CN109422970B - High-gas-barrier thermoplastic vulcanized rubber and preparation method thereof - Google Patents
High-gas-barrier thermoplastic vulcanized 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
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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
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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 invention relates to a high-gas-barrier thermoplastic vulcanized rubber and a preparation method thereof. The thermoplastic vulcanized rubber comprises the following main raw materials: the halogen-free butyl rubber modified polypropylene composite material comprises halogenated butyl rubber, polyamide or EVOH, a compatibilizer, a vulcanizing agent and an antioxidant, wherein the compatibilizer is a glycidyl methacrylate grafted polyisobutylene copolymer prepared from polyisobutylene, glycidyl methacrylate, a comonomer and an initiator. The high-gas-barrier thermoplastic vulcanizate containing the polyamide or the EVOH and having fine micro-phase structure, excellent physical and mechanical properties, air tightness, hardness and the like is prepared from a rubber-plastic premix consisting of the polyamide or the EVOH and the halogenated butyl rubber which are blended and grafted with the compatibilizer in advance through a dynamic vulcanization technology.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to high-gas-barrier thermoplastic vulcanized rubber and a preparation method thereof.
Background
Thermoplastic vulcanizate is a special thermoplastic elastomer obtained by dynamic vulcanization reaction processing technology. When a small amount of plastic phase and a large amount of rubber are melt blended, the rubber is chemically crosslinked under the action of a crosslinking agent, and the viscosity is increased, so that the rubber is crushed into micron-sized rubber particles under the action of strong mechanical shearing, and finally a special phase state structure taking the rubber as a dispersed phase and the plastic as a continuous phase is formed. The special structure ensures that the thermoplastic vulcanized rubber has high elasticity and flexibility of the traditional rubber, and also has the performance of thermoplasticity processing and recycling of plastics.
The thermoplastic vulcanized rubber prepared by mixing the butyl rubber and the polyamide or the polyethylene vinyl alcohol copolymer and dynamically crosslinking has the characteristics of good physical and mechanical properties and air tightness, easy processability, repeatable processability and the like, and is mainly applied to tire air barriers, refrigerator hoses or rental material linings and the like. Compared with the traditional thermosetting tire inner liner, the tire inner liner has lighter weight and better air tightness. However, butyl rubber has poor compatibility with polyamide or polyvinyl alcohol copolymer, so it is difficult to improve the compatibility of butyl rubber/polyamide or polyvinyl alcohol copolymer. If the rubber and plastic have poor compatibility, the crosslinked rubber is not easy to be cut into uniform and fine dispersed phase particles, and finally the micro phase structure of the thermoplastic vulcanizate is affected. In the preparation process of butyl rubber/polyamide or polyethylene vinyl alcohol copolymer TPV, a compatibilizer is added to improve the compatibility of the butyl rubber/polyamide or polyethylene vinyl alcohol copolymer TPV so as to obtain a product with good performance. Patent CN 103012971A discloses an EPDM/EVOH-MAA dynamically vulcanized thermoplastic elastomer, a preparation method and application thereof, wherein EPDM and EVOH-MAA are dynamically vulcanized in an internal mixer, ethylene propylene diene monomer grafted maleic anhydride (EPDM-g-MAH) is used as a compatibilizer, but the compatibility problem is only solved, and the obtained thermoplastic vulcanized rubber still has the problem of poor air tightness. Patent CN103030895A discloses a thermoplastic vulcanizate with high gas barrier property and a preparation method thereof, wherein a compatibilizer (a "premix" of chlorinated butyl rubber, polyisobutylene and maleic anhydride) is added into a chlorinated butyl rubber/polyamide 12 system, and the thermoplastic vulcanizate with excellent mechanical property and gas barrier property is prepared by dynamic vulcanization in a twin-screw. However, the problem of poor compatibility of the butyl polyamide is not obviously improved, and the problem of higher hardness of the prepared thermoplastic vulcanizate is solved. Patent CN105255026A discloses a reactive compatibilization method for preparing butyl rubber/polyamide thermoplastic vulcanizate, wherein butyl rubber graft-modified by bifunctional compounds is used as a compatibilizer, the particle size of the dispersed phase of the obtained thermoplastic vulcanizate is obviously reduced, but the particle size of the dispersed phase of the rubber is still in the micrometer level, and the phase structure needs to be further optimized.
