CN109422968A - A kind of high gas-obstructing character thermoplastic sulfurized rubber and preparation method thereof - Google Patents
A kind of high gas-obstructing character thermoplastic sulfurized rubber and preparation method thereof Download PDFInfo
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- CN109422968A CN109422968A CN201710728157.XA CN201710728157A CN109422968A CN 109422968 A CN109422968 A CN 109422968A CN 201710728157 A CN201710728157 A CN 201710728157A CN 109422968 A CN109422968 A CN 109422968A
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- polypropylene
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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
- C08L23/26—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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- 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
- C08K3/18—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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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
Abstract
The present invention relates to a kind of high gas-obstructing character halogenated butyl rubber/polypropylene/Nylon thermoplastic sulfurized rubbers and preparation method thereof.Thermoplastic sulfurized rubber primary raw material group becomes halobutyl polypropylene thermoplastic elastomer, polypropylene grafted maleic anhydride, nylon and antioxidant, and wherein halobutyl polypropylene thermoplastic elastomer is obtained by halogenated butyl rubber, polypropylene and vulcanizing agent dynamic vulcanization.Halogenated butyl rubber produced by the present invention/polypropylene/Nylon thermoplastic sulfurized rubber has fine Micro-Structure and excellent physical and mechanical property, air-tightness, hardness etc..
Description
Technical field
The invention belongs to polymeric material fields, and in particular to and a kind of high gas-obstructing character halogenated butyl rubber/polypropylene/
Nylon thermoplastic's vulcanizate and preparation method thereof.
Background technique
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 a large amount of rubber melt blending, rubber issues biochemical crosslinking in crosslinking action, and viscosity increases, therefore
And it is broken into micron-sized rubber grain under strong mechanical shearing effect, it ultimately forms using rubber as dispersed phase and is with plastics
The special Phase stracture of continuous phase.This special construction makes thermoplastic sulfurized rubber have both the high resiliency and softness of traditional rubber
Property, also with plastics can thermoplastic processing and recoverable performance, gradually replace traditional thermoset rubber.
Butyl rubber and nylon mix and the thermoplastic sulfurized rubber for passing through dynamic crosslinking preparation has preferable physical mechanical
Performance and air-tightness also have the characteristics that workability and repeatable processability, and it is soft to be mainly used in tyre airtight layer, refrigerator
Pipe or rental period material lining etc..Compared with traditional thermosetting property tyre airtight layer, quality is lighter, and air-tightness is more preferable.However fourth
Base rubber and nylon compatibility are poor, and therefore, for butyl rubber/nylon system, the compatibility for improving the two is difficult point
Place.The rubber of crosslinking can be made to be not easy to be cut into uniform and tiny dispersion particle if rubber and plastic two-phase poor compatibility,
It finally will affect the Micro-Structure of thermoplastic sulfurized rubber.Usually in butyl rubber/nylon TPV preparation process, we
Expanding material can be added to improve the two compatibility, to obtain product of good performance.Patent CN102964702A discloses one kind
Polyamide/halogenated butyl rubber thermoplastic elastomer (TPE) and its preparation method and application, by halogenated butyl rubber and ternary polymerization
Polyamide dynamic vulcanization in mixer, respectively with haloflex (CPE) and the pungent dilute copolymer of maleic anhydride grafted polyethylene
(POE-g-MAH) it is used as expanding material, but the patent is not apparent from the problem for improving butyl rubber and nylon compatibility difference, and obtained
There are the higher problems of hardness for thermoplastic sulfurized rubber.Patent CN 105255026A discloses a kind of reactive compatibilization and prepares butyl
Rubber/polyamide thermoplastic vulcanizate and preparation method thereof uses the butyl rubber of bifunctional compound graft modification to make
For expanding material, but gained thermoplastic sulfurized rubber Dispersed Phase Size is relatively large, and Phase stracture is not fine, and compatibilization effect can't
Reach industrial high request.
