CN104725729B - A kind of EPT rubber composite material and its preparation - Google Patents

Abstract

The invention provides a high-reinforcement EPDM/polypropylene composite material and a preparation method thereof. Specifically, the composite material of the invention has the following components by weight: 30-70 parts of EPDM; 70-30 parts of polypropylene; 1-10 parts of alkenyl-terminated montmorillonite; 0.1-1 part of modified graphene oxide; 1-6 parts of vulcanizing agent; 1-10 parts of auxiliary agent. The high-reinforcement EPDM rubber/polypropylene rubber-plastic composite material prepared by the invention has excellent mechanical properties such as tensile strength, and is especially suitable for special requirements in fields such as automobiles and constructions.

Description

A kind of EPDM/polypropylene composite material and its preparation

technical field

The invention belongs to the preparation of rubber-plastic composite materials, and relates to a preparation method of high-reinforcement EPDM/polypropylene rubber-plastic composite materials.

Background technique

Thermoplastic elastomer material (TPE) is a material developed in recent years, and its structural characteristics are composed of rubber and plastic. The use of EPDM rubber and polypropylene to prepare rubber-plastic composite materials can not only solve the shortcomings of polypropylene after molding, such as insufficient toughness, low notched impact strength, low thermal deformation temperature, and poor creep resistance, but also solve the problems of EPDM. The disadvantage of low tear strength of rubber. EPDM/PP rubber-plastic composites can be used as composite materials with excellent performance, and have broad application prospects in the fields of automobiles and construction.

Among the existing invention patents, the Chinese patent with the publication number CN 1546561 A proposes a method for preparing a halogen-free flame-retardant EPDM/PP thermoplastic elastomer by using dynamic vulcanization technology. The Chinese patent with the publication number CN1687218 A proposes a method for preparing EPDM/PP thermoplastic elastomers using a vulcanization system composed of bis(3-triethoxysilylpropyl)tetrasulfide and the like. The above thermoplastic elastomers have different preparation formulas and processes, but each has its own characteristics. However, the formulation and process of these thermoplastic elastomers are relatively cumbersome, and they are easy to cause pollution to the environment, and the mechanical properties generally need to be further improved, for example, the tensile strength does not exceed 15 MPa.

Therefore, there is an urgent need in this field to select a suitable formula and process, a more effective reinforcement system, and improve the mechanical properties of rubber and plastic materials, which is of great significance to industrial production.

Contents of the invention

The invention provides an EPDM rubber/polypropylene rubber-plastic composite material with high reinforcing performance and a preparation method thereof.

The first aspect of the present invention provides a kind of EPDM/polypropylene composite material, the composite material has the following components by weight:

Wherein, the terminal alkenyl group is a C2-C6 straight chain or branched hydrocarbon group with a double bond at the terminal position.

In another preferred example, the weight portion of the alkenyl-terminated montmorillonite is 1-10 parts, more preferably 3-7 parts.

In another preferred example, the graphene oxide is 0.1-1 part by weight, preferably 0.2-0.3 part by weight.

In another preferred example, the terminal alkenyl group includes vinyl, propenyl and butenyl.

In another preferred example, the terminal alkenyl group is provided by a silane coupling agent containing a terminal alkenyl functional group.

In another preferred embodiment, the vinyl group is provided by a silane coupling agent containing a vinyl functional group.

In another preferred embodiment, the silane coupling agent containing vinyl functional groups includes vinyltriethoxysilane or vinyltrimethoxysilane or a combination thereof.

In another preferred example, the graphene oxide includes modified or unmodified graphene oxide.

In another preferred example, the modified graphene oxide is prepared by modifying graphene oxide with a graphene oxide modifier, such as hexadecylamine and octadecylamine.

In another preferred example, the alkenyl-terminated montmorillonite is prepared from montmorillonite and a montmorillonite modifier.

In another preferred example, the montmorillonite modifier includes a vinyl functional group-containing silane coupling agent and a quaternary ammonium salt;

Preferably, the silane coupling agent containing vinyl functional groups includes vinyltriethoxysilane, vinyltrimethoxysilane or a combination thereof; and/or

In another preferred example, the quaternary ammonium salt includes cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyltrimethylammonium trimethylammonium chloride or combinations thereof.