Disclosure of Invention
In order to solve the problems, the invention prepares the polyisobutylene copolymer grafted and modified by the glycidyl methacrylate by a method of melting and mixing polyisobutylene, glycidyl methacrylate, comonomer and initiator in a batch mixer; then, the graft modified polyisobutylene copolymer is used as a compatibilizer, and the rubber-plastic premix consisting of the high-gas-barrier-property plastic and the halogenated butyl rubber which are blended and grafted with the compatibilizer in advance is prepared into the high-gas-barrier-property thermoplastic vulcanizate containing the polyamide or the EVOH, which has a fine micro-phase structure, excellent physical and mechanical properties, air tightness, hardness and the like, by a dynamic vulcanization technology.
The invention aims to provide a high-gas-barrier thermoplastic vulcanized rubber which is prepared from the following raw materials in parts by weight:
the compatibilizer is prepared from the following raw materials in parts by weight:
the halogenated butyl rubber is at least one of brominated polyisobutylene-p-methyl styrene rubber, chlorinated butyl rubber or brominated butyl rubber.
The high gas barrier plastic is polyamide or ethylene-vinyl alcohol copolymer.
The polyamide is at least one of polyamide 6, polyamide 66, polyamide 1010, polyamide 12 and terpolymer polyamide or a copolymer thereof.
The ethylene-vinyl alcohol copolymer has an ethylene content of 20-60% and a vinyl alcohol content of 40-80%.
The antioxidant is an antioxidant commonly used in the art, such as hindered phenol antioxidant 1010.
The vulcanizing agent is a vulcanizing agent commonly used in the field, and preferably at least one of phenolic resin, zinc oxide, stearic acid and N, N' -m-phenylene bismaleimide.
The polyisobutene is medium-low molecular weight polyisobutene, and the number average molecular weight range is 1000-50000.
The comonomer is at least one of styrene, acrylic acid or acrylonitrile.
The initiator is an initiator commonly used in the art, and preferably at least one of dicumyl peroxide, di-t-butyl peroxide, or dibutyl azodiisobutyrate.
The compatibilizer is prepared by adopting the following method: placing polyisobutylene, glycidyl methacrylate, a comonomer and an initiator into an intermittent mixer at room temperature, premixing for 10-20 minutes until the polyisobutylene, the glycidyl methacrylate, the comonomer and the initiator are uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (the setting range is 100-200 ℃) and mixing for 10-15 minutes.
Among the batch mixers, a Rheocord Haake type batch mixer is preferred.
In the high gas barrier thermoplastic vulcanizate of the invention, various additives such as paraffin oil, RL16 and the like can be added according to the processing requirements, and the dosage is all conventional dosage or adjusted according to the requirements of actual conditions.
The second purpose of the invention is to provide a preparation method of the thermoplastic vulcanizate with high gas barrier property, which comprises the following steps:
(1) blending and grafting the compatibilizer and the high-gas barrier plastic;
(2) rubber and plastic premixing: uniformly mixing the product obtained in the step (1) with halogenated butyl rubber, an antioxidant and a vulcanizing agent to obtain a rubber-plastic premix;
(3) dynamic vulcanization: dynamically vulcanizing the rubber-plastic premix obtained in the step (2) to obtain the high-gas-barrier thermoplastic vulcanized rubber.
Preferably, the method comprises the following steps:
(1) blending and grafting the compatibilizer and the high-gas barrier plastic in an internal mixer at the temperature of 150 ℃ and 220 ℃ for 5-10 min;
(2) rubber and plastic premixing: drying the product obtained in the step (1), mixing the dried product with halogenated butyl rubber at the temperature of 150-220 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; then uniformly mixing the rubber-plastic premix with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix;
(3) dynamic vulcanization: and (3) placing the rubber-plastic premix obtained in the step (2) into a screw extruder, setting the screw temperature to be 150-220 ℃ and the rotating speed to be 300-700 rpm, and dynamically vulcanizing to obtain the high-gas-barrier thermoplastic vulcanized rubber.
The invention has the advantages that the high-gas-barrier thermoplastic vulcanizate containing polyamide or EVOH, which has fine micro-phase structure, excellent physical and mechanical properties, air tightness, hardness and the like, is prepared by adopting the glycidyl methacrylate graft modified polyisobutylene copolymer as the compatibilizer and using the rubber-plastic premix consisting of the high-gas-barrier plastic and the halogenated butyl rubber which are blended and grafted with the compatibilizer in advance through a dynamic vulcanization technology.
The method for preparing the compatibilizer is simple and convenient to operate and easy to realize industrial production. The traditional solution grafting method has the disadvantages of large solvent loss amount, high production cost and severe operating environment in the production process, and the product quality is poor due to the fact that the product contains residual solvent.
