Vulcanization aid and preparation method therefor, rubber composition, rubber product and tire

Abstract

The present invention provides a vulcanization aid and a preparation method therefor, a rubber composition, a rubber product, and a tire. The preparation method comprises: pre-reacting an anti-aging agent with a vulcanization system agent under the action of a catalyst, wherein the catalyst includes stearic acid. Under the catalytic action of stearic acid, the anti-aging agent reacts with a reagent in a vulcanization system to generate an active intermediate. The active intermediate has the function of promoting vulcanization and plays a role of activating an accelerator in advance, so that the active intermediate can functionally replace zinc oxide, can be used for preparing a rubber product completely free of the element zinc, e.g., a tire, can achieve zinc-free emission, and is environmentally friendly.

Description

Vulcanizing aids and their preparation methods, rubber compositions, rubber products and tires

[0001] This application claims priority to Chinese patent applications 2024106924399 and 2024106934545, both filed on May 30, 2024. The full text of the aforementioned Chinese patent applications is incorporated herein by reference. Technical Field

[0002] This invention relates to the field of tread rubber preparation technology, and more specifically, to a vulcanization aid and its preparation method, a rubber composition, a rubber product, and a tire. Background Technology

[0003] Zinc in tire treads can pollute the environment. The European Commission Directive 2400 / 73 / EC and the California SB1260 bill proposed in 2016 both recommend restricting the use of zinc or zinc oxide in tires.

[0004] However, zinc oxide or zinc-based additives act as vulcanizing activators during vulcanization, increasing crosslinking density, thereby improving rubber compound hardness and ensuring compound performance. Tires manufactured using this method maintain good rolling resistance and grip. Removing zinc from commonly used formulations, under current production processes, often results in reduced crosslinking, leading to decreased mechanical properties, lower hardness, increased hysteresis, higher rolling resistance, and reduced grip. Typically, diene rubber compositions require at least 2 phr of zinc oxide. Existing rubber compositions without zinc, using conventional tire rubber manufacturing processes, exhibit low mechanical properties, low hardness, and significantly reduced grip and abrasion resistance.

[0005] Researchers both domestically and internationally have begun investigating the environmental issues associated with zinc in tire tread rubber. Patent application CN115678038B discloses a method using lignin-zinc salt complexes to replace zinc oxide. Leveraging the good dispersion of this complex, the amount of zinc oxide used is reduced. When applied to tire tread rubber, it can ensure tire wear resistance, reduce rolling resistance, and extend tire lifespan. While this patent reduces zinc usage by improving zinc dispersion, it cannot completely eliminate the environmental hazards of zinc. Patent CN102300917B discloses a rubber composition containing no zinc or less than 0.5 phr of zinc for tire manufacturing. It improves the processability of the zinc-free composition (i.e., reduces viscosity and extends scorch time) through the application of end-capped mercaptosilanes. Although this patent can reduce zinc usage or even eliminate zinc altogether, it requires the use of specific end-capped mercaptosilanes. During high-temperature mixing, these silaptosilanes may further react to generate mercapto groups, which have a certain degree of irritation and odor, posing safety concerns.

[0006] Improving the performance of tire tread rubber without using zinc is of significant social and economic value. Summary of the Invention

[0007] The main objective of this invention is to provide a vulcanization aid and its preparation method, a rubber composition, a rubber product, and a tire, in order to solve the environmental pollution problem caused by zinc in the tread rubber of the prior art.

[0008] To achieve the above objectives, according to one aspect of the present invention, a method for preparing a masterbatch-type vulcanization aid is provided, the method comprising: pre-reacting an antioxidant and a vulcanization system reagent under the action of a catalyst, wherein the catalyst includes stearic acid.

[0009] Furthermore, the above preparation method includes: step S1, pre-reacting the catalyst, antioxidant and vulcanization system to obtain a pre-reaction mixture, wherein the catalyst is stearic acid; step S2, mixing the pre-reaction mixture with rubber to obtain a vulcanization aid.

[0010] Furthermore, the above preparation method includes: pre-reacting the catalyst, antioxidant, and vulcanization system reagent in a solvent, wherein the catalyst is zinc oxide and stearic acid, and after the pre-reaction, the zinc is removed by filtration and the solvent is removed in sequence to obtain the vulcanization aid.

[0011] Furthermore, the pre-reaction temperature is 100-190℃, and the reaction time is 1 min-120 min;

[0012] Preferably, the pre-reaction temperature is 110-170℃ and the reaction time is 5-50 min.

[0013] Furthermore, the pre-reaction is carried out in a solvent, preferably one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene, and xylene.

[0014] Furthermore, the antioxidant is a phenylenediamine-based antioxidant; preferably, the antioxidant has the structure shown in Formula I:

[0015] In formula I, R 1 Selected from C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18 aromatic 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 R4 With R 5 They can also form adipose rings individually or simultaneously, R 6 Selected from H, C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18 The aromatic 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.

[0016] Furthermore, the vulcanization system includes any one or more of vulcanizing agents and accelerators. The vulcanizing agents include any one or more of sulfur-based and sulfur carrier-based agents, and the accelerators include any one or more of sulfenamide-based and thiazole-based accelerators. Preferably, the accelerators include any one or more of CZ, DCBS, MBTS, MBT, and TBBS.

[0017] 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.

[0018] Further, step S2 includes removing the solvent from the pre-reaction mixture and then mixing it with the rubber to obtain the masterbatch-type vulcanizing aid; or, step S2 includes mixing the pre-reaction mixture containing solvent with the rubber, then removing the solvent to obtain the masterbatch-type vulcanizing aid.

[0019] Furthermore, zinc oxide (10-20 phr), stearic acid (5-15 phr), antioxidant (5-15 phr), and vulcanization system chemicals (5-15 phr) are added to the pre-reaction process.

[0020] Furthermore, the vulcanizing aid also includes 50-150 phr of rubber, and the preparation method of the vulcanizing aid including rubber further includes a first mixing or a second mixing. The first mixing includes: mixing the filtrate obtained after zinc removal by filtration with the rubber and then removing the solvent; the second mixing includes: removing the solvent from the filtrate obtained after zinc removal by filtration and then mixing it with the rubber.