Summary of the invention
In order to solve problem above, halogenated butyl rubber, polypropylene, vulcanizing agent are passed through dynamic vulcanization skill first by the present invention
Art prepares halogenated butyl rubber/polypropylene thermoplastic vulcanizate that compatibility is preferable and Phase stracture is fine；Then again by it
With a certain amount of nylon and polypropylene grafted maleic anhydride melt blending, it has been prepared with fine Micro-Structure,
The halogenated butyl rubber of excellent physical mechanical property, air-tightness, hardness etc./polypropylene/Nylon thermoplastic sulfurized rubber.
An object of the present invention is to provide a kind of high gas-obstructing character halogenated butyl rubber/polypropylene/Nylon thermoplasticity
Vulcanizate is prepared by the raw material comprising following components, in parts by weight:
Wherein the halobutyl polypropylene thermoplastic elastomer is obtained by including the raw material dynamic vulcanization of following components,
In parts by weight:
100 parts of halogenated butyl rubber；
10-80 parts of polypropylene；It is preferred that 15-65 parts；
1-5 parts of vulcanizing agent；It is preferred that 2-4 parts.
The halogenated butyl rubber is selected from chlorinated scoline, brombutyl or brominated isobutylene-to methylbenzene second
At least one of alkene copolymer.
The vulcanizing agent may be selected vulcanizing agent commonly used in the art, preferably phenolic resin, zinc oxide, stearic acid, N, between N'-
At least one of penylene bismaleimide.
The halobutyl polypropylene thermoplastic elastomer is made using following steps:
(1) it requires to weigh each component according to the proportion；
(2) rubber and plastic premixes: polypropylene is mixed with halogenated butyl rubber first, is preferably mixed at 150~200 DEG C, to
Discharging is cooled to room temperature after mixing；Then it is uniformly mixed to obtain rubber and plastic pre-composition with vulcanizing agent at normal temperature again；
(3) rubber and plastic pre-composition dynamic vulcanization obtained by step (2) dynamic vulcanization: is obtained into the halobutyl polypropylene thermoplastic
Property elastomer.
Wherein, dynamic vulcanization can carry out in the process equipment that the prior art uses, and be preferably disposed in double screw extruder,
150~200 DEG C of extruder temperature of setting, revolving speed are 300~700rpm.
The nylon is selected from one of nylon 6, nylon66 fiber, nylon 1010, nylon 12 or terpolyamide or several
Kind.
Antioxidant commonly used in the art may be selected in the antioxidant, preferably such as Hinered phenols antioxidant 1010.
In high gas-obstructing character thermoplastic sulfurized rubber of the invention, it can also be needed to add paraffin oil, RL16 according to processing
Etc. various auxiliary agents, dosage is conventional amount used, or requirement according to the actual situation is adjusted.
The second object of the present invention is to providing a kind of high gas-obstructing character halogenated butyl rubber/polypropylene/Nylon thermoplasticity sulphur
The preparation method for changing glue, including by the nylon of the amount, polypropylene grafted maleic anhydride, antioxidant and halobutyl polypropylene thermal
Thermoplastic elastic melt blending.
Preferably, specific steps include: by the nylon of drying, polypropylene grafted maleic anhydride, antioxidant and halobutyl
Polypropylene thermoplastic elastomer is put into melt blending in double screw extruder, is arranged 170 DEG C~220 DEG C of extruder temperature, head temperature
Degree is 200 DEG C, and revolving speed is 300~700rpm, obtains high performance halogenated butyl rubber/polypropylene/Nylon thermoplastic sulfurized rubber.
It is an advantage of the invention that rubber and plastic premix, dynamic vulcanization technology is used to be prepared for first, compatibility is good and Phase stracture essence
Thin halogenated butyl rubber/polypropylene thermoplastic vulcanizate；Then again by itself and a certain amount of nylon and polypropylene grafted Malaysia
Acid anhydrides melt blending has been prepared with fine Micro-Structure, excellent physical mechanical property, air-tightness, hardness etc.
Aspect is superior to the high gas barrier thermoplastic sulfurized rubber of existing patent.
