Masterbatch vulcanization aid and method for its preparation, rubber composition, rubber article and tire

Abstract

The application provides a masterbatch type vulcanization aid and a preparation method thereof, a rubber composition, a rubber product and a tire. The preparation method comprises the following steps: S1, pre-reaction of stearic acid, an antioxidant and a vulcanization system to obtain a pre-reaction mixture; and S2, mixing of the pre-reaction mixture with rubber to obtain the masterbatch type vulcanization aid. Under the catalysis of stearic acid, the reagents in the antioxidant and the vulcanization system react to generate active intermediates. The active intermediates have the effect of promoting vulcanization and play the role of activating accelerators in advance, so that the active intermediates can replace the role of zinc oxide. The product after reaction is mixed with rubber, and the masterbatch formed can be used to prepare rubber products such as tires without containing zinc elements, so that zinc emission can be realized, and the environment is friendly.

Description

TECHNICAL FIELD

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

[0002] The presence of zinc in tire tread rubber pollutes the environment, and the European Commission Directive 2400 / 73 / EC and the SB1260 bill proposed by California in 2016 both suggest limiting the use of zinc or zinc oxide in tires.

[0003] However, zinc oxide or zinc-based additives play the role of vulcanizing activators in vulcanization, can improve crosslinking density, and thus improve the hardness of the rubber compound and ensure the performance of the rubber compound, and the rolling resistance and grip of the tire manufactured thereby can be guaranteed. If zinc is removed from the commonly used formula, the crosslinking degree is often reduced according to the existing production process, resulting in reduced mechanical properties, low hardness, increased hysteresis, increased rolling resistance of the tire, and reduced grip.

[0004] In view of the environmental problem of zinc in tire tread rubber, researchers at home and abroad have begun to study it. Among them, the patent application with publication number CN115678038B discloses a method for replacing zinc oxide with lignin zinc salt complex, which achieves the purpose of reducing the amount of zinc oxide by taking advantage of its good dispersion, and is applied to tire tread rubber to ensure the wear resistance of the tire and reduce the rolling resistance of the tire, and improve the service life of the tire. The patent achieves the purpose of reducing the amount of zinc by improving the dispersion of zinc, but cannot completely eliminate the harm of zinc to the environment. Patent CN102300917B discloses a rubber composition containing no zinc or containing 0.5 phr or less of zinc and applied to tire manufacturing, which improves the processability (i.e., reduces viscosity and prolongs scorch time) of the rubber composition without zinc by using an end-capped mercaptosilane. Although the patent can reduce the amount of zinc or even contain no zinc, it needs to use a specific end-capped mercaptosilane, which may further react to generate mercapto groups at high temperature, has a certain irritancy and odor, and has safety problems.

[0005] It is of great social significance and economic value to improve the performance of tire tread rubber without using zinc elements. SUMMARY

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

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

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

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

[0010] Further, the pre-reaction is performed in a solvent, preferably, the solvent is any one or more of butanol, octanol, N-methyl pyrrolidone, octane, nonane, decane, toluene and xylene.

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

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

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

[0014] Formula I

[0015] In Formula I, R 1 is selected from a C1-C 18 alkyl chain, a C3-C 18 alicyclic chain or a C6-C 18 aromatic chain, R 2 , R 3 , R 4 , R 5 are each independently selected from a C1-C 18 alkyl chain, R 2 and R 3 or R 4 and R 5 may also form an aliphatic ring respectively or simultaneously, R 6 is selected from, R 6 is selected from H, a C1-C 18 alkyl chain, a C3-C 18 alicyclic chain or a C6-C 18an aromatic hydrocarbon group; x = 0 or 1, y = 0 or 1, z = 0 or 1, w = 0 or 1, and at least one of x and w is 1, and at least one of y and z is 1.

[0016] Further, the vulcanization system includes any one or more of a vulcanizing agent including any one or more of sulfur and a sulfur carrier, and an accelerator including any one or more of a sulfenamide accelerator and a thiazole accelerator, preferably, the accelerator includes any one or more of CZ, DCBS, MBTS, MBT and TBBS.

[0017] The rubber is any one or more of natural rubber, styrene butadiene rubber, isoprene rubber, natural gutta-percha, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and ethylene-propylene-diene rubber; preferably, the rubber is a rubber containing Formula II:

[0018] Formula II

[0019] wherein a, b, c, d, e and f are each independently an integer greater than or equal to 0, and a, b, c, d, e and f are not simultaneously 0.