[0021] Further, the rubber includes any one or more of natural polymers or synthetic polymers. Preferably, the rubber is selected from any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural eucommia gum, polyisoprene rubber, butadiene rubber, halogenated butyl rubber, and ethylene propylene diene monomer (EPDM) rubber. Preferably, the molecular weight of the rubber is 10 million to 40 million, more preferably 50 million to 30 million, and even more preferably 10 million to 8 million.

[0022] Preferably, the rubber comprises a diene rubber having the structure shown in Formula II:

[0023] Among them, a, b, c, d, e, and f are each independent integers greater than or equal to 0, and a, b, c, d, e, and f are not all 0 at the same time.

[0024] To achieve the above objectives, according to one aspect of the present invention, a vulcanization aid is provided, which is prepared by any of the above preparation methods.

[0025] According to another aspect of this application, a rubber composition is provided, characterized in that, in parts by weight,

[0026] Furthermore, the filler includes any one or more of carbon-based fillers, silicon-based fillers, carbon-silicon dual-phase fillers, and clay; preferably, the specific surface area of ​​the filler is 10–500 m². 2 / g, further preferably 30-300m 2 / g, more preferably 50-300m 2 / g;

[0027] Preferably, the rubber composition further includes other additives, which include one or more of resins, processing oils, vulcanizing agents and silane coupling agents;

[0028] Preferably, the rubber composition comprises, by weight, 100 phr of elastomer, 20 to 170 phr of filler, 10 to 50 phr of zinc-free vulcanizing agent and other additives; or, the rubber composition comprises 0 to 130 parts of elastomer, 25 to 35 parts of masterbatch-type vulcanizing agent, 20 to 170 parts of filler and 1 to 5 parts of other additives; more preferably, the rubber composition comprises 30 to 100 parts of elastomer, 26 to 31 parts of masterbatch-type vulcanizing agent, 50 to 130 parts of filler and 1.4 to 4.5 parts of other additives.

[0029] According to an advantageous aspect of this application, a rubber article is provided, which is prepared from any of the rubber compositions described above.

[0030] According to another aspect of this application, a tire is provided that contains the aforementioned rubber article.

[0031] By applying the technical solution of this invention, under the action of a catalyst, the antioxidant and the reagents in the vulcanization system react to generate an active intermediate. This active intermediate promotes vulcanization and acts as an early activation accelerator, allowing it to replace zinc oxide in the preparation of completely zinc-free tires and other rubber products, achieving zero zinc emissions and being environmentally friendly. At the same time, the vulcanization aid prepared by the above method enables rubber compositions containing it to achieve crosslinking density, hardness, tensile stress, and hysteresis properties close to those of zinc-containing rubber compositions, even without zinc. Detailed Implementation

[0032] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0033] As analyzed in the background section of this application, the existing technology has the problem of environmental pollution caused by zinc in tire tread rubber. The existing methods can only reduce the zinc content in the rubber, but cannot completely avoid the environmental impact caused by zinc. On the other hand, it is difficult to meet the usage requirements of tire tread rubber without zinc. In order to solve this problem, this application provides a vulcanization aid and its preparation method, a rubber composition, a rubber product and a tire.

[0034] According to a typical embodiment of this application, a method for preparing a vulcanization auxiliaries is provided, the method comprising: pre-reacting an antioxidant and a vulcanization system reagent under the action of a catalyst, wherein the catalyst comprises stearic acid.

[0035] In the above preparation method, under the action of a catalyst, the antioxidant and the reagents in the vulcanization system react to generate an active intermediate. This active intermediate promotes vulcanization and acts as an early activation accelerator, allowing it to replace zinc oxide. It can be used to prepare tires and other rubber products that are completely free of zinc, achieving zinc-free emissions and being environmentally friendly. At the same time, the vulcanization auxiliaries prepared by the above method enable rubber compositions containing them to achieve crosslinking density, hardness, tensile stress, and hysteresis properties close to those of zinc-containing rubber compositions, even without zinc.

[0036] In some embodiments of this application, the preparation method includes: step S1, pre-reacting stearic acid, antioxidant, and vulcanization system to obtain a pre-reaction mixture; step S2, mixing the pre-reaction mixture with rubber to obtain a vulcanization aid. This masterbatch-type vulcanization aid does not contain zinc. Because it contains an active intermediate that can replace the function of zinc oxide, this masterbatch-type vulcanization aid can be used to prepare rubber products such as tires that are completely free of zinc.

[0037] There are no special requirements for the proportion of rubber in masterbatch-type vulcanizing auxiliaries. In some embodiments of this application, for ease of subsequent use, the rubber content in masterbatch-type vulcanizing auxiliaries is 50-95 wt%.

[0038] In some embodiments of this application, the pre-reaction mixture containing solvent is first desolventized before being mixed with rubber. That is, step S2 includes: removing the solvent from the pre-reaction mixture and then mixing it with rubber to obtain a masterbatch-type vulcanization aid.

[0039] In some embodiments of this application, the solvent-containing pre-reaction mixture is mixed with rubber, and then the solvent is removed. That is, step S2 includes mixing the solvent-containing pre-reaction mixture with rubber, removing the solvent, and obtaining a masterbatch-type vulcanization aid.

[0040] In some typical embodiments of this 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 resulting product has higher activity.

[0041] In some embodiments of this application, the preparation method of the above-mentioned vulcanization aid includes: pre-reacting a catalyst, an antioxidant, and a vulcanization system reagent in a solvent, wherein the catalyst is zinc oxide and stearic acid; after the pre-reaction, the mixture is sequentially filtered to remove zinc and the solvent is removed to obtain the vulcanization aid. In this preparation method, zinc oxide and stearic acid are used simultaneously as catalysts for the pre-reaction, and zinc is removed by filtration after the reaction. The antioxidant and the vulcanization system reagent can generate an active intermediate more efficiently during the pre-reaction, and the prepared vulcanization aid does not contain zinc and replaces zinc oxide in the formulation.

