CN105400088B - A kind of ethylene propylene diene rubber and neoprene co-vulcanization material and preparation method thereof - Google Patents

Abstract

The invention provides a co-vulcanized material of EPDM rubber and chloroprene rubber and a preparation method thereof, which is prepared by mixing and vulcanizing the mixed material in sequence; in parts by mass, the mixed material includes: 60-100 Parts of EPDM rubber; x parts of chloroprene rubber; 0<x<40; 5-10 parts of zinc oxide; 3-4 parts of magnesium oxide; 4-6 parts of stearic acid; 10-30 parts carbon black; 1-5 parts of silane coupling agent Si69; 1-10 parts of maleic anhydride; 1-5 parts of glycidyl methacrylate; 1-2 parts of sulfur; 4-8 parts of vulcanization accelerator agent. The present invention adopts silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to process EPDM rubber, improve the binding ability of EPDM and sulfur, improve the vulcanization rate of EPDM phase, thereby improve the EPDM rubber and The co-vulcanization effect of chloroprene rubber makes EPDM/CR co-vulcanized rubber have excellent mechanical properties and other characteristics.

Description

A kind of EPDM rubber and neoprene co-vulcanized material and preparation method thereof

technical field

The invention relates to the technical field of composite rubber, in particular to a co-vulcanized material of EPDM rubber and chloroprene rubber and a preparation method thereof.

Background technique

The modernization of society has made the rubber industry flourish, and rubber products are widely used in various industries. Among them, ethylene-propylene-diene rubber (EPDM) is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, because of its excellent electrical insulation, low density and high filling, low temperature resistance, heat resistance, ozone resistance Properties such as weather resistance and aging resistance have been widely used, accounting for about 7% of the world's total synthetic rubber consumption, ranking third. However, EPDM has poor self-adhesiveness, poor mutual adhesion, poor flame retardancy, and obvious shortcomings of oil resistance, which limit the application range of EPDM.

Neoprene (referred to as neoprene, CR) enjoys the reputation of "universal glue". It not only has good oil resistance, heat resistance, ozone resistance, acid and alkali resistance and chemical medium resistance, but also has room temperature curing. , Flame retardant, high initial adhesion, high bonding strength and excellent comprehensive performance. After mixing CR into EPDM, the corresponding modified product can not only solve the shortcomings of EPDM such as difficult processing, flammability and oil resistance, but also obtain elastic materials with excellent comprehensive properties such as aging resistance, acid and alkali resistance, and easy bonding.

However, the structures of EPDM and CR are quite different. EPDM is a non-polar rubber with a saturated main chain, and CR is a polar rubber with a large number of double bonds. Under the same conditions, the vulcanization rate of CR is significantly higher than that of EPDM, and the solubility of the vulcanizing agent in CR is much higher than that in EPDM. In the EPDM/CR rubber prepared by the traditional sulfur vulcanization process, the CR phase is often vulcanized relatively completely, while the EPDM phase is short of sulfur, or even has no sulfur, and its performance is poor, which limits the application of EPDM/CR materials.

Contents of the invention

In view of this, the application provides a kind of EPDM and neoprene co-vulcanization material and preparation method thereof, the co-vulcanization effect of EPDM and neoprene co-vulcanization material provided by the invention is good, has excellent mechanical properties.

The invention provides a co-vulcanization material of EPDM rubber and chloroprene rubber, which is made of mixed materials through mixing and vulcanization in sequence; in parts by mass, the mixed materials include:

60-100 parts of EPDM rubber;

x parts of neoprene; 0<x<40;

5-10 parts of zinc oxide;

3-4 parts of magnesium oxide;

4-6 parts of stearic acid;

10-30 parts of carbon black;

1-5 parts of silane coupling agent Si69;

1 to 10 parts of maleic anhydride;

1 to 5 parts of glycidyl methacrylate;

1-2 parts of sulfur;

4 to 8 parts of vulcanization accelerator.

Preferably, the EPDM rubber is made of materials including ethylene, propylene and ethylidene norbornene.

Preferably, the neoprene rubber includes 80wt%-90wt% trans-1,4-polychloroprene and 1wt%-2wt% 1,2-polychloroprene.