Nonpolar butyl rubber and polar polyamide-compatible are poor, and how to improve the two compatibility is also that preparation is high
The key technology of gas barrier thermoplastic sulfurized rubber.It is well known that nylon is a kind of polar thermoplastics, halogenated butyl rubber
It is a kind of nonpolar saturated rubber, and polypropylene is then also nonpolar, and halogenated butyl rubber and polyacrylic solubility
Parameter is very close, so halogenated butyl rubber and polypropylene are as thermoplasticity sulphur obtained after primary raw material progress dynamic crosslinking
It is preferable to change glue compatibility, and there is fine Micro-Structure.The present invention uses halogenated butyl rubber and polypropylene system first
The preferable halobutyl polypropylene thermoplastic elastomer of compatibility, then by itself and a certain amount of nylon and polypropylene grafted Malaysia
Acid anhydrides melt blending.Polypropylene grafted maleic anhydride can carry out reactive increasing as compatilizer, acid anhydrides with the Amino End Group of nylon
Hold.This method avoid because rubber and plastic compatibility is bad brought to dynamic vulcanization the problem of, be prepared with fine microcosmic
Phase stracture, excellent physical mechanical property, air-tightness, hardness etc. are superior to the high gas barrier thermoplasticity sulphur of existing patent
Change glue.
Detailed description of the invention
Fig. 1 is to prepare halogenated butyl rubber/polypropylene/Nylon thermoplastic sulfurized rubber schematic illustration.
Description of symbols: 1- halogenated butyl rubber dispersed phase；2- polypropylene continuous phase；3- polypropylene, nylon continuous phase；
4- halogenated butyl rubber/polypropylene thermoplastic vulcanizate；5- halogenated butyl rubber/polypropylene/Nylon thermoplastic sulfurized rubber.
Preparation principle are as follows: the preferable halobutyl polypropylene thermoplastic of compatibility is made using halogenated butyl rubber and polypropylene
Property elastomer, then by itself and a certain amount of nylon and polypropylene grafted maleic anhydride melt blending, being then prepared has
The halogenated butyl rubber of fine Micro-Structure/polypropylene/Nylon thermoplastic sulfurized rubber.Wherein polypropylene grafted maleic acid
The anhydride group of acid anhydride can carry out reactive compatibilization with the Amino End Group of nylon.
Specific embodiment
Below with reference to embodiment, the present invention will be further described:
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 measurement.
Gas permeability coefficient carries out gas barrier property test by ISO2782 standard self-control automatic air tightness testing instrument,
Test condition are as follows: 40 DEG C, N2 atmosphere
Embodiment 1:
The raw material of selection form substantially and mass fraction is as follows:
Wherein brominated butyl polypropylene thermoplastic elastomer is that a kind of brombutyl and polypropylene dynamic vulcanization are made
Thermoplastic elastomer (TPE), substantially composition and mass fraction it is as follows:
By above-mentioned formula, first brombutyl is mixed at 180 DEG C with polypropylene, uniformly rear discharging cooling to be mixed
To room temperature；Then it is uniformly mixed to obtain rubber and plastic pre-composition with vulcanizing agent at normal temperature again；Rubber and plastic pre-composition is placed in twin-screw to squeeze
Out in machine, setting curing temperature is 180 DEG C, and revolving speed 300rpm, dynamic vulcanization obtains brombutyl/polypropylene thermoplastic
Vulcanizate.Then again by it in proportion with the terpolyamide of drying and polypropylene grafted maleic anhydride in double screw extruder
Melt blending 8 minutes at 200 DEG C, revolving speed 300rpm obtain brombutyl/polypropylene/Nylon thermoplastic sulfurized rubber.
For TPV according to standard press at the thin slice and test performance of 2mm thickness, performance is shown in Table 1.
Comparative example 1
The raw material of selection form substantially and mass fraction is as follows:
The terpolyamide of drying is mixed at 200 DEG C with brombutyl, is proportionally added into antioxidant, to mixed
Discharging is cooled to room temperature after closing uniformly；Then again at normal temperature with zinc oxide and N, the mixing of penylene bismaleimide is equal between N'-
It is even to obtain rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in double screw extruder, setting curing temperature is 200 DEG C, and revolving speed is
500rpm, dynamic vulcanization obtain brombutyl/nylon thermoplastic's vulcanizate.TPV is according to standard press at the thin slice of 2mm thickness
And test performance, performance are shown in Table 1.
