Master batch type vulcanizing aid and preparation method thereof, rubber composition, rubber product and tire

Abstract

The invention provides a masterbatch type vulcanizing aid and a preparation method thereof, a rubber composition, a rubber product and a tire. The preparation method comprises the following steps: S1, carrying out pre-reaction on stearic acid, an anti-aging agent and a vulcanization system to obtain a pre-reaction mixture; and S2, mixing the pre-reaction mixture with rubber to obtain the rubber master batch type vulcanizing aid. Under the catalytic action of stearic acid, an anti-aging agent reacts with a reagent in a vulcanization system to generate an active intermediate, the active intermediate has the effect of promoting vulcanization and has the effect of activating an accelerant in advance, so that the active intermediate can replace zinc oxide, and a product obtained after the reaction is mixed with rubber, so that the rubber is obtained. The formed masterbatch can be used for preparing rubber products such as tires which are completely free of zinc elements, zinc-free emission can be realized, and the masterbatch is environment-friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of tread rubber preparation, and in particular to a masterbatch type vulcanization aid and a preparation method thereof, a rubber composition, a rubber product and a tire. Background Art

[0002] Zinc contained in tire treads is polluting to the environment. The European Commission Directive 2400 / 73 / EC and the SB1260 bill proposed by California in 2016 both recommend limiting the use of zinc or zinc oxide in tires.

[0003] However, zinc oxide or zinc additives act as vulcanization activators during vulcanization, which can increase the crosslinking density, thereby increasing the hardness of the rubber and ensuring the performance of the rubber. The rolling resistance and grip of the tires manufactured by them can be guaranteed. Removing zinc from the commonly used formula, according to the existing production process, often results in a reduced degree of crosslinking, resulting in reduced mechanical properties, low hardness, increased hysteresis, increased rolling resistance of the tire, and reduced grip. Usually, the amount of zinc oxide in the diene rubber composition is required to be at least 2phr; if the existing rubber composition does not contain zinc, through the conventional tire rubber preparation process, its mechanical properties are low, the hardness is low, and the grip and wear resistance are also significantly reduced.

[0004] Researchers at home and abroad have begun to study the environmental problems of zinc in tread rubber. Among them, the patent application with publication number CN115678038B discloses a method of using a lignin zinc salt complex to replace zinc oxide. By utilizing its good dispersion characteristics, the purpose of reducing the application of zinc oxide is achieved, and it is applied to tire tread rubber, which can ensure the wear resistance of the tire and reduce the rolling resistance of the tire, thereby improving the service life of the tire. The patent achieves the purpose of reducing the amount of zinc by improving the dispersion of zinc, but it cannot completely eliminate the harm of zinc to the environment. Patent CN102300917B discloses a rubber composition that does not contain zinc or contains less than 0.5phr of zinc and is used in tire manufacturing. It improves the processability of the rubber composition due to the absence of zinc (i.e., reducing viscosity and extending the scorch time) by applying blocked mercaptosilane. Although the patent can reduce the amount of zinc or even contain no zinc, it requires the use of a specific blocked mercaptosilane, which may further react to generate mercapto groups during high-temperature mixing, has certain irritation and odor, and has safety issues.

[0005] How to improve the performance of tread rubber without using zinc has important social significance and economic value. Summary of the invention

[0006] The main purpose of the present invention is to provide a masterbatch type vulcanization aid and its preparation method, rubber composition, rubber product and tire, so as to solve the problem of environmental pollution caused by zinc contained in tread rubber in the prior art.

[0007] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a method for preparing a masterbatch type vulcanization aid is provided, the preparation method comprising: step S1, pre-reacting stearic acid, an antioxidant and a vulcanization system to obtain a pre-reaction mixture; step S2, mixing the pre-reaction mixture with rubber to obtain a masterbatch type vulcanization aid.

[0008] Further, the reaction temperature of the pre-reaction is 100-190°C, and the reaction time is 1min-120min;

[0009] Preferably, the reaction temperature of the pre-reaction is 110-170° C., and the reaction time is 5 min-50 min.

[0010] Further, the pre-reaction is carried out in a solvent, preferably, the solvent is any one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene and xylene;

[0011] Preferably, step S2 comprises removing the solvent from the pre-reaction mixture and mixing it with rubber to obtain a masterbatch type vulcanization aid; or,

[0012] Step S2 includes mixing the pre-reaction mixture containing the solvent with the rubber, and then removing the solvent to obtain a masterbatch type vulcanization aid.