The compatibility of the halogenated butyl rubber and the polyamide or the polyethylene vinyl alcohol copolymer is poor, and how to improve the compatibility of the halogenated butyl rubber and the polyamide or the polyethylene vinyl alcohol copolymer is also a key technology for preparing the high-gas-barrier thermoplastic vulcanizate. The glycidyl methacrylate adopted by the invention contains epoxy groups, and the epoxy groups can react with terminal amino in polyamide or hydroxyl in polyethylene vinyl alcohol copolymer, thereby playing a role in reactive compatibilization. And the rubber-plastic premix consisting of the high-gas-barrier plastic and the halogenated butyl rubber which are blended and grafted with the compatibilizer in advance is prepared by a dynamic vulcanization technology to obtain the high-gas-barrier thermoplastic vulcanizate with fine micro-phase structure, excellent physical and mechanical properties, air tightness, hardness and the like which are superior to those of the high-gas-barrier thermoplastic vulcanizate of the prior patent. In the processing technology, a mode of blending and grafting the compatibilizer and the high-gas barrier plastic is adopted, so that the combination between interfaces is greatly enhanced, a good compatibilization effect is achieved, and the mechanical property of the system is effectively improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Tensile strength, elongation at break and Shore A hardness in the examples were determined according to the following standards GB/T528-2009, GB/T528-2009 and GB/T531.1-2008, respectively. And (3) carrying out gas barrier performance test on the gas permeability coefficient according to an ISO2782 standard self-made automatic gas tightness tester, wherein the test conditions are as follows: 40 ℃ C, N2An atmosphere.
Example 1:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, polyisobutylene, glycidyl methacrylate, styrene and dicumyl peroxide are placed into a Rheocorp Haake type batch mixer at room temperature, premixed for 15 minutes until the mixture is uniformly mixed, then the mixture is placed into a mixing chamber preheated to the required temperature (set to be 150 ℃), and mixed for 12 minutes to obtain the low molecular weight polyisobutylene blend grafted and modified by the glycidyl methacrylate; then blending and grafting the compatibilizer and polyamide in an internal mixer at 200 ℃ for 5min, drying the obtained product, mixing the dried product with brominated butyl rubber at 200 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the mixture with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 200 ℃ and the rotating speed at 500rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Comparative example 1
TPV was prepared by dynamic vulcanization in the same manner and under the same conditions according to the formulation of example 1 but without the addition of the low molecular weight polyisobutylene blend graft-modified with glycidyl methacrylate (compatibilizer), pressed to 2mm thick sheets according to the standard and tested for properties, the properties being given in Table 1.
Example 2:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing medium molecular weight polyisobutylene, glycidyl methacrylate, acrylonitrile and di-tert-butyl peroxide into a Rheocord Haake type batch mixer, premixing for 12 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (set to be 170 ℃), and mixing for 15 minutes to obtain a glycidyl methacrylate graft-modified medium molecular weight polyisobutylene blend; then blending and grafting the compatibilizer and polyamide 66 in an internal mixer at 200 ℃ for 8min, drying the obtained product, mixing the dried product with brominated polyisobutene-p-methylstyrene based rubber at 190 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the mixture with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 190 ℃ and the rotating speed at 400rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Comparative example 2
TPV was prepared by dynamic vulcanization in the same manner and under the same conditions according to the formulation of example 2 but without the addition of the glycidyl methacrylate graft-modified medium molecular weight polyisobutylene blend (compatibilizer), pressed to 2mm thick sheets according to the standard and tested for properties, the properties being given in Table 1.
Example 3:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing low molecular weight polyisobutylene, glycidyl methacrylate, acrylic acid and dibutyl azodiisobutyrate into a Rheocorp Haake type intermittent mixer, premixing for 18 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (set to be 160 ℃), and mixing for 15 minutes to obtain a glycidyl methacrylate graft-modified low molecular weight polyisobutylene blend; then blending and grafting the compatibilizer and polyamide 12 in an internal mixer at 200 ℃ for 8min, drying the obtained product, mixing the dried product with chlorinated butyl rubber at 210 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the rubber-plastic premix with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 210 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Comparative example 3
Comparative example 2 was prepared according to the formulation and method of patent CN105255026A, the selected raw materials had the following basic composition and parts by mass:
the self-made compatibilizer comprises the following basic components in percentage by mass:
100 parts of halogen-free butyl rubber;
0.01 of glycidyl methacrylate;
1 part of dicumyl peroxide.