Embodiment 2:
The raw material of selection form substantially and mass fraction is as follows:
Wherein chlorinated butyl polypropylene thermoplastic elastomer is that a kind of chlorinated scoline and polypropylene dynamic vulcanization are made
Thermoplastic elastomer (TPE), substantially composition and mass fraction it is as follows:
By above-mentioned formula, first chlorinated scoline is mixed at 180 DEG C with polypropylene, uniformly rear discharging cooling to be mixed
To room temperature；Then it is uniformly mixed to obtain rubber and plastic pre-composition with vulcanizing agent at normal temperature again；Rubber and plastic pre-composition is placed in twin-screw to squeeze
Out in machine, setting curing temperature is 180 DEG C, and revolving speed 300rpm, dynamic vulcanization obtains chlorinated scoline/polypropylene thermoplastic
Vulcanizate.Then again by it in proportion with the nylon of drying 6 and polypropylene grafted maleic anhydride at 200 DEG C of double screw extruder
Melt blending 8 minutes, revolving speed 500rpm obtained chlorinated scoline/polypropylene/Nylon thermoplastic sulfurized rubber.TPV is according to mark
Standard is pressed into the thin slice and test performance of 2mm thickness, and performance is shown in Table 1.
Comparative example 2
Comparative example 2 is prepared according to the formula and method of patent CN105255026A, the raw material of selection form substantially and matter
It is as follows to measure number:
Its for wherein making expanding material by oneself forms and mass fraction is as follows substantially:
Without 100 parts of haLobutyl rubbers；
Glycidyl methacrylate 0.01；
1 part of cumyl peroxide.
It, first will be without haLobutyl rubbers, glycidyl methacrylate and cumyl peroxide in Hakke by above-mentioned formula
At 150 DEG C of mixer melting mixing react 5 minutes, obtain graft modification without haLobutyl rubbers；Then by the polyamide of drying
1010 mix at 190 DEG C with no haLobutyl rubbers, be proportionally added into graft modification without haLobutyl rubbers and antioxidant etc., to
Discharging is cooled to room temperature after mixing；Then it is mixed with anti-aging agent, plasticizer, vulcanizing agent and vulcanization aid at normal temperature again
It is even to obtain rubber and plastic pre-composition；Rubber and plastic pre-composition is placed in double screw extruder, setting curing temperature is 210 DEG C, and revolving speed is
300rpm, dynamic vulcanization obtain butyl rubber/polyamide thermoplastic vulcanizate.TPV according to standard press at 2mm thickness thin slice simultaneously
Test performance, performance are shown in Table 1.
Embodiment 3:
The raw material of selection form substantially and mass fraction is as follows:
Wherein brominated butyl polypropylene thermoplastic elastomer is that a kind of brombutyl and polypropylene dynamic vulcanization are made
Thermoplastic elastomer (TPE), substantially composition and mass fraction it is as follows:
By above-mentioned formula, first brombutyl is mixed at 180 DEG C with polypropylene, uniformly rear discharging cooling to be mixed
To room temperature；Then it is uniformly mixed to obtain rubber and plastic pre-composition with vulcanizing agent at normal temperature again；Rubber and plastic pre-composition is placed in twin-screw to squeeze
Out in machine, setting curing temperature is 180 DEG C, and revolving speed 300rpm, dynamic vulcanization obtains brombutyl/polypropylene thermoplastic
Vulcanizate.Then again by it in proportion with the nylon of drying 12 and polypropylene grafted maleic anhydride at 200 DEG C of double screw extruder
Lower melt blending 8 minutes, revolving speed 400rpm, obtain brombutyl/polypropylene/Nylon thermoplastic sulfurized rubber.TPV according to
For standard press at the thin slice and test performance of 2mm thickness, performance is shown in Table 1.
