Vulcanization aids and methods for producing the same, rubber compositions, rubber products and tires

Abstract

This invention provides a vulcanization aid, a method for producing the same, a rubber composition, a rubber product, and a tire. The production method involves pre-reacting an antioxidant with a vulcanization chemical under the action of a catalyst containing stearic acid. Under the catalytic action of stearic acid, the antioxidant and the reagents in the vulcanization system react to produce an active intermediate, which has a vulcanization-promoting effect and performs the function of pre-activating the accelerator. As a result, the active intermediate can replace the action of zinc oxide and can be used in the production of rubber products such as tires that do not contain any zinc element, enabling zinc-free emissions and being environmentally friendly.

Description

Detailed description of the invention

[0001] Cross-reference of related applications This application claims priority to Chinese patent applications 2024106924399 and 2024106934545, filed on May 30, 2024. This application incorporates the full text of the aforementioned Chinese patent applications. [Technical Field]

[0002] The present invention relates to the technology of manufacturing tread rubber, and more specifically to vulcanization aids and methods for producing the same, rubber compositions, rubber products and tires. [Background technology]

[0003] The inclusion of zinc in tire treads contributes to environmental pollution, and both the European Commission Directive 2400 / 73 / EC and the SB1260 bill introduced by the state of California in 2016 recommend restricting the use of zinc or zinc oxide in tires.

[0004] However, zinc oxide or zinc-based additives function as vulcanization activators in vulcanization, improving crosslinking density, further enhancing the hardness of the rubber compound, and guaranteeing the performance of the rubber compound, thereby ensuring both rolling resistance and grip of tires manufactured using them. Removing zinc from commonly used compound formulations and following conventional production processes often results in a decrease in the degree of crosslinking, leading to reduced mechanical performance, lower hardness, increased hysteresis, increased tire rolling resistance, and reduced grip. Generally, the amount of zinc oxide in diene rubber compositions should be at least 2 phr. If conventional rubber compositions do not contain zinc, the manufacturing process of tire rubber will result in lower mechanical performance, lower hardness, and significantly reduced grip and wear resistance.

[0005] Researchers both domestically and internationally have already begun studying the environmental problems caused by zinc in tire tread rubber. Among these, patent application CN115678038B discloses a method of replacing zinc oxide with a lignin zinc salt composite. By utilizing its excellent dispersibility, it achieves the goal of reducing the amount of zinc oxide used and, when applied to tire tread rubber, can ensure tire wear resistance, reduce tire rolling resistance, and improve tire lifespan. While this patent achieves the goal of reducing zinc usage by improving zinc dispersibility, it cannot completely eliminate the environmental harm caused by zinc. Patent CN102300917B discloses a rubber composition that is zinc-free or contains less than 0.5 phr of zinc, which is applied to tire manufacturing. It improves the zinc-free processability of the rubber composition (i.e., reduces viscosity and extends scorch time) through the application of end-sealed mercaptosilanes. Although the patent reduces the amount of zinc used and thus eliminates zinc, it requires the use of specific end-sealed mercaptosilanes, which may react further during high-temperature kneading to generate mercapto groups, resulting in a certain degree of irritation and odor, and posing safety problems.

[0006] Improving the performance of tread rubber without using zinc elements has significant social and economic value. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The main objective of the present invention is to provide a vulcanization aid, a method for producing the same, a rubber composition, a rubber product, and a tire in order to solve the problem of environmental pollution caused by the zinc content in tread rubber in the prior art. [Means for solving the problem]

[0008] To achieve the above objective, according to one aspect of the present invention , Canada A method for producing a sulfurizing agent is provided, wherein the production method involves the action of an antioxidant and a vulcanizing system under the action of a catalyst containing stearic acid. Auxiliary drugscomprising pre-reacting the above.

[0009] Further, the above production method comprises a catalyst that is stearic acid, an anti-aging agent and a vulcanization system Auxiliary drugs comprising: step S1 of pre-reacting the above components to obtain a pre-reaction mixture; and step S2 of mixing the pre-reaction mixture with rubber to obtain a vulcanization auxiliary.

[0010] Further, the above production method comprises pre-reacting zinc oxide, a catalyst that is stearic acid, an anti-aging agent and a vulcanization system Auxiliary drugs in a solvent, sequentially performing zinc removal by filtration and solvent removal after the pre-reaction, to obtain a vulcanization auxiliary.

[0011] Further, the reaction temperature of the pre-reaction is 100 to 190°C, and the reaction time is 1 min to 120 min, preferably, the reaction temperature of the pre-reaction is 110 to 170°C, and the reaction time is 5 min to 50 min.

[0012] Further, the pre-reaction is carried out in a solvent, preferably, the solvent is one or more selected from the group consisting of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene and xylene, Further, the anti-aging agent is a phenylenediamine-based anti-aging agent, and preferably, the anti-aging agent has a structure shown in Formula I.

[0013]

Chemical Formula

[0014] Furthermore, vulcanization system Auxiliary drugs The mixture comprises one or more of either a vulcanizing agent and an accelerator, the vulcanizing agent comprising one or more of either a sulfur-based or sulfur-donating system, the accelerator comprising one or more of either a sulfenamide-based accelerator and a thiazole-based accelerator, preferably the accelerator being CZ (N-Cyclohexyl-2-benzothiazolesulfenamide, CBS) , including one or more of DCBS, MBTS, MBT, and TBBS.

[0015] Furthermore, the weight ratio of stearic acid to antioxidant is 1:1 to 1:1.25, and vulcanization system Auxiliary drugs The weight ratio of the anti-aging agent to the anti-aging agent is 0.8:1 to 1.15:1.

[0016] Furthermore, step S2 removes the solvent from the preliminary reaction mixture and further mixes it with the rubber. ,before The process includes obtaining a vulcanization aid, or step S2 involves mixing the preliminary reaction mixture containing a solvent with the rubber, and then removing the solvent. ,before This includes obtaining the described vulcanization aid.

[0017] Furthermore, in the preliminary reaction, 10-20 phr of zinc oxide, 5-15 phr of stearic acid, 5-15 phr of antioxidant, and vulcanization system are used. Auxiliary drugs Add 5-15 phr.

[0018] Furthermore, the vulcanization aid further contains 50 to 150 phr of rubber, and the method for producing the vulcanization aid containing rubber further includes a first mixture or a second mixture, the first mixture comprising mixing the filtrate obtained after zinc removal by filtration with rubber and then removing the solvent, and the second mixture comprising removing the solvent from the filtrate obtained after zinc removal by filtration and then mixing it with rubber.