Preferably, the vulcanization accelerator includes 1-2 parts of thiourea accelerator, 1-2 parts of thiazole accelerator and 2-4 parts of thiuram accelerator.

Preferably, the vulcanization accelerator includes 1 to 2 parts of 1,2-ethylenethiourea, 1 to 2 parts of dibenzothiazole disulfide and 2 to 4 parts of bis(thiocarbonyldimethylamine disulfide ).

Preferably, the mixed material further includes 1-2 parts of anti-aging agent.

Preferably, the mixed material further includes 10-15 parts of anti-radiation agent and 5-10 parts of waterproofing agent.

The present invention also provides a kind of preparation method of above-mentioned EPDM rubber and neoprene co-vulcanization material, comprises the following steps:

A) mixing EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to obtain modified EPDM rubber;

Mixing the modified EPDM rubber, carbon black, 1/2 mass of stearic acid and 1/2 mass of zinc oxide to obtain an EPDM rubber masterbatch;

Mixing neoprene, magnesium oxide and 1/2 quality stearic acid to obtain a neoprene masterbatch;

B) mixing the EPDM masterbatch, the chloroprene rubber masterbatch, sulfur, vulcanization accelerator and zinc oxide of 1/2 quality to obtain a rubber compound;

C) Vulcanizing the rubber material to obtain a co-vulcanized material of EPDM rubber and chloroprene rubber.

Preferably, in the step A), the temperature for kneading EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate is 110°C-120°C.

Preferably, the step B) is specifically:

Prevulcanizing the EPDM masterbatch with 1/2 mass of sulfur to obtain prevulcanized EPDM;

The pre-vulcanized EPDM rubber, the chloroprene rubber masterbatch, the vulcanization accelerator, 1/2 mass of sulfur and 1/2 mass of zinc oxide are mixed to obtain a rubber compound.

Compared with the prior art, the present invention mainly adopts EPDM rubber, chloroprene rubber, zinc oxide, magnesium oxide, stearic acid, carbon black, silane coupling agent Si69, maleic anhydride, glycidyl methacrylate The mixed material of ester, sulfur and vulcanization accelerator is sequentially mixed and vulcanized to prepare the co-vulcanized material of EPDM rubber and chloroprene rubber. Characteristic of the present invention mainly is, adopts silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to process EPDM (EPDM), improve the bonding ability of EPDM and sulfur, improve the vulcanization rate of EPDM phase, Thereby improving the effect of co-vulcanization of EPDM rubber and chloroprene rubber (CR), so that EPDM/CR co-vulcanized rubber has excellent mechanical properties and other characteristics.

detailed description

The following clearly and completely describes the technical solutions in the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides a co-vulcanization material of EPDM rubber and chloroprene rubber, which is made by mixing and vulcanizing the mixed materials in sequence; in parts by mass, the mixed materials include:

60-100 parts of EPDM rubber;

x parts of neoprene; 0<x<40;

5-10 parts of zinc oxide;

3-4 parts of magnesium oxide;

4-6 parts of stearic acid;

10-30 parts of carbon black;

1-5 parts of silane coupling agent Si69;

1 to 10 parts of maleic anhydride;

1 to 5 parts of glycidyl methacrylate;

1-2 parts of sulfur;

4 to 8 parts of vulcanization accelerator.

The co-vulcanized materials of EPDM rubber and chloroprene rubber provided by the invention are EPDM/CR composite rubber and EPDM/CR co-vulcanized rubber, which have excellent mechanical properties and the like.

The co-vulcanization material of EPDM rubber and chloroprene rubber provided by the present invention is obtained by mixing and vulcanizing the mixed materials in sequence; in parts by mass, the mixed materials include 60-100 parts of EPDM rubber, It preferably includes 70-80 parts of EPDM rubber. In the embodiment of the present invention, the used ethylene propylene diene rubber (EPDM) is a non-polar, non-crystalline rubber. Preferably, the third monomer of EPDM is ethylidene norbornene (ENB), that is, the EPDM rubber is made of materials including ethylene, propylene and ethylidene norbornene. The present invention has no special limitation on the source of the EPDM rubber, and commercially available products, such as EP35 produced by Japan Synthetic Rubber Company, can be used.

