Rubber composition as well as preparation method and application thereof

Abstract

The invention provides a rubber composition as well as a preparation method and application thereof, and the rubber composition comprises the following raw materials in parts by mass: 15-60 parts of butadiene rubber, 5-25 parts of butadiene styrene rubber and 11-50 parts of an auxiliary agent, the content of fluorine in the butadiene rubber is less than or equal to 50 ppm, the molecular weight distribution index is 2.8-3.7, the cis content is greater than or equal to 96%, and the weight-average molecular weight is 190000-270000. According to the rubber composition provided by the invention, the butadiene rubber with good use performance is matched with the styrene-butadiene rubber, and compared with the traditional butadiene rubber, the butadiene rubber has the characteristics of narrow molecular weight distribution, high linearization, small weight-average molecular weight and low fluorine content, so that the transparency and yellowing resistance of the rubber composition can be effectively improved.

Description

Technical Field

[0001] This application relates to the technical field of rubber, and particularly to a rubber composition, a preparation method thereof, and an application thereof. Background Art

[0002] Traditional sole materials are mainly semi-transparent materials with a sulfur vulcanization system and opaque materials such as ethylene-vinyl acetate copolymer. With the improvement of the requirements for product design aesthetics and function visualization, thermoplastic polyurethane (TPU), polyvinyl chloride (PVC), and modified rubber materials with high light transmittance have been gradually applied to sole manufacturing. However, it is difficult for the above materials to maintain high transparency while meeting performance requirements such as yellowing resistance. Summary of the Invention

[0003] Based on this, it is necessary to provide a rubber composition with high transparency and yellowing resistance, a preparation method thereof, and an application thereof.

[0004] This application provides a rubber composition. In terms of parts by mass, the raw materials include 15 parts to 60 parts of cis-butadiene rubber, 5 parts to 25 parts of styrene-butadiene rubber, and 11 parts to 50 parts of additives.

[0005] The content of fluorine element in the cis-butadiene rubber is less than or equal to 50 ppm, the molecular weight distribution index is 2.8 to 3.7, the cis content is greater than or equal to 96%, and the weight average molecular weight is 190000 to 270000.

[0006] In one embodiment, the additives include one or more of a reinforcing agent, a plasticizer, a dispersant, an antioxidant, an anti-frost agent, and a cross-linking agent.

[0007] In one embodiment, the additives include the reinforcing agent, the plasticizer, the antioxidant, the dispersant, the anti-frost agent, and the cross-linking agent in a mass ratio of (8 to 25):(2 to 15):(0.3 to 1.5):(0.5 to 2.4):(0.3 to 1.5):(0.1 to 1).

[0008] In one embodiment, the additives satisfy one or more of the following conditions:

[0009] (1) The plasticizer includes one or more of stearic acid, dibutyl phthalate, and white oil;

[0010] (2) The antioxidant includes one or more of 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), octadecyl propionate, 4,6-bis(octylthiomethyl)o-cresol, and pentaerythritol ester;

[0011] (3) The dispersant includes one or two of polyethylene glycol and polyethylene wax;

[0012] (4) The antifrost agent includes one or both of Shanghai Dunmei New Materials Antifrost Agent 606 and Shengyiwei HW-50 Defrosting Agent;

[0013] (5) The bridging agent includes one or both of 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane and bis(2,5-dimethyl-2,5-di-tert-butyl peroxy)hexane;

[0014] (6) The reinforcing agent includes fumed silica.

[0015] In one embodiment, the raw materials of the rubber composition include, by mass, 15 to 60 parts of butadiene rubber, 5 to 25 parts of styrene butadiene rubber, 8 to 25 parts of the reinforcing agent, 2 to 15 parts of the plasticizer, 0.3 to 1.5 parts of the antioxidant, 1 to 3 parts of the dispersant, 0.3 to 1.5 parts of the anti-frost agent and 0.1 to 1 part of the bridging agent.

