A double-layer composite non-sparking and anti-static rubber mat and its preparation method

Abstract

The present application discloses a double-layer composite non-sparking anti-static rubber mat and a preparation method thereof, relating to the technical field of rubber mats. The double-layer composite non-sparking anti-static rubber mat prepared in the present application comprises a surface layer and a bottom layer adhered to one side of the surface layer. The surface layer comprises modified neoprene rubber; the bottom layer comprises chloropropylene rubber. First, the surface layer material and the bottom layer material are respectively prepared, then the obtained materials are respectively kneaded and processed, and finally, after compounding, calendering and vulcanization, the double-layer composite non-sparking anti-static rubber mat is obtained. The double-layer composite non-sparking anti-static rubber mat prepared in the present application has excellent anti-static performance, and the surface layer is smooth and wear-resistant, having anti-static stability under frequent friction conditions and remarkable non-sparking performance, and has broad application prospects.

Description

Technical Field

[0001] This application relates to the technical field of rubber pads, and particularly relates to a double-layer composite non-sparking and anti-static rubber pad and a preparation method thereof. Background Art

[0002] In many current industrial fields and special places with strict requirements for static electricity protection, such as electronic chip manufacturing workshops, chemical production workshops, etc., safety issues are always of top priority. On the one hand, flammable and explosive substances often exist in these places, and static electricity sparks generated by tiny triboelectrification may trigger catastrophic explosion accidents, endangering the lives of personnel and huge property safety; on the other hand, static electricity accumulation will also damage precision electronic equipment, affect its normal operation and service life, lead to product quality defects, and cause huge economic losses. Therefore, a series of non-sparking and anti-static rubber pads need to be developed to ensure effective safety protection.

[0003] The design concept of the double-layer composite non-sparking and anti-static rubber pad thus emerged. Through the combination of different functional layers, it is expected to integrate various excellent properties, so that the rubber pad can ensure static electricity protection and fire safety even under severe impact and friction.

[0004] Chinese Patent Application with Publication No. CN 106079755A discloses an anti-static floor mat for computer rooms, including a bottom layer and a surface layer. The bottom layer uses a conductive rubber layer, and the surface layer is a resin layer with anti-static properties. The bottom layer and the surface layer are bonded by thermal composite to form an anti-static floor mat. The combination of the surface layer and the bottom layer makes the floor mat have good anti-static performance, and at the same time, it is not easy to warp and is convenient for installation.

[0005] However, the anti-static floor mat prepared by this scheme has poor wear resistance and the surface is not smooth enough, and it is easy to accumulate charges in the environment and generate frictional static electricity; therefore, it does not have anti-static stability under frequent friction conditions and other harsh environments and significant non-sparking performance, and there is great room for improvement. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, this application provides a double-layer composite non-sparking and anti-static rubber pad and a preparation method thereof. Using modified chloroprene rubber copolymerized from 2-chloro-1,3-butadiene and vinylpyridine as the main component of the surface layer, and using chloropropylene rubber as the main component of the bottom layer, the surface layer mixed rubber and the bottom layer mixed rubber are respectively prepared and then vulcanized and pressure-compounded to finally obtain a double-layer composite non-sparking and anti-static rubber pad. This double-layer composite non-sparking and anti-static rubber pad has excellent anti-static performance, and the surface layer is smooth and wear-resistant, with anti-static stability under frequent friction conditions and significant non-sparking performance, and has excellent performance and application value in dust-free anti-static application scenarios.

[0007] To achieve the above object, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a double-layer composite non-sparking and anti-static rubber mat, including a bottom layer and a surface layer adhered to one side of the bottom layer; the surface layer includes modified chloroprene rubber; the bottom layer includes chloropropylene rubber; the modified chloroprene rubber is copolymerized from 2-chloro-1,3-butadiene and vinylpyridine; the structure of the modified chloroprene rubber is:

[0009] ,

[0010] wherein, n is an integer in the range of 10 to 20; m is an integer in the range of 50 to 100; and the surface roughness Ra value of the surface layer is 0.8 to 1.6 μm.

[0011] In a second aspect, the present application provides a preparation method of a double-layer composite non-sparking and anti-static rubber mat, including the following steps:

[0012] In a reaction kettle protected by nitrogen, 2-chloro-1,3-butadiene and vinylpyridine are copolymerized by emulsion copolymerization under the action of an emulsifier and an initiator, stirred and reacted for a first set time at a first set temperature, and after discharging, washing and drying, modified chloroprene rubber is obtained;

[0013] The modified chloroprene rubber and nitrile rubber are put into a mixer and kneaded for a second set time at a second set temperature;

[0014] An antioxidant and nano-zinc oxide are put into the mixer and continue to be kneaded for a third set time at the second set temperature;

[0015] Aluminum hydroxide, white carbon black, antistatic agent, tricresyl phosphate and accelerator DM are sequentially added to the mixer and kneaded for a fourth set time at a third set temperature to prepare a surface layer mixing rubber;

[0016] After the surface layer mixing rubber stands for a fifth set time, it is put into an open mill and pressed into sheets at a fourth set temperature and a first set pressure to obtain a calendered surface layer;

[0017] Chloropropylene rubber and styrene-butadiene rubber are added to the mixer and kneaded for a fourth set time at a fifth set temperature;

[0018] Superconductive carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane are added to the mixer and kneaded for a sixth set time at a sixth set temperature;

[0019] Dioctyl sebacate, paraffin oil and accelerator CZ are sequentially added to the mixer and continue to be kneaded for a sixth set time at the sixth set temperature to obtain a bottom layer mixing rubber;

[0020] After the base stock rubber is left standing for the seventh set time, it is put into a two-roll mill and sheeted under the fourth set temperature and the first set pressure to obtain a calendered base layer;

[0021] The calendered surface layer is covered on the calendered base layer, then put into a mold and sent into a drum vulcanizer, and vulcanized for the eighth set time under the seventh set temperature, the second set pressure and the first vulcanization speed, and finally a double-layer composite non-sparking anti-static rubber mat is made.