[0013] Furthermore, the antioxidant is a phenylenediamine antioxidant; preferably, the antioxidant has a structure shown in Formula I:

[0014]

[0015] In Formula I, R 1 Selected from C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18 The aromatic hydrocarbon group, R 2 , R 3 , R 4 , R 5 Each independently selected from C1-C 18 The chain hydrocarbon group, R 2 With R 3 or R 4 With R 5 They can also form aliphatic rings separately or simultaneously, R 6 Selected from, R 6 Selected from H, C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18x=0 or 1, y=0 or 1, z=0 or 1, w=0 or 1, and at least one of x and w has a value of 1, and at least one of y and z has a value of 1.

[0016] Further, the vulcanization system chemicals include any one or more of vulcanizing agents and accelerators, the vulcanizing agents include any one or more of sulfur and sulfur carriers, the accelerators include any one or more of sulfonamide accelerators and thiazole accelerators, preferably, the accelerators include any one or more of CZ, DCBS, MBTS, MBT and TBBS;

[0017] The rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural eucommia gum, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and EPDM rubber; preferably, the rubber is a rubber containing formula II:

[0018]

[0019] Wherein, a, b, c, d, e and f are each independently an integer greater than or equal to 0, and a, b, c, d, e and f are not 0 at the same time.

[0020] Furthermore, the weight ratio of stearic acid to antioxidant is 1:1 to 1:1.25; the weight ratio of vulcanization system to antioxidant is 0.8:1 to 1.15:1.

[0021] In order to achieve the above object, according to one aspect of the present invention, a masterbatch type vulcanization aid is provided. The masterbatch type vulcanization aid is prepared by any one of the above preparation methods.

[0022] According to another aspect of the present application, a rubber composition is provided, which is characterized in that, in parts by weight, it includes 0 to 130 parts of elastomer, 25 to 35 parts of masterbatch type vulcanization aid, 20 to 170 parts of filler and 1 to 5 parts of other additives, and the masterbatch type vulcanization aid is the above-mentioned masterbatch type vulcanization aid.

[0023] Furthermore, the filler includes any one or more of a carbon-based filler, a silicon-based filler, a carbon-silicon dual-phase filler and clay; preferably, the specific surface area of ​​the filler is 10 to 500 m 2 / g, more preferably 30 to 300 m 2 / g, more preferably 50 to 300 m 2 / g;

[0024] Other additives include any one or more of resin, process oil, vulcanizing agent and silane coupling agent;

[0025] Preferably, based on weight, it includes 30 to 100 parts of elastomer, 26 to 31 parts of masterbatch type vulcanization aid, 50 to 130 parts of filler and 1.4 to 4.5 parts of other additives.

[0026] According to an advantageous aspect of the present application, a rubber product is provided, wherein the rubber product is prepared from any one of the above-mentioned rubber compositions.

[0027] According to another aspect of the present application, a tire is provided, wherein the tire contains the above-mentioned rubber product.

[0028] By applying the technical scheme of the present invention, under the catalytic action of stearic acid, the antioxidant reacts with the reagent in the vulcanization system to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of an early activation accelerator, so that the active intermediate can replace the role of zinc oxide. The product after the reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires that are completely free of zinc elements, and can achieve zinc-free emissions and be environmentally friendly. At the same time, the masterbatch-type vulcanization aid prepared by the above preparation method can enable the rubber composition containing it to obtain a crosslinking density close to that of a zinc-containing rubber composition without zinc, and rubber properties such as hardness, tensile stress and hysteresis. DETAILED DESCRIPTION

[0029] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0030] As analyzed in the background technology of the present application, there is a problem in the prior art that zinc contained in tread rubber causes environmental pollution. The methods in the prior art can only reduce the zinc content in the rubber, but cannot completely avoid the environmental impact caused by zinc. However, it is difficult for tread rubber without zinc to meet the use requirements. In order to solve this problem, the present application provides a masterbatch vulcanization aid and a preparation method thereof, a rubber composition, a rubber product and a tire.

[0031] According to a typical embodiment of the present application, a method for preparing a masterbatch type vulcanization aid is provided, the preparation method comprising: step S1, pre-reacting stearic acid, an antioxidant and a vulcanization system to obtain a pre-reaction mixture; step S2, mixing the pre-reaction mixture with rubber to obtain a masterbatch type vulcanization aid.