[0016] The present application also provides a method for preparing a rubber composition, comprising the following steps:

[0017] Mixing the raw materials for the first time to prepare a rubber compound;

[0018] vulcanizing the rubber mixture;

[0019] The raw materials include, by weight, 15 to 60 parts of cis-1,4-butadiene rubber, 5 to 25 parts of styrene-butadiene rubber and 11 to 50 parts of additives. The fluorine content in the cis-1,4-butadiene rubber is ≤50 ppm, the molecular weight distribution index is 2.8 to 3.7, and the cis content is greater than or equal to 96%.

[0020] In one embodiment, the first mixing satisfies one or both of the following conditions:

[0021] (1) The mixing temperature is 60℃~90℃;

[0022] (2) The mixing time is 7 minutes to 12 minutes.

[0023] In one embodiment, the sulfurization treatment satisfies one or more of the following conditions:

[0024] (1) The temperature of the vulcanization treatment is 145°C to 155°C;

[0025] (2) The pressure of the vulcanization treatment is 15MPa~20MPa;

[0026] (3) The vulcanization treatment time is 22 min to 30 min.

[0027] In one embodiment, before the vulcanization treatment, the kneaded rubber is further subjected to a discharging treatment.

[0028] Furthermore, the present application provides a sole, which comprises the rubber composition as described above or the rubber composition prepared by the preparation method as described above.

[0029] The rubber composition provided by the present application uses cis-butadiene rubber with good performance in combination with styrene-butadiene rubber. Since cis-butadiene rubber has the characteristics of narrow molecular weight distribution, high linearization degree, small weight-average molecular weight and low fluorine element content compared with traditional cis-butadiene rubber, the transparency and yellowing resistance of the rubber composition can be effectively improved after being combined with styrene-butadiene rubber. Detailed implementation manners

[0030] For the convenience of understanding the present application, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosed content of the present application more thorough and comprehensive.

[0031] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of such features. In the description of the invention, the meaning of "a plurality" is at least two, such as two, three, etc., unless otherwise specifically defined. In the description of the present application, the meaning of "several" is at least one, such as one, two, etc., unless otherwise specifically defined.

[0032] The terms "preferably", "more preferably", etc. in the present application refer to the embodiments of the present application that can provide certain beneficial effects in certain cases. However, in the same cases or other cases, other embodiments may also be preferred. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not available, nor is it intended to exclude other embodiments from the scope of the present application.

[0033] When a numerical range is disclosed herein, the above range is considered continuous and includes the minimum value and the maximum value of the range, as well as each value between such minimum value and maximum value. Further, when the range refers to an integer, it includes each integer between the minimum value and the maximum value of the range. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terms used in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0035] This application provides a rubber composition. In parts by mass, the raw materials include 15 to 60 parts of cis-1,4-polybutadiene rubber, 5 to 25 parts of styrene-butadiene rubber, and 11 to 50 parts of additives.

[0036] Among them, the content of fluorine element in the cis-1,4-polybutadiene rubber is less than or equal to 50 ppm, the molecular weight distribution index is 2.8 to 3.7, the cis content is greater than or equal to 96%, and the weight average molecular weight is 190,000 to 270,000.

[0037] Furthermore, the number average molecular weight of the cis-1,4-polybutadiene rubber is 50,000 to 90,000; the weight average molecular weight is 210,000 to 240,000, the molecular weight distribution index is 3.1 to 3.3; the Mooney viscosity of the raw rubber is 38 to 50; the cis content is 96.5% to 97.2%, the volatile content is ≤0.3%, and the ash content is ≤0.2%.

[0038] Specifically, the number average molecular weight of the cis-1,4-polybutadiene rubber can be, but is not limited to, 50,000, 60,000, 70,000, 80,000, or 90,000. The weight average molecular weight can be, but is not limited to, 210,000, 215,000, 220,000, 225,000, 230,000, 235,000, or 240,000. The molecular weight distribution index PDI can be, but is not limited to, 3.1, 3.2, or 3.3. The Mooney viscosity of the raw rubber can be, but is not limited to, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50. The cis content can be, but is not limited to, 96.5%, 96.6%, 96.7%, 96.8%, 96.9%, 97%, 97.1%, or 97.2%.