[0022] Beneficial technical effects:

[0023] In this application, the matrix material of the surface layer of the double-layer composite non-sparking anti-static rubber mat is modified chloroprene rubber, which is copolymerized from 2-chloro-1,3-butadiene and vinylpyridine. On the one hand, the strong polarity of the vinylpyridine unit changes the surface properties of the rubber molecules, making the modified chloroprene rubber have better surface activity, reducing the interfacial tension between the filler and the rubber, so that the filler is dispersed in the surface layer modified chloroprene rubber matrix, enhancing the mechanical properties and stability of the modified chloroprene rubber and making it more wear-resistant. On the other hand, the surface of the rubber mat surface layer is very smooth (the surface roughness Ra value is 0.8 - 1.6 μm), and even if there is attached charge, it is easy to be evenly dispersed, and it is not easy to cause electrostatic accumulation due to surface roughness, so it is difficult to generate electrostatic sparks. Finally, the strong polar rigid pyridine ring structure will form a dipole interaction with the chlorine atoms in the molecular chain, improving the cohesion between polymer chains and making the flame retardant performance of the modified chloroprene rubber improve. The combination of multiple aspects makes the surface layer have good non-sparking performance. Further, under the combined action of other fillers and additives in the surface layer, the prepared rubber mat still has stable anti-static performance under frequent friction working conditions and other harsh environments. In addition, the matrix material of the base layer of the double-layer composite non-sparking anti-static rubber mat is chloropropene rubber, which has excellent chemical stability. After being combined with fillers and additives such as superconducting carbon black and metal powder, it can quickly conduct the generated static electricity to the ground and avoid the generation of electric sparks caused by static electricity accumulation. After the two layers are compounded by vulcanization and pressurization, they are firmly combined, further enhancing the anti-static performance and non-sparking performance of the prepared double-layer composite non-sparking anti-static rubber mat. Description of the Drawings

[0024] Figure 1 is a schematic structural diagram of a double-layer composite non-sparking anti-static rubber mat.

[0025] Figure 2 is a schematic process diagram for preparing a double-layer composite non-sparking anti-static rubber mat.

[0026] Figure 3 is a physical picture of the prepared double-layer composite non-sparking anti-static rubber mat.

[0027] Reference numerals: 1, base layer; 2, surface layer. Detailed Embodiments

[0028] In order to make the technical problems, technical solutions, and beneficial effects to be solved by this application more clearly understood, the following further details this application in conjunction with embodiments. However, this should not be construed as limiting the scope of this application to the following examples. Without departing from the above-mentioned method concept of this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of this application.

[0029] In this application, the terms used are merely for the purpose of describing specific embodiments and are not intended to limit this application.

[0030] In this application, the singular forms of "is", "or", "a", "any one", and "the" are intended to include the plural forms unless the context clearly indicates otherwise.

[0031] In addition, if the terms "first" and "second" appear, they are only for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0032] In a first aspect, it includes a bottom layer 1 and a surface layer 2 attached to one side of the bottom layer 1. As Figure 1 shown, the surface layer 2 includes modified neoprene; the bottom layer 1 includes chloropropene rubber; the modified neoprene is copolymerized from 2-chloro-1,3-butadiene and vinylpyridine; the structure of the modified neoprene is:

[0033] ,

[0034] wherein, n is an integer in the range of 10 to 20; m is an integer in the range of 50 to 100; and the surface roughness Ra value of the surface layer 2 is 0.8 to 1.6 μm.

[0035] In a feasible implementation scenario, the surface layer 2 further includes nitrile rubber, aluminum hydroxide, silica, antistatic agent, tricresyl phosphate, antioxidant, nano zinc oxide, and accelerator DM.

[0036] In a feasible implementation scenario, the antistatic agent includes at least one of fatty alcohol polyoxyethylene ether, cetyl trimethyl ammonium bromide, and octadecyl dimethyl benzyl ammonium chloride.

[0037] In a feasible implementation scenario, the antioxidant includes at least one of antioxidant 2246 and antioxidant 264.

[0038] In a feasible implementation case, in the surface layer 2, the mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, silica, antistatic agent, tricresyl phosphate, antioxidant, nano zinc oxide and accelerator DM is (30~50):(15~20):(10-15):(10~20):(5~10):(3~10):(1~3):(2~5):(1~2).

[0039] In a feasible implementation case, the bottom layer 1 further includes styrene-butadiene rubber, super conductive carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ.

[0040] In a feasible implementation case, in the bottom layer 1, the mass ratio of chloropropylene rubber, styrene-butadiene rubber, super conductive carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is (40~50):(10~15):(15~25):(5~10):(10~20):(1~3):(5~10):(3~10):(1~2).

[0041] Second, the present application provides a preparation method of a double-layer composite non-sparking and antistatic rubber mat, as Figure 2 shown, including the following steps:

[0042] In a reaction kettle under nitrogen protection, 2-chloro-1,3-butadiene and vinyl pyridine are copolymerized by emulsion copolymerization under the action of an emulsifier and an initiator, stirred and reacted for a first set time at a first set temperature, and after discharging, washing and drying, modified chloroprene rubber is prepared;

[0043] Put the modified chloroprene rubber and nitrile rubber into a mixer and knead for a second set time at a second set temperature;

[0044] Put the antioxidant and nano zinc oxide into the mixer and continue to knead for a third set time at the second set temperature;

[0045] Add aluminum hydroxide, silica, antistatic agent, tricresyl phosphate and accelerator DM into the mixer in sequence, and knead for a fourth set time at a third set temperature to make the surface layer mixing rubber;

[0046] After the surface layer mixing rubber stands for a fifth set time, put it into an open mill and press it into sheets at a fourth set temperature and a first set pressure to obtain the calendared and formed surface layer 2;