[0032] In the above preparation method, under the catalytic action of stearic acid, the antioxidant reacts with the reagent in the vulcanization system to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of an early activation accelerator, so that the active intermediate can replace the role of zinc oxide. The product after the reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires that are completely free of zinc elements, and can achieve zinc-free emissions and be environmentally friendly. At the same time, the masterbatch-type vulcanization aid prepared by the above preparation method can enable the rubber composition containing it to obtain a crosslinking density close to that of a zinc-containing rubber composition without zinc, and rubber properties such as hardness, tensile stress and hysteresis.

[0033] Taking the phenylenediamine antioxidant and 2-thiobenzothiazole vulcanization system chemicals as an example, the reaction occurring in the pre-reaction is shown in the following reaction equation, and the product has the effect of promoting the vulcanization reaction.

[0034]

[0035] In some embodiments of the present application, in order to promote the efficient progress of the pre-reaction, the reaction temperature of the pre-reaction is 100-190°C, and the reaction time is 1min-120min; in order to further improve the activity of the intermediate, preferably, the reaction temperature of the pre-reaction is 110-170°C, and the reaction time is 5min-50min.

[0036] In some typical embodiments of the present application, in order to evenly disperse the components involved in the pre-reaction and improve the reaction speed and conversion rate, the pre-reaction is carried out in a solvent. Preferably, the solvent is any one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene and xylene, which not only has good solubility for the various components involved in the reaction, but also is conducive to promoting the progress of the pre-reaction.

[0037] In some embodiments of the present application, the pre-reaction mixture containing a solvent is first desolventized and then mixed with the rubber, that is, step S2 includes: removing the solvent from the pre-reaction mixture and then mixing it with the rubber to obtain a masterbatch type vulcanization aid.

[0038] In some embodiments of the present application, the solvent is removed after the pre-reaction mixture containing the solvent is mixed with the rubber. That is, the step S2 includes removing the solvent after the pre-reaction mixture containing the solvent is mixed with the rubber to obtain a masterbatch type vulcanization aid.

[0039] The method for removing the solvent added in the pre-reaction process can be selected from the prior art, and the present application has no limitation. For example, by using a distillation method, the removed solvent can be recovered and reused.

[0040] The above antioxidant can be selected from the prior art. Preferably, the antioxidant is a phenylenediamine antioxidant. Preferably, the antioxidant has a structure shown in Formula I. The antioxidant having this structure not only forms an active intermediate after pre-reaction with the vulcanization system, but also has low toxicity and is more environmentally friendly.

[0041]

[0042] In Formula I, R 1 Selected from C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18 The aromatic hydrocarbon group, R 2 , R 3 , R 4 , R 5 Each independently selected from C1-C 18 The chain hydrocarbon group, R 2 With R 3 or R 4 With R 5 They can also form aliphatic rings separately or simultaneously, R 6 Selected from, R 6 Selected from H, C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18 Aromatic hydrocarbon group; x = 0 or 1, y = 0 or 1, z = 0 or 1, w = 0 or 1, and at least one of x and w is 1, and at least one of y and z is 1. Further, the above-mentioned vulcanization system chemicals include any one or more of vulcanizing agents and accelerators, the vulcanizing agents include any one or more of sulfur and sulfur carriers, the accelerators include any one or more of sulfonamide accelerators and thiazole accelerators, and preferably, the accelerators include any one or more of CZ, DCBS, MBTS, MBT and TBBS.

[0043] The rubber can be selected from the prior art, such as natural polymers or synthetic polymers. For example, the natural rubber includes but is not limited to natural rubber, eucommia gum, guayule gum, etc.; the synthetic polymer includes but is not limited to monomers polymerized in solution (i.e., solution rubber), monomers polymerized in emulsion (i.e., emulsion rubber), and monomers polymerized in bulk. The solution rubber is a homopolymer or copolymer of ethylene, propylene, butene, pentene, hexene, heptene, diene with 4-7 carbon atoms or triene with 6-7 carbon atoms, or olefin monomers containing other atoms or functional groups, wherein the other atoms or functional groups are silicon atoms, fluorine atoms, chlorine atoms, nitrogen atoms, oxygen atoms, sulfur atoms, ester groups, aminoester groups, cyano groups, and also includes homopolymers and copolymers containing the above monomers, including but not limited to polybutadiene, polyisoprene, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber, nitrile rubber, chloroprene rubber, silicone rubber, fluororubber, polyurethane rubber, chlorosulfonated polyethylene rubber, acrylate rubber, etc.