[0039] The rubber composition provided by this application uses cis-1,4-polybutadiene rubber with good performance in combination with styrene-butadiene rubber. Since the cis-1,4-polybutadiene rubber has the characteristics of narrow molecular weight distribution, high linearization degree, small weight average molecular weight, and low fluorine element content compared with traditional cis-1,4-polybutadiene rubber, the transparency and yellowing resistance of the rubber composition can be effectively improved.

[0040] In a specific example, the additives include one or more of a reinforcing agent, a plasticizer, an antioxidant, a dispersant, an anti-frosting agent, and a cross-linking agent.

[0041] In a specific example, the auxiliaries include a reinforcing agent, a plasticizer, an antioxidant, a dispersant, an anti-frosting agent, and a cross-linking agent in a mass ratio of (8-25):(2-15):(0.3-1.5):(0.5-2.4):(0.3-1.5):(0.1-1).

[0042] In a specific example, based on mass parts, the raw materials of the rubber composition include 15 parts to 60 parts of cis-butadiene rubber, 5 parts to 20 parts of styrene-butadiene rubber, 8 parts to 25 parts of white carbon black, 2 parts to 15 parts of plasticizer, 0.3 parts to 1.5 parts of antioxidant, 1.2 parts to 2.5 parts of dispersant, 0.3 parts to 1.5 parts of anti-frosting agent, and 0.1 parts to 1 part of cross-linking agent.

[0043] In a specific example, the plasticizer includes one or more of stearic acid, dibutyl phthalate, and white oil.

[0044] In a specific example, the antioxidant includes one or more of 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), octadecyl propionate, 4,6-bis(octylthiomethyl)o-cresol, and pentaerythritol ester. Specifically, the antioxidant includes one or more of 2,6-di-tert-butyl-p-cresol (antioxidant 264), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (antioxidant 2246), octadecyl propionate (antioxidant 1076), 4,6-bis(octylthiomethyl)o-cresol (antioxidant 1520), and pentaerythritol ester (antioxidant 1010).

[0045] In a specific example, the dispersant includes one or both of polyethylene glycol and polyethylene wax.

[0046] In a specific example, the anti-frosting agent includes one or both of Shanghai Dunmei New Material Anti-frosting Agent 606 and Shengyiwei HW-50 Defroster.

[0047] In a specific example, the cross-linking agent includes one or both of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and bis(2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane). Specifically, the cross-linking agent includes one or both of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane (3M) and bis(2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane) (bis-25).

[0048] This application also provides a preparation method of a rubber composition, including the following steps:

[0049] Mix the raw materials for the first time to prepare a kneaded rubber.

[0050] Vulcanize the kneaded rubber.

[0051] Among them, based on parts by mass, the raw materials include 15 to 60 parts of cis-butadiene rubber, 5 to 25 parts of styrene-butadiene rubber, and 11 to 50 parts of additives. The content of fluorine element in the cis-butadiene rubber is less than or equal to 50 ppm, the molecular weight distribution index is 2.8 to 3.7, the cis content is greater than or equal to 96%, and the weight-average molecular weight is 190,000 to 270,000.

[0052] In a specific example, the temperature of the first mixing is 60°C to 90°C. Specifically, the temperature of the first mixing can be, but is not limited to, 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C or 90°C.

[0053] In a specific example, the time of the first mixing is 7 min to 12 min. Specifically, the time of the first mixing can be, but is not limited to, 7 min, 8 min, 9 min, 10 min, 11 min or 12 min.

[0054] In a specific example, the temperature of the vulcanization treatment is 145°C to 155°C. Specifically, the temperature of the vulcanization treatment can be, but is not limited to, 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C or 155°C.

[0055] In a specific example, the pressure of the vulcanization treatment is 15 MPa to 20 MPa. Specifically, the pressure of the vulcanization treatment can be, but is not limited to, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa or 20 MPa.

[0056] In a specific example, the time of the vulcanization treatment is 22 min to 30 min. The time of the vulcanization treatment can be, but is not limited to, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min or 30 min.

[0057] In a specific example, before the vulcanization treatment, it also includes degassing the mixed rubber.

[0058] Furthermore, the present application provides a sole, including the rubber composition as described above or the rubber composition prepared by the preparation method as described above.