[0047] Put chloropropylene rubber and styrene-butadiene rubber into a mixer and knead for a fourth set time at a fifth set temperature;

[0048] Add superconducting carbon black, aluminum powder, calcium carbonate, and γ-glycidoxypropyltrimethoxysilane into the internal mixer, and knead for the sixth set time at the sixth set temperature;

[0049] Subsequently, add dioctyl sebacate, paraffin oil, and accelerator CZ into the internal mixer in sequence, and continue to knead for the sixth set time at the sixth set temperature to obtain the bottom layer mixing rubber;

[0050] Let the bottom layer mixing rubber stand for the seventh set time and then put it into the open mill, and roll it into sheets at the fourth set temperature and the first set pressure to obtain the calendered bottom layer 1;

[0051] Cover the calendered surface layer 2 onto the calendered bottom layer 1, then put it into the mold, send it into the drum vulcanizer, and vulcanize for the eighth set time at the seventh set temperature, the second set pressure, and the first vulcanization speed, and finally manufacture a double-layer composite non-sparking and anti-static rubber mat, as Figure 3 shown.

[0052] In a feasible implementation case, the emulsifier includes any one of sodium dodecylbenzenesulfonate, sodium stearate, and sodium dodecyl sulfate; the initiator includes any one of potassium persulfate and ammonium persulfate; the mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, emulsifier, and initiator is (70~85):(10~30):(2~5):(0.2~0.8).

[0053] In a feasible implementation case, the first set temperature is 40~50°C; the second set temperature is 55~65°C; the third set temperature is 70~80°C; the fourth set temperature is 150~160°C; the fifth set temperature is 65~75°C; the sixth set temperature is 75~85°C; the seventh set temperature is 160~170°C.

[0054] In a feasible implementation case, the first set time is 8~12h; the second set time is 8~12min; the third set time is 5~10min; the fourth set time is 10~15min; the fifth set time is 12~24h; the sixth set time is 15~20min; the seventh set time is 6~12h; the eighth set time is 20~25min.

[0055] In a feasible implementation case, the first set pressure is 10~15MPa; the second set pressure is 15~18MPa; the first vulcanization speed is 0.1~0.3m / min.

[0056] In a feasible implementation case, the thickness of the surface layer 2 is controlled at 0.4~0.5μm; the thickness of the bottom layer 1 is controlled at 1.5~4.6μm;

[0057] The following will specifically describe a double-layer composite non-sparking and anti-static rubber mat and its preparation method provided by the present application in combination with different embodiments.

[0058] Example 1:

[0059] As Figure 2 shown, a preparation method of a double-layer composite non-sparking and anti-static rubber mat includes the following steps:

[0060] 1. In a reaction kettle under nitrogen protection, 2-chloro-1,3-butadiene and vinylpyridine are copolymerized by emulsion copolymerization under the action of sodium dodecylbenzenesulfonate and potassium persulfate, and stirred at 45 °C for 10 h. After discharging, washing and drying, modified chloroprene rubber is obtained;

[0061] The mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, sodium dodecylbenzenesulfonate and potassium persulfate is 75:20:4.5:0.5;

[0062] 2. Put the modified chloroprene rubber and nitrile rubber into a mixer and knead at 55 °C for 8 min;

[0063] 3. Put antioxidant 2246 and nano-zinc oxide into the mixer and continue to knead at 55 °C for 5 min;

[0064] 4. Add aluminum hydroxide, silica, fatty alcohol polyoxyethylene ether, tricresyl phosphate and accelerator DM to the mixer in sequence and knead at 70 °C for 10 min to prepare the surface layer mixing rubber;

[0065] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, silica, fatty alcohol polyoxyethylene ether, tricresyl phosphate, antioxidant 2246, nano-zinc oxide and accelerator DM is 40:18:10:15:5:8:1:2:1;

[0066] 5. After the surface layer mixing rubber stands for 15 h, put it into a calender and press at 150 °C and 10 MPa to obtain the calendered and formed surface layer 2;

[0067] 6. Add chloropropene rubber and styrene-butadiene rubber to the mixer and knead at 65 °C for 10 min;

[0068] 7. Add superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane to the mixer and knead at 75 °C for 15 min;

[0069] 8. Add dioctyl sebacate, paraffin oil and accelerator CZ to the mixer in sequence and continue to knead at 75 °C for 15 min to obtain the bottom layer mixing rubber;

[0070] The mass ratio of chloroprene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 50:10:15:5:10:1:5:3:1;

[0071] 9. After the bottom layer compounded rubber is left standing for 8 h, it is put into a two-roll mill and sheeted at 150 °C and 10 MPa to obtain the calendered bottom layer 1;

[0072] 10. The calendered surface layer 2 is covered on the calendered bottom layer 1, then put into a mold and sent into a drum vulcanizer, and vulcanized at 160 °C, 15 MPa and 0.1 m / min for 20 min to finally produce a double-layer composite non-sparking and antistatic rubber pad.