In another preference, the mass ratio of the montmorillonite to the silane coupling agent containing vinyl functional groups (especially vinyltriethoxysilane) is 5-50:0.5-3; preferably, 8-20: 0.8-2.5; more preferably, 10-15: 1-2.

In another preferred embodiment, the weight ratio of the montmorillonite to the quaternary ammonium salt is 4-25:4-10, preferably 8-20:4-8; more preferably, 8-16:5 -8.

In another preferred example, the alkenyl-terminated montmorillonite is prepared from montmorillonite, a montmorillonite modifier and water.

In another preferred example, the water includes deionized water, reverse osmosis water, distilled water, more preferably, deionized water.

In another preferred embodiment, the mass ratio of the deionized water to the montmorillonite is 2-20:1, preferably 4-8:1.

In another preference, the vulcanizing agent includes dicumyl peroxide or benzoyl peroxide; and/or

The auxiliary agents include antioxidants and compatibilizers.

In another preferred example, the antioxidant includes pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1010).

In another preferred example, the compatibilizer includes paraffin oil and hydroxyl silicone oil.

In another preferred example, the weight part of the antioxidant 1010 is 1-5 parts.

In another preferred example, the weight part of the paraffin oil is 1-5 parts.

In another preferred example, the described alkenyl-terminated montmorillonite is prepared through the following steps:

(a1) providing a reaction mixture of montmorillonite, a silane coupling agent containing terminal alkenyl functional groups and water;

Wherein, the mass ratio of the montmorillonite to the silane coupling agent containing alkenyl-terminated functional groups is 5-50:0.5-3, preferably 10-15:1-2; and/or

The mass ratio of the montmorillonite to water is 1:2-20, preferably 3:4-20, more preferably 1:4-8.

(b1) heating the reaction mixture in (a1) to obtain alkenyl-terminated montmorillonite.

In another preferred example, the reaction mixture in step (a1) further includes a quaternary ammonium salt.

In another preferred example, the mass ratio of the montmorillonite to the quaternary ammonium salt is 8-16:5-8.

In another preferred example, the step (a1) further includes dissolving the reaction mixture in an alcohol solution, preferably absolute ethanol.

In another preferred example, the mass ratio of the absolute ethanol to the montmorillonite is 2-10:1, preferably 3-5:1.

In another preferred embodiment, the heating temperature in step (b) is 30-100°C, preferably 50-80°C.

In another preferred example, the heating time is 2-10 hours, preferably 3-6 hours.

The second aspect of the present invention provides a method for preparing the EPDM/PP composite material described in the first aspect of the present invention, using montmorillonite, graphene oxide, and EPDM modified by terminal alkenyl groups Rubber, polypropylene, vulcanizing agent prepare described EPDM rubber/polypropylene composite material, wherein the montmorillonite modified by the terminal alkenyl group is prepared by montmorillonite and montmorillonite modifier, modified graphite oxide Graphene is prepared from graphene oxide and graphene oxide modifier.

In another preferred example, the montmorillonite modifier includes a silane coupling agent containing terminal alkenyl functional groups and a quaternary ammonium salt.

In another preferred example, the modified graphene oxide is prepared by modifying graphene oxide with hexadecylamine or octadecylamine.

In another preferred example, comprising the steps of:

(i) Provide a modified montmorillonite and modified graphene oxide through terminal alkenyl group, wherein, the montmorillonite modified by terminal alkenyl group is composed of montmorillonite, vinyltriethoxysilane, hexadecyl Prepared by reacting trimethylammonium bromide and water; and the modified graphene oxide is prepared by modifying graphene oxide with hexadecylamine;

Wherein, the mass ratio of the montmorillonite to vinyltriethoxysilane containing terminal alkenyl groups is 10-15:1-2; and/or the ratio of montmorillonite to cetyltrimethylammonium bromide The mass ratio is 8-16:5-8; and/or the mass ratio of the montmorillonite to deionized water is 1:2-20, preferably 3:4-20, more preferably 1:4 -8.

