubber/polyamide thermoplastic vulcanizate.TPV is shown in Table according to standard press into thick 2mm thin slice and test performance, performance
1。
Embodiment 4：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Without haLobutyl rubbers 100
Acrylic anhydride 10
Dibenzoyl peroxide 0.01
, first will be without haLobutyl rubbers, acrylic anhydride, dibenzoyl peroxide in 210 DEG C of Haake banburies by above-mentioned formula
Lower melting mixing is reacted 15 minutes, obtain graft modification without haLobutyl rubbers；Then by the polyamide 12 of drying and Halogen fourth
Base rubber mixes at 180 DEG C, be proportionally added into graft modification without haLobutyl rubbers and antioxidant etc., it is to be mixed uniformly after go out
Material is cooled to room temperature；Then it is well mixed with age resistor, plasticizer, vulcanizing agent and vulcanization aid to obtain rubber and plastic at normal temperatures again pre-
Mixed thing；Rubber and plastic pre-composition is placed in screw extruder, it is 200 DEG C to set curing temperature, and rotating speed 700rpm, dynamic vulcanization obtains
To butyl rubber/polyamide thermoplastic vulcanizate.TPV is shown in Table according to standard press into thick 2mm thin slice and test performance, performance
1。
Embodiment 5：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Chlorinated scoline 100
GMA 15
Dibenzoyl peroxide 5
By above-mentioned formula, first by chlorinated scoline, GMA, dibenzoyl peroxide in Haake
Melting mixing is reacted 3 minutes at 230 DEG C of banbury, obtains the chlorinated scoline of graft modification；Then by the polyamide of drying
1010 mix with chlorinated scoline at 185 DEG C, are proportionally added into chlorinated scoline and antioxidant of graft modification etc., treat
Discharging is cooled to room temperature after well mixed；Then mixed with age resistor, plasticizer, vulcanizing agent and vulcanization aid at normal temperatures again
It is even to obtain rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in screw extruder, it is 185 DEG C to set curing temperature, and rotating speed is
600rpm, dynamic vulcanization obtain butyl rubber/polyamide thermoplastic vulcanizate.TPV according to standard press into thin slice thick 2mm simultaneously
Test performance, performance are shown in Table 1.
Embodiment 6：
The raw material of selection form as follows with mass fraction substantially：
Wherein make by oneself bulking agent basic composition and mass ratio be：
Brombutyl 100
1,2- butadiene monoxides 20
Dibenzoyl peroxide 1
By above-mentioned formula, first by brombutyl, 1,2- butadiene monoxides, dibenzoyl peroxide in Haake banburies
Melting mixing is reacted 20 minutes at 200 DEG C, obtains the brombutyl of graft modification；Then by the polyamide 1212 of drying with
Brombutyl mixes at 195 DEG C, is proportionally added into brombutyl and antioxidant of graft modification etc., to be mixed equal
Discharging is cooled to room temperature after even；Then it is well mixed to obtain with age resistor, plasticizer, vulcanizing agent and vulcanization aid at normal temperatures again
Rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in screw extruder, it is 180 DEG C, rotating speed 500rpm to set curing temperature, dynamic
Vulcanization obtains butyl rubber/polyamide thermoplastic vulcanizate.Thin slices and test performance of the TPV according to standard press into 2mm thickness, property
1 can be shown in Table.
The performance comparision of the embodiment of the present invention of table 1 and comparative example
In the contrast of above-mentioned table 1, comparative example 1,2 is corresponding with embodiment 1,2 respectively, and comparative example 1 does not have compared to embodiment 1
Bulking agent (bifunctional compound graft modification butyl rubber) is added, comparative example 2 is no compared to embodiment 2 to add bulking agent,
As a result show add bulking agent after butyl rubber/polyamide thermoplastic vulcanizate physical and mechanical property and air-tightness all improve,
Hardness reduces, and surface polishes, and illustrates that the self-control bulking agent that the present invention uses has preferable compatibilization effect.
It is that performance is best in existing product using product made from the technology in the A of patent CN 103030895.By
Compare it was found that the product (embodiment 2~6) being prepared using the technology of the present invention is in tensile strength and elongation at break
On all show more outstanding, hardness is relatively low and significant airtight sexual clorminance (air transmission coefficient is small).
