CN115011026B - A kind of high temperature resistant oil resistant high barrier thermoplastic vulcanizate and preparation method thereof - Google Patents

Abstract

The invention discloses a high-temperature-resistant, oil-resistant, high-barrier thermoplastic vulcanizate and a preparation method thereof, and relates to the field of thermoplastic vulcanizates. The thermoplastic vulcanizate is dynamically vulcanized by raw materials comprising the following components: temperature-resistant and oil-resistant rubber, High gas-barrier plastic, vulcanizing agent and vulcanization aid; components by weight: 100 parts by weight of heat-resistant and oil-resistant rubber; 30-181 parts by weight of high-gas-barrier plastic; 0.2-7 parts by weight of vulcanizing agent; vulcanization Auxiliary 0.5-7 parts by weight. The thermoplastic vulcanizate of the present invention has the characteristics of simple preparation process, no need for compatibilizer, excellent mechanical properties, high temperature resistance, excellent oil resistance, high barrier and recyclable utilization. It can replace traditional thermoplastic rubber in automotive hoses, wire and cable insulation layers, tool handles, etc.

Description

A kind of high temperature resistant oil resistant high barrier thermoplastic vulcanizate and preparation method thereof

technical field

The invention relates to the field of thermoplastic vulcanizates, in particular to a high-temperature-resistant, oil-resistant, high-barrier thermoplastic vulcanizate and a preparation method thereof.

Background technique

In the field of automotive applications, with the advancement of science and technology and the improvement of social development, automotive fuels are gradually becoming more complex (especially the use of alcohol-containing fuels), and the environment in which materials are used is becoming harsher. Coupled with the requirements for environmental protection, automotive fuel pipes Materials put forward higher requirements, higher temperature resistance, better oil resistance and barrier performance to reduce fuel leakage emissions.

Thermoplastic vulcanizate (TPV) prepared by dynamic vulcanization reaction processing technology based on high-temperature oil-resistant rubber and high-barrier high-temperature-resistant thermoplastics not only has excellent high-temperature oil resistance and high barrier properties, but also has the softness of traditional rubber and thermoplastics Thermoformable and easy to process, it can be applied to automobile fuel pipes.

Chinese patent CN102690479A discloses a dynamically cross-linked polyamide/ethylene-vinyl acetate rubber thermoplastic elastomer and a preparation method thereof. Blending under temperature, obtained polyamide/ethylene vinyl acetate rubber thermoplastic elastomer of dynamic vulcanization; Chinese patent CN103059401A discloses a kind of oil-resistant thermoplastic elastomer and preparation method thereof, adopts ethylene vinyl acetate (EVM) masterbatch (EVM Mixed rubber with vulcanizing agent) and ethylene-vinyl acetate (EVA) are dynamically vulcanized at a certain temperature to prepare oil-resistant thermoplastic elastomers; Chinese patent CN106009449A uses ethylene-vinyl acetate rubber, polycarbodiimide, PVDF and antioxidant 1010 are premixed at high temperature, mixed with a crosslinking agent at room temperature, and then dynamically vulcanized under certain conditions to obtain a thermoplastic elastomer that is resistant to oil and high temperature; Chinese patent CN103396639A discloses a dynamic vulcanization Fluoroplastic/fluororubber/silicone rubber thermoplastic elastomer and its preparation method, adopting the method of mixing fluoroplastic, fluororubber, acid absorbing agent, silicone rubber and interface modifier at a certain temperature and then adding a cross-linking system for dynamic Vulcanization yields a thermoplastic elastomer.

The thermoplastic elastomers in the prior art still have the problem of being difficult to balance high temperature resistance, oil resistance and high barrier properties.