In parts by mass, the mixture of co-vulcanized materials includes x parts of chloroprene rubber, where 0<x<40, preferably 20-30 parts of chloroprene rubber. Neoprene rubber, also known as chloroprene rubber, is a synthetic rubber made of chloroprene as the main raw material for α-polymerization. The invention adopts the blending of chloroprene rubber (CR) and EPDM to prepare EPDM/CR composite rubber, so that it has excellent properties such as flame retardancy, low temperature resistance, heat resistance, ozone resistance and weather aging resistance. In an embodiment of the invention, the neoprene used is a sulfur regulated rubber. Preferably, the chloroprene rubber includes 80wt%-90wt% trans-1,4-polychloroprene and 1wt%-2wt% 1,2-polychloroprene. In a preferred embodiment of the present invention, the neoprene rubber includes 85wt% trans-1,4-polychloroprene and 1.5wt% 1,2-polychloroprene. The present invention has no special limitation on the source of the neoprene, and commercially available products can be used, such as neoprene CR126 produced by the German Lanxess Group.

In parts by mass, the mixed material includes 1-5 parts of silane coupling agent Si69, preferably 3-5 parts of silane coupling agent Si69. The mixed material includes 1-10 parts of maleic anhydride (MAH), preferably 5-10 parts of maleic anhydride. The mixed material includes 1-5 parts of glycidyl methacrylate (GMA), preferably 4-5 parts of glycidyl methacrylate. The present invention mainly adds silane coupling agent Si69, maleic anhydride and glycidyl methacrylate in EPDM, improves the binding ability of EPDM and sulfur, improves the vulcanization rate of EPDM phase, thereby improves EPDM rubber and chloroprene rubber (CR) co-vulcanization effect, so that EPDM/CR co-vulcanized rubber has excellent mechanical properties and other characteristics. The present invention solves the problem of uneven vulcanization of traditional EPDM/CR composite rubber from the perspective of increasing the vulcanization performance of EPDM; in the present invention, the crosslinking degree of the two phases in the EPDM/CR co-vulcanized rubber is relatively perfect, and the interfacial bonding of the two phases is strong , with excellent performance.

In parts by mass, the mixed material includes 5-10 parts of zinc oxide, 3-4 parts of magnesium oxide and 4-6 parts of stearic acid. In one embodiment of the present invention, the mixed material includes 10 parts of zinc oxide, 4 parts of magnesium oxide and 6 parts of stearic acid. In the present invention, the zinc oxide, magnesium oxide and stearic acid form an active agent system for rubber vulcanization, which can make the vulcanization more complete, and can also play a role in ensuring fluidity and oxygen resistance, and can also increase the tensile strength of rubber. Tensile strength and impact resistance; Described zinc oxide, magnesium oxide and stearic acid adopt the product commonly used in this field and get final product. The mixed material includes 10-30 parts of carbon black, preferably 15-20 parts of carbon black. The carbon black is a commonly used rubber reinforcing agent in the field, and the present invention has no special limitation on it.

In terms of parts by mass, the mixed material includes 1-2 parts of sulfur, preferably 1.4-1.9 parts of sulfur. The sulfur is a commonly used rubber vulcanizing agent in the field, and the present invention has no special limitation on it. Correspondingly, the mixed material includes 4-8 parts of a vulcanization accelerator (abbreviated as accelerator), which forms a vulcanization system with sulfur. The vulcanization accelerator is used together with a vulcanizing agent in the rubber vulcanization process, which can shorten the vulcanization time, reduce the vulcanization temperature, reduce the amount of vulcanization agent and improve the physical and mechanical properties of rubber. It can be divided into For: dithiocarbamates, guanidines, thioureas, thiazoles and thiurams, etc.