[0042] The proportions of zinc oxide, stearic acid, antioxidant, and vulcanizing agent added in the above pre-reaction can be set according to the proportions of the corresponding components in existing formulations. In some typical embodiments of this application, zinc oxide (10-20 phr), stearic acid (5-15 phr), antioxidant (5-15 phr), and vulcanizing agent (5-15 phr) are added in the pre-reaction. The resulting zinc-free vulcanizing aid has a more significant promoting effect on improving the crosslinking density and rubber properties of the composition. In some typical embodiments of this application, the vulcanizing aid also includes 50-150 phr of rubber. The preparation method of the vulcanizing aid including rubber further includes a first mixing or a second mixing. The first mixing includes: mixing the filtrate obtained after zinc removal with the rubber and then removing the solvent; the second mixing includes: removing the solvent from the filtrate obtained after zinc removal and then mixing it with the rubber. The vulcanizing auxiliaries containing rubber are masterbatch-type auxiliaries. Because they are already dispersed in the rubber, they perform better in subsequent applications and are more conducive to the role of antioxidants and the active intermediates generated from the pre-reaction of the vulcanizing system in improving crosslinking density and the rubber compound. In particular, through the first mixing described above, the filtrate obtained after zinc removal can be mixed evenly with the rubber using a relatively simple method, such as stirring, resulting in more thorough and uniform mixing of the rubber with other components. In the second mixing described above, the solvent-removed zinc-removed product and the rubber can be mixed using existing techniques, such as compounding.

[0043] Taking phenylenediamine antioxidants and 2-thiobenzothiazole sulfurization system pharmaceuticals as an example, the reaction that occurs in the pre-reaction is shown in the following reaction equation, and the product has the effect of promoting the sulfurization reaction.

[0044] In some embodiments of this application, in order to promote the efficient conduct of the pre-reaction, the reaction temperature of the pre-reaction is 100-190°C and the reaction time is 1 min-120 min; in order to further improve the activity of the intermediate, preferably, the reaction temperature of the pre-reaction is 110-170°C, such as 120°C, 130°C, 140°C, 150°C, 160°C or 170°C, which has a better effect on the pre-reaction. Preferably, the reaction time of the pre-reaction is 5 min-50 min, such as 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min or 50 min.

[0045] In some typical embodiments of this application, to ensure uniform dispersion of the components involved in the pre-reaction and improve the reaction rate and conversion rate, the pre-reaction is carried out in a solvent. When the catalyst contains zinc oxide, the pre-reaction is also carried out in a solvent to facilitate the separation of zinc oxide and accelerate the efficiency of the pre-reaction. The solvent in the pre-reaction should be able to dissolve the stearic acid, antioxidant, and sulfurization system reagents involved in the pre-reaction, but not dissolve zinc oxide, and should not adversely affect the reaction of the antioxidant and sulfurization system reagents. This can be selected from existing technologies. The amount of solvent added can be adjusted according to its solubility in the pre-reaction raw materials. Preferably, the solvent is any one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene, and xylene, which not only have good solubility in the various components involved in the reaction but also promote the pre-reaction.

[0046] The method for removing the solvent added during the pre-reaction process can be selected from the existing technology, and this application is not limited to it. For example, the solvent removed by distillation can be recovered and reused.

[0047] The antioxidants mentioned above can be selected from existing technologies. Preferably, the antioxidants are phenylenediamine antioxidants. In some embodiments of this application, the antioxidants in the pre-reaction are p-phenylenediamine antioxidants, such as any one or more of 4020 (6PPD), 4010NA (IPPD), and 7PPD.

[0048] In some preferred embodiments of this application, the antioxidant has the structure shown in Formula I. The antioxidant having this structure not only has high activity as an active intermediate formed after the pre-reaction with the vulcanization system, but also low toxicity and is more environmentally friendly.

[0049] In formula I, R 1 Selected from C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18 aromatic 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 adipose rings individually or simultaneously, R 6 Selected from H, C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18The aromatic 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.

[0050] In some embodiments of this application, the vulcanizing system reagents added to the pre-reaction include any one or more of vulcanizing agents and accelerators. The vulcanizing agents include any one or more of sulfur-based and sulfur-carrier-based reagents, and the accelerators include any one or more of sulfenamide-based and thiazole-based accelerators. Preferably, the accelerators include any one or more of CZ, DCBS, MBTS, MBT, and TBBS. In other embodiments of this application, the vulcanizing system reagents added to the pre-reaction are any one or more of accelerators, and the vulcanizing agents are added later during the preparation of the rubber products.

[0051] The aforementioned rubbers can be selected from existing technologies, such as using natural polymers or synthetic polymers. For example, the natural rubbers include, but are not limited to, natural rubber, eucommia gum, and chrysanthemum gum. The synthetic polymers include, but are not limited to, monomers polymerized in solution (i.e., solution-polymerized rubber), monomers polymerized in emulsion (i.e., emulsion-polymerized rubber), and monomers polymerized in bulk. The solution-polymerized rubber is a homopolymer or copolymer of ethylene, propylene, butene, pentene, hexene, hepten, dienes with 4-7 carbon atoms or trienes with 6-7 carbon atoms, or olefin monomers containing other atoms or functional groups. These other atoms or functional groups include silicon atoms, fluorine atoms, chlorine atoms, nitrogen atoms, oxygen atoms, sulfur atoms, ester groups, amino ester groups, and cyano groups. Homopolymers and copolymers containing the aforementioned monomers are also included, 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, and acrylate rubber.

[0052] In some embodiments of this application, the rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural eucommia rubber, polyisoprene rubber, butadiene rubber, halogenated butyl rubber, and EPDM rubber, and has better overall performance.

[0053] In some embodiments of this application, the rubber in the above-mentioned vulcanization aid is preferably a diene rubber. Preferably, the diene rubber structure contains branches and / or side groups, and the branches and / or side groups contain alkenyl double bonds and / or aromatic groups.

[0054] The zinc oxide and stearic acid added in the pre-reaction can be selected from existing technologies, and this application does not have any special requirements.

[0055] In some preferred embodiments of this application, the rubber described above is a rubber containing Formula II, which can better exert a synergistic effect with the pre-reaction mixture and significantly improve the overall effect of the masterbatch-type vulcanizing aid. Preferably, the rubber containing Formula II accounts for more than 35 wt% of the total rubber in the masterbatch-type vulcanizing aid, and more preferably 60 wt% to 100 wt%.

[0056] In Equation II, a, b, c, d, e, and f are each independent integers greater than or equal to 0, and a, b, c, d, e, and f are not all 0 at the same time.