Contents of the invention

In order to solve the problems existing in the prior art, the present invention provides a high-temperature-resistant, oil-resistant, high-barrier thermoplastic vulcanizate and a preparation method thereof. The rubber and plastic selected in the present invention not only have the characteristics of high temperature resistance and oil resistance, but also are polar polymer materials, and have good compatibility without adding a compatibilizer. The thermoplastic vulcanizate prepared by the technology of rubber-plastic blending and dynamic vulcanization has the characteristics of simple preparation process, excellent mechanical properties, low hardness, excellent high temperature resistance and oil resistance, high barrier and recyclable utilization. The thermoplastic vulcanizate of the present invention can replace traditional thermoplastic rubber and be used in automobile rubber hoses, wire and cable insulation layers, tool handles and the like.

One of the objectives of the present invention is to provide a high-temperature-resistant, oil-resistant, high-barrier thermoplastic vulcanizate, which is obtained after dynamic vulcanization of raw materials comprising the following components:

Temperature-resistant and oil-resistant rubber, high gas barrier plastics, vulcanizing agents and vulcanization aids;

Each component is calculated in parts by weight:

Preferably, each component is by weight:

Preferably, the temperature-resistant and oil-resistant rubber is at least one of hydrogenated nitrile rubber, acrylic rubber, ethylene-vinyl acetate rubber, and fluororubber.

Preferably, the double bond content of the hydrogenated nitrile rubber is 0.9-10%, preferably 0.9-5%; the acrylonitrile content is 20-50%; preferably 30-45%; the hydrogenated nitrile rubber double bond content Increasing the heat resistance and aging resistance of the thermoplastic vulcanizate will reduce the heat resistance and aging resistance of the thermoplastic vulcanizate. The increase of the acrylonitrile content will improve the oil resistance of the invented thermoplastic vulcanizate. The purpose of controlling the double bond content and acrylonitrile content within this range is to ensure that the prepared thermoplastic vulcanizate Has excellent oil and heat resistance.

The acrylate rubber is heat-resistant active chlorine acrylate rubber; acrylate rubber can be classified into active chlorine, polyamine crosslinking, ammonium carboxylate, epoxy, self-crosslinking Among them, the active chlorine acrylate rubber has better heat resistance, aging resistance, oil resistance, small compression deformation, and can cancel the second-stage vulcanization after vulcanization.

The vinyl acetate (VA) content in the ethylene-vinyl acetate rubber is 45-90%; the higher the VA content, the more favorable it is to reduce the volume expansion of the prepared thermoplastic vulcanizate in oil.

The fluororubber is at least one of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer (246 type fluororubber), perfluoroether rubber and fluorosilicone rubber; Vulcanizate has excellent high temperature and oil resistance.

Preferably, the high gas barrier plastic is at least one of fluoroplastics, ethylene-vinyl alcohol copolymer (EVOH), and polyvinylidene chloride (PVDC).

Preferably, the fluoroplastic is at least one of ethylene-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene-hexafluoropropylene copolymer;

The ethylene content in the ethylene-vinyl alcohol copolymer is 20-45%, and the vinyl alcohol content is 55-80%. The higher the vinyl alcohol content, the better the barrier performance and oil resistance of the prepared thermoplastic vulcanizate.

Preferably, the vulcanizing agent is at least one of dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, sulfur, and thiocyanic acid kind;

The vulcanization aid is at least one of triallyl isocyanurate, N,N'-m-phenylene bismaleimide, and zinc dibutyl dithiocarbamate (accelerator BZ).

Preferably, the thermoplastic vulcanizate also includes the following raw materials:

At least one of antioxidant, anti-aging agent, plasticizer, zinc oxide, calcium hydroxide, stearic acid, anti-scorch agent, anti-hydrolysis agent.

Preferably, the plasticizer is at least one of dioctyl phthalate, paraffin oil, dibutyl phthalate, and trioctyl trimellitate;

The anti-scorch agent is at least one of N-cyclohexylthiophthalimide (PVI), N-cyclohexylthiophthalimide (CTP);

Taking the temperature-resistant and oil-resistant rubber as 100 parts by weight;

5-20 parts by weight of plasticizer;

Anti-scorch agent 0.1-1 part by weight.