In the present invention, the vulcanization accelerator preferably includes 1-2 parts of thiourea accelerator, 1-2 parts of thiazole accelerator and 2-4 parts of thiuram accelerator such as vulcanization accelerator TMTD. Various types of vulcanization accelerators can be mixed and used in the present invention, and the acceleration effect is better. Wherein, the thiourea accelerator such as vulcanization accelerator NA-22 or accelerator ETU; the thiazole accelerator such as vulcanization accelerator M or accelerator DM. In a preferred embodiment of the present invention, the vulcanization accelerator includes 1 to 2 parts of 1,2-ethylenethiourea, 1 to 2 parts of dibenzothiazole disulfide and 2 to 4 parts of disulfide disulfide (thiocarbonyldimethylamine). The present invention has no special restrictions on the source of the vulcanization accelerator, and generally adopts commercially available products; wherein, 1,2-ethylenethiourea is a commercially available accelerator ETU, and dibenzothiazole disulfide is a commercially available accelerator Agent DM, bis(thiocarbonyl dimethylamine) disulfide is a commercially available accelerator TMTD. In one embodiment of the present invention, the vulcanization accelerator includes 1 part of accelerator ETU, 1.2 parts of accelerator DM and 4 parts of accelerator TMTD. In addition, in one embodiment of the present invention, zinc oxide and accelerator ETU (NA-22) are used together to reduce the consumption of sulfur by double bonds in CR.

In parts by mass, the mixed material preferably further includes 1-2 parts of anti-aging agent, more preferably further includes 1-1.4 parts of anti-aging agent. The anti-aging agent refers to a compounding agent that can prevent or inhibit factors such as oxygen, heat, light, ozone and mechanical stress from destroying the performance of the product and prolong the storage and service life of the product, including amines and phenols. The present invention preferably adopts amine anti-aging agent, more preferably adopts anti-aging agent 4010NA (N-isopropyl-N'-phenyl-p-phenylenediamine).

In terms of parts by mass, the mixed material preferably also includes 10 to 15 parts of anti-radiation agent, more preferably 10 to 12 parts of anti-radiation agent (also known as anti-radiation agent), which can improve the radiation protection stability of rubber sex. The mixed material preferably further includes 5-10 parts of waterproofing agent, more preferably 8-10 parts of waterproofing agent. In some embodiments of the present invention, the mixed material further includes 10-15 parts of anti-radiation agent and 5-10 parts of waterproofing agent. In other embodiments of the present invention, the mixed material further includes 1-2 parts of anti-aging agent, 10-15 parts of anti-radiation agent and 5-10 parts of waterproofing agent.

The co-vulcanized material of EPDM rubber and chloroprene rubber in the present invention can be prepared by mixing and vulcanizing processes, and the cross-linking degree of the two phases is relatively perfect, the interface of the two phases is strongly bonded, and the mechanical properties are good.

Correspondingly, the embodiment of the present invention also provides a method for preparing the co-vulcanized material of EPDM rubber and chloroprene rubber as described above, comprising the following steps:

A) mixing EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to obtain modified EPDM rubber;

Mixing the modified EPDM rubber, carbon black, 1/2 mass of stearic acid and 1/2 mass of zinc oxide to obtain an EPDM rubber masterbatch;

Mixing neoprene, magnesium oxide and 1/2 quality stearic acid to obtain a neoprene masterbatch;

B) mixing the EPDM masterbatch, the chloroprene rubber masterbatch, sulfur, vulcanization accelerator and zinc oxide of 1/2 quality to obtain a rubber compound;

C) Vulcanizing the rubber material to obtain a co-vulcanized material of EPDM rubber and chloroprene rubber.

In the embodiment of the present invention, in the process of preparing EPDM and neoprene co-vulcanized materials, EPDM (EPDM) is processed with silane coupling agent Si69, maleic anhydride and glycidyl methacrylate, Improve its ability to combine with sulfur, so that the mechanical properties of the prepared EPDM/CR co-vulcanized rubber are good.

In the closed rubber mixing machine, the embodiment of the present invention uses EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to mix, and EPDM is modified. After mixing evenly, the obtained Modified EPDM. The content of each material is as described above, and will not be repeated here. When mixing in a closed rubber mixer, the present invention has no special restrictions on the order of adding materials. Preferably, the temperature for kneading EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate is 110°C to 120°C, more preferably 120°C. The kneading time is preferably 5 min to 10 min, more preferably 6 min to 8 min.