[0019] Furthermore, the rubber comprises one or more natural polymers or synthetic polymers, preferably one or more selected from natural rubber, styrene-butadiene rubber, isoprene rubber, natural Eucommia rubber, polyisoprene rubber, butadiene rubber, halogenated butyl rubber, and ethylene propylene rubber, preferably the molecular weight of the rubber is 1,000 to 40 million, more preferably 5,000 to 30 million, and more preferably 10,000 to 8 million. Preferably, the rubber includes a diene-based rubber having the structure shown in formula II.

[0020] [ka] (In the formula, a, b, c, d, e, and f are all independent integers of 0 or greater, and a, b, c, d, e, and f cannot all be 0 at the same time.)

[0021] To achieve the above objective, according to one aspect of the present invention, a vulcanization aid is provided, which is manufactured by any of the above manufacturing methods.

[0022] According to other aspects of this application, The present invention comprises an elastomer, a filler, and a zinc-free vulcanization aid, wherein the zinc-free vulcanization aid is the above-mentioned vulcanization aid. We provide rubber compositions. do.

[0023] Furthermore, the filler comprises one or more of the following: carbon-based filler, silicon-based filler, carbon-silicon two-phase filler, and clay. Preferably, the specific surface area of ​​the filler is 10 to 500 m². 2 The value is / g, and more preferably 30-300m 2 It is / g, more preferably 50~300m 2 / g Preferably, the rubber composition further comprises other additives, the other additives comprising one or more of the following: resin, processing oil, vulcanizing agent, and silane coupling agent. Preferably, calculated by parts by weight, the rubber composition comprises 100 phr of elastomer, 20 phr to 170 phr of filler, 10 to 50 phr of zinc-free vulcanization aid and other additives, or When calculated in units of weight, The rubber composition consists of 0-130 parts elastomer and 25-35 parts Addition The rubber composition comprises a sulfur additive, 20 to 170 parts of filler and 1 to 5 parts of other additives, more preferably 30 to 100 parts of elastomer and 26 to 31 parts Addition It is characterized by comprising a sulfurizing agent, 50 to 130 parts of filler, and 1.4 to 4.5 parts of other additives.

[0024] A further aspect of the present invention provides a rubber product which is manufactured from any of the above rubber compositions. A further embodiment of the present invention provides a tire which contains the above-mentioned rubber product. [Effects of the Invention]

[0025] When the technical solution of the present invention is applied, the antioxidant and vulcanization system are activated under the action of a catalyst. Auxiliary drugs The reagents in the process react to produce an active intermediate, which has a vulcanization-promoting effect and acts as a pre-activation agent for the accelerator. As a result, the active intermediate can replace the action of zinc oxide and can be used in the manufacture of rubber products such as tires that do not contain any zinc element, enabling zinc-free emissions and being environmentally friendly. At the same time, the vulcanization aid produced by the above manufacturing method allows rubber compositions containing it to obtain crosslinking density, hardness, tensile stress, and hysteresis properties similar to those of zinc-containing rubber compositions, even when zinc is not present. [Modes for carrying out the invention]

[0026] In addition, the embodiments and features described herein can be combined with each other, provided that no contradictions arise. The present invention will now be described in detail with reference to the embodiments.

[0027] As analyzed in the background art of this application, the prior art has problems with environmental pollution caused by the zinc content in tread rubber. Although the methods in the prior art can reduce the zinc content in the rubber, they cannot completely avoid the environmental impact of zinc. On the other hand, if the element zinc is not included, it becomes difficult to meet the requirements for use in tread rubber. To solve this problem, this application provides a vulcanization aid, a method for producing the same, a rubber composition, a rubber product, and a tire.

[0028] According to one typical embodiment of the present application, a method for producing a vulcanization aid is provided, the method for producing an antioxidant and a vulcanization system under the action of a catalyst containing stearic acid. Auxiliary drugs This includes a preliminary reaction between the two.

[0029] In the above manufacturing method, under the action of a catalyst, the antioxidant and the vulcanization system Auxiliary drugs The reagents in the process react to produce an active intermediate, which has a vulcanization-promoting effect and acts as a pre-activation agent for the accelerator. As a result, the active intermediate can replace the action of zinc oxide and can be used in the manufacture of rubber products such as tires that do not contain any zinc element, enabling zinc-free emissions and being environmentally friendly. At the same time, the vulcanization aid produced by the above manufacturing method allows rubber compositions containing it to obtain crosslinking density, hardness, tensile stress, and hysteresis properties similar to those of zinc-containing rubber compositions, even when zinc is not present.

[0030] In some embodiments of the present application, the above manufacturing method involves stearic acid, an antioxidant, and a vulcanizing system. Auxiliary drugs The process includes step S1, which involves a preliminary reaction to obtain a preliminary reaction mixture, and step S2, which involves mixing the preliminary reaction mixture with rubber to obtain a vulcanization aid. The additional The sulfur additive does not contain zinc and contains an active intermediate that can substitute for the action of zinc oxide, The additional Sulfur additives can be used in the manufacture of rubber products such as tires that do not contain any zinc element.

[0031] Canada The proportion of rubber in the sulfur additive is not particularly required, and in some embodiments of this application, to facilitate subsequent use , Canada In sulfur additives, the rubber content is 50-95 wt%.

[0032] In some embodiments of the present application, the solvent is first removed from the pre-reaction mixture containing the solvent, and then the mixture is further mixed with rubber; that is, step S2 removes the solvent from the pre-reaction mixture and then mixes it with rubber. , Canada This includes obtaining a sulfurizing agent.

[0033] In some embodiments of the present application, a preliminary reaction mixture containing a solvent is mixed with rubber, and then the solvent is removed. That is, step S2 involves mixing a preliminary reaction mixture containing a solvent with rubber, and then removing the solvent. , Canada This includes obtaining a sulfurizing agent.

[0034] In some typical embodiments of the present application, in order to better exhibit the catalytic effect of stearic acid, the weight ratio of stearic acid to the antioxidant is 1:1 to 1:1.25, and preferably, a vulcanizing system Auxiliary drugs The weight ratio of the anti-aging agent to the anti-aging agent is 0.8:1 to 1.15:1, and the activity of the resulting product is higher.

[0035] In some embodiments of this application, the method for producing the above-mentioned vulcanization aid is a catalyst, antioxidant, and vulcanization system, which are zinc oxide and stearic acid. Auxiliary drugs The method involves carrying out a preliminary reaction in a solvent, followed by sequential removal of zinc by filtration and solvent to obtain a vulcanization aid. In this manufacturing method, zinc oxide and stearic acid are used simultaneously as catalysts to carry out the preliminary reaction, and after the reaction is completed, zinc is removed by filtration to obtain an anti-aging agent and a vulcanization system. Auxiliary drugsThis allows for more efficient generation of the active intermediate in the preliminary reaction, and the resulting vulcanization aid does not contain zinc and exerts its effect in the formulation in place of zinc oxide.