[0073] Example 2:

[0074] As Figure 2 shown, a preparation method of a double-layer composite non-sparking and antistatic rubber pad includes the following steps:

[0075] 1. In a reaction kettle under nitrogen protection, 2-chloro-1,3-butadiene and vinylpyridine are copolymerized by emulsion copolymerization under the action of sodium stearate and ammonium persulfate, and stirred and reacted at 50 °C for 8 h. After discharging, washing and drying, modified chloroprene rubber is obtained;

[0076] The mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, sodium stearate and ammonium persulfate is 70:25:4.5:0.5;

[0077] 2. The modified chloroprene rubber and nitrile rubber are put into a mixer and kneaded at 58 °C for 9 min;

[0078] 3. The antioxidant 264 and nano-zinc oxide are put into the mixer and continue to be kneaded at 58 °C for 6 min;

[0079] 4. Aluminum hydroxide, white carbon black, cetyltrimethylammonium bromide, tricresyl phosphate and accelerator DM are sequentially added into the mixer and kneaded at 72 °C for 11 min to prepare the surface layer compounded rubber;

[0080] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, white carbon black, cetyltrimethylammonium bromide, tricresyl phosphate, antioxidant 264, nano-zinc oxide and accelerator DM is 30:16:14:15:10:6:6:2:1;

[0081] 5. After the surface layer compounded rubber is left standing for 18 h, it is put into a two-roll mill and sheeted at 152 °C and 11 MPa to obtain the calendered surface layer 2;

[0082] 6. Add chloroprene rubber and styrene-butadiene rubber into an internal mixer, and knead them at 68 °C for 11 min;

[0083] 7. Add super conducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane into the internal mixer, and knead them at 78 °C for 16 min;

[0084] 8. Sequentially add dioctyl sebacate, paraffin oil and accelerator CZ into the internal mixer, and continue to knead them at 78 °C for 16 min to obtain the bottom layer mixed rubber;

[0085] The mass ratio of chloroprene rubber, styrene-butadiene rubber, super conducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 42:12:15:6:12:1:6:5:1;

[0086] 9. Let the bottom layer mixed rubber stand for 10 h and then put it into a two-roll mill to roll at 152 °C and 11 MPa to obtain the calendered bottom layer 1;

[0087] 10. Cover the calendered surface layer 2 onto the calendered bottom layer 1, then put it into a mold and send it into a drum vulcanizer to vulcanize at 162 °C, 16 MPa and 0.2 m / min for 22 min to finally manufacture the double-layer composite non-sparking and antistatic rubber mat.

[0088] Example 3:

[0089] As Figure 2 shown, a preparation method of a double-layer composite non-sparking and antistatic rubber mat includes the following steps:

[0090] 1. In a reaction kettle under nitrogen protection, copolymerize 2-chloro-1,3-butadiene and vinylpyridine by emulsion copolymerization under the action of sodium dodecyl sulfate and potassium persulfate, stir and react at 42 °C for 12 h, and obtain modified chloroprene rubber after discharging, washing and drying;

[0091] The mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, sodium dodecyl sulfate and potassium persulfate is 78:18:3.2:0.8;

[0092] 2. Put the modified chloroprene rubber and nitrile rubber into an internal mixer, and knead them at 60 °C for 10 min;

[0093] 3. Put antioxidant 2246 and nano zinc oxide into the internal mixer, and continue to knead them at 60 °C for 7 min;

[0094] 4. Sequentially add aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate and accelerator DM into the internal mixer, and knead them at 75 °C for 12 min to prepare the surface layer mixed rubber;

[0095] The mass ratio of the modified chloroprene rubber, nitrile rubber, aluminum hydroxide, silica, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate, antioxidant 2246, nano zinc oxide and accelerator DM is 42:17:12:13:6:4:2:3:1;

[0096] 5. After the surface layer mixing rubber is left standing for 20 h, it is put into a two-roll mill and sheeted at 155 °C and 12 MPa to obtain the calendered surface layer 2;

[0097] 6. Add chloropropene rubber and styrene-butadiene rubber into an internal mixer and knead for 12 min at 70 °C;

[0098] 7. Add super conducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane into the internal mixer and knead for 17 min at 80 °C;

[0099] 8. Sequentially add dioctyl sebacate, paraffin oil and accelerator CZ into the internal mixer and continue to knead for 17 min at 80 °C to obtain the bottom layer mixing rubber;

[0100] The mass ratio of chloropropene rubber, styrene-butadiene rubber, super conducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 42:11:16:6:11:2:7:4:1;

[0101] 9. After the bottom layer mixing rubber is left standing for 12 h, it is put into a two-roll mill and sheeted at 155 °C and 12 MPa to obtain the calendered bottom layer 1;

[0102] 10. Cover the calendered surface layer 2 onto the calendered bottom layer 1, then put it into a mold and feed it into a drum vulcanizer to vulcanize for 22 min at 165 °C, 17 MPa and 0.3 m / min, and finally manufacture a double-layer composite non-sparking antistatic rubber mat.

[0103] Example 4:

[0104] As Figure 2 shown, a preparation method of a double-layer composite non-sparking antistatic rubber mat comprises the following steps:

[0105] 1. In a reaction kettle under nitrogen protection, copolymerize 2-chloro-1,3-butadiene and vinyl pyridine by emulsion copolymerization under the action of sodium dodecyl benzene sulfonate and ammonium persulfate, stir and react for 9 h at 48 °C, and obtain the modified chloroprene rubber after discharging, washing and drying;

[0106] The mass ratio of 2-chloro-1,3-butadiene, vinyl pyridine, sodium dodecyl benzene sulfonate and ammonium persulfate is 80:15:4.4:0.6;

[0107] 2. Put the modified chloroprene rubber and nitrile rubber into the internal mixer and knead for 11 min at 62 °C;

[0108] 3. Put antioxidant 264 and nano-zinc oxide into the internal mixer and continue to knead for 8 min at 62 °C;

[0109] 4. Add aluminum hydroxide, silica white, fatty alcohol polyoxyethylene ether, tricresyl phosphate and accelerator DM into the internal mixer in sequence and knead for 13 min at 78 °C to prepare the surface layer mixing rubber;

[0110] The mass ratio of the modified chloroprene rubber, nitrile rubber, aluminum hydroxide, silica white, fatty alcohol polyoxyethylene ether, tricresyl phosphate, antioxidant 264, nano-zinc oxide and accelerator DM is 38:20:13:12:7:5:1:2:2;

[0111] 5. After the surface layer mixing rubber stands for 24 h, put it into the open mill and press into sheets at 158 °C and 14 MPa to obtain the calendered surface layer 2;