(ii) the montmorillonite, modified graphene oxide, EPDM rubber, and polypropylene are mixed and reacted to obtain the modified EPDM rubber/polypropylene coarse mixture through terminal alkenyl group modification;

(iii) adding a vulcanizing agent to the modified EPDM/PP crude mixture and reacting, so as to obtain the EPDM/PP composite material as described in any one of claims 1-6.

In another preferred example, the vulcanizing agent is dicumyl peroxide.

In another preferred embodiment, the reactions in steps (i), (ii) and (iii) are heating reactions.

In another preferred example, step (ii) further includes adding an antioxidant 1010 before the reaction.

In another preferred example, step (ii) further includes adding paraffin oil to the crude mixture.

It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.

Description of drawings

Fig. 1 is the SEM image of the brittle section of the EPDM rubber/polypropylene rubber-plastic composite material prepared in Example 3 of the present invention.

Detailed ways

After extensive and in-depth research, the present inventor unexpectedly found for the first time that adding modified montmorillonite and modified graphene oxide containing unsaturated groups in the EPDM/PP rubber-plastic composite material can effectively Improve the tensile strength and hardness of the rubber-plastic composite material to form a highly-reinforced rubber-plastic composite material with better mechanical properties than existing rubber-plastic materials. In addition, by adjusting different component ratios, rubber-plastic composite materials with different industrial mechanical needs can be prepared. On this basis, the present invention has been accomplished.

EPDM/PP

Thermoplastic elastomer material (TPE) is a material developed in recent years, and its structural characteristics are composed of rubber and plastic. For details, see the rubber-plastic composite of EPDM and polypropylene (PP), which can not only solve the shortcomings of PP after molding, such as insufficient toughness, low notched impact strength, low thermal deformation temperature, and poor creep resistance, but also Solve the shortcomings of EPDM's low tear strength. PP/EPDM rubber-plastic composite material can be used as a composite material with excellent performance in the fields of automobiles and construction.

Montmorillonite and Modified Montmorillonite

Montmorillonite is a viscous mineral with a lamellar structure, which can be widely used to reinforce polymer materials, and can effectively improve the mechanical properties of polymers such as tensile strength, Young's modulus, and impact strength. At the same time, It can also improve the processability of the polymer. However, the commonly used montmorillonite has poor compatibility with the rubber-plastic matrix, and the interfacial bonding force is not high, resulting in poor mechanical properties of rubber-plastic composites, so it is often difficult to be directly applied to the preparation of rubber-plastic composites.

As used herein, the terms "modified montmorillonite", "montmorillonite modified with terminal alkenyl groups", and "modified montmorillonite containing unsaturated groups" are used interchangeably, and all refer to Agent-modified montmorillonite containing terminal alkenyl groups. In order to make the structural properties of montmorillonite more suitable for rubber-plastic composite materials, the inventors hydrolyzed the silane coupling agent containing terminal alkenyl groups in water, and the hydrolyzed product reacted with the hydroxyl groups of the montmorillonite layer to obtain unsaturated bis Bond-modified montmorillonite can enhance the interfacial bonding between montmorillonite and rubber-plastic matrix. In addition, in the present invention, the quaternary ammonium salt can also be used as a supplement to the montmorillonite modifier, so as to more effectively expand the interlayer interval of the montmorillonite and facilitate the insertion of polymer molecules.

As used herein, the montmorillonite modifier refers to any modifier capable of making the montmorillonite contain unsaturated groups after reacting with the montmorillonite. Usually, the montmorillonite modifier can make the montmorillonite contain terminal alkenyl groups, so that the montmorillonite can enhance the interfacial bonding with the composite material during the vulcanization process.

Typically, modifiers capable of imparting terminal alkenyl groups to montmorillonite include silane coupling agents containing terminal alkenyl functional groups. A preferred silane coupling agent containing terminal alkenyl functional groups is a silane coupling agent containing vinyl, preferably vinyltriethoxysilane and vinyltrimethoxysilane.

In addition, a preferred montmorillonite modifier includes a combination of a silane coupling agent containing terminal alkenyl functional groups and a quaternary ammonium salt.