[0036] Zinc oxide, stearic acid, antioxidant, and vulcanizing agent added in the above preliminary reaction. Auxiliary drugs The proportions can be set based on the proportions between each corresponding component in conventional formulations. In some typical examples of this application, in the preliminary reaction, zinc oxide 10-20 phr, stearic acid 5-15 phr, antioxidant 5-15 phr, vulcanization system Auxiliary drugs Adding 5-15 phr of rubber to the manufactured zinc-free vulcanization aid exhibits a more pronounced promoting effect that improves the crosslinking density and rubber compounding performance of the composition. In some typical examples of this application, the vulcanization aid further contains 50-150 phr of rubber, and the method for producing the rubber-containing vulcanization aid further includes a first or second mixing, where the first mixing includes mixing the filtrate obtained after zinc removal by filtration with rubber and then removing the solvent, and the second mixing includes removing the solvent from the filtrate obtained after zinc removal by filtration and then mixing it with rubber. The rubber-containing vulcanization aid is a masterbatch type aid, and since dispersion in rubber is already achieved, it is more effective in subsequent applications, and acts as an antioxidant and vulcanization system Auxiliary drugs This is advantageous because the active intermediate produced by the preliminary reaction enhances the crosslinking density and rubber compounding effect. In particular, the first mixing allows the filtrate obtained after zinc removal by filtration and the rubber to be uniformly mixed by simple methods such as stirring, and the mixing of the rubber and other components becomes more sufficient and uniform. In the second mixing, the zinc removal product obtained by filtration from which the solvent has been removed and the rubber can be mixed by conventional mixing methods such as kneading.

[0037] Phenylenediamine-based antioxidants and 2-mercaptobenzothiazole-based vulcanizing agents Auxiliary drugs Taking this as an example, the reaction that occurs in the preliminary reaction is as shown in the following reaction equation, and the product has the effect of promoting the vulcanization reaction.

[0038] [ka]

[0039] In some embodiments of the present application, in order to promote the efficient progress of the preliminary reaction, the reaction temperature of the preliminary reaction is 100 to 190°C and the reaction time is 1 to 120 minutes. Preferably, in order to further improve the activity of the intermediate, the reaction temperature of the preliminary reaction is 110 to 170°C, for example 120°C, 130°C, 140°C, 150°C, 160°C, or 170°C. Preferably, in order to have a better effect of the preliminary reaction, the reaction time of the preliminary reaction is 5 to 50 minutes, for example 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, or 50 minutes.

[0040] In some typical embodiments of the present invention, the preliminary reaction is carried out in a solvent to uniformly disperse the components involved in the preliminary reaction and to improve the reaction rate and conversion rate. When the catalyst contains zinc oxide, the preliminary reaction is carried out in a solvent to facilitate the separation of zinc oxide and to accelerate the efficiency of the preliminary reaction. The solvent in the preliminary reaction is the stearic acid, antioxidant, and vulcanizing system involved in the preliminary reaction. Auxiliary drugs It can dissolve zinc oxide, and also contains an anti-aging agent and a vulcanizing system. Auxiliary drugs Any solvent that does not adversely affect the reaction is acceptable and can be selected from the prior art. The amount of solvent added can be adjusted based on its solubility with respect to the preliminary reaction raw materials. Preferably, the solvent is one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene, and xylene, which not only have excellent solubility with respect to the various components involved in the reaction but are also advantageous in promoting the progress of the preliminary reaction.

[0041] The method for removing the solvent added in the above preliminary reaction process can be selected from the prior art, and this application does not impose any restrictions on this. For example, if distillation is used, the removed solvent can be recovered and reused.

[0042] The above-mentioned antioxidant can be selected from the prior art, preferably the antioxidant is a phenylenediamine-based antioxidant, and in some embodiments of this application, the antioxidant in the above-mentioned preliminary reaction is a paraphenylenediamine-based antioxidant, for example, 4020( N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6PPD), 4010NA ( N-isopropyl-N'-phenyl-p-phenylenediamine, It is one or more of the following: IPPD and 7PPD.

[0043] In some preferred embodiments of the present application, the antioxidant has the structure shown in formula I, and the antioxidant having said structure is used in vulcanization systems Auxiliary drugs Not only does it efficiently form an active intermediate after a preliminary reaction, but it also has relatively high activity, low toxicity, and is more environmentally friendly.

[0044] [ka] (In formula I, R 1 is C1-C 18 Chain-like hydrocarbon group, C3-C 18 Alicyclic hydrocarbon group or C6-C 18 Selected from the aromatic hydrocarbon groups, R 2 , R 3 , R 4 , R 5 Each is independently C1-C 18 Selected from the chain hydrocarbon groups, R 2 and R 3 or R 4 and R 5 Each or simultaneously may form an aliphatic ring, R 6 H, C1-C 18 Chain-like hydrocarbon group, C3-C 18 Alicyclic hydrocarbon group or C6-C 18 A selection of aromatic hydrocarbon groups, where 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.

[0045] In some embodiments of this application, the vulcanizing system added in the preliminary reaction Auxiliary drugsThe mixture comprises one or more of either a vulcanizing agent and an accelerator, the vulcanizing agent comprising one or more of either a sulfur-based or sulfur-donating system, the accelerator comprising one or more of either a sulfenamide-based accelerator and a thiazole-based accelerator, preferably the accelerator being CZ (CBS) , comprising one or more of DCBS, MBTS, MBT, and TBBS. In other embodiments of the present application, the vulcanizing system added in the preliminary reaction Auxiliary drugs This refers to one or more accelerators, and vulcanizing agents are added further during the manufacturing process of rubber products.

[0046] The above-mentioned rubber can be selected from the prior art, for example, natural polymers or synthetic polymers may be used. For example, the above-mentioned natural rubber includes, but is not limited to, natural rubber, Eucommia ulmoides rubber, guayule rubber, etc., and the above-mentioned synthetic polymer includes, but is not limited to, those obtained by polymerizing monomers in solution (i.e., solution polymerized rubber), those obtained by polymerizing monomers in emulsion (i.e., emulsion polymerized rubber), and those obtained by polymerizing the monomer body itself. The solution polymerized rubber is a homopolymer or copolymer of an olefin monomer containing ethylene, propylene, butene, pentene, nonene, heptene, a diene with 4 to 7 carbon atoms or a triene with 6 to 7 carbon atoms, or 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, and cyano groups, and includes, but is not limited to, homopolymers and copolymers containing the above monomers, including polybutadiene, polyisoprene, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber, nitrile rubber, chloroprene rubber, silicone rubber, fluororubber, polyurethane rubber, chlorosulfonated polyethylene rubber, and acrylic rubber.

[0047] In some embodiments of this application, the rubber is one or more of the following: natural rubber, styrene-butadiene rubber, isoprene rubber, natural Eucommia rubber, polyisoprene rubber, butadiene rubber, halogenated butyl rubber, and ethylene propylene rubber, and exhibits excellent overall performance.