According to the formula, firstly, melting, mixing and reacting the halogen-free butyl rubber, the epoxypropyl methacrylate and the dicumyl peroxide for 5 minutes at the temperature of 150 ℃ in a Hakke internal mixer to obtain the graft-modified halogen-free butyl rubber; then mixing the dried polyamide 1010 with the halogen-free butyl rubber at 190 ℃, adding the graft modified halogen-free butyl rubber, the antioxidant and the like in proportion, discharging and cooling to room temperature after uniform mixing; then uniformly mixing the rubber-plastic premix with an anti-aging agent, a plasticizer, a vulcanizing agent and a vulcanizing aid at normal temperature to obtain a rubber-plastic premix; and (3) placing the rubber-plastic premix into a double-screw extruder, setting the vulcanization temperature to be 210 ℃ and the rotating speed to be 300rpm, and dynamically vulcanizing to obtain the butyl rubber/polyamide thermoplastic vulcanizate. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 4:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing low molecular weight polyisobutylene, glycidyl methacrylate, acrylic acid and di-tert-butyl peroxide into a Rheocorp Haake type batch mixer, premixing for 17 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (the set range is 180 ℃), and mixing for 13 minutes to obtain a low molecular weight polyisobutylene blend grafted and modified by glycidyl methacrylate; then blending and grafting the compatibilizer and polyamide 12 in an internal mixer at 200 ℃ for 8min, drying the obtained product, mixing the dried product with brominated butyl rubber at 200 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the mixture with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 200 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 5:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing medium molecular weight polyisobutylene, glycidyl methacrylate, styrene and dicumyl peroxide into a Rheocorp Haake type intermittent mixer, premixing for 16 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (the set range is 170 ℃), and mixing for 15 minutes to obtain a glycidyl methacrylate graft modified medium molecular weight polyisobutylene blend; then blending and grafting the compatibilizer and the ternary copolymer polyamide in an internal mixer at 210 ℃ for 8min, drying the obtained product, mixing the dried product with brominated butyl rubber at 210 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the rubber-plastic premix with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 210 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 6:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing low molecular weight polyisobutylene, glycidyl methacrylate, styrene and dicumyl peroxide into a Rheocorp Haake type intermittent mixer, premixing for 16 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (the set range is 180 ℃), and mixing for 15 minutes to obtain a low molecular weight polyisobutylene blend grafted and modified by glycidyl methacrylate; then blending and grafting the compatibilizer and polyamide 6 in an internal mixer at 210 ℃ for 10min, drying the obtained product, mixing the dried product with brominated polyisobutene-p-methylstyrene-based rubber at 210 ℃, and adding antioxidant
Uniformly mixing the agents, discharging and cooling to room temperature; and then uniformly mixing the rubber-plastic premix with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 210 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the polyamide-containing high-gas-barrier thermoplastic vulcanized rubber. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
Example 7:
the selected raw materials comprise the following basic components in parts by weight:
the compatibilizer comprises the following basic components in percentage by mass:
according to the formula, at room temperature, placing medium molecular weight polyisobutylene, glycidyl methacrylate, styrene and dicumyl peroxide into a Rheocorp Haake type intermittent mixer, premixing for 16 minutes until the mixture is uniformly mixed, then placing the mixture into a mixing chamber preheated to the required temperature (the set range is 180 ℃), and mixing for 15 minutes to obtain a low molecular weight polyisobutylene blend grafted and modified by glycidyl methacrylate; then blending and grafting the compatibilizer and EVOH in an internal mixer at 190 ℃ for 10min, drying the obtained product, mixing the dried product with brominated polyisobutene-p-methylstyrene rubber at 190 ℃, adding an antioxidant, uniformly mixing, discharging and cooling to room temperature; and then uniformly mixing the rubber-plastic premix with a vulcanizing agent at normal temperature to obtain a rubber-plastic premix, placing the rubber-plastic premix in a screw extruder, setting the screw temperature at 190 ℃ and the rotating speed at 600rpm, and dynamically vulcanizing to obtain the high-gas-barrier thermoplastic vulcanized rubber containing EVOH. TPV was pressed to 2mm thick sheets according to the standard and tested for properties, which are shown in Table 1.
TABLE 1 comparison of the Performance of the examples and comparative examples
In the comparison of the table 1, the comparative examples 1 and 2 correspond to the examples 1 and 2 respectively, and the comparative examples 1 and 2 do not add the compatibilizer (the polyisobutylene blend grafted and modified by glycidyl methacrylate) compared with the examples 1 and 2, and the results show that the physical and mechanical properties and the air tightness of the high-gas-barrier thermoplastic vulcanizate with the compatibilizer are better, the hardness is reduced, and the surface is smooth, which shows that the compatibilizer used in the invention has better compatibilization effect.