Described antioxidant can adopt the commonly used antioxidant in this field, as: phosphite antioxidant; Its consumption is conventional consumption, and preferred consumption is 1-2 weight part among the present invention; Technical personnel can according to actual situation Make a selection.

Described anti-aging agent can adopt anti-aging agent commonly used in this field, as: p-phenylenediamine type rubber anti-aging agent, quinoline type rubber anti-aging agent etc.; Its consumption is conventional consumption, and preferred consumption among the present invention is 0.5-2 weight part ; Technicians can choose according to the actual situation.

The zinc oxide and stearic acid are used as the activator, and the amount thereof is conventional. In the present invention, preferably: 1-7 parts by weight of zinc oxide; 1-2 parts by weight of stearic acid; technicians can choose according to the actual situation.

The calcium hydroxide is used as an acid absorbing agent in the fluororubber formulation, and its dosage is conventional. In the present invention, the preferred dosage is 1-5 parts by weight.

Described anti-hydrolysis agent can adopt anti-hydrolysis agent commonly used in this field, as: polyimide carbonate; Its consumption is conventional consumption, and preferred consumption among the present invention is 1-5 weight part; The skilled person can select according to actual situation .

In the formula of the present invention, conventional auxiliary agents can also be added according to actual conditions, such as calcium carbonate and montmorillonite, and their consumption is conventional, and technicians can add them according to actual conditions.

Two of object of the present invention is to provide a kind of preparation method of thermoplastic vulcanizate, described method comprises:

The thermoplastic vulcanizate is prepared by dynamic vulcanization after the components are premixed according to the parts by weight.

Preferably, the premixing temperature of rubber and plastic is 190-250° C., the dynamic vulcanization temperature is 200-250° C., and the rotation speed is 200-600 rpm.

The present invention adopts the complete pre-dispersion dynamic vulcanization technology. The specific operation is to pre-mix the rubber and plastics in the internal mixer at high temperature, then discharge and cool, and mix various small material additives on the open mixer at room temperature until uniform. Then the mixture is crushed and put into a twin-screw extruder for dynamic vulcanization; finally, a "sea-island" structure in which the plastic is the continuous phase and the crosslinked rubber is the dispersed phase is formed, which is recyclable and reprocessable.

Concrete preparation method of the present invention is:

(1) Rubber and plastic premixing: at room temperature, mix heat-resistant and oil-resistant rubber with high gas barrier plastic at 190-250°C, and then discharge and cool to room temperature; Oxygen, anti-aging agent, zinc oxide, stearic acid, plasticizer, anti-scorch agent and anti-hydrolysis agent are mixed uniformly to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: the rubber-plastic premix is placed in a twin-screw extruder, and the thermoplastic vulcanizate is obtained by dynamic vulcanization at a temperature of 200-250° C. and a rotational speed of 200-600 rpm.

The temperature-resistant and oil-resistant rubber and high gas-barrier plastic selected in the present invention not only have excellent high temperature resistance and oil resistance, but also the selected materials are polar polymers, and the compatibility of the two phases of rubber and plastic is good, and there is no need to add compatibilizers agent.

The thermoplastic vulcanizate prepared by the present invention adopts rubber-plastic premixing and dynamic vulcanization technology, and finally forms a structure in which the plastic is the continuous phase and the cross-linked rubber is the dispersed phase. It not only has the characteristics of excellent oil resistance, but also has a Excellent oil resistance, on the one hand, as the matrix, there is a strong force between the main chains of the high gas barrier plastic molecular chains, so that when the temperature is lower than its melting point, the crystal lattice is not destroyed, the molecular chains are closely arranged, and the gas Molecules have an excellent barrier effect; on the other hand, as a dispersed phase, the heat-resistant and oil-resistant rubber has excellent oil-resistant and high-temperature resistant properties due to the existence of polar groups. In addition, the thermoplastic vulcanizate of the present invention also has the characteristics of simple preparation process, excellent mechanical properties, low hardness, recyclability and the like. The thermoplastic vulcanizate of the present invention can replace traditional thermoplastic rubber and be used in automobile rubber hoses, wire and cable insulation layers, tool handles and the like.