[0048] In some embodiments of the present application, the rubber in the vulcanization aid is preferably a diene rubber, and more preferably the diene rubber structure contains a branched chain and / or side chains, and the branched chain and / or side chains contain an alkenyl double bond and / or aromatic group.

[0049] The zinc oxide and stearic acid added in the preliminary reaction can be selected from the prior art, and this application does not have any special requirements.

[0050] In some preferred embodiments of the present application, the rubber is a rubber containing formula II, which exhibits a better synergistic effect with the pre-reaction mixture. , Canada The overall effect of the sulfur additive can be significantly improved. Preferably, a rubber containing the above formula II. added It accounts for 35 wt% or more of the total amount of rubber in the sulfur additive, preferably 60 wt% to 100 wt%.

[0051] [ka] (In equation II, a, b, c, d, e, and f are all independent integers of 0 or greater, and a, b, c, d, e, and f cannot all be 0 at the same time.) Preferably, at least two of a, b, c, d, e, and f are not zero. The repeating units are randomly distributed. In some preferred embodiments of the present application, the rubber having the chemical formula II structure is such that a, b, c are 0 and d, e, f are not 0, or a, b, c are not 0 and d, e, f are 0, or a, b, c, d are 0 and e, f are not 0, and the diene rubber having this structure has a higher crosslinking density.

[0052] Furthermore, the sum of the number of alkenyl double bonds and aromatic groups in the side chains and branched chains of the rubber shown in Formula II accounts for 15% or more of the total number of alkenyl double bonds and aromatic groups in the rubber, for example, in the range of 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, or any of the two. As will be understood by those skilled in the art, the Formula II structure may contain only side chains or branched chains, or may contain only alkenyl double bonds or aromatic groups in the side chains or branched chains, and the number of alkenyl double bonds or aromatic groups in the side chains or branched chains accounts for 15% or more of the total number of alkenyl double bonds and aromatic groups in the rubber molecular structure.

[0053] Sara Add To improve the performance of the sulfur additive, 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.

[0054] Furthermore, the rubber with the formula II structure accounts for 35% or more of the weight of the diene rubber, preferably 60% or more. For example, the weight content of the rubber with the formula II structure in the diene rubber is 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%.

[0055] The stearic acid used in step S1 can be selected from the prior art, and there are no special requirements for it in this application, so a detailed explanation is omitted here.

[0056] According to another typical embodiment of the present application, a vulcanization aid is provided which is manufactured by any of the manufacturing methods described above.

[0057] In the vulcanization aid produced by the above method, the antioxidant reacts with the vulcanization system under the catalytic action of stearic acid. Auxiliary drugsThe reagents in the mixture react to produce an active intermediate, which has a vulcanization-promoting effect and acts as a pre-activation agent for the accelerator. As a result, the active intermediate can replace the action of zinc oxide and can be used in the manufacture of rubber products such as tires that do not contain any zinc element, enabling zinc-free emissions and being environmentally friendly. At the same time, the vulcanization aid allows rubber compositions containing it to obtain crosslinking density, hardness, tensile stress, and hysteresis properties similar to those of zinc-containing rubber compositions, even when zinc is not present.

[0058] According to yet another typical embodiment of the present application, a rubber composition is provided comprising an elastomer, a filler, and a zinc-free vulcanization aid, wherein the zinc-free vulcanization aid is any of the above vulcanization aids.

[0059] The rubber composition of this application can be used in the manufacture of rubber products such as tires that do not contain any zinc element by using the above-mentioned zinc-free vulcanization aid, thereby achieving zinc-free emissions and being environmentally friendly. At the same time, by using the zinc-free vulcanization aid, the rubber composition containing it can obtain crosslinking density, hardness, tensile stress, and hysteresis properties of a zinc-containing rubber composition that are similar to those of a zinc-free rubber composition.

[0060] The above elastomers can be selected from conventional technologies, and is added It can be selected in the same way as rubber in sulfur additives, Taka The type of rubber used in the sulfurizing agent may be the same as or different from that used in the sulfurizing agent.

[0061] The rubber composition of this application exhibits excellent applicability to fillers, and can be selected from fillers in the prior art. For example, the filler may include one or more of the following: carbon-based fillers, silicon-based fillers, carbon-silicon two-phase fillers, and clay. Preferably, the specific surface area of ​​the filler is 10 to 500 m². 2 The value is / g, and more preferably 30-300m 2 It is / g, more preferably 50~300m2 It is / g.

[0062] Those skilled in the art can select other additives having suitable functions based on the specific usage environment and requirements of the rubber, and exemplary these additives include one or more of the following: resins, processing oils, vulcanizing agents, and silane coupling agents. The types of these additives can be selected from the prior art, and there are no special requirements in this application, so a detailed explanation is omitted here.

[0063] In some embodiments of this application, when calculated in parts by weight, the rubber composition is 0 to 130 The mixture comprises 25 to 35 parts elastomer, 20 to 170 parts zinc-free vulcanization aid, 20 to 170 parts filler, and 1 to 5 parts other aids, of which the zinc-free vulcanization aid is the masterbatch type zinc-free vulcanization aid described above.

[0064] In some embodiments of the present application, in order to better exhibit the synergistic effect of each component, the above rubber composition, calculated by parts by weight, comprises 30 to 100 parts elastomer, 26 to 31 parts zinc-free vulcanization aid, 50 to 130 parts filler, and 1.4 to 4.5 parts other aids, of which the vulcanization aid is the masterbatch type vulcanization aid.

[0065] In some typical embodiments of the present application, in order to better exhibit the synergistic effect of each component, the rubber composition comprises 100 phr of elastomer, 20 phr to 170 phr of filler, and 10 to 50 phr of zinc-free vulcanizing aid. Preferably, the rubber composition comprises 100 phr of elastomer, 50 phr to 130 phr of filler, and 20 to 35 phr of zinc-free vulcanizing aid. Preferably, the rubber composition further comprises 3 to 30 parts of other aids, one or more of which are selected from resins, processing oils, vulcanizing agents, and silane coupling agents. The rubber composition of the present application may also contain a vulcanizing agent, and the vulcanizing agent is a vulcanizing system Auxiliary drugs It may be added as one type to the preliminary reaction for producing a zinc-free vulcanization aid, or it may be included in the rubber composition on its own.

[0066] According to yet another typical embodiment of the present application, a rubber product is provided, the rubber product being manufactured from any of the above rubber compositions. Addition By using a sulfur-adding agent, the rubber product can achieve zinc-free emissions, making it environmentally friendly. At the same time, when the rubber product does not contain zinc, it acquires crosslinking density, hardness, tensile stress, and hysteresis properties of the rubber compound that are similar to those of zinc-containing rubber products.