Preferred quaternary ammonium salts useful in the present invention include cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyltrimethylammonium Quaternary ammonium salts such as ammonium chloride or combinations thereof.

In the present invention, the weight ratio of the montmorillonite modifier to the montmorillonite is not particularly limited, and can be any ratio that can successfully modify the montmorillonite so that the montmorillonite contains unsaturated groups. Preferably, when selecting vinyltriethoxysilane and cetyltrimethylammonium bromide as the montmorillonite modifier, the mass ratio of montmorillonite: vinyltriethoxysilane is 10-15: 1-2; Montmorillonite: cetyltrimethylammonium bromide 8-16:5-8.

Usually, the montmorillonite and the montmorillonite modifier can be mixed and then fully dispersed in the solvent system, or the montmorillonite and the montmorillonite modifier can be separately dispersed in the solvent system and mixed, in order to speed up the reaction and make the montmorillonite To fully modify the soil, it is preferable to heat the dispersed montmorillonite and montmorillonite modifier.

In a preferred embodiment, the preparation method of alkenyl-terminated montmorillonite is as follows:

Mix montmorillonite, deionized water and absolute ethanol evenly, under magnetic stirring, add hydrochloric acid to adjust the pH value of the mixture to 3-4, then add vinyltriethoxysilane, heat to 50-100°C After modification for several hours, add cetyltrimethylammonium bromide, stir at 50-80°C, suction filter, wash, and dry to finally obtain a modified montmorillonite containing unsaturated groups. Wherein, the mass ratio of montmorillonite: vinyltriethoxysilane is 10-15:1-2; the mass ratio of montmorillonite: hexadecyltrimethylammonium bromide is 8-16:5 -8. The mass ratio of described absolute ethanol and described montmorillonite is 1-10:1, is preferably 3-5:1; The mass ratio of described deionized water and described montmorillonite is 2-20: 1, preferably 4-8:1.

Graphene oxide

Graphene oxide is generally obtained by oxidation of graphite with strong acid. Since graphene oxide is a single atomic layer, it can expand to tens of microns in the lateral dimension at any time. As an excellent soft material, it has high Young's modulus, tensile strength, and fracture strength. In the present invention, it is further preferred to use modified graphene oxide. The surface-modified graphene oxide has improved compatibility with the polymer matrix, which can effectively improve the reinforcing effect.

Modified graphene oxide usable in the present invention is not particularly limited. Generally, various modified graphene oxides can be obtained by surface modification of graphene oxide with suitable modifiers.

A preferred graphene oxide that can be used in the present invention is further modified graphene oxide. Wherein, the modifying agent used for further modification includes cetylamine, octadecylamine and the like.

Generally, modified graphene oxide can be prepared according to conventional methods in the prior art, and can also be prepared according to the following method:

Disperse graphene oxide in a solvent system composed of deionized water and absolute ethanol, mix uniformly, add hexadecylamine, heat and carry out reflux reaction for 12-28 hours, more preferably 18-24 hours. After suction filtration, washing and drying, the modified modified graphene oxide is finally obtained.

Vulcanizing agent

The vulcanizing agent that can be used in the present invention is not particularly limited, and it is a peroxide vulcanizing agent commonly used in the preparation of rubber-plastic composite materials in this field. Preferred vulcanizing agents include dicumyl peroxide, benzoyl peroxide.

In the present invention, it is preferable to add the vulcanizing agent at the initial stage of dynamic vulcanization.

Auxiliary

The auxiliaries that can be used in the present invention are not particularly limited, and are any auxiliaries that improve the performance of raw materials in the preparation of rubber-plastic composite materials in the field. Usually, additives include antioxidants and compatibilizers.

Wherein, the antioxidant includes tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol (1010); the compatibilizer includes paraffin oil and hydroxy silicone oil.

In a preferred example, the antioxidant is added in the initial heating and kneading stage of preparing the rubber-plastic composite material, so as to enhance the oxidation resistance of the raw materials for preparation.

The number of parts of the additives and the adding time are not particularly limited, and they are the conventional dispersion and adding time that can be used in the preparation of rubber-plastic composite materials in this field.