[0112] 6. Put chloropropene rubber and styrene-butadiene rubber into the internal mixer and knead for 13 min at 72 °C;

[0113] 7. Add superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane into the internal mixer and knead for 18 min at 82 °C;

[0114] 8. Add dioctyl sebacate, paraffin oil and accelerator CZ into the internal mixer in sequence and continue to knead for 18 min at 82 °C to obtain the bottom layer mixing rubber;

[0115] The mass ratio of the chloropropene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 47:10:15:8:10:1:5:3:1;

[0116] 9. After the bottom layer mixing rubber stands for 6 h, put it into the open mill and press into sheets at 158 °C and 14 MPa to obtain the calendered bottom layer 1;

[0117] 10. Cover the calendered surface layer 2 on the calendered bottom layer 1, then put it into the mold and send it into the drum vulcanizer to vulcanize for 23 min at 168 °C, 17 MPa and 0.15 m / min, and finally manufacture the double-layer composite non-sparking and antistatic rubber mat.

[0118] Example 5:

[0119] As Figure 2 shown, a preparation method of a double-layer composite non-sparking and antistatic rubber mat includes the following steps:

[0120] 1. In a reaction kettle under nitrogen protection, 2-chloro-1,3-butadiene and vinylpyridine are copolymerized by emulsion copolymerization under the action of sodium stearate and potassium persulfate, stirred and reacted at 40 °C for 11 h, and after discharging, washing and drying, modified chloroprene rubber is obtained;

[0121] The mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, sodium stearate and potassium persulfate is 74:22:3.5:0.5;

[0122] 2. Put the modified chloroprene rubber and nitrile rubber into a mixer and knead at 65 °C for 12 min;

[0123] 3. Put antioxidant 2246 and nano zinc oxide into the mixer and continue to knead at 65 °C for 10 min;

[0124] 4. Add aluminum hydroxide, silica, cetyltrimethylammonium bromide, tricresyl phosphate and accelerator DM into the mixer in sequence and knead at 80 °C for 15 min to make the surface layer mixing rubber;

[0125] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, silica, cetyltrimethylammonium bromide, tricresyl phosphate, antioxidant 2246, nano zinc oxide and accelerator DM is 50:16:10:12:5:3:1:2:1;

[0126] 5. After the surface layer mixing rubber stands for 12 h, put it into an open mill and press at 160 °C and 15 MPa to obtain the calendered surface layer 2;

[0127] 6. Put chloropropene rubber and styrene-butadiene rubber into a mixer and knead at 75 °C for 15 min;

[0128] 7. Add superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidyletheroxypropyltrimethoxysilane into the mixer and knead at 85 °C for 20 min;

[0129] 8. Add dioctyl sebacate, paraffin oil and accelerator CZ into the mixer in sequence and continue to knead at 85 °C for 20 min to obtain the bottom layer mixing rubber;

[0130] The mass ratio of chloropropene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidyletheroxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 50:10:15:5:10:1:5:3:1;

[0131] 9. After the bottom layer mixing rubber stands for 10 h, put it into an open mill and press at 160 °C and 15 MPa to obtain the calendered bottom layer 1;

[0132] 10. Cover the calendered surface layer 2 onto the calendered bottom layer 1, then place it into a mold and feed it into a drum vulcanizer, and vulcanize it at 170 °C, 18 MPa and 0.2 m / min for 25 min to finally produce a double-layer composite non-sparking and anti-static rubber mat.

[0133] Example 6:

[0134] As Figure 2 shown, a preparation method of a double-layer composite non-sparking and anti-static rubber mat includes the following steps:

[0135] 1. In a reaction kettle under nitrogen protection, copolymerize 2-chloro-1,3-butadiene and vinylpyridine by emulsion copolymerization under the action of sodium dodecyl sulfate and ammonium persulfate, stir and react at 50 °C for 8.5 h, and obtain modified chloroprene rubber after discharging, washing and drying;

[0136] The mass ratio of 2-chloro-1,3-butadiene, vinylpyridine, sodium dodecyl sulfate and ammonium persulfate is 77:20:2.8:0.2;

[0137] 2. Put the modified chloroprene rubber and nitrile rubber into a mixer and knead at 57 °C for 9 min;

[0138] 3. Put antioxidant 264 and nano-zinc oxide into the mixer and continue to knead at 57 °C for 7 min;

[0139] 4. Add aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate and accelerator DM into the mixer in sequence and knead at 73 °C for 12 min to prepare the surface layer mixing rubber;

[0140] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate, antioxidant 264, nano-zinc oxide and accelerator DM is 46:17:13:10:5:4:1:3:1;

[0141] 5. After the surface layer mixing rubber stands for 16 h, put it into an open mill and roll at 153 °C and 12 MPa to obtain the calendered surface layer 2;

[0142] 6. Add chloropropene rubber and styrene-butadiene rubber into a mixer and knead at 67 °C for 12 min;

[0143] 7. Add superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane into the mixer and knead at 77 °C for 17 min;

[0144] 8. Add dioctyl sebacate, paraffin oil and accelerator CZ into the mixer in sequence and continue to knead at 77 °C for 17 min to obtain the bottom layer mixing rubber;

[0145] The mass ratio of chloroprene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 43:12:16:6:11:1:6:3:2;

[0146] 9. After the bottom layer compounded rubber is left standing for 9 h, it is put into a two-roll mill and sheeted at 153 °C and 12 MPa to obtain the calendered bottom layer 1;

[0147] 10. The calendered surface layer 2 is covered on the calendered bottom layer 1, then put into a mold and sent into a drum vulcanizer, and vulcanized at 163 °C, 17 MPa and 0.25 m / min for 24 min to finally manufacture the double-layer composite non-sparking and antistatic rubber pad.