[0059] The present application is further described in detail below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance given in the present application, and can also be based on the experimental manuals or conventional conditions in the art, can also be based on the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0060] In the following specific embodiments, the measured parameters of raw material components may have slight deviations within the range of weighing accuracy unless otherwise specified. For temperature and time parameters, acceptable deviations caused by instrument test accuracy or operation accuracy are allowed. "Normal temperature" refers to 25°C; "normal pressure" refers to 100KPa or 101KPa.

[0061] Example 1

[0062] The present embodiment provides a rubber composition, which comprises, by mass, 25 parts of butadiene rubber (TF08S, Zhejiang Chuanhua Synthetic Materials Co., Ltd.), 11 parts of styrene-butadiene rubber (SSBR303, Asahi Chemical Industry, Japan), 13 parts of a reinforcing agent (ultrafine white carbon black purchased from Shandong Lihua New Materials), 7 parts of a plasticizer (15# white oil purchased from Shanghai Beite Chemical), 0.7 parts of an antioxidant 1076 (Tianjin Lianlong), 1.6 parts of a dispersant (PEG4000 purchased from Jiangsu Pules Biotechnology), 0.5 parts of a bridging agent (3M, Guangzhou Qiansheng Trading), and 0.8 parts of an anti-frost agent 606 (Shanghai Dunmei New Materials).

[0063] The preparation method of the rubber composition comprises the following steps: the temperature of the internal mixer is controlled at 80°C and the speed is 80r / min. Butadiene rubber TF08S and styrene-butadiene rubber are added to the internal mixer for plasticization for 60s; an antioxidant, a dispersant, half of the white carbon black and half of the plasticizer are sequentially added to the internal mixer, and after mixing for 130s, the remaining half of the white carbon black and the plasticizer are added, and after mixing for 130s, the remaining anti-frost agent and the bridging agent are finally added, and mixed for 30s, and the mixing temperature is controlled to be lower than 120°C. After the internal mixer is discharged, the mixture is cooled in an open mixer for sheeting, and the roller spacing is 30. After passing the roller 3 times, the final mixed rubber is placed on a clean glass bracket.

[0064] After the mixed rubber is cut into a size suitable for the mold, the product is placed in a vulcanization mold for vulcanization. The vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15-20MPa, and the vulcanization time is 3 minutes added to the T90 time measured on the rotorless vulcanizer.

[0065] Example 2

[0066] This embodiment provides a rubber composition, the composition of which includes 29 parts by mass of cis-butadiene rubber (TF08S, Zhejiang Transfar Synthetic Materials Co., Ltd.), 13 parts of styrene-butadiene rubber (SSBR303, Asahi Kasei, Japan), 15 parts of reinforcing agent (ultrafine silica, Shandong Lihua New Materials Co., Ltd.), 8 parts of plasticizer (15# white oil, Shanghai Beit Chemical Industry Co., Ltd.), 0.7 part of antioxidant 1076 (Tianjin Rianlon Co., Ltd.), 1.7 parts of dispersant PEG4000 (Jiangsu Pulosi Biotechnology Co., Ltd.); 0.5 part of crosslinking agent (3M, Guangzhou Qiansheng Trading Co., Ltd.), 0.8 part of anti-frosting agent 606 (Shanghai Dunmei New Materials Co., Ltd.).

[0067] The preparation method of the above rubber composition includes the following steps: The temperature of the internal mixer is controlled at 80°C and the rotation speed is 80 r / min. Add cis-butadiene rubber TF08S and styrene-butadiene rubber into the internal mixer for plasticizing for 60 s; successively add antioxidant, dispersant, half of the silica and half of the plasticizer into the internal mixer, after mixing for 130 s, add the remaining half of the silica and plasticizer, after mixing for 130 s, finally add the remaining anti-frosting agent and crosslinking agent, mix for 30 s, control the mixing temperature below 120°C, after the internal mixer discharges the rubber, go to the open mill for sheet pressing and cooling, the roll gap is 30, after passing through the rolls 3 times, place the final mixed rubber on a cleaned glass bracket.

[0068] After cutting the mixed rubber into a size suitable for the mold, place the product in a vulcanization mold for vulcanization, the vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15 - 20 MPa, and the vulcanization time is increased by 3 minutes based on the T90 time measured on a rotorless vulcanizer.