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

[0021] To achieve the above object, according to one aspect of the present application, there is provided a masterbatch type vulcanization aid prepared by any one of the above preparation methods.

[0022] According to another aspect of the present application, there is provided a rubber composition, characterized by comprising 0 to 130 parts by weight of an elastomer, 25 to 35 parts by weight of the masterbatch type vulcanization aid, 20 to 170 parts by weight of a filler, and 1 to 5 parts by weight of other aids, the masterbatch type vulcanization aid being the masterbatch type vulcanization aid described above.

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

[0024] The other aids include any one or more of a resin, an operating oil, a vulcanizing agent and a silane coupling agent.

[0025] Preferably, the rubber composition comprises 30-100 parts by weight of the elastomer, 26-31 parts by weight of the masterbatch vulcanization aid, 50-130 parts by weight of the filler, and 1.4-4.5 parts by weight of the other additives.

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

[0027] According to another aspect of the present application, there is provided a tire comprising the above rubber product.

[0028] According to the technical solution of the present application, under the catalysis of stearic acid, the anti-aging agent and the reagent in the vulcanization system react to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of activating the accelerator in advance, so that the active intermediate can replace the role of zinc oxide. The product after reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires without containing zinc element, which can realize zinc-free emission and is friendly to the environment. At the same time, the masterbatch vulcanization aid prepared by the above preparation method can enable the rubber composition containing it to obtain a crosslinking density, hardness, modulus and hysteresis and other properties close to those of the zinc-containing rubber composition without containing zinc. DETAILED DESCRIPTION

[0029] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments.

[0030] As analyzed in the background art of the present application, the existing technology has the problem of environmental pollution caused by the presence of zinc in the tread rubber. The method in the prior art can only reduce the content of zinc in the rubber, but cannot completely avoid the environmental impact of zinc. It is difficult to meet the use requirements of the tread rubber without containing zinc element. In order to solve this problem, the present application provides a masterbatch vulcanization aid and its preparation method, rubber composition, rubber product and tire.

[0031] According to a typical embodiment of the present application, there is provided a preparation method of a masterbatch vulcanization aid, which comprises: step S1, pre-reacting stearic acid, an anti-aging agent and a vulcanization system to obtain a pre-reaction mixture; and step S2, mixing the pre-reaction mixture with rubber to obtain a masterbatch vulcanization aid.

[0032] In the above preparation method, under the catalysis of stearic acid, the anti-aging agent and the reagent in the vulcanization system react to generate an active intermediate, which has the effect of promoting vulcanization, plays the role of activating the accelerator in advance, so that the active intermediate can replace the role of zinc oxide, the product after reaction is mixed with rubber to form a masterbatch which can be used to prepare rubber products such as tires without containing zinc element, and zinc emission can be realized, which is friendly to the environment; at the same time, the masterbatch vulcanization aid prepared by the above preparation method can make the rubber composition containing the same obtain a crosslinking density close to that of the zinc-containing rubber composition without containing zinc, and the properties of the rubber compound such as hardness, modulus and hysteresis.

[0033] Taking the phenylenediamine type anti-aging agent and the 2-thiobenzothiazole type vulcanization system reagent as examples, the reaction occurring in the pre-reaction is shown in the following reaction equation, and the product has the effect of promoting the vulcanization reaction.

[0034]

[0035] In some embodiments of the present application, in order to promote the efficient progress of the pre-reaction, the reaction temperature of the pre-reaction is 100-190 °C, and the reaction time is 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, and the reaction time is 5 min-50 min.

[0036] In some typical embodiments of the present application, in order to uniformly disperse each component participating in the pre-reaction and improve the reaction speed and conversion rate, the above 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, which not only has good solubility for various components participating in the reaction, but also is conducive to promoting the progress of the pre-reaction.

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

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

[0039] The removal method of the solvent added in the pre-reaction process can be selected in the prior art, and the present application does not limit it, for example, the distillation method is used, and the removed solvent can be recycled and reused.

[0040] The antioxidants mentioned above can be selected from existing technologies. Preferably, the antioxidants are phenylenediamine antioxidants. More preferably, the antioxidants have the structure shown in Formula I. Antioxidants with this structure not only have high activity in the active intermediate formed after the pre-reaction with the vulcanization system, but also have low toxicity and are more environmentally friendly.