[0044] In some embodiments of the present application, the rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural eucommia gum, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and EPDM rubber, and has better comprehensive performance.

[0045] In some preferred embodiments of the present application, the rubber is a rubber containing formula II, which can better play a synergistic role with the pre-reaction mixture and significantly improve the comprehensive effect of the masterbatch type vulcanization accelerator. Preferably, the rubber containing formula II accounts for more than 35wt% of the total amount of rubber in the masterbatch type vulcanization accelerator, preferably 60wt% to 100wt%.

[0046]

[0047] In Formula II, a, b, c, d, e and f are each independently an integer greater than or equal to 0, and a, b, c, d, e and f are not 0 at the same time.

[0048] Preferably, at least two of a, b, c, d, e and f are not 0. The repeating units are randomly distributed.

[0049] In some preferred embodiments of the present application, in the rubber having the structure of chemical formula II, a, b, c are 0, d, e, f are not 0; or a, b, c are not 0, d, e, f are 0; or a, b, c, d are 0, e, f are not 0, and the diene rubber having this structure has a higher crosslinking density.

[0050] Further, the sum of the number of alkenyl double bonds and aromatic groups on the side groups and side chains of the rubber shown in formula II accounts for more than 15% of the sum of the number of alkenyl double bonds and aromatic groups of the rubber, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90% or any range therebetween. It can be understood by those skilled in the art that the structure of formula II may contain only side groups or side chains, and may contain only alkenyl double bonds or aromatic groups on the side groups or side chains, and the number of alkenyl double bonds or aromatic groups on the side groups or side chains accounts for more than 15% of the sum of the number of all alkenyl double bonds and aromatic groups in the rubber molecular structure.

[0051] In order to further improve the performance of the masterbatch type vulcanization aid, the molecular weight of the rubber is preferably 1,000 to 40 million, more preferably 5,000 to 30 million, and even more preferably 10,000 to 4 million.

[0052] In some typical embodiments of the present application, in order to better exert the catalytic effect of stearic acid, the weight ratio of stearic acid to antioxidant is 1:1 to 1:1.25; preferably, the weight ratio of vulcanization system to antioxidant is 0.8:1 to 1.15:1, and the generated product has higher activity. There is no special requirement for the proportion of rubber in the masterbatch type vulcanization accelerator. In some embodiments of the present application, in order to facilitate subsequent use, the content of rubber in the masterbatch type vulcanization accelerator is 50 to 95wt%.

[0053] The stearic acid used in step S1 can be selected from the prior art. There is no special requirement for this application and it will not be described here.

[0054] According to another typical embodiment of the present application, a masterbatch type vulcanization aid is provided, and the masterbatch type vulcanization aid is prepared by any one of the above-mentioned preparation methods.

[0055] In the masterbatch type vulcanization aid prepared by the above method, the antioxidant reacts with the reagent in the vulcanization system under the catalytic action of stearic acid to generate an active intermediate, which has the function of promoting vulcanization and plays the role of an early activation accelerator, so that the active intermediate can replace the role of zinc oxide. The product after the reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires that are completely free of zinc elements, can achieve zinc-free emissions, and is environmentally friendly; at the same time, the masterbatch type vulcanization aid can enable the rubber composition containing it to obtain a crosslinking density close to that of a zinc-containing rubber composition without containing zinc, and rubber properties such as hardness, tensile stress and hysteresis.

[0056] According to another typical embodiment of the present application, a rubber composition is provided, which includes, by weight, 0 to 100 parts of elastomer, 25 to 35 parts of masterbatch type vulcanization aid, 20 to 170 parts of filler and 1 to 5 parts of other additives, wherein the masterbatch type vulcanization aid is the above-mentioned masterbatch type vulcanization aid.

[0057] The rubber composition of the present application can be used to prepare rubber products such as tires that are completely free of zinc elements through the use of the above-mentioned masterbatch type vulcanization aid, which can achieve zinc-free emissions and is environmentally friendly; at the same time, the masterbatch type vulcanization aid can enable the rubber composition containing it to obtain a cross-linking density close to that of a zinc-containing rubber composition, and rubber properties such as hardness, tensile stress and hysteresis without containing zinc.