[0067] The manufacturing method for producing rubber from the above rubber composition can be selected from the prior art, and this application does not impose any restrictions thereon. For example, rubber products can be manufactured using the above rubber composition as a raw material by the following method: (a) by kneading, elastomer, filler, zinc-free - Add (b) Mix the sulfurizing agent and other functional additives in one or more batches, and when the kneading temperature reaches 125°C to 200°C, discharge the rubber to obtain a first-stage masterbatch. (b) Perform thermomechanical kneading on the first-stage masterbatch in one or more batches, and while maintaining the kneading temperature at 125°C to 180°C, hold for 0 to 1200 seconds and discharge the rubber to obtain a second-stage masterbatch, and if there are any remaining processing aids, fillers, or antioxidants, add them all in one or more batches at this stage. (3) Second-stage masterbatch and vulcanization system Auxiliary drugs (4) The mixture is kneaded together in a closed-type kneader, the kneading temperature is ≤ 120°C, and the rubber is discharged to obtain the final kneaded rubber.

[0068] In some embodiments of this application, the vulcanization system added in the preliminary reaction for producing a zinc-free vulcanization aid Auxiliary drugs(c) The above rubber product is manufactured using the zinc-free vulcanization aid by the following method: (a) Mix the elastomer, filler, zinc-free vulcanization aid and other selectable aids in one or more batches using a kneading method, and discharge the rubber when the kneading temperature reaches 125°C to 200°C to obtain a first-stage masterbatch. (b) Perform thermomechanical kneading on the first-stage masterbatch one or more times, and discharge the rubber after holding the kneading temperature at 125°C to 180°C for 0 to 1200 seconds to obtain a second-stage masterbatch, and if there are any remaining other aids, fillers, or antioxidants, add them all in one or more batches at this stage. Auxiliary drugs The materials are kneaded together in a closed-type kneader at a kneading temperature of ≤120°C, and the rubber is discharged to obtain the final kneaded rubber. In the above method, the performance of the manufactured rubber product can be further improved by adopting specific kneading conditions for the zinc-free vulcanization aid. Preferably, the final kneaded rubber produced in the above process is vulcanized in a flat plate vulcanizer to obtain vulcanized rubber.

[0069] According to a fifth typical embodiment of the present application, a tire is provided, the tire containing the above-mentioned rubber product. Addition By using sulfur-adding agents, these tires can achieve zinc-free emissions, making them environmentally friendly. At the same time, the absence of zinc results in superior overall performance.

[0070] The achievable beneficial effects of this application will be further explained below with reference to the examples and comparative examples.

[0071] (Example 1) 10Phr stearic acid, 10Phr anti-aging agent 4020 (6PPD) Then, 10 phr of the vulcanization accelerator TBBS was mixed in decane and pre-reacted at 160°C for 30 min. After removing the solvent from the reaction system, it was further mixed with 96.3 phr of SSBR and 30 phr of BR to obtain a zinc-free masterbatch type vulcanization aid. SSBR and BR are added to a closed-type kneader, kneading is performed, then carbon black N234 and the above zinc-free masterbatch type vulcanization aid are added, and kneading is continued until uniformly mixed, with the temperature controlled to 150-160°C during kneading. Sulfur is added, and the dough is kneaded, ensuring that the temperature during kneading does not exceed 110°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0072] (Comparative Example 1) SSBR and BR are added to a closed kneader and kneaded for a certain period of time, then carbon black N234, stearic acid, zinc oxide, and antioxidant 4020 are added. (6PPD) Then, add the accelerator TBBS and continue kneading until uniformly mixed, controlling the temperature during kneading to 150-160°C. Sulfur is added, and the dough is kneaded, ensuring that the temperature during kneading does not exceed 110°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0073] (Example 2) 10 phr of stearic acid, 12.5 phr of antioxidant A, 11.5 phr of vulcanization accelerator CZ (CBS) The mixture was mixed in xylene and pre-reacted at 130°C for 40 minutes. After removing the solvent from the reaction system, it was further mixed with 100 phr of IR to obtain a zinc-free masterbatch type vulcanization aid. In a closed-type kneader, IR is added and kneading is performed. Then, white carbon black, Si69, and the above zinc-free masterbatch type vulcanization aid are added, and kneading is continued until uniformly mixed, while the temperature during kneading is controlled to 150-160°C. Sulfur and DPG are added, and the mixture is kneaded, ensuring that the temperature during kneading does not exceed 120°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0074] (Comparative Example 2) In a closed-type kneader, IR is added and kneading is performed, followed by white carbon black, Si69, stearic acid, zinc oxide, antioxidant A, and accelerator CZ. (CBS) Add the ingredients and continue kneading until uniformly mixed, controlling the temperature during kneading to 150-160°C. Sulfur and DPG are added, and the mixture is kneaded, ensuring that the temperature during kneading does not exceed 120°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested. The formulations for the above-mentioned rubber compounding agents are summarized in Table 1 below.

[0075] [Table 1]

[0076] The origins and parameter status of the various raw materials used in Examples 1-14 and Comparative Examples 1-9 are as follows. IR, Qingdao Ikos New Materials Co., Ltd. White carbon black, NEWSIL1165-MP, Wuxi Hecheng Silicon Industry Co., Ltd., specific surface area 165 m² 2 / g, Carbon black, N234, Shandong Zhongru Polymer Materials Co., Ltd., specific surface area 119 m² 2 / g, Silane coupling agent Si69, Nanjing Shuguang Chemical Group Co., Ltd. SSBR, Dushanzi Petrochemical (25% styrene, 64% vinyl), SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%) BR, Qilu Petrochemical BR9000 (nickel-based high-cis polybutadiene, cis content 97%) NR, Xishuangban Nazhonghua Rubber Co., Ltd. SCR5, Stearic acid, PF1808, Malaysia Licheng Co., Ltd. Zinc oxide, Dalian Zinc Oxide Plant, Anti-aging agent 4020 (6PPD) , Jiangsu Shengoku Chemical Co., Ltd. Anti-aging agent 4010NA (IPPD) , Shandong Shangshun Chemical Co., Ltd. Anti-aging agent 7PPD, Jiangsu Shengoku Chemical Co., Ltd. Anti-aging agent A, independently synthesized, [ka] Anti-aging agent B, independently synthesized, [ka] Anti-aging agent C, independently synthesized, [ka] Anti-aging agent D, independently synthesized, [ka] Anti-aging agent E, independently synthesized, [ka] Anti-aging agent F, independently synthesized, [ka] CZ accelerator (CBS) , Shandong Shangshun Chemical Co., Ltd. Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd. Accelerator MBTS, Chaoyang Tianming Industry and Trade Co., Ltd. Accelerator DPG, Shandong Danxian Chemical Co., Ltd. Sulfur, Wudian Jinsheng Chemical Co., Ltd.