Detailed ways

The present invention is specifically described below in conjunction with specific embodiment, it is necessary to point out here that following embodiment is only used for the further description of the present invention, can not be interpreted as the restriction to protection scope of the present invention, those skilled in the art can understand the present invention according to the content of the present invention Some non-essential improvements and adjustments made by the invention still belong to the protection scope of the present invention.

The raw materials used in the following examples are all commercially available products.

Example 1

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: at room temperature, mix hydrogenated nitrile rubber and DOP evenly with an open mill; mix with EFEP and antioxidant 168 at 220°C in an internal mixer, mix evenly, and then discharge and cool to room temperature; At room temperature, with 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide and stearic acid in the open Mix evenly in the mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber and plastic premix in a twin-screw extruder (Nanjing Rubber and Plastic Machinery Factory Co., Ltd., HTS-40, the same below), set the screw temperature to 220°C, and the speed to 200rpm, and dynamically vulcanize to obtain Thermoplastic vulcanizate.

Example 2

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber and plastic blending: at room temperature, mix hydrogenated nitrile rubber and paraffin oil evenly with an open mill; mix with EFEP and antioxidant 168 at 220°C in an internal mixer, mix evenly, and then discharge and cool to room temperature ; At room temperature, with 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide and stearic acid in Mix evenly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 300 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 3

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber and plastic blending: at room temperature, mix hydrogenated nitrile rubber and dibutyl phthalate evenly with an open mill; mix with ETFE and antioxidant 168 at 250°C in an internal mixer, and mix evenly The discharge is cooled to room temperature; at room temperature, with 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide Mix evenly with stearic acid in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 250° C., and the rotation speed at 600 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 4

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, acrylate rubber and antioxidant 168 in an internal mixer at 220°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with TCY, sulfur, accelerator BZ, anti-oxidant The coke agent PVI is mixed uniformly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 5

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, acrylate rubber and antioxidant 168 in an internal mixer at 220°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with TCY, sulfur, accelerator BZ, anti-oxidant The coke agent CTP is mixed uniformly in an open mill to obtain a rubber and plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 6

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, ethylene-vinyl acetate rubber and antioxidant 1010 in an internal mixer at 220°C, mix evenly and cool to room temperature; at room temperature, mix with DCP, HVA-2, Mix polyimide carbonate and antioxidant RD uniformly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 7

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, ethylene-vinyl acetate rubber and antioxidant 1010 in an internal mixer at 220°C, mix evenly and cool to room temperature; at room temperature, mix with DCP, HVA-2, Mix polyimide carbonate and antioxidant RD uniformly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 8

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, ethylene-vinyl acetate rubber and antioxidant 1010 in an internal mixer at 220°C, mix evenly and cool to room temperature; at room temperature, mix with DCP, HVA-2, Mix polyimide carbonate and antioxidant RD uniformly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 9

The basic composition and parts by weight of selected raw materials are as follows:

(1) Rubber-plastic blending: Mix EVOH, fluororubber and antioxidant 168 in an internal mixer at 220°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with AD, TAIC, zinc oxide, calcium hydroxide Mix evenly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 10

The basic composition and parts by weight of selected raw materials are as follows:

(1) Rubber-plastic blending: Mix EVOH, fluororubber and antioxidant 168 in an internal mixer at 220°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with AD, TAIC, zinc oxide, calcium hydroxide Mix evenly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Example 11

The basic composition and parts by weight of selected raw materials are as follows:

(1) Rubber and plastic blending: Mix EVOH, fluororubber and antioxidant 168 in an internal mixer at 190°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with AD, TAIC, zinc oxide, calcium hydroxide Mix evenly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Comparative example 1