Preparation

The present invention also provides a method for EPDM/PP composite material, which is to utilize montmorillonite, modified graphene oxide, EPDM rubber, polypropylene, vulcanized The EPDM rubber/polypropylene composite material is prepared by using an agent, wherein the alkenyl-terminated montmorillonite is prepared from montmorillonite and a montmorillonite modifier.

A preferred montmorillonite modifier includes vinyltriethoxysilane and cetyltrimethylammonium bromide. In addition, modified graphene oxide is prepared by further modification of graphene oxide.

In a preferred mode, the method of the present invention comprises:

(i) Provide a modified montmorillonite and modified graphene oxide through terminal alkenyl group, wherein, described unsaturated montmorillonite is made of montmorillonite, vinyltriethoxysilane, hexadecyltrimethyl and the modified graphene oxide is obtained by modifying and modifying graphene oxide with hexadecylamine;

(ii) the montmorillonite, modified graphene oxide, EPDM rubber, and polypropylene are mixed and reacted to obtain the modified EPDM rubber/polypropylene coarse mixture through terminal alkenyl group modification;

(iii) Adding a vulcanizing agent to the modified EPDM/PP rough mixture and reacting, so as to prepare the EPDM/PP composite material.

In another preferred example, the vulcanizing agent is dicumyl peroxide.

In another preferred embodiment, the reactions in steps (i), (ii) and (iii) are heating reactions.

In another preferred example, step (ii) also includes adding an antioxidant before the reaction.

In another preferred example, step (ii) further includes adding a compatibilizer into the crude mixture.

Beneficial effects of the present invention

1. Montmorillonite has been modified in multiple steps and contains unsaturated groups. During the vulcanization process, it can form chemical bonds with the molecular chains of EPDM rubber to enhance its interface bonding with rubber-plastic composite materials and improve the strength of composite materials. mechanical properties.

2. Use montmorillonite containing unsaturated groups and modified graphene oxide as the reinforcement system to fill EPDM rubber/polypropylene. While maintaining the thermoplastic processing type and rubber elasticity, different pulleys can be prepared according to needs. Tensile strength, elongation at break, and hardness of EPDM/PP rubber-plastic composite materials.

3. Compared with the existing EPDM/PP rubber-plastic composite material (such as Chinese Patent Publication No. CN1687218A), the rubber-plastic composite material of the present invention has obvious advantages in terms of mechanical properties.

4. The present invention has little environmental pollution and strong pertinence, which is beneficial to popularization and application in industrial production.

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed. Percentages and parts are by weight unless otherwise indicated.

The preparation of the EPDM rubber/polypropylene composite material in the prior art of embodiment 1

The composite material of this embodiment can be prepared by conventional methods in the art, specifically as follows:

Mix EPDM rubber, polypropylene and antioxidant for 5 minutes on the internal mixer at 170°C and 80r/min, add dicumyl peroxide for dynamic vulcanization for 3 minutes, granulate the mixture, and vulcanize on a plate at 180°C for 40 minutes , that is, a highly reinforced EPDM/PP composite material.

Embodiment 2 only contains the preparation of the composite material of modified montmorillonite

2.1 Preparation of modified montmorillonite:

According to the mass ratio of montmorillonite: deionized water: absolute ethanol is 1:4:3, mix montmorillonite, deionized water, and absolute ethanol evenly, under magnetic stirring, add 0.1mol/L hydrochloric acid to dissolve The pH of the mixture was adjusted to 3.5;

According to the mass ratio of montmorillonite: vinyltriethoxysilane of 10:1, add vinyltriethoxysilane and modify at 60°C for 4h;

According to the mass ratio of montmorillonite: hexadecyltrimethylammonium bromide is 5:2, add hexadecyltrimethylammonium bromide, stir at 60°C for 45h, filter with suction, wash 4 times, and dry , and finally get modified montmorillonite.

2.2 Preparation of EPDM/PP rubber-plastic composite material: Mix EPDM rubber, polypropylene, and antioxidant for 5 minutes on an internal mixer at 170°C and 80 r/min, add paraffin oil, modified Mongolian Remove the soil and mix for 7 minutes, add dicumyl peroxide and dynamically vulcanize for 3 minutes. After the mixture is granulated, vulcanize on a flat plate at 170°C for 40 minutes to obtain a high-reinforcement EPDM/PP composite material.