[0077] In accordance with "GB / T16584-1996 Method for Determining the Vulcanization Characteristics of Rubber Using a Rotaryless Vulcanization Tester," the vulcanization characteristics of the rubber compounding agents produced in the above examples and comparative examples were measured, and the test results are shown in Table 2. In accordance with "GB / T528-2009 Measurement of Tensile Stress-Strain Characteristics of Vulcanized Rubber or Thermoplastic Rubber," the physical properties (tensile strength, elongation at break, 100% elongation stress, 300% elongation stress) of the rubber compounding agents produced in the above examples and comparative examples were measured, and the results are shown in Table 2. The hardness of the rubber compounding agents produced in the above examples and comparative examples was measured in accordance with "GB / T531.1-2008 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. In accordance with "GB / T9870.1-2006 Measurement of the dynamic properties of vulcanized rubber or thermoplastic rubber, Part 1: General rules," the elastic modulus of the rubber compound was measured at 20°C, and the tanδmax of the rubber compound produced in the above examples and comparative examples was measured using a rotational rheometer. The test results are shown in Table 2. In Table 2 and the subsequent table of physical property test results, for the sake of ease of comparison, the test data for each example are index values ​​obtained based on a comparative example in which the composition other than the corresponding zinc oxide is the same. For example, in Table 1, the MH value for Example 1 is the ratio of its measured value to the measured value of MH for Comparative Example 1 * 100, and a larger value indicates a higher index.

[0078] [Table 2]

[0079] As can be seen from the results in Table 2, the rubber compounding agents produced from the rubber composition of the present invention (Examples 1 and 2) approximate the crosslinking density, modulus, stress, hardness, mechanical performance, and hysteresis characteristics of conventional zinc-containing rubber compounding agents (corresponding to Comparative Examples 1 and 2, respectively), and can be used in rubber products and tires.

[0080] The manufacturing process for zinc-free masterbatch type vulcanization aids 3-9 is the same as that for the zinc-free masterbatch type vulcanization aid in Example 1. The differences lie in the specific amounts of components used in the manufacturing process and the process parameters of the preliminary reaction. The specific amounts of components used for zinc-free masterbatch type vulcanization aids 3-9 are shown in Table 3 below, and the process parameters are shown in Table 4 below.

[0081] [Table 3]

[0082] [Table 4]

[0083] Zinc-free masterbatch type vulcanization aids 10-14 were manufactured, with their formulations and manufacturing processes being the same as those of zinc-free masterbatch type vulcanization aid 6, the only difference being the parameters of the preliminary reaction described in Table 5.

[0084] [Table 5]

[0085] Examples 3-9 were manufactured according to the same method as Example 1, and Comparative Examples 3-9 were manufactured according to the same method as Comparative Example 1, with the final kneaded rubber and vulcanized rubber being shown in Tables 6 and 7 below. Furthermore, the rubber compounding formulations and manufacturing processes for Examples 10-14 were the same as in Example 6, the only difference being that the zinc-free masterbatch type vulcanization aids in Examples 10-14 were zinc-free masterbatch type vulcanization aids 10-14, respectively, and this is not described in the table.

[0086] [Table 6]

[0087] [Table 7]

[0088] Examples 3-9 and Comparative Examples 3-9 were tested according to the same test method as in Example 1, and the results are shown in Tables 8 and 9.

[0089] [Table 8]

[0090] [Table 9]

[0091] As can be seen from Tables 8 and 9, the rubber compounding agents containing the zinc-free masterbatch type vulcanization aid produced by the method of the present invention (Examples 3-9) and conventional zinc-containing rubber compounding agents (corresponding to Comparative Examples 3-9, respectively) all met the required performance parameters after vulcanization testing and can be applied to the production and manufacture of rubber products and tires.

[0092] Furthermore, after aging the rubber compounding agents of the vulcanized rubbers in Examples 2, 3, 5, and 7-9, extraction was performed, and the extracts were detected by liquid chromatography-high-resolution tandem mass spectrometry (UPLC-HRMS / MS). No quinone compounds were detected, demonstrating that the environmentally friendly para-aniline-based antioxidants A-F used in this application do not generate highly toxic quinone conversion products in the rubber residue, thus demonstrating their environmental friendliness.

[0093] [Table 10]

[0094] The origins or technical parameters of the raw materials or reagents used in Examples 15-28 and Comparative Examples 10-18 are as follows. IR, Qingdao Ikos New Materials Co., Ltd. White carbon black, NEWSIL1165-MP, Wuxi Hecheng Silicon Industry Co., Ltd. Carbon black, N234, Shandong Zhongru Polymer Materials Co., Ltd. Silane coupling agent Si69, Nanjing Shuguang Chemical Group Co., Ltd. SSBR, Dushanzi Petrochemical (25% styrene, 64% vinyl), SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%) BR, Qilu Petrochemical BR9000 (nickel-based high-cis polybutadiene, cis content 97%) NR, Xishuangban Nazhonghua Rubber Co., Ltd. SCR5, Stearic acid, PF1808, Malaysia Licheng Co., Ltd. Zinc oxide, Dalian Zinc Oxide Plant, Anti-aging agent 4020 (6PPD) , Jiangsu Shengoku Chemical Co., Ltd. Anti-aging agent 4010NA (IPPD) , Shandong Shangshun Chemical Co., Ltd. Anti-aging agent 7PPD, Jiangsu Shengoku Chemical Co., Ltd. Anti-aging agent a, independently synthesized, structural formula [ka] Anti-aging agent b, independently synthesized, structural formula [ka] Anti-aging agent c, auto-synthesized, structural formula [ka] Anti-aging agent d, auto-synthesized, structural formula [ka] Anti-aging agent e, independently synthesized, structural formula [ka] Anti-aging agent f, auto-synthesized, structural formula [ka] CZ accelerator (CBS) , Shandong Shangshun Chemical Co., Ltd. Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd. Accelerator MBTS, Chaoyang Tianming Industry and Trade Co., Ltd. Accelerator DPG, Shandong Danxian Chemical Co., Ltd. Sulfur, Wudian Jinsheng Chemical Co., Ltd.