[0041] Formula I

[0042] 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, 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 has a value of 1, and at least one of y and z has a value of 1. Further, the above-mentioned vulcanization system includes any one or more of vulcanizing agents and accelerators. The vulcanizing agent includes any one or more of sulfur-based and sulfur-carrier-based agents, and the accelerator includes any one or more of sulfenamide-based and thiazole-based accelerators. Preferably, the accelerator includes any one or more of CZ, DCBS, MBTS, MBT, and TBBS.

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

[0044] In some embodiments of the present application, the above rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural gutta-percha, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and ethylene-propylene-diene rubber, which has better comprehensive performance.

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

[0046] Formula II

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

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

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

[0050] Further, the sum of the number of the alkenyl double bonds and the aromatic groups on the side groups and the branches of the rubber of Formula II is more than 15%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, or any range between any two of them, of the sum of the number of the alkenyl double bonds and the aromatic groups of the rubber. Those skilled in the art can understand that the structure of Formula II can only contain side groups or branches, and can only contain alkenyl double bonds or aromatic groups on the side groups or branches, and the number of the alkenyl double bonds or the aromatic groups on the side groups or branches is more than 15% of the sum of the number of all alkenyl double bonds and aromatic groups in the molecular structure of the rubber.

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

[0052] In some typical embodiments of the present application, in order to better exert the catalytic effect of stearic acid, the weight ratio of stearic acid to antioxidant is 1:1 to 1:1.25; preferably, the weight ratio of the vulcanizing system to the antioxidant is 0.8:1 to 1.15:1, and the generated product has higher activity. The proportion of the rubber in the masterbatch type vulcanizing aid is not particularly required, and in some embodiments of the present application, in order to facilitate subsequent use, the content of the rubber in the masterbatch type vulcanizing aid is 50 to 95 wt%.

[0053] The stearic acid used in step S1 can be selected in the prior art, and the present application does not have a particular requirement, which will not be described here.

[0054] According to another typical embodiment of the present application, a masterbatch type vulcanizing aid is provided, which is prepared by any one of the preparation methods described above.

[0055] In the masterbatch type vulcanizing aid prepared by the above method, the antioxidant reacts with the reagents in the vulcanizing system under the catalytic action of stearic acid to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of activating the accelerator in advance, so that the active intermediate can replace the role of zinc oxide. The product after reaction is mixed with rubber to form a masterbatch, which can be used to prepare rubber products such as tires that do not contain zinc elements at all, and can realize zinc-free emission and be friendly to the environment; at the same time, the masterbatch type vulcanizing aid can enable the rubber composition containing it to obtain a crosslinking density, hardness, modulus and hysteresis and other properties of the rubber compound close to those of the zinc-containing rubber composition without containing zinc.

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

[0057] The rubber composition of the present application, by using the master batch type vulcanization aid described above, can be used to prepare rubber products such as tires that are completely free of zinc elements, and can achieve zinc-free emissions and be environmentally friendly. At the same time, the master batch type vulcanization aid can enable the rubber composition containing it to achieve a crosslinking density, and rubber properties such as hardness, modulus, and hysteresis that are close to those of a zinc-containing rubber composition, without containing zinc.

[0058] The elastomer described above can be selected in the prior art, or selected in the same way as the rubber in the master batch type vulcanization aid, and the type of the rubber in the master batch type vulcanization aid can be the same or different.

[0059] The rubber composition of the present application is suitable for a wide range of fillers, and the filler can be selected in the prior art. As an example, 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, and more preferably 50-300 m 2 / g.

[0060] A person skilled in the art can select other additives with suitable functions according to the specific use environment and requirements of the rubber. Exemplarily, the 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 in the prior art, and the present application does not have special requirements, and will not be introduced one by one here.

[0061] In some embodiments of the present application, in order to better exert the synergistic effect of the components, the rubber composition described above comprises 30-100 parts by weight of an elastomer, 26-31 parts by weight of the master batch type vulcanization aid, 50-130 parts by weight of a filler, and 1.4-4.5 parts by weight of other additives.

[0062] According to another typical embodiment of the present application, a rubber product is provided, which is prepared from any one of the rubber compositions described above. By using the master batch type vulcanization aid described above, the rubber product can achieve zinc-free emissions and be environmentally friendly. At the same time, the rubber product, without containing zinc, achieves a crosslinking density, and rubber properties such as hardness, modulus, and hysteresis that are close to those of a zinc-containing rubber product.