Embodiment 4:
The raw material of selection form substantially and mass fraction is as follows:
Wherein brominated isobutylene-p-methylstyrene base rubber polypropylene thermoplastic elastomer is a kind of brominated isobutylene-
Thermoplastic elastomer (TPE) made from p-methylstyrene base rubber and polypropylene dynamic vulcanization, substantially composition and mass fraction are such as
Under:
By above-mentioned formula, first brominated isobutylene-p-methylstyrene base rubber is mixed at 180 DEG C with polypropylene, to
Discharging is cooled to room temperature after mixing；Then it is uniformly mixed to obtain rubber and plastic pre-composition with vulcanizing agent at normal temperature again；By rubber and plastic
Pre-composition is placed in double screw extruder, and setting curing temperature is 180 DEG C, and revolving speed 300rpm, dynamic vulcanization obtains bromination fourth
Base rubber/polypropylene thermoplastic vulcanizate.Then again by its in proportion with the nylon66 fiber of drying and polypropylene grafted maleic anhydride
Melt blending 8 minutes, revolving speed 300rpm at 200 DEG C of double screw extruder, obtain brominated isobutylene-p-methylstyrene base
Rubber/polypropylene/nylon thermoplastic's vulcanizate.According to standard press at the thin slice and test performance of 2mm thickness, performance is shown in Table TPV
1。
1 embodiment of table is compared with the performance of comparative example
In the comparison of above-mentioned table 1, comparative example 1 is corresponding with embodiment 1, and comparative example 1 is compared to embodiment 1 directly by bromination fourth
Thermoplastic sulfurized rubber is made in base rubber and nylon dynamic vulcanization, the results showed for preparing brombutyl/polypropylene thermoplastic first
Property elastomer, then brombutyl/polypropylene/Nylon thermoplastic sulfurized rubber physics prepared by itself and nylon melt blending
Mechanical property improves, and hardness reduces, and air-tightness is close, and surface polishes, and illustrates that the present invention used prepares halobutyl first
Rubber/polypropylene thermoplastic elastomer, then halobutyl rubber is prepared by what it was blended with nylon and polypropylene grafted maleic anhydride
Glue/polypropylene/Nylon thermoplastic vulcanizates gluing method has better effects.
It is that performance is best in existing product using product made from comparative example 2 (technology in patent CN105255026A)
's.Through comparison it was found that the product being prepared using technology of the invention in tensile strength and elongation at break all
Show more outstanding, hardness is lower and significant airtight sexual clorminance (air transmission coefficient is small).
Claims (8)
1. a kind of high gas-obstructing character thermoplastic sulfurized rubber, it is characterised in that the thermoplastic sulfurized rubber is by including following components
Raw material is prepared, in parts by weight:
Wherein, the halobutyl polypropylene thermoplastic elastomer is obtained by including the raw material dynamic vulcanization of following components, respectively
Component is in parts by weight:
100 parts of halogenated butyl rubber；
10-80 parts of polypropylene；
1-5 parts of vulcanizing agent.
2. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that the thermoplastic sulfurized rubber
It is prepared by the raw material comprising following components, in parts by weight:
3. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that:
The halobutyl polypropylene thermoplastic elastomer be by include following components raw material dynamic vulcanization and obtain, each component with
Parts by weight meter:
100 parts of halogenated butyl rubber；
15-65 parts of polypropylene；
2-4 parts of vulcanizing agent.
4. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that:
It is total that the halogenated butyl rubber is selected from chlorinated scoline, brombutyl or brominated isobutylene-p-methylstyrene
At least one of polymers.
5. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that:
The vulcanizing agent is selected from phenolic resin, zinc oxide, stearic acid, N, at least one of penylene bismaleimide between N'-.
6. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that:
The halobutyl polypropylene thermoplastic elastomer is made using following steps:
(1) it requires to weigh each component according to the proportion；
(2) rubber and plastic premixes: first mixing polypropylene with halogenated butyl rubber, uniformly rear discharging cooling to be mixed；Then with sulphur
Agent is uniformly mixed and obtains rubber and plastic pre-composition；
(3) rubber and plastic pre-composition dynamic vulcanization obtained by step (2) dynamic vulcanization: is obtained into the halobutyl polypropylene thermoplastic bullet
Property body.