[0069] Example 3

[0070] This embodiment provides a rubber composition, the composition of which includes 45 parts by mass of cis-butadiene rubber (TF08S, Zhejiang Transfar Synthetic Materials Co., Ltd.), 22 parts of styrene-butadiene rubber (SSBR303, Asahi Kasei, Japan), 13 parts of reinforcing agent (ultrafine silica, Shandong Lihua New Materials Co., Ltd.), 7 parts of plasticizer (15# white oil, Shanghai Beit Chemical Industry Co., Ltd.), 0.7 part of antioxidant 1076 (Tianjin Rianlon Co., Ltd.), 2.1 parts of dispersant PEG4000 (Jiangsu Pulosi Biotechnology Co., Ltd.); 0.5 part of crosslinking agent (3M, Guangzhou Qiansheng Trading Co., Ltd.), 0.8 part of anti-frosting agent 606 (Shanghai Dunmei New Materials Co., Ltd.).

[0071] The preparation method of the rubber composition comprises the following steps: the temperature of the internal mixer is controlled at 80°C and the speed is 80r / min. Butadiene rubber TF08S and styrene-butadiene rubber are added to the internal mixer for plasticization for 60s; an antioxidant, a dispersant, half of the white carbon black and half of the plasticizer are sequentially added to the internal mixer, and after mixing for 130s, the remaining half of the white carbon black and the plasticizer are added, and after mixing for 130s, the remaining anti-frost agent and the bridging agent are finally added, and mixed for 30s, and the mixing temperature is controlled to be lower than 120°C. After the internal mixer is discharged, the mixture is cooled in an open mixer for sheeting, and the roller spacing is 30. After passing the roller 3 times, the final mixed rubber is placed on a clean glass bracket.

[0072] After the mixed rubber is cut into a size suitable for the mold, the product is placed in a vulcanization mold for vulcanization. The vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15-20MPa, and the vulcanization time is 3 minutes added to the T90 time measured on the rotorless vulcanizer.

[0073] Example 4

[0074] The present embodiment provides a rubber composition, which comprises, by mass, 28 parts of butadiene rubber (TF08S Zhejiang Chuanhua Synthetic Materials Co., Ltd.), 12 parts of styrene-butadiene rubber (SSBR303, Asahi Chemical of Japan), 22 parts of white carbon black (ultrafine white carbon black Shandong Lihua New Materials), 10 parts of plasticizer (15# white oil Shanghai Beite Chemical), 0.7 parts of antioxidant 1076 (Tianjin Lianlong), 1.7 parts of dispersant PEG4000 (Jiangsu Pules Biotechnology), 0.5 parts of bridging agent (3M, Guangzhou Qiansheng Trading), and 0.8 parts of anti-frost agent 606 (Shanghai Dunmei New Materials).

[0075] The preparation method of the rubber composition comprises the following steps: the temperature of the internal mixer is controlled at 80°C and the speed is 80r / min. Butadiene rubber TF08S and styrene-butadiene rubber are added to the internal mixer for plasticization for 60s; an antioxidant, a dispersant, half of the white carbon black and half of the plasticizer are sequentially added to the internal mixer, and after mixing for 130s, the remaining half of the white carbon black and the plasticizer are added, and after mixing for 130s, the remaining anti-frost agent and the bridging agent are finally added, and mixed for 30s, and the mixing temperature is controlled to be lower than 120°C. After the internal mixer is discharged, the mixture is cooled in an open mixer for sheeting, and the roller spacing is 30. After passing the roller 3 times, the final mixed rubber is placed on a clean glass bracket.

[0076] After the mixed rubber is cut into a size suitable for the mold, the product is placed in a vulcanization mold for vulcanization. The vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15-20MP, and the vulcanization time is 3 minutes added to the T90 time measured on the rotorless vulcanizer.

[0077] Example 5

[0078] The difference from Example 1 is that styrene butadiene rubber (SSBR303, Asahi Chemical Industry, Japan) is replaced by styrene butadiene rubber (SSBR1205, Asahi Chemical Industry, Japan).