Embodiment 3 only contains the preparation of the composite material of modified graphene oxide

3.1 Preparation of modified graphene oxide: According to the mass ratio of graphene oxide: deionized water: absolute ethanol is 1:100:100, add graphene oxide, deionized water, absolute ethanol and mix evenly, under magnetic stirring , adding hexadecylamine at a mass ratio of graphene oxide: hexadecylamine of 1:1, reflux reaction at 100°C for 20 hours, suction filtration, four washings, and drying to finally obtain modified graphene oxide.

3.2 Preparation of EPDM/PP rubber-plastic composite material: Mix EPDM rubber, polypropylene, and antioxidant for 5 minutes on an internal mixer at 170°C and 80 r/min, add paraffin oil, and modified graphite Mix ethylene for 7 minutes, add dicumyl peroxide and dynamically vulcanize for 3 minutes. After the mixture is granulated, vulcanize on a plate at 170°C for 40 minutes to obtain a high-reinforcement EPDM/PP composite material.

Example 4 Preparation of EPDM/PP rubber-plastic composite material of the present invention 1

4.1 Preparation of modified montmorillonite: According to the mass ratio of montmorillonite: deionized water: absolute ethanol is 1:5:3, mix montmorillonite, deionized water, and absolute ethanol evenly, and stir under magnetic force , add 0.1mol/L hydrochloric acid to adjust the pH of the mixture to 3, according to the mass ratio of montmorillonite: vinyltriethoxysilane 10:1, add vinyltriethoxysilane, modify at 60 °C 3h, according to the mass ratio of montmorillonite: hexadecyltrimethylammonium bromide is 5:2, add hexadecyltrimethylammonium bromide, stir at 60°C for 3h, filter with suction and wash 3 times , drying, and finally obtain the modified montmorillonite.

4.2 Preparation of modified graphene: According to the mass ratio of graphene oxide: deionized water: absolute ethanol is 1:100:100, add graphene oxide, deionized water, and absolute ethanol to mix evenly, under magnetic stirring, Hexadecylamine was added at a mass ratio of graphene oxide: hexadecylamine of 1:1, refluxed at 90°C for 18 hours, suction filtered, washed three times, and dried to finally obtain modified graphene oxide.

4.3 Preparation of EPDM/PP rubber-plastic composite material: Mix EPDM rubber, polypropylene, and antioxidant for 5 minutes on an internal mixer at 170°C and 80 r/min, add paraffin oil, and reinforce the system Mix for 7 minutes, add dicumyl peroxide and dynamically vulcanize for 3 minutes. After the mixture is granulated, vulcanize on a plate at 170°C for 40 minutes to obtain a high-reinforcement EPDM/PP composite material.

Example 5 Preparation of EPDM/PP rubber-plastic composite material of the present invention 2

5.1 Preparation of modified montmorillonite: According to the mass ratio of montmorillonite: deionized water: absolute ethanol is 1:6:4, mix montmorillonite, deionized water, and absolute ethanol evenly, and stir under magnetic force , add 0.2mol/L hydrochloric acid to adjust the pH of the mixed solution to 3.5, according to the mass ratio of montmorillonite: vinyltrimethoxysilane 10:1, add vinyltrimethoxysilane, modify at 70°C for 4h, According to the mass ratio of montmorillonite:octadecyltrimethylammonium bromide of 5:2, add octadecyltrimethylammonium bromide, stir at 70°C for 4 hours, filter with suction, wash 4 times, and dry , and finally get modified montmorillonite.

5.2 Preparation of modified graphene: According to the mass ratio of graphene oxide: deionized water: absolute ethanol is 1:100:100, add graphene oxide, deionized water, and absolute ethanol to mix evenly, under magnetic stirring, Hexadecylamine was added at a mass ratio of graphene oxide: hexadecylamine of 1:1, refluxed at 100°C for 20 hours, suction filtered, washed 4 times, and dried to finally obtain modified graphene oxide.