Claims (5)
1. a kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate, it is formed substantially and mass fraction is：
Wherein make the butyl rubber that bulking agent is bifunctional compound graft modification under radical initiator effect, butyl by oneself
The mass ratio of rubber, bifunctional compound and radical initiator is 100：0.01-20：0.01-5；
Described bifunctional compound is GMA, 1,2- butadiene monoxides or acrylic anhydride；It is described from
It is cumyl peroxide or dibenzoyl peroxide by base initiator；
Described self-control bulking agent is prepared using following method：Butyl rubber, bifunctional compound, radical initiator are existed
Melting mixing is reacted 3~20 minutes at 150 DEG C~230 DEG C, obtains the butyl rubber self-control bulking agent of graft modification.
2. reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate according to claim 1, it is characterised in that institute
The butyl rubber stated is without haLobutyl rubbers, chlorinated scoline or brombutyl.
3. reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate according to claim 1, it is characterised in that institute
The polyamide stated is selected from polyamide 1010, polyamide 12 or polyamide 1212.
4. reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate according to claim 1, it is characterised in that institute
The antioxidant stated is Hinered phenols antioxidant 1010；Age resistor is 2,2,4- trimethyl -1,2- dihyaroquinoline condensates；Plasticising
Agent is paraffin oil；Vulcanizing agent is zinc oxide；Vulcanization aid is N, a N '-penylene BMI.
5. a kind of preparation method of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate described in claim 1, specifically
Step is：
(1) by butyl rubber, bifunctional compound, radical initiator at 150 DEG C~230 DEG C melting mixing reaction 3~
20 minutes, obtain the butyl rubber self-control bulking agent of graft modification；
(2) rubber and plastic premixes：Polyamide is mixed at 180 DEG C~210 DEG C with butyl rubber, is proportionally added into antioxidant and step
(1) the self-control bulking agent obtained, uniformly rear discharging to be mixed are cooled to room temperature；Then again at room temperature with age resistor, plasticizer,
Vulcanizing agent and vulcanization aid, which are well mixed, obtains rubber and plastic pre-composition；
(3) dynamic vulcanization：Rubber and plastic pre-composition obtained by step (2) is placed in screw extruder, set extruder temperature be 180 DEG C~
210 DEG C, rotating speed is 300~700rpm, and dynamic vulcanization obtains reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate.
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| CN107955277B (en) * | 2016-10-14 | 2020-07-21 | 中国石油化工股份有限公司 | Rubber product and preparation method thereof |
| CN109422970B (en) * | 2017-09-04 | 2020-05-22 | 北京化工大学 | High-gas-barrier thermoplastic vulcanized rubber and preparation method thereof |
| CN109988368A (en) * | 2019-05-05 | 2019-07-09 | 淮安瑞祥新材料有限公司 | A kind of dynamic-vulcanization thermoplastic sizing material and preparation method thereof |
| CN110041632B (en) * | 2019-05-05 | 2022-01-28 | 淮安瑞祥新材料有限公司 | High-performance dynamically vulcanized thermoplastic elastomer and preparation method thereof |
| CN113929913B (en) * | 2021-10-19 | 2022-10-25 | 福建师范大学 | Bismaleimide/polyether siloxane resin and preparation method thereof |
| CN113943461A (en) * | 2021-11-05 | 2022-01-18 | 道恩高材(北京)科技有限公司 | Temperature-resistant high-gas-barrier dynamic vulcanization alloy for tire inner liner |
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| CN103788515A (en) * | 2014-01-21 | 2014-05-14 | 北京化工大学 | Thermoplastic vulcanizate having high gas barrier property and preparation method of thermoplastic vulcanizate |
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| CN103788515A (en) * | 2014-01-21 | 2014-05-14 | 北京化工大学 | Thermoplastic vulcanizate having high gas barrier property and preparation method of thermoplastic vulcanizate |
| CN104513434A (en) * | 2014-11-27 | 2015-04-15 | 北京化工大学 | Butyl rubber/long carbon chain polyamide thermoplastic vulcanized rubber and preparation method thereof |
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