[0063] The method for preparing the rubber product from the above rubber composition can be selected from the prior art, and the present application has no limitation in this regard. As an example, the following method can be used to prepare the rubber product from the above rubber composition: (a) mixing the elastomer, filler, zinc-free masterbatch type vulcanization aid, and other functional aids by kneading in one or more times, and the mixing temperature is 125 °C~200 °C to remove the gum, as a first-stage masterbatch; (b) performing one or more times of thermal mechanical kneading on the first-stage masterbatch, and keeping the kneading temperature at 125 °C~180 °C for 0~1200 s to remove the gum, as a second-stage masterbatch; if there is any remaining processing aid, filler, and antioxidant, they are all added at this stage in one or more times; (3) mixing the second-stage masterbatch with the vulcanization system in an internal mixer, and the mixing temperature is ≤120 °C to remove the gum, to obtain a final mixed rubber; (4) vulcanizing the final mixed rubber on a flat vulcanizing machine to obtain a vulcanized rubber.

[0064] According to a fifth typical embodiment of the present application, a tire is provided, which contains the above rubber product. By using the above masterbatch type vulcanization aid, the tire can achieve zinc-free emission, which is friendly to the environment; at the same time, the tire has excellent comprehensive performance without zinc.

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

[0066] Example 1

[0067] Mix 10 phr stearic acid, 10 phr antioxidant 4020, and 10 phr vulcanization accelerator TBBS in decane, and pre-react at 160 °C for 30 min; after removing the solvent from the reaction system, mix with 96.3 phr SSBR and 30 phr BR to obtain a zinc-free masterbatch type vulcanization aid;

[0068] Add SSBR and BR into an internal mixer, and knead; then add carbon black N234 and the above zinc-free masterbatch type vulcanization aid, and continue to knead until uniform mixing, and the temperature during kneading is controlled at 150-160 °C;

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

[0070] Vulcanize the obtained rubber composition to obtain a vulcanized rubber, and perform the physical property test of the rubber.

[0071] Comparative Example 1

[0072] Into the internal mixer, add SSBR and BR, knead for a period of time, then add carbon black N234, stearic acid, zinc oxide, antioxidant 4020, accelerator TBBS, continue to knead until uniform, the temperature during kneading is controlled at 150-160 °C;

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

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

[0075] Example 2

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

[0077] Into the internal mixer, add IR, knead, then add white carbon black, Si69, and the above zinc-free masterbatch type vulcanizing aid, continue to knead until uniform, the temperature during kneading is controlled at 150-160 °C;

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

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

[0080] Comparative Example 2

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

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

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

[0084] The above rubber formula is summarized in Table 1 as follows.

[0085] Table 1

[0086]

[0087] The sources and parameters of various raw materials used in each example and comparative example are as follows:

[0088] IR, Qingdao Yikesin New Material Co., Ltd.

[0089] White carbon black, NEWSIL 1165-MP, Wuxi Sure Chemical Silicon Co., Ltd., specific surface area 165 m 2 / g;

[0090] Carbon black, N234, Shandong Zhongxiao High Molecular Material Co., Ltd., specific surface area 119 m 2 / g;

[0091] Silane coupling agent Si69, Nanjing Shuguang Chemical Group Co., Ltd.

[0092] SSBR, Dushanzhi Petrochemical (styrene 25%, vinyl 64%);

[0093] SBR, Qilu Petrochemical ESBR1502 (styrene content 23.5%);

[0094] BR, Qilu Petrochemical BR9000 (nickel-based high-cis butadiene, cis content 97%);

[0095] NR, Xibianba Zhonghua Rubber Co., Ltd. SCR5;

[0096] Stearic acid, PF1808, Malaysia Licheng Co., Ltd.

[0097] Zinc oxide, Dalian Zinc Oxide Factory

[0098] Antioxidant 4020, Jiangsu Shengao Chemical Co., Ltd.

[0099] Antioxidant 4010NA, Shandong Shangshun Chemical Co., Ltd.

[0100] Antioxidant 7PPD, Jiangsu Shengao Chemical Co., Ltd.

[0101] Antioxidant A, self-synthesis,

[0102]

[0103] Antioxidant B, self-synthesis,

[0104]

[0105] Antioxidant C, self-synthesis,

[0106]

[0107] Antioxidant D, self-synthesis,

[0108]

[0109] Antioxidant E, self-synthesis,

[0110]

[0111] Antioxidant F, self-made,

[0112]

[0113] Accelerator CZ, Shandong Shangshun Chemical Co., Ltd.;

[0114] Accelerator TBBS, Shandong Shangshun Chemical Co., Ltd.;

[0115] Accelerator MBTS, Chaoyang Tm Chemical Co., Ltd.;

[0116] Accelerator DPG, Shandong Shunxian Chemical Co., Ltd.;

[0117] Sulfur, Jinsheng Chemical Co., Ltd.