[0079] The present embodiment provides a rubber composition, which comprises, by mass, 28 parts of butadiene rubber (TF08S Zhejiang Chuanhua Synthetic Materials Co., Ltd.), 12 parts of styrene-butadiene rubber (SSBR1205, Asahi Chemical of Japan), 22 parts of white carbon black (ultrafine white carbon black Shandong Lihua New Materials), 10 parts of plasticizer (15# white oil Shanghai Beite Chemical), 0.7 parts of antioxidant 1076 (Tianjin Lianlong), 1.7 parts of dispersant PEG4000 (Jiangsu Pules Biotechnology), 0.5 parts of bridging agent (3M, Guangzhou Qiansheng Trading), and 0.8 parts of anti-frost agent 606 (Shanghai Dunmei New Materials).

[0080] The preparation method of the rubber composition comprises the following steps: the temperature of the internal mixer is controlled at 80°C and the speed is 80r / min. Butadiene rubber TF08S and styrene butadiene rubber are added to the internal mixer for plasticization for 60s; an antioxidant, a dispersant, half of white carbon black and half of a plasticizer are sequentially added to the internal mixer, and after mixing for 130s, the remaining half of the white carbon black and the plasticizer are added, and after mixing for 130s, the remaining anti-frost agent and the bridging agent are finally added, and mixed for 30s, and the mixing temperature is controlled to be lower than 120°C. After the internal mixer is discharged, the mixture is cooled in an open mixer for sheeting, and the roller spacing is 30. After passing the roller 3 times, the final mixed rubber is placed on a clean glass bracket.

[0081] After the mixed rubber is cut into a size suitable for the mold, the product is placed in a vulcanization mold for vulcanization. The vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15-20MP, and the vulcanization time is 3 minutes added to the T90 time measured on the rotorless vulcanizer.

[0082] Comparative Example 1

[0083] This comparative example provides a rubber composition, which comprises 25 parts by mass of cis-1,4-dibutyl rubber (1208BRLG Chemical tested by the applicant (detection limit is 50ppm), 1208BR has a fluorine content of 100ppm~150ppm), 11 parts of styrene-butadiene rubber (SSBR303, Asahi Chemical, Japan), 13 parts of white carbon black (ultrafine white carbon black Shandong Lihua New Materials), 7 parts of plasticizer (15# white oil Shanghai Beite Chemical), 0.7 parts of antioxidant 1076 (Tianjin Lianlong), 1.6 parts of dispersant PEG4000 (Jiangsu Pules Biotechnology); 0.5 parts of bridging agent (3M, Guangzhou Qiansheng Trading), 0.8 parts of anti-frost agent (Shanghai Dunmei New Materials). The preparation method of the above rubber composition comprises the following steps: the temperature of the internal mixer is controlled at 80°C and the speed is 80r / min. Add cis-1,4-butadiene rubber TF08S and styrene-butadiene rubber into an internal mixer and plasticize for 60 seconds; add antioxidant, dispersant, half of white carbon black and half of plasticizer into the internal mixer in turn, mix for 130 seconds, add the remaining half of white carbon black and plasticizer, mix for 130 seconds, finally add the remaining anti-frost agent and bridging agent, mix for 30 seconds, and control the mixing temperature below 120°C. After the internal mixer is discharged, cool it to the open mixer for sheeting, with a roller distance of 30. After passing the roller 3 times, place the final mixed rubber on a clean glass stand.

[0084] After the mixed rubber is cut into a size suitable for the mold, the product is placed in a vulcanization mold for vulcanization. The vulcanization temperature is 145°C to 155°C, the vulcanization pressure is 15-20MPa, and the vulcanization time is 3 minutes added to the T90 time measured on the rotorless vulcanizer.

[0085] Test methods and results

[0086] The rubber compositions of the above embodiments and comparative examples were tested, wherein the yellowing resistance was tested by using a vulcanized film, the yellowing resistance lamp of method A for 12 hours, and the lamp tube of method B for 6 hours, and the transparency was tested by naked eye, the wear resistance was tested by using the GB / T9867-2008 standard, and the hardness was tested by using the Shore (A) durometer in the GB / T531.1-2008 standard. The results are shown in Table 1 below.