[0095] (Example 15) 10 phr stearic acid, 17.5 phr zinc oxide, 10 phr anti-aging agent 4020 (6PPD)10 phr of the vulcanization accelerator TBBS was mixed in decane, a preliminary reaction was carried out at 160°C for 30 min, and after returning to room temperature, zinc oxide was removed by filtration, the filtrate was dried, and then mixed with 96.3 phr of SSBR and 30 phr of BR to obtain a zinc-free vulcanization aid. The rubber compounding agent is manufactured according to the formulation shown in Table 11, and the specific method is as follows. After adding SSBR and BR to a closed-type kneader and kneading, carbon black N234 and the above zinc-free vulcanization aid are added, and kneading is continued until uniformly mixed, while controlling the temperature to 150-160°C during kneading. Sulfur is added, and the dough is kneaded, ensuring that the temperature during kneading does not exceed 110°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0096] (Comparative Example 10) The rubber compounding agent is manufactured according to the formulation shown in Table 11, and the specific method is as follows. After adding SSBR and BR to a closed kneader and kneading, carbon black N234, stearic acid, zinc oxide, and antioxidant 4020 are added. (6PPD) Then, add the accelerator TBBS and continue kneading until uniformly mixed, controlling the temperature during kneading to 150-160°C. Sulfur is added, and the dough is kneaded, ensuring that the temperature during kneading does not exceed 110°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0097] (Example 16) 10 phr of stearic acid, 17.5 phr of zinc oxide, 12.5 phr of antioxidant a, 11.5 phr of vulcanization accelerator CZ (CBS) The mixture was mixed in xylene, a preliminary reaction was carried out at 130°C for 40 minutes, and after returning to room temperature, zinc oxide was removed by filtration, the filtrate was dried and mixed with 100 phr of IR to obtain a zinc-free vulcanization aid. The rubber compounding agent is manufactured according to the formulation shown in Table 11, and the specific method is as follows. After adding IR to a closed-type kneader and kneading, white carbon black, Si69, and the above zinc-free vulcanization aid are added, and kneading is continued until uniformly mixed, with the temperature controlled to 150-160°C during kneading. Sulfur and DPG are added, and the mixture is kneaded, ensuring that the temperature during kneading does not exceed 120°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested.

[0098] (Comparative Example 11) The rubber compounding agent is manufactured according to the formulation shown in Table 11, and the specific method is as follows. After adding IR to a closed-type kneader and kneading, white carbon black, Si69, stearic acid, zinc oxide, antioxidant a, and accelerator CZ are added. (CBS) Add the ingredients and continue kneading until uniformly mixed, controlling the temperature during kneading to 150-160°C. Sulfur and DPG are added, and the mixture is kneaded, ensuring that the temperature during kneading does not exceed 120°C. The obtained rubber composition was vulcanized to obtain vulcanized rubber, and the physical properties of the rubber compounding agent were tested. Comparative Examples 0-1 and 0-2 were established as zero-zinc blank samples. The difference between Comparative Examples 0-1 and 0-2 and Comparative Examples 1 and 2 is that zinc oxide was not added to either Comparative Example 0-1 or Comparative Example 0-2.

[0099] [Table 11]

[0100] The zinc content in the rubber compound was measured in accordance with "SN / T2945-2011 Measurement of lead, cadmium, chromium, copper, manganese, and zinc content in rubber and its products - Inductively coupled plasma atomic emission spectroscopy," and the test results are shown in Table 12.

[0101] [Table 12]

[0102] As can be seen from the results in Table 12, the zinc content in rubber compositions containing zinc-free vulcanization aids is equivalent to the zinc content in zero-zinc blank samples without added zinc oxide, and in both cases, it is clearly lower than the zinc content in typical zinc-containing formulations.

[0103] Performance tests of the rubber compound were performed on the above examples using the same method as in Example 1, and the test results are shown in Table 13. In Table 13 and the subsequent physical property test results table, to facilitate comparison, the test data for each example are index values ​​obtained based on a comparative example in which the composition other than the corresponding zinc oxide is the same. For example, in Table 13, the MH value for Example 15 is the ratio of its measured value to the measured value of MH for Comparative Example 10 * 100, and a larger value indicates a higher index.

[0104] [Table 13]

[0105] The results in Table 13 demonstrate that the rubber compounding agents produced from the zinc-free rubber composition of the present invention (Examples 15 and 16) approximate the crosslinking density, modulus, stress, hardness, mechanical performance, and hysteresis characteristics of conventional zinc-containing rubber compounding agents (corresponding to Comparative Examples 10 and 11, respectively), and can be used in rubber products and tires.

[0106] Zinc-free vulcanization aids numbered #3' to #9' were manufactured. The specific amounts of components used in the manufacturing process are shown in Table 14 below, and the process parameters are shown in Table 15 below. The manufacturing process is as follows: Stearic acid, zinc oxide, antioxidant, and vulcanization accelerator were mixed in a solvent, allowed to pre-react for a certain period of time, and after returning to room temperature, zinc oxide was removed by filtration. The filtrate was then mixed with rubber after removing the solvent (#5' to #9'), or mixed with rubber in the liquid phase and then the solvent was removed (#3' to #4') to obtain zinc-free vulcanization aids. Measurements showed that the zinc content of all zinc-free vulcanization aids #3' to #9' was 0.

[0107] Zinc-free vulcanization aids numbered #10' to #14' were manufactured using the same formulation and manufacturing process as zinc-free vulcanization aid #6', with the only difference being the preliminary reaction parameters described in Table 15. Measurements revealed that the zinc content of all zinc-free vulcanization aids #10' to #14' was 0.

[0108] [Table 14]

[0109] [Table 15]

[0110] Examples 17-23 were manufactured according to the same method as Example 15, and Comparative Examples 12-18 were manufactured according to the same method as Comparative Example 10. The final compounded rubber and vulcanized rubber are shown in Tables 16 and 17 below.

[0111] [Table 16]

[0112] [Table 17]

[0113] The formulations of Examples 24-28 were identical to those of Example 20, except for the zinc-free vulcanization aid. The zinc-free vulcanization aids in Examples 24-28 were zinc-free vulcanization aids #10' to #14', respectively. The final kneaded rubber and vulcanized rubber were produced in the same manner as in Example 15.

[0114] Examples 17-28 and Comparative Examples 12-21 were tested according to the same test method as in Example 1, and the results are shown in Tables 18 and 19.

[0115] [Table 18]

[0116] [Table 19]

[0117] [Table 20]

[0118] Tables 18 and 19 show that the rubber compounding agents containing the zinc-free vulcanization aid produced by the present invention (Examples 17-23) and conventional zinc-containing rubber compounding agents (corresponding to Comparative Examples 12-18, respectively) all met the required performance parameters after vulcanization testing and can be applied to the production and manufacture of rubber products and tires. After aging the rubber compounding agents of the vulcanized rubbers in Examples 16, 19-28, extraction was performed, and the extract was detected by ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UPLC-HRMS / MS). No quinone compounds were detected, proving that the environmentally friendly para-aniline-based antioxidants a-f used did not produce highly toxic quinone conversion products in the rubber residue, thus demonstrating that they are environmentally friendly rubber compounding agents.

[0119] Table 20 shows that when manufacturing zinc-free vulcanization aids, relatively high temperatures and appropriate pre-reaction times are advantageous in improving their performance, and as a result, rubber compounding agents containing them exhibit relatively superior performance.