[0148] Comparative Example 1:

[0149] A preparation method of a double-layer composite non-sparking and antistatic rubber pad includes the following steps:

[0150] 1. Unmodified chloroprene rubber and nitrile rubber are put into a mixer and kneaded at 55 °C for 8 min;

[0151] 2. Antioxidant 2246 and nano-zinc oxide are put into the mixer and continue to be kneaded at 55 °C for 5 min;

[0152] 3. Aluminum hydroxide, white carbon black, fatty alcohol polyoxyethylene ether, tricresyl phosphate and accelerator DM are sequentially added into the mixer and kneaded at 70 °C for 10 min to prepare the surface layer compounded rubber;

[0153] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, white carbon black, fatty alcohol polyoxyethylene ether, tricresyl phosphate, antioxidant 2246, nano-zinc oxide and accelerator DM is 40:18:10:15:5:8:1:2:1;

[0154] 4. After the surface layer compounded rubber is left standing for 15 h, it is put into a two-roll mill and sheeted at 150 °C and 10 MPa to obtain the calendered surface layer 2;

[0155] 5. Chloroprene rubber and styrene-butadiene rubber are added into a mixer and kneaded at 65 °C for 10 min;

[0156] 6. Superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane are added into the mixer and kneaded at 75 °C for 15 min;

[0157] 7. Dioctyl sebacate, paraffin oil and accelerator CZ are sequentially added into the mixer and continue to be kneaded at 75 °C for 15 min to obtain the bottom layer compounded rubber;

[0158] The mass ratio of chloropropylene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ is 50:10:15:5:10:1:5:3:1;

[0159] 8. After the bottom layer masterbatch is left standing for 8 h, it is put into a mill and sheeted at 150 °C and 10 MPa to obtain the calendered bottom layer 1;

[0160] 9. The calendered surface layer 2 is covered on the calendered bottom layer 1, then put into a mold and sent into a drum vulcanizer, and vulcanized at 160 °C, 15 MPa and 0.1 m / min for 20 min to finally produce a double-layer composite non-sparking and antistatic rubber mat.

[0161] Comparative Example 2:

[0162] A preparation method of a double-layer composite non-sparking and antistatic rubber mat includes the following steps:

[0163] 1. Styrene-modified chloroprene rubber and nitrile rubber are put into a mixer and kneaded at 60 °C for 10 min;

[0164] 2. Antioxidant 2246 and nano-zinc oxide are put into the mixer and continue to be kneaded at 60 °C for 7 min;

[0165] 3. Aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate and accelerator DM are sequentially added into the mixer and kneaded at 75 °C for 12 min to prepare the surface layer masterbatch;

[0166] The mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate, antioxidant 2246, nano-zinc oxide and accelerator DM is 42:17:12:13:6:4:2:3:1;

[0167] 4. After the surface layer masterbatch is left standing for 20 h, it is put into a mill and sheeted at 155 °C and 12 MPa to obtain the calendered surface layer 2;

[0168] 5. Chloropropylene rubber and styrene-butadiene rubber are added into a mixer and kneaded at 70 °C for 12 min;

[0169] 6. Superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidoxypropyltrimethoxysilane are added into the mixer and kneaded at 80 °C for 17 min;

[0170] 7. Next, dioctyl sebacate, paraffin oil, and accelerator CZ were successively added to the internal mixer, and mixing was continued at 80 °C for 17 min to obtain the bottom-layer mixed rubber.

[0171] The mass ratio of chloropropylene rubber, styrene-butadiene rubber, super-conductive carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil, and accelerator CZ was 42:11:16:6:11:2:7:4:1.

[0172] 8. After the bottom-layer mixed rubber was left standing for 12 h, it was put into the open mill and sheeted at 155 °C and 12 MPa to obtain the calendered bottom layer 1.

[0173] 9. The calendered surface layer 2 was covered on the calendered bottom layer 1, then placed in a mold and sent into a drum vulcanizer, where it was vulcanized at 165 °C, 17 MPa, and 0.3 m / min for 22 min to finally produce a double-layer composite non-sparking and anti-static rubber mat.

[0174] Comparative Example 3:

[0175] A preparation method of a double-layer composite non-sparking and anti-static rubber mat includes the following steps:

[0176] 1. Vinylpyridine-modified cis-butadiene rubber and nitrile rubber were put into the internal mixer and mixed at 57 °C for 9 min.

[0177] 2. Antioxidant 264 and nano-zinc oxide were put into the internal mixer, and mixing was continued at 57 °C for 7 min.

[0178] 3. Aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate, and accelerator DM were successively added to the internal mixer and mixed at 73 °C for 12 min to prepare the surface-layer mixed rubber.

[0179] The mass ratio of modified chloropropylene rubber, nitrile rubber, aluminum hydroxide, white carbon black, octadecyl dimethyl benzyl ammonium chloride, tricresyl phosphate, antioxidant 264, nano-zinc oxide, and accelerator DM was 46:17:13:10:5:4:1:3:1.

[0180] 4. After the surface-layer mixed rubber was left standing for 16 h, it was put into the open mill and sheeted at 153 °C and 12 MPa to obtain the calendered surface layer 2.

[0181] 5. Chloropropylene rubber and styrene-butadiene rubber were added to the internal mixer and mixed at 67 °C for 12 min.

[0182] 6. Super-conductive carbon black, aluminum powder, calcium carbonate, and γ-glycidoxypropyltrimethoxysilane were added to the internal mixer and mixed at 77 °C for 17 min.

[0183] 7. Add dioctyl sebacate, paraffin oil, and accelerator CZ into the internal mixer in sequence, and continue to knead at 77 °C for 17 min to obtain the bottom layer compounded rubber.

[0184] The mass ratio of chloropropylene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidoxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil, and accelerator CZ is 43:12:16:6:11:1:6:3:2.

[0185] 8. After standing for 9 h, the bottom layer compounded rubber is put into the open mill and sheeted at 153 °C and 12 MPa to obtain the calendered bottom layer 1.