5.3 Preparation of EPDM/PP rubber-plastic composite material: Mix EPDM rubber, polypropylene, and antioxidant for 7 minutes on an internal mixer at 175°C and 85 r/min, add paraffin oil, and reinforce the system Mix for 9 minutes, add dicumyl peroxide and dynamically vulcanize for 3.5 minutes. After the mixture is granulated, vulcanize on a plate at 175°C for 50 minutes to obtain a high-reinforcement EPDM/PP composite material.

Example 6 Preparation of EPDM/PP rubber-plastic composite material of the present invention 3

6.1 Preparation of modified montmorillonite: According to the mass ratio of montmorillonite: deionized water: absolute ethanol is 1:6:5, mix montmorillonite, deionized water, and absolute ethanol evenly, and stir under magnetic force , add 0.3mol/L hydrochloric acid to adjust the pH of the mixture to 4, according to the mass ratio of montmorillonite: vinyltriethoxysilane 10:1, add vinyltriethoxysilane, modify at 80 °C 5h, according to the mass ratio of montmorillonite: cetyltrimethylammonium chloride 3:1, add cetyltrimethylammonium chloride, stir at 80°C for 5h, filter with suction and wash 5 times , drying, and finally obtain the modified montmorillonite.

6.2 Preparation of modified graphene: According to the mass ratio of graphene oxide: deionized water: absolute ethanol is 1:100:100, add graphene oxide, deionized water, and absolute ethanol to mix evenly, under magnetic stirring, Octadecylamine was added at a mass ratio of graphene oxide: octadecylamine of 1:1, refluxed at 110°C for 22 hours, suction filtered, washed four times, and dried to obtain modified graphene oxide.

6.3 Preparation of EPDM/PP rubber-plastic composite material: Mix EPDM rubber, polypropylene, and antioxidant for 9 minutes on an internal mixer at 180°C and 90 r/min, add paraffin oil, and reinforce the system Mix for 10 minutes, add dicumyl peroxide and dynamically vulcanize for 4 minutes. After the mixture is granulated, vulcanize on a plate at 180°C for 30 minutes to obtain a high-reinforcement EPDM/PP composite material.

The formulations of each embodiment are shown in Table 1.

Table 1

In the above examples, all raw materials are commercially available products.

In the above examples, the amounts of all raw materials are in parts by weight, and EPDM+PP=100.

In the above-mentioned embodiments, the amount of raw materials used in each step and the process parameters (temperature, rotating speed, time, etc.) are range values, and any point can be used.

The performance measurement of composite material in embodiment 7 embodiment 1-6

Using Example 3, the SEM image of the brittle section of the EPDM/PP rubber-plastic composite material is obtained, as shown in FIG. 1 . In the figure, modified montmorillonite and modified graphene oxide are uniformly dispersed in a matrix composed of EPDM rubber and polypropylene.

The performance results obtained by using Examples 1-6 are shown in Table 2.

Table 2

Tensile strength, MPa Elongation at break, % Hardness, D Example 1 8.6 326 47 Example 2 15.1 410 49 Example 3 10.7 380 48 Example 4 17.6 440 50 Example 5 18.1 451 50 Example 6 18.8 445 50

As can be seen from Table 2, the performance of the EPDM/PP composite (embodiment 1) prepared according to the prior art is the worst, and the modified montmorillonite of the present invention and modified graphene oxide have been added respectively. The properties of the composite materials (Examples 2 and 3) are slightly improved, but far inferior to the composite materials (Examples 4-6) of the present invention which added modified montmorillonite and modified graphene oxide at the same time.

All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (13)