[0057] Preferably, at least two of a, b, c, d, e, and f are not zero. The repeating units are randomly distributed.

[0058] In some preferred embodiments of this application, the rubber having the chemical formula II structure has a higher crosslinking density, where a, b, and c are 0 and d, e, and f are not 0; or a, b, and c are not 0 and d, e, and f are 0; or a, b, c, and d are 0 and e and f are not 0.

[0059] Furthermore, the sum of the number of alkenyl double bonds and aromatic groups on the side groups and branches of the rubber shown in Formula II accounts for more than 15% of the total number of alkenyl double bonds and aromatic groups in the rubber, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, or any range between the two. Those skilled in the art will understand that the structure of Formula II may contain only side groups or branches, and the side groups or branches may contain only alkenyl double bonds or aromatic groups, wherein the number of alkenyl double bonds or aromatic groups on the side groups or branches accounts for more than 15% of the total number of all alkenyl double bonds and aromatic groups in the rubber molecule.

[0060] To further improve the performance of masterbatch-type vulcanization aids, the molecular weight of the rubber is preferably 10 million to 40 million, more preferably 50 million to 30 million, and even more preferably 10 million to 4 million.

[0061] Furthermore, the rubber of Formula II comprises 35% or more of the weight of the diene rubber, preferably 60% or more of the weight of the diene rubber, for example, the weight content of the rubber of Formula II in the diene rubber is 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.

[0062] The stearic acid used in step S1 can be selected from existing technologies. This application does not have any special requirements, and will not be elaborated here.

[0063] According to another typical embodiment of this application, a vulcanization aid is provided, which is prepared by any of the preparation methods described above.

[0064] In the vulcanization accelerator prepared by the above method, the antioxidant reacts with the reagents in the vulcanization system under the catalysis of stearic acid to generate an active intermediate. This active intermediate promotes vulcanization and acts as an early activation accelerator, allowing it to replace zinc oxide. It can be used to prepare rubber products such as tires that are completely free of zinc, achieving zinc-free emissions and being environmentally friendly. At the same time, this vulcanization accelerator enables rubber compositions containing it to achieve crosslinking density, hardness, tensile stress, and hysteresis properties close to those of zinc-containing rubber compositions, even without zinc.

[0065] According to another typical embodiment of this application, a rubber composition is provided, the rubber composition comprising: an elastomer, a filler, and a zinc-free vulcanizing agent, wherein the zinc-free vulcanizing agent is any of the above-mentioned vulcanizing agents.

[0066] The rubber composition of this application, through the use of the aforementioned zinc-free vulcanizing agent, can be used to prepare rubber products such as tires that are completely free of zinc, achieving zero zinc emissions and being environmentally friendly. At the same time, the zinc-free vulcanizing agent enables the rubber composition containing it to obtain crosslinking density, hardness, tensile stress, and hysteresis properties close to those of zinc-containing rubber compositions, even without zinc.

[0067] The elastomers mentioned above can be selected from existing technologies, or selected in the same way as the rubbers in masterbatch-type vulcanizing auxiliaries, and can be the same or different from the rubbers in masterbatch-type vulcanizing auxiliaries.

[0068] The rubber composition of this application exhibits good adaptability to fillers, which can be selected from existing fillers. For example, the fillers include any one or more of carbon-based fillers, silicon-based fillers, carbon-silicon dual-phase fillers, and clay. Preferably, the specific surface area of ​​the filler is 10–500 m². 2 / g, further preferably 30-300m 2 / g, more preferably 50-300m 2 / g.

[0069] Those skilled in the art can select other additives with suitable functions according to the specific application environment and requirements of the rubber. For example, other additives include any one or more of resins, processing oils, vulcanizing agents, and silane coupling agents. The types of these additives can be selected from the prior art, and this application does not have any special requirements, so they will not be described in detail here.

[0070] In some embodiments of this application, the rubber composition comprises, by weight, 0 to 100 parts elastomer, 25 to 35 parts zinc-free vulcanizing aid, 20 to 170 parts filler and 1 to 5 parts other additives, wherein the zinc-free vulcanizing aid is the aforementioned masterbatch-type zinc-free vulcanizing aid.

[0071] In some embodiments of this application, in order to better leverage the synergistic effect of each component, the rubber composition comprises, by weight, 30 to 100 parts of elastomer, 26 to 31 parts of zinc-free vulcanizing agent, 50 to 130 parts of filler and 1.4 to 4.5 parts of other additives, wherein the vulcanizing agent is the masterbatch type vulcanizing agent described above.

[0072] In some typical embodiments of this application, to better leverage the synergistic effect of the components, the rubber composition includes 100 phr of elastomer, 20-170 phr of filler, and 10-50 phr of zinc-free vulcanizing agent. Preferably, the rubber composition includes 100 phr of elastomer, 50-130 phr of filler, and 20-35 phr of zinc-free vulcanizing agent. Preferably, the rubber composition also includes 3-30 parts of other additives, which are selected from any one or more of resins, processing oils, vulcanizing agents, and silane coupling agents. The rubber composition of this application may contain a vulcanizing agent, which may be added as one of the reagents in the vulcanization system to the pre-reaction for preparing the zinc-free vulcanizing agent, or it may be included alone in the rubber composition.

[0073] According to another typical embodiment of this application, a rubber article is provided, which is prepared from any of the above-described rubber compositions. By using the aforementioned masterbatch-type vulcanizing aid, the rubber article achieves zinc-free emissions, making it environmentally friendly; simultaneously, the rubber article, without zinc, obtains crosslinking density, and rubber compound properties such as hardness, tensile stress, and hysteresis close to those of zinc-containing rubber articles.

[0074] The method for preparing rubber using the above rubber composition can be selected from the prior art, and this application does not limit it. As an example, rubber products can be prepared using the above rubber composition as raw material by the following method: (a) the elastomer, filler, zinc-free masterbatch type vulcanizing agent, and other functional additives are mixed in one or more batches by kneading, and the mixing temperature reaches 125℃~200℃ to discharge the rubber as a first-stage masterbatch; (b) the first-stage masterbatch is subjected to one or more thermomechanical kneadings, and the rubber is discharged at a kneading temperature of 125℃~180℃ for 0~1200s to obtain a second-stage masterbatch; any remaining processing aids, fillers, and antioxidants are added at once or in batches at this stage; (3) the second-stage masterbatch is mixed with the vulcanization system in an internal mixer at a mixing temperature ≤120℃, and the rubber is discharged to obtain the final compound; (4) the final compound is vulcanized on a flat vulcanizing machine to obtain vulcanized rubber.