The embodiment of the present invention utilizes the obtained modified EPDM rubber to prepare EPDM masterbatch, that is, the modified EPDM rubber, carbon black, 1/2 mass of stearic acid and 1 /2 mass of zinc oxide mixed to obtain EPDM masterbatch. The content of each material is as described above, and will not be repeated here. In some embodiments of the present invention, the order of feeding the EPDM masterbatch is: modified EPDM→1/2 part of stearic acid→1/2 part of zinc oxide→carbon black→anti-aging agent→accelerator , more specifically: modified EPDM → 1/2 part of stearic acid → 1/2 part of zinc oxide → carbon black N330 → antiaging agent 4010NA → accelerator DM. Preferably, the temperature for kneading the modified EPDM rubber, carbon black, 1/2 mass of stearic acid and 1/2 mass of zinc oxide is ≤90°C, more preferably 80°C-88°C. The kneading time is preferably 5 min to 10 min, more preferably 6 min to 8 min.

In the closed rubber mixing machine, neoprene rubber, magnesium oxide and 1/2 mass of stearic acid were mixed in the embodiment of the present invention to prepare a neoprene rubber masterbatch. The content of each material is as described above, and will not be repeated here. In one embodiment of the present invention, the feeding sequence for preparing the chloroprene rubber masterbatch is: CR → magnesium oxide → 1/2 part of stearic acid. Among them, the material before the arrow is added first, the material after the arrow is added last, and so on. Preferably, the temperature for kneading chloroprene rubber, magnesium oxide and 1/2 mass of stearic acid is ≤70°C, more preferably 60°C-68°C. The kneading time is preferably 5 min to 10 min, more preferably 6 min to 8 min.

After obtaining the EPDM rubber masterbatch and the chloroprene rubber masterbatch, the embodiment of the present invention prepares EPDM/CR mixed rubber on an open rubber mixer. In the embodiment of the present invention, the EPDM masterbatch, the neoprene masterbatch, sulfur, a vulcanization accelerator and 1/2 mass of zinc oxide were mixed to obtain a rubber compound. Specifically, in the embodiment of the present invention, the EPDM masterbatch and 1/2 mass of sulfur are pre-vulcanized to obtain pre-vulcanized EPDM rubber; the pre-vulcanized EPDM rubber, the Neoprene rubber masterbatch, vulcanization accelerator, 1/2 mass of sulfur and 1/2 mass of zinc oxide are mixed to obtain rubber compound. The content of each material is as described above, and will not be repeated here.

In the embodiment of the present invention, 1/2 mass of sulfur is added to the prepared modified EPDM on an open rubber mixing machine, and placed on a flat vulcanizer for pre-vulcanization molding to obtain pre-vulcanized EPDM. The temperature of the pre-vulcanization is preferably 100°C to 120°C, more preferably 105°C to 115°C. The pressure of the pre-vulcanization is preferably 10 MPa-12 MPa; the time of the pre-vulcanization is preferably 10 min-12 min.

On the open rubber mixer, the embodiment of the present invention mixes the prevulcanized EPDM rubber, the chloroprene rubber masterbatch, the vulcanization accelerator, the sulfur of 1/2 quality and the zinc oxide of 1/2 quality, And other rubber additives such as anti-radiation agent and/or waterproofing agent, carry out mixing to obtain rubber compound.

In some embodiments of the present invention, the order of adding materials to prepare EPDM/CR compound rubber is: pre-vulcanized EPDM, CR masterbatch → anti-radiation agent → waterproofing agent → 1/2 part of zinc oxide → 1/2 part of sulfur → Accelerator, more specifically: pre-vulcanized EPDM, CR masterbatch → radiation protection agent → waterproofing agent → 1/2 part of zinc oxide → 1/2 sulfur → accelerator ETU → accelerator DM → accelerator TMTD. Preferably, the temperature for mixing the prevulcanized EPDM rubber, the chloroprene rubber masterbatch, the vulcanization accelerator, 1/2 mass of sulfur and 1/2 mass of zinc oxide is ≤70°C, more preferably Preferably it is 60°C to 70°C. The kneading time is preferably 5 min to 10 min, more preferably 6 min to 8 min. In addition, the embodiment of the present invention can pass 6 times at the end.

After obtaining the sizing material, the embodiment of the present invention takes the sizing material out and parks it. In the embodiment of the present invention, the rubber material is thinly passed and released, and the thickness may be 0.8cm-1cm. Then, the embodiment of the present invention is parked at room temperature for more than 8 hours under a weight of 5 kg; the parking environment is required to be no direct sunlight, moderate humidity, dust-free, and good ventilation conditions.