[0058] The above-mentioned elastomer can be selected from the prior art, or selected in the same way as the rubber in the masterbatch type vulcanizing accelerator, and the type of the elastomer can be the same as or different from the type of the rubber in the masterbatch type vulcanizing accelerator.

[0059] The rubber composition of the present application has good adaptability to fillers, and can be selected from fillers in the prior art. For example, the filler includes any one or more of a carbon-based filler, a silicon-based filler, a carbon-silicon dual-phase filler and clay; preferably, the specific surface area of ​​the filler is 10 to 500 m 2 / g, more preferably 30 to 300 m 2 / g, more preferably 50 to 300 m 2 / g.

[0060] Those skilled in the art can select other additives with suitable functions according to the specific use environment and requirements of the rubber. For example, other additives include any one or more of resin, process oil, vulcanizing agent and silane coupling agent. The types of these additives can be selected from the prior art. There is no special requirement for this application, and they will not be introduced one by one here.

[0061] In some embodiments of the present application, in order to better exert the synergistic effect of each component, the rubber composition includes, by weight, 30 to 100 parts of elastomer, 26 to 31 parts of masterbatch type vulcanizing aid, 50 to 130 parts of filler and 1.4 to 4.5 parts of other additives.

[0062] According to another typical embodiment of the present application, a rubber product is provided, which is prepared from any of the above-mentioned rubber compositions. By using the above-mentioned masterbatch type vulcanization aid, the rubber product can achieve zinc-free emission and is environmentally friendly; at the same time, the rubber product, without zinc, obtains a cross-linking density close to that of zinc-containing rubber products, and rubber properties such as hardness, tensile stress and hysteresis.

[0063] The method for preparing rubber by the above-mentioned rubber composition can be selected from the prior art, and the present application has no limitation on this. As an example, the following method can be used to prepare rubber products using the above-mentioned rubber composition as raw material: (a) by kneading, the elastomer, filler, zinc-free masterbatch type vulcanizing agent, and other functional additives are mixed once or multiple times, and the mixing temperature reaches 125°C to 200°C for rubber removal, as a first-stage masterbatch; (b) the first-stage masterbatch is thermomechanically kneaded once or multiple times, maintained at a kneading temperature of 125°C to 180°C, and maintained for 0 to 1200s for rubber removal, as a second-stage masterbatch; if there are remaining processing aids, fillers, and antioxidants, all of them are added at this stage once or in batches; (3) the second-stage masterbatch is mixed with the vulcanization system in an internal mixer, the mixing temperature is ≤120°C, and the rubber is removed to obtain a final rubber mix; (4) the final rubber mix is ​​vulcanized on a flat vulcanizer to obtain a vulcanized rubber.

[0064] According to a fifth typical embodiment of the present application, a tire is provided, the tire containing the above-mentioned rubber product. By using the above-mentioned masterbatch type vulcanization aid, the tire can achieve zinc-free emission and be environmentally friendly; at the same time, in the absence of zinc, it has excellent comprehensive performance.

[0065] The beneficial effects that can be achieved by the present application will be further illustrated below in combination with embodiments and comparative examples.

[0066] Example 1

[0067] 10 phr of stearic acid, 10 phr of antioxidant 4020, and 10 phr of vulcanization accelerator TBBS were mixed in decane, pre-reacted at 160° C. for 30 min, and then the reaction system was desolventized and mixed with 96.3 phr of SSBR and 30 phr of BR to obtain a zinc-free masterbatch type vulcanization aid;

[0068] Add SSBR and BR to the internal mixer, knead, then add carbon black N234 and the above zinc-free masterbatch type vulcanizing agent, continue kneading until the mixture is uniform, and control the temperature at 150-160°C during kneading;

[0069] Add sulfur and knead, the temperature during kneading not exceeding 110°C;

[0070] The obtained rubber composition is vulcanized to obtain a vulcanized rubber, and the physical properties of the rubber are tested.

[0071] Comparative Example 1

[0072] Add SSBR and BR to the internal mixer, knead for a while, then add carbon black N234, stearic acid, zinc oxide, antioxidant 4020, and accelerator TBBS and continue kneading until the mixture is uniform. During the kneading process, the temperature is controlled at 150-160°C.