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber and plastic blending: at room temperature, mix hydrogenated nitrile rubber and trioctyl trimellitate evenly with an open mill; mix with ETFE and antioxidant 168 at 250°C in an internal mixer, and mix evenly The discharge is cooled to room temperature; at room temperature, with 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide Mix evenly with stearic acid in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 250° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Comparative example 2

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber and plastic blending: at room temperature, mix hydrogenated nitrile rubber and dioctyl phthalate evenly with an open mill; mix with EFEP and antioxidant 168 at 250°C in an internal mixer, and mix evenly The discharge is cooled to room temperature; at room temperature, with 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide Mix evenly with stearic acid in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 250° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Comparative example 3

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber and plastic blending: at room temperature, mix hydrogenated nitrile rubber and dioctyl phthalate evenly with an open mill; mix with EFEP and antioxidant 168 at 250°C in an internal mixer, and mix evenly The discharge is cooled to room temperature; at room temperature, with 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, triallyl isocyanurate, antioxidant 4010NA, zinc oxide Mix evenly with stearic acid in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 250° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Comparative example 4

The basic composition and parts by weight of selected raw materials are as follows:

Preparation process of thermoplastic vulcanizate:

(1) Rubber-plastic blending: Mix EFEP, ethylene-vinyl acetate rubber and antioxidant 1010 in an internal mixer at 220°C, mix evenly and cool to room temperature; at room temperature, mix with DCP, HVA-2, Mix polyimide carbonate and antioxidant RD uniformly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 220° C., and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

Comparative example 5

The basic composition and parts by weight of selected raw materials are as follows:

(1) Rubber-plastic blending: Mix EVOH, fluororubber and antioxidant 168 in an internal mixer at 220°C, mix evenly, and then discharge and cool to room temperature; at room temperature, mix with AD, TAIC, zinc oxide, calcium hydroxide Mix evenly in an open mill to obtain a rubber-plastic premix;

(2) Dynamic vulcanization: Put the rubber-plastic premix in a twin-screw extruder, set the screw temperature at 200°C, and the rotation speed at 200 rpm, and dynamically vulcanize to obtain thermoplastic vulcanizate.

The samples prepared in the above examples and comparative examples were pressed into thin sheets with a thickness of 2 mm, and tested for tensile strength, elongation at break, oil resistance and air tightness according to GB/T528-2009 and GB/T1690-2006 standards . Among them, the oil resistance test conditions are: temperature 125°C, time 96h, the experimental medium is IRM903 experimental oil; the air tightness test conditions are: temperature 23°C, humidity 50%, nitrogen atmosphere, pressure difference 0.5MPa. The test results are shown in Table 1:

Table 1

Table 1 data shows, by the test data of embodiment 1, embodiment 2, embodiment 3 and comparative example 1 as can be seen, the higher the acrylonitrile content in the hydrogenated nitrile rubber, the thermoplastic vulcanizate shows better oil resistance , and the increase of the amount of plasticizer makes the barrier performance of thermoplastic vulcanizate significantly decreased, which is mainly by the plasticizing effect of the plasticizer; by the test data of Example 1, Example 2, Example 3 and Comparative Example 2 As can be seen, the higher the double bond content of hydrogenated nitrile rubber, will obviously reduce the aging resistance of thermoplastic vulcanizate (the fracture at the double bond place is prone to occur), and the volume expansion rate obviously improves; by embodiment 6, embodiment 7, From the results of Example 8 and Comparative Example 4, it can be clearly seen that the higher the VA content in EVM, the lower the volume expansion of the prepared thermoplastic vulcanizate in oil, which means good oil resistance; Example 9, Example 10 , the test data of Example 11 and Comparative Example 5, it can be seen that with the increase of the ethylene segment content in EVOH, the mechanical properties of the thermoplastic vulcanizate decrease significantly, and the oil resistance and barrier properties also decrease significantly, which is mainly because ethylene The increase of the segment content means the decrease of the vinyl alcohol content in the molecular chain, and the decrease of the hydroxyl content in the vinyl alcohol will reduce the force between the molecular chains, thereby reducing the mechanical properties, oil resistance and barrier properties of the thermoplastic vulcanizate. At the same time, it also causes the melting point to drop and the heat resistance to decrease.