In the embodiment of the present invention, the rubber material or pellets obtained in the previous step are vulcanized on a flat vulcanizer, and molded to obtain a co-vulcanized material of EPDM rubber and chloroprene rubber.

In the present invention, the vulcanization temperature is preferably 170°C to 190°C, more preferably 175°C to 185°C. The pressure of the vulcanization is preferably 10 MPa-12 MPa; the time of the vulcanization is preferably 10 min-15 min. After the vulcanization is completed, the embodiment of the present invention is cooled at room temperature (25° C.) for 15 minutes to 20 minutes to form a final product.

After obtaining the co-vulcanized material of EPDM rubber and chloroprene rubber, the present invention performs a performance test on it. The present invention carries out the tensile test according to ISO 37:2005 "Determination of Tensile Stress-Strain Characteristics of Vulcanized or Thermoplastic Rubber". The test equipment is the CMT6104 microcomputer-controlled electronic universal testing machine of Shenzhen Xinsansi Material Inspection Co., Ltd.

The present invention carries out the tear test according to ISO 34-1:2004 "Determination of the Tear Strength of Vulcanized or Thermoplastic Rubber Part 1", and the test equipment is the CMT6104 microcomputer-controlled electronic universal testing machine of Shenzhen Xinsansi Material Inspection Co., Ltd.

The present invention carries out the dynamic mechanical performance experimental test according to ASTM D 7028-2007 "Dynamic Mechanical Analysis (DMA) Method for Measuring the Glass Transition Temperature (DMA Tg) of Polymer-Matrix Composite Material" SDTA861 Dynamic Thermomechanical Analyzer.

Result shows, based on above-mentioned molding method, the EPDM that the present invention makes and chloroprene co-vulcanized material are made of EPDM, chloroprene, zinc oxide, magnesium oxide, stearic acid, silane coupling agent Composed of Si69, maleic anhydride, glycidyl methacrylate, carbon black and vulcanization system, it has excellent mechanical properties. The market of the co-vulcanized material has great development potential and good industrialization prospects, and can be widely used in the manufacture of automobile window sealing strips, defense coils, rubber hoses, conveyor belts and other products.

In addition, the preparation process of the co-vulcanized material in the present invention is simple.

In order to further understand the present application, the co-vulcanized material of EPDM rubber and chloroprene rubber provided by the present application and its preparation method are specifically described below in conjunction with examples.

In the following examples, the parts of each material are parts by mass. In the following examples and comparative examples, the EPDM used is the EPDM EP35 produced by Japan Synthetic Rubber Company; the neoprene rubber is the neoprene CR 126 produced by the German Lanxess Group; the carbon black is purchased from Shanxi Fuli Hua Chemical Co., Ltd.; anti-radiation agent UV-531 provided by Shanghai Anhui Chemical Co., Ltd.; waterproof agent potassium methyl silicate provided by Jinan Dazuoxing Chemical Co., Ltd.

Example 1

Material formula: 80 parts of EPDM, 20 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 3 parts of silane coupling agent Si69, 5 parts of MAH, 4 parts of GMA, anti-aging 1 part of agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1 part of accelerator ETU, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is:

(1) In the closed rubber mixing machine, modify EPDM. The silane coupling agent Si69, MAH, GMA and EPDM were mixed in a closed rubber mixer until uniform to obtain modified EPDM. Temperature: 120°C. Mixing time: 8min.

(2) In a closed rubber mixer, prepare EPDM rubber masterbatch. The feeding order is: modified EPDM → 1/2 part of stearic acid → 1/2 part of zinc oxide → carbon black N330 → antiaging agent 4010NA → accelerator DM. Temperature: 80°C. Mixing time: 8min.

(3) In a closed rubber mixer, prepare a chloroprene rubber masterbatch. The order of addition is: CR → magnesium oxide → 1/2 part of stearic acid. Temperature: 60°C. Mixing time: 8min.

(4) Add 1/2 of the sulfur to the EPDM masterbatch prepared in (2) on the open rubber mixing machine, and place it on a flat vulcanizer for pre-vulcanization molding to obtain pre-vulcanized EPDM. The temperature is 110±5°C, the pressure is 10MPa, and the time is 10min.