[0073] Add sulfur and knead, the temperature during kneading not exceeding 110°C;

[0074] The obtained rubber composition is vulcanized to obtain a vulcanized rubber, and the physical properties of the rubber are tested.

[0075] Example 2

[0076] 10phr of stearic acid, 12.5phr of antioxidant A, and 11.5phr of vulcanization accelerator CZ were mixed in xylene, pre-reacted at 130°C for 40min, and then the solvent was removed from the reaction system and then mixed with 100phr of IR to obtain a zinc-free masterbatch type vulcanization aid;

[0077] Add IR to the internal mixer for kneading, then add white carbon black, Si69, and the above-mentioned zinc-free masterbatch type vulcanizing agent, and continue kneading until the mixture is uniform. During the kneading process, the temperature is controlled at 150-160°C;

[0078] Add sulfur and DPG, knead, and the temperature during kneading does not exceed 120°C;

[0079] The obtained rubber composition is vulcanized to obtain a vulcanized rubber, and the physical properties of the rubber are tested.

[0080] Comparative Example 2

[0081] Add IR to the internal mixer and knead, then add white carbon black, Si69, stearic acid, zinc oxide, antioxidant A, and accelerator CZ, and continue kneading until the mixture is uniform. During the kneading process, the temperature is controlled at 150-160°C.

[0082] Add sulfur and DPG, knead, and the temperature during kneading does not exceed 120°C;

[0083] The obtained rubber composition is vulcanized to obtain a vulcanized rubber, and the physical properties of the rubber are tested.

[0084] The above-mentioned rubber compound formula is summarized in Table 1 below.

[0085] Table 1

[0086]

[0087]

[0088] The sources and parameters of various raw materials used in various embodiments and comparative examples are as follows: IR, Qingdao Ecos New Materials Co., Ltd.;

[0089] White carbon black, NEWSIL1165-MP, Wuxi Quecheng Silicon Industry Co., Ltd., with a specific surface area of ​​165m 2 / g; Carbon black, N234, Shandong Zhongxiang Polymer Materials Co., Ltd., with a specific surface area of ​​119m 2 / g;

[0090] Silane coupling agent Si69, Nanjing Shuguang Chemical Group Co., Ltd.;

[0091] SSBR, Dushanzi Petrochemical (styrene 25%, vinyl 64%);

[0092] SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%);

[0093] BR, Qilu Petrochemical BR9000 (nickel-based high cis-butane, cis content 97%);

[0094] NR, SCR5 of Xishuangbanna Sinochem Rubber Co., Ltd.;

[0095] Stearic acid, PF1808, Li Cheng Sdn Bhd, Malaysia;

[0096] Zinc oxide, Dalian Zinc Oxide Factory;

[0097] Antioxidant 4020, Jiangsu Shengao Chemical Co., Ltd.;

[0098] Antioxidant 4010NA, Shandong Shangshun Chemical Co., Ltd.;

[0099] Antioxidant 7PPD, Jiangsu Shengao Chemical Co., Ltd.;

[0100] Antioxidant A, self-synthesized,

[0101]

[0102] Antioxidant B, self-synthesized,

[0103]

[0104] Antioxidant C, self-synthesized,

[0105]

[0106] Antioxidant D, self-synthesized,

[0107]

[0108] Antioxidant E, self-synthesized,

[0109]

[0110] Antioxidant F, self-synthesized,

[0111]

[0112] Accelerator CZ, Shandong Shangshun Chemical Co., Ltd.;

[0113] Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd.; Accelerator MBTS, Chaoyang Tianming Industry and Trade Co., Ltd.;

[0114] Accelerator DPG, Shandong Shanxian Chemical Co., Ltd.;

[0115] Sulfur, Wudi Jinsheng Chemical Co., Ltd.

[0116] The vulcanization characteristics of the rubber compounds prepared in the above-mentioned embodiments and comparative examples were measured in accordance with "GB / T16584-1996 Rubber Vulcanizer for Determination of Vulcanization Characteristics". The test results are shown in Table 2.

[0117] The physical properties (tensile strength, elongation at break, 100% modulus of tensile stress, 300% modulus of tensile stress) of the rubber materials prepared in the above examples and comparative examples were measured in accordance with GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber. The results are shown in Table 2.