1. a kind of EPDM/PP composite material, it is characterized in that, described composite material has the component of following parts by weight: Wherein, the terminal alkenyl group is a C2-C6 straight chain or branched chain hydrocarbon group with a double bond at the terminal position, and the described montmorillonite modified by the terminal alkenyl group is prepared by the following steps: (a1) providing a reaction mixture of montmorillonite, a silane coupling agent containing terminal alkenyl functional groups and water; Wherein, the mass ratio of the montmorillonite to the alkenyl-terminated functional group-containing silane coupling agent is 5-50:3 and/or the mass ratio of the montmorillonite to water is 1:2-20; (b1) heating the reaction mixture in (a1), thereby obtaining the montmorillonite modified by terminal alkenyl groups; Wherein, the modified graphene oxide is prepared from graphene oxide and hexadecylamine. 2. The composite material according to claim 1, wherein said terminal alkenyl group comprises vinyl, propenyl and butenyl. 3. composite material as claimed in claim 1, it is characterized in that, described modified graphene oxide preparation method is as follows: graphene oxide is dispersed in the solvent system that deionized water and dehydrated alcohol form, after uniform mixing, add ten Hexamine, heated and refluxed for 12-28 hours, then suction filtered, washed and dried to finally obtain modified graphene oxide. 4. The composite material according to claim 1, characterized in that, the montmorillonite modified with terminal alkenyl groups is prepared from montmorillonite and a montmorillonite modifier. 5. The composite material according to claim 4, wherein the montmorillonite modifier comprises a silane coupling agent containing terminal alkenyl functional groups and a quaternary ammonium salt. 6. The composite material according to claim 1, wherein said vulcanizing agent comprises dicumyl peroxide or benzoyl peroxide; and/or The auxiliary agent includes antioxidant or compatibilizer. 7. The composite material according to claim 1 or 2, wherein the mass ratio of the montmorillonite to the silane coupling agent containing terminal alkenyl functional groups is 8-20: 2.5; and/or The mass ratio of the montmorillonite to water is 1:4-8. 8. The composite material according to claim 1 or 2, wherein the mass ratio of the montmorillonite to water is 1:4-8. 9. The composite material of claim 6, wherein the antioxidant comprises tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester. 10. prepare the method for EPDM rubber/polypropylene composite material as claimed in claim 1, it is characterized in that, utilize montmorillonite, graphene oxide, EPDM rubber, polypropylene, Vulcanizing agent prepares described EPDM rubber/polypropylene composite material, wherein the montmorillonite modified by terminal alkenes is prepared from montmorillonite and montmorillonite modifier, and the graphene oxide includes modified oxide Graphene, the modified graphene oxide is prepared from graphene oxide and hexadecylamine, and the described montmorillonite modified by terminal alkenyl group is prepared by the following steps: (a1) providing a reaction mixture of montmorillonite, a silane coupling agent containing terminal alkenyl functional groups and water; Wherein, the mass ratio of the montmorillonite to the alkenyl-terminated functional group-containing silane coupling agent is 5-50:3 and/or the mass ratio of the montmorillonite to water is 1:2-20; (b1) heating the reaction mixture in (a1) to obtain alkenyl-terminated montmorillonite. 11. The method according to claim 10, wherein the modified graphene oxide preparation method is as follows: graphene oxide is dispersed in a solvent system composed of deionized water and dehydrated alcohol, and after uniform mixing, add sixteen amine, heating and carrying out reflux reaction for 12-28 hours, and then suction filtering, washing and drying to finally obtain modified modified graphene oxide. 12. The method of claim 10, comprising the steps of: (i) Provide a modified montmorillonite and modified graphene oxide through terminal alkenyl group, wherein, the montmorillonite modified by terminal alkenyl group is composed of montmorillonite, vinyltriethoxysilane, hexadecyl Prepared by reacting trimethylammonium bromide and water; and the modified graphene oxide is prepared by modifying graphene oxide with hexadecylamine; Wherein, the mass ratio of the montmorillonite to vinyltriethoxysilane containing terminal alkenyl groups is 10-15:1-2; and/or the ratio of montmorillonite to cetyltrimethylammonium bromide The mass ratio is 16:5-8; and/or the mass ratio of the montmorillonite to deionized water is 1:2-20; (ii) the montmorillonite, modified graphene oxide, EPDM rubber, and polypropylene are mixed and reacted to obtain the modified EPDM rubber/polypropylene coarse mixture through terminal alkenyl group modification; (iii) adding a vulcanizing agent to the modified EPDM/PP crude mixture and reacting, so as to obtain the EPDM/PP composite material as claimed in claim 1. 13. The composite material according to claim 6, wherein the compatibilizer comprises paraffin oil or hydroxy silicone oil.