[0186] 9. Cover the calendered surface layer 2 onto the calendered bottom layer 1, then put it into the mold and send it into the drum vulcanizer, and vulcanize at 163 °C, 17 MPa, and 0.25 m / min for 24 min to finally produce the double-layer composite non-sparking and anti-static rubber mat.

[0187] Refer to GB / T 11210-2014 to conduct resistance tests on the double-layer composite non-sparking and anti-static rubber mats prepared in the examples and comparative examples of this application to reflect their anti-static performance.

[0188] Refer to GB50209-2010 and use the test method for non-sparking properties of non-sparking (explosion-proof) building floor materials and their products to conduct non-sparking property tests on the double-layer composite non-sparking and anti-static rubber mats prepared in the examples and comparative examples of this application.

[0189] Refer to GB / T 39697.2-2020 and use a profilometer to conduct surface roughness tests on the double-layer composite non-sparking and anti-static rubber mats prepared in the examples and comparative examples of this application.

[0190] In addition, the double-layer composite non-sparking and anti-static rubber mats prepared in this application were also subjected to relevant performance test comparisons with peer competitors, as shown in Tables 2 and 3.

[0191] Table 1 Performance test results of double-layer composite non-sparking and anti-static rubber mats prepared in examples and comparative examples

[0192]

[0193] As can be seen from Table 1, the non-sparking properties of Examples 1-6 at a grinding wheel speed of 600 r / min and a pressure of 10 N are better than those of Comparative Examples 1-3, and the resistance of Examples 1-6 is higher than that of Comparative Examples 1-3, which indirectly reflects that the anti-static performance of Examples 1-6 is better than that of Comparative Examples 1-3.

[0194] This is because in Examples 1 to 6, the surface layer matrix material of the double-layer composite non-sparking and anti-static rubber pad is modified chloroprene rubber, which is copolymerized from 2-chloro-1,3-butadiene and vinylpyridine. On the one hand, the strong polarity of the vinylpyridine unit changes the surface properties of the rubber molecules, making the modified chloroprene rubber have better surface activity, reducing the interfacial tension between the filler and the rubber, so that the filler is dispersed in the surface layer modified chloroprene rubber matrix, enhancing the mechanical properties and stability of the modified chloroprene rubber and making it more wear-resistant. On the other hand, the surface of this rubber pad is very smooth (the surface roughness Ra value is 0.8 - 1.6 μm). Even if there is charge attached to the surface, it is easy to be evenly dispersed, and it is not easy to cause static electricity accumulation due to surface roughness, so it is difficult to generate static sparks. Finally, the strong polar rigid pyridine ring structure will form a dipole interaction with the chlorine atoms in the molecular chain, increasing the cohesive force between polymer chains and improving the flame retardant performance of the modified chloroprene rubber. The combination of multiple aspects makes the surface layer have good non-sparking property. Further, under the combined action of other fillers and additives in the surface layer, the prepared rubber pad still has stable anti-static property under frequent friction conditions and other harsh environments. In addition, the bottom layer matrix material of the double-layer composite non-sparking and anti-static rubber pad is chloropropene rubber, which has excellent chemical stability. After being combined with fillers and additives such as superconducting carbon black and metal powder, it can quickly conduct the generated static electricity to the ground, avoiding the generation of electric sparks due to static electricity accumulation. After the two layers are compounded by vulcanization under pressure, the combination is firm, further enhancing the anti-static property and non-sparking property of the prepared double-layer composite non-sparking and anti-static rubber pad.

[0195] In Comparative Example 1, the surface layer matrix material of the rubber pad is chloroprene rubber without vinylpyridine modification. Therefore, the filler is poorly dispersed in the surface layer rubber matrix, and due to the absence of a strong polar rigid pyridine ring structure, it will not form a dipole interaction with the chlorine atoms in the molecular chain, ultimately resulting in poor non-sparking performance of the prepared rubber pad. In Comparative Example 2, the surface layer matrix material of the rubber pad is chloroprene rubber and it has been modified, but styrene is used instead of vinylpyridine, and it will not form a dipole interaction with the chlorine atoms in the molecular chain, so the non-sparking performance is poor. In Comparative Example 3, the surface layer matrix material of the rubber pad is cis-butadiene rubber instead of chloroprene rubber. Although it has been modified and vinylpyridine is used, it will not form a dipole interaction with the molecular chain, and the non-sparking performance is also poor.

[0196] Table 2 Comparison of Physical Property Tests between Example 1 and Peer Competitors

[0197]

[0198] As can be seen from Table 2, the tensile strength, elongation at break, the change rates of elongation at break under various conditions (hot air aging, oil environment, immersion in isopropanol), and the volume change rate of Example 1 are significantly better than those of peer competitors. This is also because the strong polarity of the vinylpyridine unit changes the surface properties of the rubber molecules, making the modified neoprene have better surface activity, reducing the interfacial tension between the filler and the rubber, thus enabling the filler to disperse in the matrix of the surface layer modified neoprene and enhancing the mechanical properties and stability of the modified neoprene.

[0199] Table 3 Comparison of the durability performance tests of Example 1 and peer competitors under different environments

[0200]

[0201] As can be seen from Table 3, compared with peer competitors, Example 1 can still maintain qualified antistatic ability in a harsh environment (oven hot air). This is because the strong polar rigid pyridine ring structure will form a dipole interaction with the chlorine atoms in the molecular chain, increasing the cohesive force between polymer chains, which improves the flame retardancy of the modified neoprene; further, under the combined action of other fillers and additives in the surface layer, the rubber pad prepared still has stable antistatic properties under frequent friction conditions and other harsh environments.

[0202] The above results show and describe the basic principles, main features, and advantages of this application.

[0203] Those skilled in the art should understand that this application is not limited by the above embodiments. The above embodiments and the descriptions in the specification only illustrate the principles of this application. Without departing from the spirit and scope of this application, this application will have various changes and improvements, and these changes and improvements all fall within the scope of this application claimed. The scope of protection claimed for this application is defined by the equivalents of the appended claims.