[0118] The hardness of the rubber materials prepared in the above examples and comparative examples was measured according to GB / T 531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1: Shore hardness method (Shore hardness). The test results are shown in Table 2.

[0119] The elastic modulus of the rubber at 20°C was measured according to GB / T9870.1-2006 Determination of dynamic properties of vulcanized rubber or thermoplastic rubber Part 1: General rules. The tanδmax of the rubber prepared in the above examples and comparative examples was measured using a rotational rheometer. The test results are shown in Table 2.

[0120] In Table 2 and the subsequent physical property test result tables, for the convenience of comparison, the test data of each embodiment are based on the corresponding comparative example with the same composition except zinc oxide, and the index value is obtained. For example, in Table 1, the value of MH of Example 1 is the ratio of its measured value to the measured number of MH of Comparative Example 1*100; the larger the value, the higher the index.

[0121] Table 2

[0122] name Comparative Example 1 Example 1 Comparative Example 2 Example 2 MH, dNm 100 96 100 88 Tensile strength, MPa 100 95 100 92 Elongation at break, % 100 96 100 89 100% tensile stress, MPa 100 95 100 90 300% tensile stress, MPa 100 95 100 88 T300 / T100 100 100 100 98 Hardness, Shore A 100 97 100 85 <![CDATA[60℃tanδ max ]]> 100 106 100 111 20℃E',MPa 100 95 100 89

[0123] It can be seen from the results in Table 2 that the rubber materials prepared by the rubber composition of the present invention (Examples 1 and 2) are close to the conventional zinc-containing rubber materials (corresponding to Examples 1 and 2, respectively) in terms of crosslinking density, modulus, stress, hardness, mechanical properties, and hysteresis properties, and can be used in rubber products and tires.

[0124] The preparation process of zinc-free masterbatch vulcanization aids 3 to 9 is the same as that of the zinc-free masterbatch vulcanization aid of Example 1, except that the amounts of specific components involved in the preparation process and the process parameters of the pre-reaction. The amounts of specific components involved in zinc-free masterbatch vulcanization aids 3 to 9 are shown in Table 3 below, and the process parameters are shown in Table 4 below.

[0125] Table 3

[0126]

[0127] Table 4

[0128]

[0129]

[0130] Zinc-free masterbatch type vulcanization aids 10 to 14 were prepared. Their formulas and preparation processes were the same as those of zinc-free masterbatch type vulcanization aid 6. The only difference was the pre-reaction parameter conditions listed in Table 5.

[0131] Table 5

[0132]

[0133] In Examples 3 to 9, final rubber mixes and vulcanized rubbers were prepared in the same manner as in Example 1, and in Comparative Examples 3 to 9, final rubber mixes and vulcanized rubbers were prepared in the same manner as in Comparative Example 1, and their formulations are shown in Tables 6 and 7 below. Furthermore, the formulations and preparation processes of the rubber materials of Examples 10 to 14 were the same as in Example 6, except that the zinc-free masterbatch type vulcanization aids in Examples 10 to 14 were zinc-free masterbatch type vulcanization aids 10 to 14, respectively, which were not listed.

[0134] Table 6

[0135]

[0136]

[0137] Table 7

[0138]

[0139]

[0140] Examples 3 to 9 and Comparative Examples 3 to 9 were tested using the same testing method as Example 1. The results are shown in Tables 8 and 9.

[0141] Table 8

[0142]

[0143] Table 9

[0144]

[0145]

[0146] It can be seen from Table 8 and Table 9 that the performance parameters of the rubbers containing zinc-free masterbatch type vulcanization aids prepared by the method of the present invention (Examples 3-9) and the conventional zinc-containing rubbers (corresponding to Examples 3-9, respectively) after vulcanization tests all meet the requirements and can be used in the production of rubber products and tires.

[0147] In addition, the vulcanized rubber materials of Examples 2, 3, 5, 7-9 were extracted after aging, and the extracts were detected by liquid chromatography-tandem high resolution mass spectrometry (UPLC-HRMS / MS), and no quinone compounds were detected, indicating that the environmentally friendly para-aniline antioxidant AF used in the present application did not produce highly toxic quinone conversion products in the rubber residue, and was relatively environmentally friendly.