[0087] Table 1

[0088]

[0089] The comparative example used LG Chemical's 1208BR, which was tested by the applicant to have a higher fluorine content than the butadiene rubber TF08S used in the example (detection limit of 50 ppm). The transparency and wear resistance of the rubber composition obtained in the final comparative example did not meet the standards of the rubber composition in the example.

[0090] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as falling within the scope described in this specification.

[0091] The above-described embodiments merely represent several implementation manners of the present application, which are convenient for understanding the technical solutions of the present application specifically and in detail, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments based on the technical solutions provided in the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A rubber composition, characterized in that, By mass parts, the raw materials include 15 to 60 parts of cis-1,4-polybutadiene rubber, 5 to 25 parts of styrene-butadiene rubber, and 11 to 50 parts of additives; The content of fluorine element in the cis-1,4-polybutadiene rubber is less than or equal to 50 ppm, the molecular weight distribution index is 2.8 to 3.7, the cis content is greater than or equal to 96%, and the weight-average molecular weight is 190,000 to 270,000.

2. The rubber composition according to claim 1, wherein The additives include one or more of a reinforcing agent, a plasticizer, a dispersant, an antioxidant, an anti-frosting agent, and a cross-linking agent.

3. The rubber composition according to claim 2, characterized in that, The additives include the reinforcing agent, the plasticizer, the antioxidant, the dispersant, the anti-frosting agent, and the cross-linking agent in a mass ratio of (8 to 25):(2 to 15):(0.3 to 1.5):(0.5 to 2.4):(0.3 to 1.5):(0.1 to 1).

4. The rubber composition according to claim 3, characterized in that, The additives meet one or more of the following conditions: (1) The plasticizer includes one or more of stearic acid, dibutyl phthalate, and white oil; (2) The antioxidant includes one or more of 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), octadecyl propionate, 4,6-bis(octylthiomethyl)o-cresol, and pentaerythritol ester; (3) The dispersant includes one or two of polyethylene glycol and polyethylene wax; (4) The anti-frosting agent includes one or two of Shanghai Dunmei New Material Anti-frosting Agent 606 and Sheng Yiwei HW-50 Defroster; (5) The cross-linking agent includes one or two of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane and bis(2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane); (6) The reinforcing agent includes fumed silica.

5. The rubber composition according to any one of claims 2 to 4, characterized in that, By mass parts, the raw materials of the rubber composition include 15 to 60 parts of cis-1,4-polybutadiene rubber, 5 to 25 parts of styrene-butadiene rubber, 8 to 25 parts of the reinforcing agent, 2 to 15 parts of the plasticizer, 0.3 to 1.5 parts of the antioxidant, 1 to 3 parts of the dispersant, 0.3 to 1.5 parts of the anti-frosting agent, and 0.1 to 1 part of the cross-linking agent.

6. A method for preparing a rubber composition, characterized in that, It includes the following steps: Mix the raw materials for the first time to prepare a mixed rubber; Perform vulcanization treatment on the mixed rubber; Among them, by mass parts, the raw materials include 15 to 60 parts of cis-1,4-polybutadiene rubber, 5 to 25 parts of styrene-butadiene rubber, and 11 to 50 parts of additives. The content of fluorine element in the cis-1,4-polybutadiene rubber is ≤50 ppm, the molecular weight distribution index is 2.8 to 3.7, and the cis content is greater than or equal to 96%.

7. The preparation method according to claim 6, characterized in that, The first mixing meets one or two of the following conditions: (1) The mixing temperature is 60°C to 90°C; (2) The mixing time is 7 min to 12 min.

8. The preparation method according to claim 6, characterized in that, The vulcanization treatment meets one or more of the following conditions: (1) The temperature of the vulcanization treatment is 145°C to 155°C; (2) The pressure of the vulcanization treatment is 15 MPa to 20 MPa; (3) The time of the vulcanization treatment is 22 min to 30 min.

9. The preparation method according to any one of claims 6 to 8, characterized in that, Before the vulcanization treatment, it also includes discharging the mixed rubber.

10. A sole, characterized in that, Comprising the rubber composition according to any one of claims 1 to 5 or the rubber composition prepared by the preparation method according to any one of claims 6 to 9.

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