Comparative example 3 (product made using the technique of patent CN 105255026A) is the best performing of the existing products. The comparison shows that the products (examples 1 to 7) prepared by the technology of the invention have excellent tensile strength and elongation at break, low hardness and obvious air tightness advantage (small air permeability coefficient).
Claims (8)
1. The high-gas-barrier thermoplastic vulcanized rubber is characterized by being prepared from the following raw materials in parts by weight:
100 parts of halogenated butyl rubber;
30-90 parts of high-gas-barrier plastic;
1-15 parts of a compatibilizer;
1-10 parts of a vulcanizing agent;
0.5-2 parts of antioxidant;
the compatibilizer is prepared from the following raw materials in parts by weight:
100 parts of polyisobutylene;
0.1-20 parts of glycidyl methacrylate;
0.1-10 parts of comonomer;
0.01-5 parts of an initiator;
the high gas barrier plastic is polyamide or ethylene-vinyl alcohol copolymer;
the comonomer is at least one of styrene, acrylic acid or acrylonitrile;
the compatibilizer is prepared by the following steps:
placing polyisobutylene, glycidyl methacrylate, a comonomer and an initiator into an intermittent mixer at room temperature, premixing for 10-20 minutes until the polyisobutylene, the glycidyl methacrylate, the comonomer and the initiator are uniformly mixed, then placing the mixture into a mixing chamber preheated to 100-200 ℃, and mixing for 10-15 minutes.
2. The high gas barrier thermoplastic vulcanizate according to claim 1, characterized in that the thermoplastic vulcanizate is prepared from raw materials comprising the following components, in parts by weight:
100 parts of halogenated butyl rubber;
35-80 parts of high-gas-barrier plastic;
1-12 parts of a compatibilizer;
2-7 parts of a vulcanizing agent;
1-2 parts of an antioxidant.
3. The high gas barrier thermoplastic vulcanizate of claim 1, wherein:
the compatibilizer is prepared from the following raw materials in parts by weight:
100 parts of polyisobutylene;
1-10 parts of glycidyl methacrylate;
1-10 parts of a comonomer;
1-5 parts of an initiator.
4. The high gas barrier thermoplastic vulcanizate of claim 1, wherein:
the halogenated butyl rubber is at least one of brominated polyisobutylene-p-methyl styrene rubber, chlorinated butyl rubber or brominated butyl rubber.
5. The high gas barrier thermoplastic vulcanizate of claim 1, wherein:
the polyamide is at least one of polyamide 6, polyamide 66, polyamide 1010, polyamide 12 and terpolymer polyamide.
6. The high gas barrier thermoplastic vulcanizate of claim 1, wherein:
the ethylene-vinyl alcohol copolymer has ethylene content of 20-60% and vinyl alcohol content of 40-80%.
7. The high gas barrier thermoplastic vulcanizate of claim 1, wherein:
the number average molecular weight of the polyisobutylene is 1000-50000.
8. A method for preparing a thermoplastic vulcanizate with high gas barrier properties according to any one of claims 1 to 7, characterized by comprising the following steps:
(1) blending and grafting the compatibilizer and the high-gas barrier plastic;
(2) rubber and plastic premixing: uniformly mixing the product obtained in the step (1) with halogenated butyl rubber, an antioxidant and a vulcanizing agent to obtain a rubber-plastic premix;
(3) dynamic vulcanization: dynamically vulcanizing the rubber-plastic premix obtained in the step (2) to obtain the high-gas-barrier thermoplastic vulcanized rubber.
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| CN101531741B (en) * | 2009-04-02 | 2010-10-20 | 上海交通大学 | Preparation method of glycidyl methacrylate graft polyisobutene copolymer |
| CN103030895A (en) * | 2012-12-12 | 2013-04-10 | 北京化工大学 | High-gas-barrier-property thermoplastic vulcanized rubber and preparation method thereof |
| CN103788515B (en) * | 2014-01-21 | 2016-04-06 | 北京化工大学 | A kind of high gas-obstructing character energy thermoplastic sulfurized rubber and preparation method thereof |
| CN104513434B (en) * | 2014-11-27 | 2017-02-01 | 北京化工大学 | Butyl rubber/long carbon chain polyamide thermoplastic vulcanized rubber and preparation method thereof |
| CN105037967B (en) * | 2015-04-24 | 2017-11-24 | 北京化工大学 | A kind of butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof |
| CN105255026B (en) * | 2015-10-21 | 2018-03-30 | 北京化工大学 | A kind of reactive compatibilization butyl rubber/polyamide thermoplastic vulcanizate and preparation method thereof |
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