(5) Prepare EPDM/CR compound rubber on an open rubber mixer. The order of feeding is: pre-vulcanized EPDM, CR masterbatch → anti-radiation agent → waterproofing agent → 1/2 part of zinc oxide → 1/2 part of sulfur → accelerator ETU → accelerator TMTD. Temperature: 60°C. Mixing time: 8min. Finally, thin pass 6 times.

(6) After the rubber material is thinned, the sheet is released, with a thickness of 0.8-1.0cm. Park at room temperature for 12 hours under a weight of 5kg; the required parking environment is no direct sunlight, moderate humidity, no dust, and good ventilation.

(7) The pellets obtained in the previous step are vulcanized and molded on a flat vulcanizing machine under the following conditions: the temperature is 180±5°C, the pressure is 10MPa, and the time is 10min. Then it was cooled at room temperature (25° C.) for 20 minutes to form a final product.

Example 2

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 3 parts of silane coupling agent Si69, 5 parts of MAH, 4 parts of GMA, anti-aging 1 part of agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1 part of accelerator ETU, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as that of the above-mentioned Example 1.

Example 3

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 5 parts of silane coupling agent Si69, 10 parts of MAH, 5 parts of GMA, anti-aging 1 part of agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1 part of accelerator ETU, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as that of the above-mentioned Example 1.

According to the method described above, the properties of the EPDM/CR co-vulcanized materials obtained in Examples 1-3 were tested. The performance results are shown in Table 1, and Table 1 is the performance test results of the EPDM/CR co-vulcanized materials obtained in Examples 1-3.

Table 1 Performance test results of EPDM/CR co-vulcanized materials obtained in Examples 1-3

Comparative example 1

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 1 part of anti-aging agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent , 1.4 parts of sulfur, 1 part of accelerator ETU, 1.2 parts of accelerator DM, 4 parts of accelerator TMTD.

The specific preparation method is the same as the addition sequence and mixing conditions of steps (2) to (7) in the above Example 1, without adding silane coupling agents Si69, MAH and GMA, to prepare EPDM/CR vulcanized rubber.

Comparative example 2

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 4 parts of chlorinated polyethylene CPE (chlorine content: 35.0±2wt%), 1 part of anti-aging agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1 part of accelerator ETU, 1.2 parts of accelerator DM, 4 parts of accelerator TMTD.

The specific preparation method is the same as the preparation method of the above-mentioned Example 1, only CPE is added to obtain EPDM/CR vulcanized rubber.

Comparative example 3

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 10 parts of MAH, 1 part of anti-aging agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as the preparation method of the above-mentioned Example 1, only MAH is added to obtain EPDM/CR vulcanized rubber.

Comparative example 4

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 4 parts of GMA, 1 part of anti-aging agent 4010NA, 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as the preparation method of the above-mentioned Example 1, only GMA is added to obtain EPDM/CR vulcanized rubber.

Comparative Example 5

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 10 parts of silane coupling agent Si69, 1 part of anti-aging agent 4010NA, radiation protection 10 parts of water repellent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as the preparation method of the above-mentioned Example 1, only silane coupling agent Si69 is added to obtain EPDM/CR vulcanized rubber.

Comparative Example 6

Material formula: 70 parts of EPDM, 30 parts of CR, 10 parts of zinc oxide, 4 parts of magnesium oxide, 6 parts of stearic acid, 20 parts of carbon black N330, 5 parts of silane coupling agent Si69, 4 parts of GMA, 1 part of antioxidant 4010NA , 10 parts of anti-radiation agent, 10 parts of waterproofing agent, 1.4 parts of sulfur, 1.2 parts of accelerator DM, and 4 parts of accelerator TMTD.

The specific preparation method is the same as the preparation method of the above-mentioned Example 1, only the silane coupling agent Si69 and GMA are added to prepare EPDM/CR vulcanized rubber.

According to the method described above, the properties of the vulcanized rubber obtained in Comparative Examples 1-6 were tested. The performance results are shown in Table 2, and Table 2 is the performance test results of the vulcanized rubber obtained in Comparative Examples 1-6.