[0075] In some embodiments of this application, the vulcanizing agent added in the pre-reaction of preparing the zinc-free vulcanizing aid is an accelerator. The rubber product is prepared using the zinc-free vulcanizing aid by the following method: (a) the elastomer, filler, zinc-free vulcanizing aid, and optional other additives are mixed in one or more batches by kneading, with the mixing temperature reaching 125°C–200°C, to obtain a first-stage masterbatch; (b) the first-stage masterbatch is subjected to one or more thermomechanical kneading cycles, maintained at a kneading temperature of 125°C–180°C, and discharged for 0–1200 seconds to obtain a second-stage masterbatch; any remaining additives, fillers, and antioxidants are added in one or more batches at this stage; and (c) the second-stage masterbatch is mixed with the vulcanizing system in a Banbury mixer at a mixing temperature ≤120°C, and discharged to obtain the final rubber compound. In the above method, specific mixing conditions are used based on the zinc-free vulcanizing aid, which can further improve the performance of the prepared rubber product. Preferably, the final rubber prepared by the above process is vulcanized on a flat vulcanizing machine to obtain vulcanized rubber.

[0076] According to a fifth typical embodiment of this application, a tire is provided that contains the aforementioned rubber product. Through the use of the masterbatch-type vulcanizing agent, the tire achieves zinc-free emissions, making it environmentally friendly; simultaneously, it exhibits excellent overall performance without the need for zinc.

[0077] The beneficial effects that this application can achieve will be further illustrated below with reference to embodiments and comparative examples.

[0078] Example 1

[0079] 10 phr of stearic acid, 10 phr of antioxidant 4020, and 10 phr of vulcanization accelerator TBBS were mixed in decane and pre-reacted at 160°C for 30 min. After the solvent was removed from the reaction system, it was mixed with 96.3 phr of SSBR and 30 phr of BR to obtain a zinc-free masterbatch type vulcanization aid.

[0080] Add SSBR and BR to the internal mixer and knead. Then add carbon black N234 and the above-mentioned zinc-free masterbatch type vulcanizing aid, and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0081] Add sulfur and knead the mixture, ensuring the temperature does not exceed 110°C during the kneading process.

[0082] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0083] Comparative Example 1

[0084] Add SSBR and BR to the internal mixer, knead for a period of time, then add carbon black N234, stearic acid, zinc oxide, antioxidant 4020, and accelerator TBBS and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0085] Add sulfur and knead the mixture, ensuring the temperature does not exceed 110°C during the kneading process.

[0086] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0087] Example 2

[0088] 10 phr stearic acid, 12.5 phr antioxidant A, and 11.5 phr vulcanization accelerator CZ were mixed in xylene and pre-reacted at 130°C for 40 min. After the solvent was removed from the reaction system, it was mixed with 100 phr IR to obtain a zinc-free masterbatch type vulcanization aid.

[0089] Add IR to the internal mixer and knead, then add silica, Si69, and the above-mentioned zinc-free masterbatch type vulcanizing agent, and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0090] Add sulfur and DPG, knead, and keep the temperature below 120°C during kneading.

[0091] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0092] Comparative Example 2

[0093] Add IR to the internal mixer and knead. Then add silica, Si69, stearic acid, zinc oxide, antioxidant A, and accelerator CZ. Continue kneading until the mixture is uniform. During kneading, the temperature should be controlled at 150-160℃.

[0094] Add sulfur and DPG, knead, and keep the temperature below 120°C during kneading.

[0095] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0096] The above rubber compound formulations are summarized in Table 1 below.

[0097] Table 1

[0098] The sources and parameters of the various raw materials used in Examples 1-14 and Comparative Examples 1-9 are as follows: IR, Qingdao Yikesi New Materials Co., Ltd.;

[0099] Silica, NEWSIL 1165-MP, Wuxi Quecheng Silicon Industry Co., Ltd., with a specific surface area of ​​165m³. 2 / g;

[0100] Carbon black, N234, Shandong Zhongxiang Polymer Materials Co., Ltd., with a specific surface area of ​​119 m². 2 / g;

[0101] Si69, a silane coupling agent, is produced by Nanjing Shuguang Chemical Group Co., Ltd.

[0102] SSBR, Dushanzi Petrochemical (25% styrene, 64% vinyl);

[0103] SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%);

[0104] BR, Qilu Petrochemical BR9000 (nickel-based high cis-butadiene, cis content 97%);

[0105] NR, Xishuangbanna Sinochem Rubber Co., Ltd. SCR5;

[0106] Stearic acid, PF1808, Licheng Sdn Bhd, Malaysia;

[0107] Zinc oxide, Dalian Zinc Oxide Plant;

[0108] Antioxidant 4020, Jiangsu Sheng'ao Chemical Co., Ltd.;

[0109] Antioxidant 4010NA, Shandong Shangshun Chemical Co., Ltd.;

[0110] Antioxidant 7PPD, Jiangsu Shengao Chemical Co., Ltd.;

[0111] Anti-aging agent A, synthesized in-house.

[0112] Anti-aging agent B, synthesized in-house.

[0113] Anti-aging agent C, synthesized in-house.

[0114] Anti-aging agent D, synthesized in-house.

[0115] Anti-aging agent E, synthesized in-house.

[0116] Anti-aging agent F, synthesized in-house.

[0117] Accelerator CZ, Shandong Shangshun Chemical Co., Ltd.;

[0118] Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd.;

[0119] Accelerator MBTS, Chaoyang Tianming Industry & Trade Co., Ltd.;

[0120] Accelerator DPG, Shandong Shanxian Chemical Co., Ltd.;

[0121] Sulfur, Wudi Jinsheng Chemical Co., Ltd.

[0122] The vulcanization characteristics of the rubber compounds prepared in the above examples and comparative examples were determined according to GB / T16584-1996 "Determination of vulcanization characteristics of rubber using a rotorless vulcanizing apparatus". The test results are shown in Table 2.