7. high gas-obstructing character thermoplastic sulfurized rubber according to claim 1, it is characterised in that:
The nylon is selected from one of nylon 6, nylon66 fiber, nylon 1010, nylon 12 or terpolyamide or several.
8. a kind of preparation method of described in any item high gas-obstructing character thermoplastic sulfurized rubbers according to claim 1~7,
Be characterized in that the described method includes:
The nylon of the amount, polypropylene grafted maleic anhydride, antioxidant and halobutyl polypropylene thermoplastic elastomer are melted
It is blended, obtains the high gas-obstructing character thermoplastic sulfurized rubber.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484684A (en) * | 2020-06-04 | 2020-08-04 | 青岛科技大学 | High-damping low-odor environment-friendly butyl rubber/polypropylene thermoplastic vulcanized rubber and preparation method thereof |
| CN111995812A (en) * | 2020-08-19 | 2020-11-27 | 中裕软管科技股份有限公司 | High-air-tightness material for repairing gas pipeline and preparation method thereof |
| CN112080080A (en) * | 2019-06-13 | 2020-12-15 | 北京化工大学 | High-temperature-resistant high-gas-barrier thermoplastic blend for automobile tires and preparation method thereof |
| CN112080081A (en) * | 2019-06-13 | 2020-12-15 | 北京化工大学 | Low-cost high-gas-barrier thermoplastic vulcanized rubber for bicycle tire and preparation method thereof |
| CN114591576A (en) * | 2022-03-18 | 2022-06-07 | 北京化工大学 | High-gas-barrier thermoplastic inner tube material and preparation method and application thereof |
| CN115975332A (en) * | 2023-03-22 | 2023-04-18 | 山东泰瑞丰新材料有限公司 | Butyl rubber ionomer modified SEBS and preparation method thereof |
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|---|---|---|---|---|
| CN112080080A (en) * | 2019-06-13 | 2020-12-15 | 北京化工大学 | High-temperature-resistant high-gas-barrier thermoplastic blend for automobile tires and preparation method thereof |
| CN112080081A (en) * | 2019-06-13 | 2020-12-15 | 北京化工大学 | Low-cost high-gas-barrier thermoplastic vulcanized rubber for bicycle tire and preparation method thereof |
| CN112080081B (en) * | 2019-06-13 | 2023-01-13 | 北京化工大学 | Low-cost high-gas-barrier thermoplastic vulcanized rubber for bicycle tire and preparation method thereof |
| CN111484684A (en) * | 2020-06-04 | 2020-08-04 | 青岛科技大学 | High-damping low-odor environment-friendly butyl rubber/polypropylene thermoplastic vulcanized rubber and preparation method thereof |
| CN111995812A (en) * | 2020-08-19 | 2020-11-27 | 中裕软管科技股份有限公司 | High-air-tightness material for repairing gas pipeline and preparation method thereof |
| CN111995812B (en) * | 2020-08-19 | 2022-06-14 | 中裕软管科技股份有限公司 | High-air-tightness material for repairing gas pipeline and preparation method thereof |
| CN114591576A (en) * | 2022-03-18 | 2022-06-07 | 北京化工大学 | High-gas-barrier thermoplastic inner tube material and preparation method and application thereof |
| CN114591576B (en) * | 2022-03-18 | 2023-10-03 | 北京化工大学 | High-gas-barrier thermoplastic inner tube material and preparation method and application thereof |
| CN115975332A (en) * | 2023-03-22 | 2023-04-18 | 山东泰瑞丰新材料有限公司 | Butyl rubber ionomer modified SEBS and preparation method thereof |
| CN115975332B (en) * | 2023-03-22 | 2023-05-12 | 山东泰瑞丰新材料有限公司 | Butyl rubber ionomer modified SEBS and preparation method thereof |
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