Claims

1. A double-layer composite non-flammable antistatic rubber pad, comprising a bottom layer (1) and a surface layer (2) attached to one side of the bottom layer (1); characterized in that: The surface layer (2) comprises modified chloroprene rubber; the bottom layer (1) comprises chloropropylene rubber; the modified chloroprene rubber is copolymerized from 2-chloro-1,3-butadiene and vinyl pyridine; the structure of the modified chloroprene rubber is: ， Wherein, n is an integer in the range of 10 to 20; m is an integer in the range of 50 to 100; and the surface roughness Ra value of the surface layer (2) is 0.8 to 1.6 μm.

2. A double-layer composite non-inflammable antistatic rubber pad according to claim 1, characterized in that: The surface layer (2) also includes nitrile rubber, aluminum hydroxide, white carbon black, an antistatic agent, tricresyl phosphate, an antioxidant, nano zinc oxide and a promoter DM.

3. A double-layer composite non-inflammable antistatic rubber pad according to claim 2, characterized in that: The antistatic agent includes at least one of fatty alcohol polyoxyethylene ether, hexadecyltrimethylammonium bromide and octadecyldimethylbenzylammonium chloride.

4. A double-layer composite non-inflammable antistatic rubber pad according to claim 2, characterized in that: The antioxidant includes at least one of the antioxidant 2246 and the antioxidant 264 .

5. A double-layer composite non-inflammable antistatic rubber pad according to claim 2, characterized in that: In the surface layer (2), the mass ratio of modified chloroprene rubber, nitrile rubber, aluminum hydroxide, white carbon black, antistatic agent, tricresyl phosphate, antioxidant, nano zinc oxide and accelerator DM is (30-50): (15-20): (10-15): (10-20): (5-10): (3-10): (1-3): (2-5): (1-2).

6. A double-layer composite non-inflammable antistatic rubber pad according to claim 1, characterized in that: The bottom layer (1) also includes styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidyloxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ.

7. A double-layer composite non-inflammable antistatic rubber pad according to claim 6, characterized in that: In the bottom layer (1), the mass ratios of chloropropylene rubber, styrene-butadiene rubber, superconducting carbon black, aluminum powder, calcium carbonate, γ-glycidyloxypropyltrimethoxysilane, dioctyl sebacate, paraffin oil and accelerator CZ are (40-50): (10-15): (15-25): (5-10): (10-20): (1-3): (5-10): (3-10): (1-2).

8. The method for preparing a double-layer composite non-inflammable antistatic rubber pad according to any one of claims 1 to 7, characterized in that: The following steps are involved: In a nitrogen-protected reactor, 2-chloro-1,3-butadiene and vinyl pyridine are copolymerized by an emulsion copolymerization method under the action of an emulsifier and an initiator, the reaction is stirred at a first set temperature for a first set time, and the material is washed and dried to obtain a modified chloroprene rubber; Putting the modified chloroprene rubber and the nitrile rubber into an internal mixer, and mixing them at a second set temperature for a second set time; Adding antioxidant and nano zinc oxide into an internal mixer, and continuing to internally mix at a second set temperature for a third set time; Adding aluminum hydroxide, white carbon black, antistatic agent, tricresyl phosphate and accelerator DM into the internal mixer in sequence, and mixing at the third set temperature for the fourth set time to prepare a surface layer rubber mixture; After the surface layer mixed rubber is allowed to stand for a fifth set time, it is put into an open mixer and pressed into a sheet at a fourth set temperature and a first set pressure to obtain a calendered surface layer (2); Adding chloropropylene rubber and styrene-butadiene rubber into an internal mixer, and mixing at a fifth set temperature for a fourth set time; Adding superconducting carbon black, aluminum powder, calcium carbonate and γ-glycidyloxypropyltrimethoxysilane into an internal mixer, and mixing at a sixth set temperature for a sixth set time; Add dioctyl sebacate, paraffin oil and accelerator CZ to the internal mixer in sequence, and continue to mix at the sixth set temperature for the sixth set time to obtain a base rubber mixture; After the bottom layer rubber mixture is allowed to stand for a seventh set time, it is put into an open mixer and pressed into a sheet at a fourth set temperature and a first set pressure to obtain a calendered bottom layer (1); The calendered surface layer (2) is covered on the calendered bottom layer (1), then placed in a mold, and sent to a drum vulcanizer, and vulcanized for an eighth set time at a seventh set temperature, a second set pressure and a first vulcanization speed, to finally produce a double-layer composite non-flammable antistatic rubber mat.

9. The method for preparing a double-layer composite non-inflammable antistatic rubber pad according to claim 8, characterized in that: The emulsifier includes any one of sodium dodecylbenzene sulfonate, sodium stearate and sodium dodecyl sulfate; the initiator includes any one of potassium persulfate and ammonium persulfate; the mass ratio of 2-chloro-1,3-butadiene, vinyl pyridine, emulsifier and initiator is (70~85): (10~30): (2~5): (0.2~0.8).

10. The method for preparing a double-layer composite non-inflammable antistatic rubber pad according to claim 8, characterized in that: The first set temperature is 40~50℃; the second set temperature is 55~65℃; the third set temperature is 70~80℃; the fourth set temperature is 150~160℃; the fifth set temperature is 65~75℃; the sixth set temperature is 75~85℃; the seventh set temperature is 160~170℃; the first setting time is 8~12h; the second setting time is 8~12min; the third setting time is 5~10min; the fourth setting time is 10~15min; the fifth setting time is 12~24h; the sixth setting time is 15~20min; the seventh setting time is 6~12h; the eighth setting time is 20~25min; the first setting pressure is 10~15MPa; the second setting pressure is 15~18MPa; the first vulcanization speed is 0.1~0.3m / min.

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