Based on the above data, the thermoplastic vulcanizate prepared by the present invention has excellent oil resistance and gas barrier properties at high temperatures, and has a low hardness and a melting point close to 200 ° C. It is a kind of high temperature resistance, oil resistance and barrier properties. Material.

Claims (7)

1. The high-temperature-resistant oil-resistant high-barrier thermoplastic vulcanized rubber is characterized by being prepared by dynamically vulcanizing the following raw materials:

temperature-resistant oil-resistant rubber, high-gas-barrier plastic, vulcanizing agent and vulcanizing aid;

the components are calculated according to parts by weight:

the temperature-resistant oil-resistant rubber is hydrogenated nitrile rubber;

the double bond content of the hydrogenated nitrile rubber is 0.9-10%, and the acrylonitrile content is 20-50%;

the high gas barrier plastic is at least one of ethylene-tetrafluoroethylene copolymer and ethylene-tetrafluoroethylene-hexafluoropropylene copolymer;

or alternatively, the first and second heat exchangers may be,

the temperature-resistant oil-resistant rubber is fluorine rubber;

the fluorine rubber is at least one of vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroether rubber and fluorosilicone rubber;

the high gas barrier plastic is ethylene-vinyl alcohol copolymer;

the ethylene content in the ethylene-vinyl alcohol copolymer is 20-45%, and the vinyl alcohol content is 55-80%;

or alternatively, the first and second heat exchangers may be,

the temperature-resistant oil-resistant rubber is at least one of acrylate rubber and ethylene-vinyl acetate rubber;

the acrylic rubber is active chlorine acrylic rubber;

the vinyl acetate content in the ethylene-vinyl acetate rubber is 45-90%;

the high gas barrier plastic is ethylene-tetrafluoroethylene-hexafluoropropylene copolymer.

2. The high temperature resistant, oil resistant and high barrier thermoplastic vulcanizate of claim 1, wherein: the components are calculated according to parts by weight:

3. the high temperature resistant, oil resistant and high barrier thermoplastic vulcanizate of claim 1, wherein:

the double bond content of the hydrogenated nitrile rubber is 0.9-5%; the acrylonitrile content is 30-45%.

4. The high temperature resistant, oil resistant and high barrier thermoplastic vulcanizate of claim 1, wherein:

the vulcanizing agent is at least one of dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, sulfur and cyanuric acid;

the vulcanization aid is at least one of triallyl isocyanurate, N' -m-phenylene bismaleimide and zinc dibutyl dithiocarbamate.

5. The high temperature resistant, oil resistant and high barrier thermoplastic vulcanizate of claim 1, wherein: the thermoplastic vulcanized rubber also comprises the following raw materials:

at least one of antioxidant, anti-aging agent, plasticizer, zinc oxide, calcium hydroxide, stearic acid, scorch retarder and anti-hydrolysis agent;

the plasticizer is at least one of dioctyl phthalate, paraffin oil, dibutyl phthalate and trioctyl trimellitate;

the scorch retarder is at least one of N-cyclohexyl thiophthalimide and N-cyclohexyl thiophthalimide;

taking the temperature-resistant oil-resistant rubber as 100 parts by weight;

5-20 parts of plasticizer;

0.1-1 part by weight of scorch retarder.

6. A method for preparing the high temperature resistant oil resistant high barrier thermoplastic vulcanizate of any one of claims 1 to 5, comprising:

the thermoplastic vulcanized rubber is prepared by premixing the components in parts by weight and then dynamically vulcanizing the components.

7. The method for preparing the high-temperature-resistant oil-resistant high-barrier thermoplastic vulcanizate according to claim 6, wherein the method comprises the following steps:

the premixing temperature of rubber and plastic is 190-250 ℃, the dynamic vulcanization temperature is 200-250 ℃, and the rotating speed is 200-600rpm.