[0120] As can be seen from the above description, the above embodiment of the present invention achieves the following technical effects. Using the manufacturing method, under the action of a catalyst, the antioxidant and vulcanization system Auxiliary drugsThe reagents in the process react to produce an active intermediate, which has a vulcanization-promoting effect and acts as a pre-activation agent for the accelerator. As a result, the active intermediate can replace the action of zinc oxide and can be used in the manufacture of rubber products such as tires that do not contain any zinc element, enabling zinc-free emissions and being environmentally friendly. At the same time, the vulcanization aid produced by the above manufacturing method allows rubber compositions containing it to obtain crosslinking density, hardness, tensile stress, and hysteresis properties similar to those of zinc-containing rubber compositions, even when zinc is not present.

[0121] The foregoing description is merely a preferred embodiment of the present invention and does not limit it; those skilled in the art will know that the present invention can be modified and altered in various ways. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for producing a vulcanization aid, characterized by comprising pre-reacting an antioxidant with a vulcanizing agent under the action of a catalyst containing stearic acid.

2. Step S1 involves pre-reacting the catalyst, which is stearic acid, the antioxidant, and the vulcanization system to obtain a preliminary reaction mixture. The manufacturing method according to claim 1, characterized by comprising step S2 of mixing the preliminary reaction mixture with rubber to obtain the vulcanization aid.

3. The manufacturing method according to claim 1, characterized in that it includes pre-reacting the catalyst, which is zinc oxide and stearic acid, the antioxidant, and the vulcanizing chemical in a solvent, and then sequentially removing the zinc and solvent by filtration after the pre-reaction to obtain the vulcanizing aid.

4. The reaction temperature of the preliminary reaction is 100 to 190°C, and the reaction time is 1 min to 120 min. Preferably, the manufacturing method according to any one of claims 1 to 3, characterized in that the reaction temperature of the preliminary reaction is 110 to 170°C and the reaction time is 5 min to 50 min.

5. The preliminary reaction is carried out in a solvent, preferably one or more of butanol, octanol, N-methylpyrrolidone, octane, nonane, decane, toluene, and xylene. and / or, the vulcanizing chemical comprises one or more of a vulcanizing agent and an accelerator, the vulcanizing agent comprises one or more of a sulfur-based and a sulfur-donating system, the accelerator comprises one or more of a sulfenamide-based accelerator and a thiazole-based accelerator, preferably the accelerator comprises one or more of CZ, DCBS, MBTS, MBT and TBBS, The manufacturing method according to any one of claims 1 to 3, characterized in that and / or the antioxidant is a phenylenediamine-based antioxidant, and preferably the antioxidant has the structure shown in formula I. 【Chemistry 1】 In formula I, R １ is C １ -C １８ acyclic hydrocarbon group, C ３ -C １８ alicyclic hydrocarbon group or C ６ -C １８ aromatic hydrocarbon group, R ２ , R ３ , R ４ , R ５ are each independently selected from C １ -C １８ acyclic hydrocarbon groups, R ２ and R ３ or R ４ and R ５ may respectively or simultaneously form an aliphatic ring, R ６ is selected from H, C １ -C １８ acyclic hydrocarbon group, C ３ -C １８ alicyclic hydrocarbon group or C ６ -C １８ aromatic hydrocarbon group, x=0 or 1, y=0 or 1, z=0 or 1, w=0 or 1, at least one of x and w is 1, and at least one of y and z is 1.)

6. The weight ratio of stearic acid to the antioxidant is 1:1 to 1:1.25, and the weight ratio of the vulcanizing system to the antioxidant is 0.8:1 to 1.15:

1. The manufacturing method according to claim 2, characterized in that the rubber content in the vulcanization aid is 50 to 95 wt%.

7. Step S2 includes removing the solvent from the preliminary reaction mixture, further mixing it with the rubber, and obtaining the masterbatch-type vulcanization aid, or The manufacturing method according to claim 2, characterized in that step S2 includes mixing the preliminary reaction mixture containing the solvent with the rubber, then removing the solvent to obtain the masterbatch type vulcanization aid.

8. The manufacturing method according to claim 3, characterized in that 10 to 20 phr of zinc oxide, 5 to 15 phr of stearic acid, 5 to 15 phr of an antioxidant, and 5 to 15 phr of a vulcanizing agent are added in the preliminary reaction.

9. The manufacturing method according to claim 8, wherein the vulcanization aid further comprises 50 to 150 phr of rubber, and the method for manufacturing the vulcanization aid containing the rubber further comprises a first mixture or a second mixture, wherein the first mixture comprises mixing the filtrate obtained after zinc removal by filtration with the rubber and then removing the solvent, and the second mixture comprises removing the solvent from the filtrate obtained after zinc removal by filtration and then mixing it with the rubber.

10. The rubber comprises one or more natural polymers or synthetic polymers, preferably one or more selected from natural rubber, styrene-butadiene rubber, isoprene rubber, natural Eucommia rubber, polyisoprene rubber, butadiene rubber, halogenated butyl rubber, and ethylene propylene rubber, preferably the molecular weight of the rubber is 1,000 to 40 million, more preferably 5,000 to 30 million, and more preferably 10,000 to 8 million. Preferably, the rubber includes a diene rubber having the structure shown in formula II, characterized in that the manufacturing method according to claim 7 or 9. 【Chemistry 2】 (In the formula, a, b, c, d, e, and f are all independent integers of 0 or greater, and a, b, c, d, e, and f cannot all be 0 at the same time.)

11. A vulcanization aid characterized by being manufactured by the manufacturing method described in any one of claims 1 to 10.

12. A rubber composition comprising an elastomer, a filler, and a zinc-free vulcanization aid, wherein the zinc-free vulcanization aid is the vulcanization aid described in claim 11.

13. The filler comprises one or more of the following: carbon-based filler, silicon-based filler, carbon-silicon two-phase filler, and clay. Preferably, the specific surface area of ​​the filler is 10 to 500 m². ２ The value is / g, and more preferably 30 to 300m ２ / g, more preferably 50 to 300m ２ / g, Preferably, the rubber composition further comprises other auxiliary agents, the other auxiliary agents comprising one or more of the following: resin, processing oil, vulcanizing agent, and silane coupling agent. Preferably, the rubber composition comprises, when calculated by weight, 100 phr of elastomer, 20 phr to 170 phr of filler, 10 to 50 phr of zinc-free vulcanization aid and other additives, or the rubber composition comprises 0 to 130 parts elastomer, 25 to 35 parts zinc-free vulcanization aid, 20 to 170 parts filler and 1 to 5 parts other additives, and more preferably, the rubber composition comprises 30 to 100 parts elastomer, 26 to 31 parts zinc-free vulcanization aid, 50 to 130 parts filler and 1.4 to 4.5 parts other additives, characterized in that the rubber composition is as described in 12.

14. A rubber product characterized by being manufactured from the rubber composition described in claim 12 or claim 13.

15. A tire characterized by containing the rubber product described in claim 14.

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