[0123] The physical properties (tensile strength, elongation at break, stress at 100% elongation, and stress at 300% elongation) of the rubber compounds prepared in the above examples and comparative examples were determined 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.

[0124] The hardness of the rubber compounds prepared in the above examples and comparative examples was determined according to GB / T 531.1-2008 Test method for indentation hardness of vulcanized rubber or thermoplastic rubber - Part 1: Shore hardness tester method (Shore hardness) and the test results are shown in Table 2.

[0125] The elastic modulus of the rubber compound at 20°C was determined 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 compounds prepared in the above examples and comparative examples was determined using a rotational rheometer. The test results are shown in Table 2.

[0126] In Table 2 and the subsequent tables of physical property test results, for ease of comparison, the test data of each embodiment are based on the corresponding comparative examples with the same composition except for zinc oxide, and the resulting index values ​​are obtained. For example, in Table 1, the MH value of Example 1 is the ratio of its measured value to the number of measured MH values ​​of Comparative Example 1 * 100; the larger the value, the higher the index.

[0127] Table 2

[0128] As can be seen from the results in Table 2, the rubber compounds prepared by the rubber composition of the present invention (Examples 1 and 2) are similar to conventional zinc-containing rubber compounds (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.

[0129] The preparation process of zinc-free masterbatch type vulcanizing aids 3-9 is the same as that of zinc-free masterbatch type vulcanizing aids in Example 1. The difference lies in the amount of specific components involved in the preparation process and the process parameters of the pre-reaction. The amount of specific components involved in zinc-free masterbatch type vulcanizing aids 3-9 is shown in Table 3 below, and the process parameters are shown in Table 4 below.

[0130] Table 3

[0131] Table 4

[0132] Zinc-free masterbatch type vulcanizing aids 10-14 were prepared. Their formulations and preparation processes were the same as those of zinc-free masterbatch type vulcanizing aid 6. The only difference was the pre-reaction parameters listed in Table 5.

[0133] Table 5

[0134] Examples 3-9 were prepared using the same method as Example 1, and Comparative Examples 3-9 were prepared using the same method as Comparative Example 1. Their formulations are shown in Tables 6 and 7 below. Further, the rubber compound formulations and preparation processes for Examples 10-14 were the same as those for Example 6, the only difference being that the zinc-free masterbatch type vulcanizing aids in Examples 10-14 were zinc-free masterbatch type vulcanizing aids 10-14, which are not listed.

[0135] Table 6

[0136] Table 7

[0137] Examples 3-9 and Comparative Examples 3-9 were tested using the same test method as Example 1, and the results are shown in Tables 8 and 9.

[0138] Table 8

[0139] Table 9

[0140] As can be seen from Tables 8 and 9, the rubber compounds containing zinc-free masterbatch type vulcanizing auxiliaries prepared by the method of the present invention (Examples 3-9) and conventional zinc-containing rubber compounds (corresponding to Examples 3-9 respectively) meet the requirements in terms of performance parameters after vulcanization testing, and can be applied to the production and manufacturing of rubber products and tires.

[0141] In addition, after aging, the vulcanized rubber compounds of Examples 2, 3, 5, 7-9 were extracted and analyzed by liquid chromatography-tandem high-resolution mass spectrometry (UPLC-HRMS / MS). No quinone compounds were detected, indicating that the environmentally friendly p-aniline antioxidant AF used in this application does not produce highly toxic quinone conversion products in the rubber residues, and is relatively environmentally friendly.

[0142] Table 10

[0143] The sources or technical parameters of the raw materials or reagents used in Examples 15-28 and Comparative Examples 10-18 are shown below:

[0144] IR, Qingdao Ecos New Materials Co., Ltd.;

[0145] Silica, NEWSIL1165-MP, Wuxi Quecheng Silicon Industry Co., Ltd.;

[0146] Carbon black, N234, Shandong Zhongxiang Polymer Materials Co., Ltd.;

[0147] Si69, a silane coupling agent, is produced by Nanjing Shuguang Chemical Group Co., Ltd.

[0148] SSBR, Dushanzi Petrochemical (25% styrene, 64% vinyl);

[0149] SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%);

[0150] BR, Qilu Petrochemical BR9000 (nickel-based high cis-butadiene, cis content 97%);

[0151] NR, Xishuangbanna Sinochem Rubber Co., Ltd. SCR5;

[0152] Stearic acid, PF1808, Licheng Sdn Bhd, Malaysia;

[0153] Zinc oxide, Dalian Zinc Oxide Plant;

[0154] Antioxidant 4020, Jiangsu Sheng'ao Chemical Co., Ltd.;

[0155] Antioxidant 4010NA, Shandong Shangshun Chemical Co., Ltd.;

[0156] Antioxidant 7PPD, Jiangsu Shengao Chemical Co., Ltd.;

[0157] Antioxidant A, synthesized in-house, has the following structural formula:

[0158] Antioxidant B, synthesized in-house, has the following structural formula:

[0159] Antioxidant C, synthesized in-house, has the following structural formula:

[0160] Antioxidant d, synthesized in-house, has the following structural formula:

[0161] Antioxidant e, synthesized in-house, has the following structural formula:

[0162] Antioxidant f, synthesized in-house, has the following structural formula:

[0163] Accelerator CZ, Shandong Shangshun Chemical Co., Ltd.;

[0164] Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd.;

[0165] Accelerator MBTS, Chaoyang Tianming Industry & Trade Co., Ltd.;

[0166] Accelerator DPG, Shandong Shanxian Chemical Co., Ltd.;

[0167] Sulfur, Wudi Jinsheng Chemical Co., Ltd.

[0168] Example 15

[0169] 10 phr stearic acid, 17.5 phr zinc oxide, 10 phr antioxidant 4020, and 10 phr tbsp ...

[0170] The rubber compound should be prepared according to the formula in Table 11, and the specific method is as follows:

[0171] After adding SSBR and BR to the internal mixer and kneading, add carbon black N234 and the above-mentioned zinc-free vulcanizing aid, and continue kneading until the mixture is uniform. During the kneading process, the temperature is controlled at 150-160℃.

[0172] Add sulfur and knead the mixture, ensuring the temperature does not exceed 110°C during the kneading process.