Table 2 Performance test results of vulcanized rubber obtained in Comparative Examples 1 to 6

Through the comparison of the above examples and comparative examples, it can be seen that the apparent properties of EPDM/CR vulcanized materials prepared by other methods are obviously worse than those of the materials of the present invention. And, through the dynamic mechanical property test, measure the glass transition temperature (Tg) of the EPDM phase of the material of the present invention and CR phase obviously close to each other, and wherein embodiment 3 has single peak, illustrates that the present invention has realized EPDM very well. /CR co-vulcanization. In summary, the present invention can break the difficult problem of co-vulcanization of non-polar EPDM rubber and polar CR rubber, and prepare EPDM/CR co-vulcanized rubber with excellent properties such as good mechanical properties, which is beneficial for application.

Claims (8)

1. A co-vulcanized material of EPDM rubber and chloroprene rubber, which is made by mixing and vulcanizing successively; in parts by mass, the mixed material comprises: 60-100 parts of EPDM rubber; x parts of neoprene; 0<x<40; 5-10 parts of zinc oxide; 3-4 parts of magnesium oxide; 4-6 parts of stearic acid; 10-30 parts of carbon black; 1-5 parts of silane coupling agent Si69; 1 to 10 parts of maleic anhydride; 1 to 5 parts of glycidyl methacrylate; 1-2 parts of sulfur; 4-8 parts of vulcanization accelerator; the vulcanization accelerator includes 1-2 parts of thiourea accelerator, 1-2 parts of thiazole accelerator and 2-4 parts of thiuram accelerator; The preparation method of described EPDM rubber and neoprene co-vulcanized material comprises the following steps: A) mixing EPDM rubber, silane coupling agent Si69, maleic anhydride and glycidyl methacrylate to obtain modified EPDM rubber; Mixing the modified EPDM rubber, carbon black, 1/2 mass of stearic acid and 1/2 mass of zinc oxide to obtain an EPDM rubber masterbatch; Mixing neoprene, magnesium oxide and 1/2 quality stearic acid to obtain a neoprene masterbatch; B) mixing the EPDM masterbatch, the chloroprene rubber masterbatch, sulfur, vulcanization accelerator and zinc oxide of 1/2 quality to obtain a rubber compound; C) Vulcanizing the rubber material to obtain a co-vulcanized material of EPDM rubber and chloroprene rubber. 2. The co-vulcanized material of EPDM and chloroprene rubber according to claim 1, wherein the EPDM rubber is made of materials comprising ethylene, propylene and ethylidene norbornene. 3. The co-vulcanized material of EPDM and chloroprene rubber according to claim 1, wherein the chloroprene rubber comprises 80wt% to 90wt% trans-1,4-polychloroprene And 1wt%～2wt% of 1,2-polychloroprene. 4. The co-vulcanization material of EPDM rubber and chloroprene rubber according to claim 1, wherein the vulcanization accelerator comprises 1 to 2 parts of 1,2-ethylenethiourea, 1 to 2 Parts of dibenzothiazole disulfide and 2 to 4 parts of bis(thiocarbonyldimethylamine) disulfide. 5. The co-vulcanized material of EPDM rubber and chloroprene rubber according to any one of claims 1-4, characterized in that, the mixed material further includes 1-2 parts of anti-aging agent. 6 . The co-vulcanized material of EPDM rubber and chloroprene rubber according to claim 5 , wherein the mixed material further comprises 10-15 parts of anti-radiation agent and 5-10 parts of waterproofing agent. 7. EPDM according to claim 1 and neoprene co-vulcanization material, is characterized in that, in described step A), with EPDM, silane coupling agent Si69, maleic anhydride and The temperature for kneading glycidyl methacrylate is 110°C to 120°C. 8. EPDM rubber and chloroprene co-vulcanized material according to claim 1 or 7, is characterized in that, described step B) is specially: Prevulcanizing the EPDM masterbatch with 1/2 mass of sulfur to obtain prevulcanized EPDM; The pre-vulcanized EPDM rubber, the chloroprene rubber masterbatch, the vulcanization accelerator, 1/2 mass of sulfur and 1/2 mass of zinc oxide are mixed to obtain a rubber compound.