[0118] The vulcanization characteristics of the rubber compounds prepared in the above examples and comparative examples were determined according to GB / T 16584-1996 Rubber-Determination of vulcanization characteristics by means of a moving die rheometer, and the test results are shown in Table 2.

[0119] The physical properties (tensile strength, elongation at break, 100% modulus, 300% modulus) of the rubber compounds prepared in the above examples and comparative examples were determined according to GB / T 528-2009 Vulcanized rubber or thermoplastic rubber-Determination of tensile stress-strain properties, and the results are shown in Table 2.

[0120] The hardness of the rubber compounds prepared in the above examples and comparative examples was determined according to GB / T 531.1-2008 Vulcanized rubber or thermoplastic rubber-Determination of indentation hardness-Part 1: Durometer method (Shore hardness), and the test results are shown in Table 2.

[0121] The modulus at 20°C of the rubber compounds was determined according to GB / T 9870.1-2006 Vulcanized rubber or thermoplastic rubber-Determination of dynamic properties-Part 1: General, and the tan δmax of the rubber compounds prepared in the above examples and comparative examples was determined using a rotational rheometer, and the test results are shown in Table 2.

[0122] In Table 2 and subsequent tables of physical property test results, in order to facilitate comparison, the test data of each example are expressed as index values based on the corresponding comparative example with the same composition except for zinc oxide, for example, in Table 1, the value of MH of Example 1 is the ratio of the measured value of Example 1 to the measured value of Comparative Example 1 x 100; the larger the value, the higher the index.

[0123] Table 2

[0124]

[0125] From the results of Table 2, it can be seen that the rubber compositions of the present application (Examples 1, 2) have crosslinking density, modulus, stress, hardness, mechanical properties, and hysteresis properties close to those of conventional zinc-containing compounds (Comparative Examples 1, 2, respectively), and can be used in rubber products and tires.

[0126] The preparation processes of zinc-free masterbatch type vulcanization aids 3-9 are the same as that of the zinc-free masterbatch type vulcanization aid of Example 1, except for the amounts of the specific components involved and the process parameters of pre-reaction. The amounts of the specific components involved in the zinc-free masterbatch type vulcanization aids 3-9 are shown in Table 3, and the process parameters are shown in Table 4.

[0127] Table 3

[0128]

[0129] Table 4

[0130]

[0131] Zinc-free masterbatch type vulcanization aids 10-14 were prepared, with the same formulation and preparation process as zinc-free masterbatch type vulcanization aid 6, except for the pre-reaction parameter conditions listed in Table 5.

[0132] Table 5

[0133]

[0134] The final compounds and vulcanized compounds of Examples 3-9 were prepared according to the same method as Example 1, and Comparative Examples 3-9 were prepared according to the same method as Comparative Example 1, with the formulations shown in Tables 6 and 7. Further, the compound formulations and preparation processes of Examples 10-14 were the same as those of Example 6, except that the zinc-free masterbatch type vulcanization aids in Examples 10-14 were zinc-free masterbatch type vulcanization aids 10-14, respectively, which are not listed.

[0135] Table 6

[0136]

[0137] Table 7

[0138]

[0139] Examples 3-9 and Comparative Examples 3-9 were tested according to the same test method as Example 1, and the results are shown in Tables 8 and 9.

[0140] Table 8

[0141]

[0142] Table 9

[0143]

[0144] As can be seen from Table 8 and Table 9, the rubber containing the zinc-free masterbatch type vulcanization aid prepared by the method of the application (Examples 3-9) and the conventional zinc-containing rubber (Comparative Examples 3-9, respectively) meet the requirements of the performance parameters of the rubber after vulcanization test, and can be applied to the production of rubber products and tires.

[0145] In addition, the vulcanized rubber of Examples 2, 3, 5, 7-9 above is aged and extracted, and the extract is detected by UPLC-HRMS / MS, and no quinone compound is detected, indicating that the environmentally friendly p-toluidine antioxidant A-F used in the application does not produce high-toxic quinone conversion products in the rubber residue, and is environmentally friendly.