[0148] Table 10

[0149]

[0150] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: using the preparation method, under the catalytic action of stearic acid, the antioxidant and the reagent in the vulcanization system react to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of an early activation accelerator, so that the active intermediate can replace the role of zinc oxide, and the product after the reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires that are completely free of zinc elements, and can achieve zinc-free emissions and be environmentally friendly; at the same time, the masterbatch-type vulcanization aid prepared by the above-mentioned preparation method can enable the rubber composition containing it to obtain a crosslinking density close to that of a zinc-containing rubber composition without zinc, and rubber properties such as hardness, tensile stress and hysteresis.

[0151] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a masterbatch type vulcanization aid, characterized in that: include: Step S1, pre-reacting stearic acid, an antioxidant and a vulcanization system to obtain a pre-reaction mixture; Step S2, mixing the pre-reaction mixture with rubber to obtain the masterbatch type vulcanization aid.

2. The preparation method according to claim 1, characterized in that: The reaction temperature of the pre-reaction is 100-190°C, and the reaction time is 1min-120min; Preferably, the reaction temperature of the pre-reaction is 110-170° C., and the reaction time is 5 min-50 min.

3. The preparation method according to claim 1, characterized in that: The pre-reaction is carried out in a solvent, preferably, the solvent is any one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene and xylene; Preferably, the step S2 comprises removing the solvent in the pre-reaction mixture and then mixing it with the rubber to obtain a masterbatch type vulcanization aid; or, The step S2 comprises mixing the pre-reaction mixture containing a solvent with the rubber, and then removing the solvent to obtain the masterbatch type vulcanization aid.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The antioxidant is a phenylenediamine antioxidant; Preferably, the antioxidant has a structure shown in Formula I: In Formula I, R 1 Selected from C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18 The aromatic hydrocarbon group, R 2 , R 3 , R 4 , R 5 Each independently selected from C1-C 18 The chain hydrocarbon group, R 2 With R 3 or R 4 With R 5 They can also form aliphatic rings separately or simultaneously, R 6 Selected from, R 6 Selected from H, C1-C 18 Chain hydrocarbon groups, C3-C 18 Alicyclic hydrocarbon or C6-C 18 x=0 or 1, y=0 or 1, z=0 or 1, w=0 or 1, and at least one of x and w has a value of 1, and at least one of y and z has a value of 1.

5. The preparation method according to any one of claims 1 to 3, characterized in that: The vulcanization system chemicals include any one or more of vulcanizing agents and accelerators, the vulcanizing agents include any one or more of sulfur and sulfur carriers, the accelerators include any one or more of sulfonamide accelerators and thiazole accelerators, preferably, the accelerators include any one or more of CZ, DCBS, MBTS, MBT and TBBS; The rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural eucommia gum, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and EPDM rubber; Preferably, the rubber is a rubber containing formula II: Wherein, a, b, c, d, e and f are each independently an integer greater than or equal to 0, and a, b, c, d, e and f are not 0 at the same time.

6. The preparation method according to any one of claims 1 to 3, characterized in that: The weight ratio of the stearic acid to the antioxidant is 1:1 to 1:1.25; the weight ratio of the vulcanization system to the antioxidant is 0.8:1 to 1.15:

1.

7. A masterbatch type vulcanization aid, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 6.

8. A rubber composition, characterized in that: The composition comprises, by weight, 0 to 130 parts of elastomer, 25 to 35 parts of masterbatch type vulcanization aid, 20 to 170 parts of filler and 1 to 5 parts of other aids. The masterbatch type vulcanization aid is the masterbatch type vulcanization aid according to claim 7.

9. The rubber composition according to claim 8, characterized in that The filler includes any one or more of a carbon-based filler, a silicon-based filler, a carbon-silicon dual-phase filler and clay; preferably, the specific surface area of ​​the filler is 10 to 500 m 2 / g, more preferably 30 to 300 m 2 / g, more preferably 50 to 300 m 2 / g; The other additives include any one or more of resin, process oil, vulcanizing agent and silane coupling agent; Preferably, based on weight, it includes 30 to 100 parts of elastomer, 26 to 31 parts of masterbatch type vulcanization aid, 50 to 130 parts of filler and 1.4 to 4.5 parts of other additives.

10. A rubber product, characterized in that: Prepared from the rubber composition according to claim 8 or claim 9.

11. A tire, characterized in that: A rubber product comprising the rubber product according to claim 10.

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