[0173] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0174] Comparative Example 10

[0175] The rubber compound should be prepared according to the formula in Table 11, and the specific method is as follows:

[0176] After adding SSBR and BR to the internal mixer and kneading, add carbon black N234, stearic acid, zinc oxide, antioxidant 4020, and accelerator TBBS and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0177] Add sulfur and knead the mixture, ensuring the temperature does not exceed 110°C during the kneading process.

[0178] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0179] Example 16

[0180] 10 phr stearic acid, 17.5 phr zinc oxide, 12.5 phr antioxidant A, and 11.5 phr vulcanization accelerator CZ were mixed in xylene and pre-reacted at 130°C for 40 min. After returning to room temperature, the zinc oxide was removed by filtration. The filtrate was dried and mixed with 100 phr IR to obtain a zinc-free vulcanization aid.

[0181] The rubber compound should be prepared according to the formula in Table 11, and the specific method is as follows:

[0182] After adding IR to the internal mixer and kneading, add silica, Si69, and the above-mentioned zinc-free vulcanizing agent, and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0183] Add sulfur and DPG, knead, and keep the temperature below 120°C during kneading.

[0184] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0185] Comparative Example 11

[0186] The rubber compound should be prepared according to the formula in Table 11, and the specific method is as follows:

[0187] After adding IR to the internal mixer and kneading, add silica, Si69, stearic acid, zinc oxide, antioxidant a, and accelerator CZ, and continue kneading until the mixture is uniform. During kneading, the temperature is controlled at 150-160℃.

[0188] Add sulfur and DPG, knead, and keep the temperature below 120°C during kneading.

[0189] The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compound were tested.

[0190] Two zero-zinc blank control samples, Comparative Example 0-1 and Comparative Example 0-2, were set up. Unlike Comparative Examples 1 and 2, Comparative Examples 0-1 and 0-2 did not contain zinc oxide.

[0191] Table 11 Rubber Compound Formulations (Unit: phr)

[0192] The zinc content in rubber compounds was determined according to the standard SN / T 2945-2011 "Determination of Lead, Cadmium, Chromium, Copper, Manganese and Zinc Content in Rubber and its Products by Inductively Coupled Plasma Atomic Emission Spectrometry". The test results are shown in Table 12.

[0193] Table 12

[0194] As can be seen from the results in Table 12, the zinc content in the rubber composition containing zinc-free vulcanizing auxiliaries is comparable to that in the zero-zinc blank sample without added zinc oxide, and both are significantly lower than the zinc content in ordinary zinc-containing formulations.

[0195] The performance tests of the rubber compounds in the above embodiments were conducted using the same method as in Example 1, and the test results are shown in Table 13. In Table 13 and the subsequent tables of physical property test results, for ease of comparison, the test data of each embodiment are based on the corresponding comparative examples with the same composition except for zinc oxide, and the resulting index values ​​are obtained. For example, in Table 13, the MH value of Example 15 is the ratio of its measured value to the number of measured MH values ​​of Comparative Example 10 multiplied by 100; the larger the value, the higher the index.

[0196] Table 13 Results of Physical Property Tests

[0197] The results in Table 13 demonstrate that the rubber compounds prepared from the zinc-free rubber compositions of the present invention (Examples 15 and 16) have similar crosslinking density, modulus, stress, hardness, mechanical properties, and hysteresis properties to conventional zinc-containing rubber compounds (corresponding to Examples 10 and 11, respectively), and can be used in rubber products and tires.

[0198] Zinc-free vulcanizing auxiliaries numbered #3' to #9' were prepared. The specific amounts of the components involved in the preparation process are shown in Table 14, and the process parameters are shown in Table 15. The preparation process is as follows: stearic acid, zinc oxide, antioxidant, and vulcanization accelerator were mixed in a solvent and pre-reacted for a period of time. After returning to room temperature, the zinc oxide was removed by filtration. The filtrate was first desolventized and then mixed with rubber (#5' to #9'), or it was mixed with rubber in the liquid phase and then desolventized (#3' to #4') to obtain zinc-free vulcanizing auxiliaries. The zinc content of all zinc-free vulcanizing auxiliaries #3' to #9' was determined to be 0.

[0199] Zinc-free vulcanizing auxiliaries #10' to #14' were prepared using the same formulation and preparation process as zinc-free vulcanizing auxiliaries #6', differing only in the pre-reaction parameters listed in Table 15. The zinc content of all zinc-free vulcanizing auxiliaries #10' to #14' was determined to be 0.

[0200] Table 14

[0201] Table 15

[0202] Examples 17-23 were prepared using the same method as Example 15, and Comparative Examples 12-18 were prepared using the same method as Comparative Example 10. Their formulations are shown in Tables 16 and 17 below.

[0203] Table 16 Rubber Compound Formulations (Unit: phr)

[0204] Table 17 Rubber Compound Formulations (Unit: phr)

[0205] The formulations of Examples 24-28 are the same as those of Example 20, except for the zinc-free vulcanizing aid. The zinc-free vulcanizing aids in Examples 24-28 are zinc-free vulcanizing aids #10' to #14', respectively. The final compound and vulcanized rubber were prepared in the same way as in Example 15.

[0206] Examples 17-28 and Comparative Examples 12-21 were tested using the same test method as Example 1, and the results are shown in Tables 18 and 19.

[0207] Table 18 Results of Physical Property Tests

[0208] Table 19 Results of Physical Property Tests

[0209] Table 20 Results of Physical Property Tests

[0210] In Tables 18 and 19, the rubber compounds containing zinc-free vulcanizing auxiliaries prepared using the present invention (Examples 17-23) and conventional zinc-containing rubber compounds (corresponding to Examples 12-18 respectively) all met the performance parameters after vulcanization testing and can be applied to the production of rubber products and tires. After aging, the vulcanized rubber compounds of Examples 16 and 19-28 were extracted, and the extracts were analyzed using ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UPLC-HRMS / MS). No quinone compounds were detected, proving that the environmentally friendly p-aniline antioxidant af used did not produce highly toxic quinone conversion products in the rubber residues, making it an environmentally friendly rubber additive.