[0146] Table 10

[0147]

[0148] From the above description, it can be seen that the above-mentioned examples of the application achieve the following technical effects: using the preparation method, the antioxidant and the reagent in the vulcanization system react under the catalysis of stearic acid to generate an active intermediate, which has the effect of promoting vulcanization and plays the role of activating the accelerator in advance, so that the active intermediate can replace the role of zinc oxide, and the product after reaction is mixed with rubber to form a masterbatch that can be used to prepare rubber products such as tires without containing zinc element, which can realize zinc-free emission and is environmentally friendly; at the same time, the masterbatch type vulcanization aid prepared by the above-mentioned preparation method can make the rubber composition containing it obtain a crosslinking density close to that of the zinc-containing rubber composition without containing zinc, and the rubber performance such as hardness, modulus and hysteresis.

[0149] The above only describes the preferred embodiments of the application and is not intended to limit the application. For those skilled in the art, the application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the application shall be included in the protection scope of the application.

Claims

1. A process for the preparation of a masterbatch curative aid, characterised in that, The preparation method comprises the following steps: S1, pre-reacting stearic acid, an antioxidant and a vulcanization system to obtain a pre-reaction mixture; wherein the weight ratio of the stearic acid to the antioxidant is 1:1-1:1.25; the weight ratio of the vulcanization system to the antioxidant is 0.8:1-1.15:1; S2, mixing the pre-reaction mixture with rubber to obtain the masterbatch type vulcanization aid; The pre-reaction is carried out at a temperature of 100-190°C for 1-120 minutes. The antioxidant is a phenylenediamine antioxidant, and the vulcanization system includes a promoter, and the promoter includes any one or more of CZ, DCBS, MBTS, MBT and TBBS.

2. The production method according to claim 1, characterized by, The pre-reaction is carried out at a temperature of 110-170°C for 5-50 minutes.

3. The preparation method according to claim 1, characterized in that, The pre-reaction is carried out in a solvent.

4. The production method according to claim 3, characterized by, The solvent is any one or more of butanol, octanol, N-methyl pyrrolidone, octane, nonane, decane, toluene and xylene.

5. The preparation method according to claim 1, characterized in that, The step S2 includes removing the solvent in the pre-reaction mixture and then mixing the pre-reaction mixture with the rubber to obtain the masterbatch type vulcanization aid; or The step S2 includes mixing the pre-reaction mixture containing the solvent with the rubber and then removing the solvent to obtain the masterbatch type vulcanization aid.

6. The preparation method according to any one of claims 1-3, wherein the antioxidant has the structure shown in formula I: The rubber is any one or more of natural rubber, styrene-butadiene rubber, isoprene rubber, natural gutta-percha, polyisoprene rubber, butadiene rubber, halogenated butyl rubber and ethylene-propylene-diene rubber. 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, 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.

7. The preparation method according to claim 5, characterized in that, The rubber is a rubber containing formula II:

8. The preparation method according to claim 7, characterized in that, wherein a, b, c, d, e and f are each independently integers greater than or equal to 0, and a, b, c, d, e and f are not all 0. Formula II Prepared by the preparation method of any one of claims 1-8.

9. A masterbatch curative aid characterized in that, The rubber composition comprises 30-100 parts of the elastomer, 26-31 parts of the masterbatch type vulcanization aid, 50-130 parts of the filler and 1.4-4.5 parts of the other auxiliary agent.

10. A rubber composition characterized in that, The filler includes any one or more of carbon-based filler, silicon-based filler, carbon-silicon dual-phase filler and clay.

11. The rubber composition according to claim 10, characterized in that, The other auxiliary agent includes any one or more of resin, operating oil, vulcanizing agent and silane coupling agent. The rubber composition comprises 30-100 parts of the elastomer, 26-31 parts of the masterbatch type vulcanization aid, 50-130 parts of the filler and 1.4-4.5 parts of the other auxiliary agent.

12. The rubber composition according to claim 11, characterized in that, The specific surface area of the filler is 10 to 500 m 2 / g.

13. The rubber composition of claim 11, wherein The specific surface area of the filler is 30 to 300 m 2 / g.

14. The rubber composition of claim 11, wherein The specific surface area of the filler is 50-300 m 2 / g.

15. The rubber composition of claim 10, wherein Prepared from the rubber composition of any one of claims 10-15.

16. A rubber article characterized in that, The rubber product of claim 16.

17. A tire characterized by ​

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