[0211] In Table 20, higher temperatures and suitable pre-reaction times are beneficial to improving the performance of zinc-free vulcanizing auxiliaries, resulting in rubber compounds containing them exhibiting superior performance.

[0212] As can be seen from the above description, the above embodiments of the present invention achieve the following technical effects: Using this preparation method, under the action of a catalyst, the antioxidant and the reagents in the vulcanization system react to generate an active intermediate. This active intermediate has the effect of promoting vulcanization and acts as an early activation accelerator, so that the active intermediate can replace the role of zinc oxide and can be used to prepare tires and other rubber products that are completely free of zinc, achieving zinc-free emissions and being environmentally friendly. At the same time, the vulcanization auxiliaries prepared by the above preparation method enable rubber compositions containing them to obtain crosslinking density, hardness, tensile stress, and hysteresis properties close to those of zinc-containing rubber compositions, even without zinc.

[0213] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A process for the preparation of a vulcanization aid, characterized in that, The application relates to a vulcanization aid and a preparation method thereof. The antioxidant and the vulcanization system are pre-reacted under the action of a catalyst, and the catalyst comprises stearic acid.

2. The production method according to claim 1, characterized by, The preparation method comprises the following steps: S1, pre-reacting the catalyst, the antioxidant and the vulcanization system to obtain a pre-reaction mixture, wherein the catalyst is stearic acid; S2, mixing the pre-reaction mixture with rubber to obtain the vulcanization aid.

3. The preparation method according to claim 1, characterized in that, The preparation method comprises the following steps: pre-reacting the catalyst, the antioxidant and the vulcanization system in a solvent, wherein the catalyst is zinc oxide and stearic acid, and after the pre-reaction, zinc is removed through filtration, and the solvent is removed to obtain the vulcanization aid.

4. The production method according to any one of claims 1 to 3, characterized by, The pre-reaction is carried out at a temperature of 100-190 DEG C for 1-120 min. Preferably, the pre-reaction is carried out at a temperature of 110-170 DEG C for 5-50 min.

5. The production method according to any one of claims 1 to 3, characterized by, The pre-reaction is carried out in a solvent, and preferably, the solvent is any one or more of butanol, octanol, N-methyl pyrrolidone, octane, nonane, decane, toluene and xylene. The vulcanization system comprises any one or more of vulcanizing agents and accelerators, wherein the vulcanizing agents comprise any one or more of sulfur and sulfur carriers, and the accelerators comprise any one or more of sulfenamide accelerators and thiazole accelerators, and preferably, the accelerators comprise any one or more of CZ, DCBS, MBTS, MBT and TBBS. And / or, the anti-aging agent is a phenylenediamine anti-aging agent; preferably, the anti-aging agent has a structure shown in Formula I: In formula I, R 1 Selected from C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18 aromatic 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 adipose rings individually or simultaneously, R 6 Selected from H, C1-C 18 chain hydrocarbon group, C3-C 18 alicyclic hydrocarbon group or C6-C 18 The aromatic 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.

6. The preparation method according to claim 2, characterized in that, The weight ratio of the stearic acid to the antioxidant is 1:1-1:1.25, and the weight ratio of the vulcanization system to the antioxidant is 0.8:1-1.15:

1. The content of the rubber in the vulcanization aid is 50-95 wt%.

7. The preparation method according to claim 2, characterized in that, The step S2 comprises the following steps: removing the solvent in the pre-reaction mixture, and then mixing the pre-reaction mixture with the rubber to obtain the vulcanization aid in the form of a masterbatch; or The step S2 comprises the following steps: mixing the pre-reaction mixture containing the solvent with the rubber, and then removing the solvent to obtain the vulcanization aid in the form of a masterbatch.

8. The preparation method according to claim 3, characterized in that, The pre-reaction is carried out by adding 10-20 phr of zinc oxide, 5-15 phr of stearic acid, 5-15 phr of the antioxidant and 5-15 phr of the vulcanization system.

9. The preparation method according to claim 8, characterized in that, The vulcanization aid further comprises 50-150 phr of rubber, and the preparation method of the vulcanization aid comprising the rubber further comprises a first mixing or a second mixing, wherein the first mixing comprises the following steps: mixing the filtrate obtained after the zinc removal with the rubber, and then removing the solvent; and the second mixing comprises the following steps: mixing the filtrate obtained after the zinc removal with the rubber after the removal of the solvent.

10. The production method according to claim 7 or 9, characterized by, The rubber comprises any one or more of natural polymers or synthetic polymers, and preferably, the rubber is selected from any one or more of natural rubber, styrene butadiene rubber, isoprene rubber, natural eucommia rubber, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and ethylene-propylene-diene rubber; preferably, the molecular weight of the rubber is 1 kilo-40 million, further preferably 5 kilo-30 million, and more preferably 10 kilo-80 million. Preferably, the rubber comprises a diene-based rubber having the structure shown in 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 simultaneously 0.

11. A vulcanization aid characterized by, Prepared by the method of any one of claims 1 to 10.

12. A rubber composition characterized in that, Comprising: an elastomer, a filler and a zinc-free curing aid, the zinc-free curing aid being the curing aid of claim 11.

13. The rubber composition according to claim 12, characterized in that, The filler includes any one or more of carbon-based fillers, silicon-based fillers, carbon-silicon dual-phase fillers, and clays; preferably, the specific surface area of the filler is 10-500 m 2 / g, further preferably 30-300 m 2 / g, more preferably 50-300 m 2 / g. Preferably, the rubber composition further comprises other additives, the other additives comprising any one or more of a resin, an operating oil, a vulcanizing agent and a silane coupling agent; Preferably, the rubber composition comprises 100 phr of the elastomer, 20 phr to 170 phr of the filler, 10 to 50 phr of the zinc-free curing aid and the other additives, or the rubber composition comprises 0 to 130 parts of the elastomer, 25 to 35 parts of the zinc-free curing aid, 20 to 170 parts of the filler and 1 to 5 parts of the other additives, more preferably, the rubber composition comprises 30 to 100 parts of the elastomer, 26 to 31 parts of the zinc-free curing aid, 50 to 130 parts of the filler and 1.4 to 4.5 parts of the other additives.

14. A rubber article characterized in that, Prepared from the rubber composition of claim 12 or claim 13.

15. A tire characterized by Containing the rubber article of claim 14.

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