A high elasticity anti-oxidation rubber material and preparation method thereof

Abstract

The present invention relates to the technical field of rubber materials, and in particular to a high elasticity anti-oxidation rubber material and a preparation method thereof, comprising the following raw materials in mass percentage: 75-85% of rubber, 2-6% of softening oil, 2-6% of vulcanizing agent, 1-3% of vulcanization accelerator, 7-13% of auxiliary agent and 2-6% of reactive hindered amine light stabilizer. The high elasticity anti-oxidation rubber material of the present invention has excellent tensile strength and elasticity, and has good anti-aging and flame retardant properties. In addition, the high elasticity anti-oxidation rubber material of the present invention has good corrosion resistance, strong mutual solubility between the components, and can effectively prevent aging caused by physical precipitation.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials, and in particular to a high-elasticity anti-oxidation rubber material and a preparation method thereof. Background Art

[0002] Rubber is a common polymer material with high elasticity, deformation and water resistance, making it widely used in aerospace, medical, petrochemical, storage and textile fields. However, rubber becomes soft when heated, hard and brittle when cooled, difficult to shape, easy to wear, easily soluble in gasoline and other organic solvents, has double bonds in the molecule, is easy to undergo addition reactions, and is easy to age. Therefore, before the rubber is used, it needs to be vulcanized. Although vulcanization can enhance the physical and mechanical properties of rubber materials, rubber materials will still age faster and lose their material properties in the process of use due to the frequent load of external factors under long-term light or high friction intensity. For example, rubber is often used in the textile field, and fiber textiles made of it need to be washed and aired frequently, which will accelerate the aging of rubber and reduce the elasticity of fiber textiles or even make them unable to rebound.

[0003] Therefore, researchers have enhanced the anti-oxidation and anti-aging properties of rubber materials by adding various additives. For example, CN113308030A "Rubber textile wheel rubber and preparation method and application" synthesizes a rubber textile wheel rubber from natural rubber, nitrile rubber, nano zinc oxide, stearic acid, graphene and carbon nanotubes, fillers, coupling agents, plasticizers and vulcanization accelerators. The rubber textile wheel rubber has anti-static, low heat generation and wear resistance properties, which solves the problems of large wear and heat generation during use of textile wheels and non-static conductivity. However, this public document does not mention and solve the problem of poor anti-aging and oxidation properties of rubber materials.

[0004] Another example is CN116555978A "Electrospinning method for modified brominated butyl rubber fiber membrane" which obtains a brominated butyl rubber fiber membrane by stirring the prepared modified brominated butyl rubber ionomer in an organic solvent and then performing electrospinning, thereby solving the problems of brominated butyl rubber being difficult to spin, easy to stick and difficult to demold. However, this public document also fails to mention and solve the problem of poor anti-aging and oxidation properties of rubber materials.

[0005] Another example is CN111995837B "An anti-aging rubber material for shoe soles and preparation method thereof" uses SBS, PS, maleic anhydride grafted modified EVA, modified silica-alumina titanium dioxide, polypropylene fiber, petroleum resin and stearic acid as raw materials to make an anti-aging rubber material with good anti-aging and wear resistance. However, most rubbers are identified as flammable materials and pose safety hazards in daily use, especially in textiles.

[0006] Therefore, it is urgent to develop a rubber material for textiles that has high elasticity, anti-aging and good flame retardancy. Summary of the invention

[0007] The main purpose of the present invention is to provide a high elasticity anti-oxidation rubber material and a preparation method thereof, so as to solve the problems in the prior art that the hindered amine light stabilizer has a single use method in the material, poor applicability, single function and poor flame retardant performance.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] On the one hand, the present invention provides a high-elasticity anti-oxidation rubber material, comprising the following raw materials in mass percentage: 75-85% of rubber, 2-6% of softening oil, 2-6% of vulcanizing agent, 1-3% of vulcanization accelerator, 7-13% of auxiliary agent and 2-6% of reactive hindered amine light stabilizer.

[0010] In some embodiments, the structure of the reactive hindered amine light stabilizer is:

[0011]

[0012] Among them, R1 is R2 is R3 is ---represents the bonding position of the free radical.

[0013] Due to the presence of carbon-carbon double bonds, rubber materials have low dissociation energy and are easily broken under the action of heat, oxygen and light, causing material aging and irreversible damage. The present application adds a homemade reactive hindered amine light stabilizer, which will produce nitroxide free radicals under light conditions and can automatically capture the free radicals produced by the polymer in the material to generate corresponding esters and peroxide esters, etc. The generated esters and peroxide esters then combine with the free radicals in the polymer to regenerate nitroxide free radicals, and the cycle prevents material aging. In addition, the reactive hindered amine light stabilizer used in the present application also has flame retardant properties to prevent the rubber material from burning and causing danger.

[0014] In some embodiments, the method for preparing the reactive hindered amine light stabilizer comprises the following steps:

[0015] (1) adding N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, hexachloro-1,3,5,2,4,6-triazatriphosphine and sodium carbonate to water, heating and stirring to obtain compound A;

[0016] (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide is mixed with Zn(OTf)2 and Zn and added to toluene, and then 4A molecular sieve is added, and the compound A prepared in step (1) is added while stirring, and after the addition is completed, 1,3-propylene glycol is slowly added dropwise to the reaction solution, the dropping rate is controlled, and the mixture is stirred at room temperature to obtain compound B;

[0017] (3) Compound B prepared in step (2), N-methyl-5-hexen-1-amine and sodium carbonate are added to water, heated and stirred to obtain a reactive hindered amine light stabilizer.

[0018] Preferably, the preparation method of the reactive hindered amine light stabilizer comprises the following steps:

[0019] (1) 470.85 mmol of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 114.84 mmol of hexachloro-1,3,5,2,4,6-triazatriphosphine and 137.81 mmol of sodium carbonate were added to water 8 times the mass volume of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the temperature was raised to 80° C., and stirred for 2 h to obtain compound A;

[0020] (2) 257.32 mmol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide was mixed with 68.62 mmol Zn(OTf)2 and 240.16 mmol Zn and added to toluene 13 times the mass volume of compound A, and then 4A molecular sieves 5 times the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide were added, and 343 mmol compound A prepared in step (1) was added while stirring. After the addition was completed, the mixture was stirred at 35° C. for 7 h, and then 154.4 mmol 1,3-propylene glycol was slowly added dropwise to the reaction solution at a dropping rate of 2 mL / min and stirred at room temperature for 16 h to obtain compound B.

[0021] (3) 137.27 mmol of compound B prepared in step (2), 178.45 mmol of N-methyl-5-hexen-1-amine and 164.72 mmol of sodium carbonate were added to water 8 times the mass volume of compound B, the temperature was raised to 80° C., and stirred for 2 h to obtain a reactive hindered amine light stabilizer.

[0022] In some embodiments, the mass ratio of the reactive hindered amine light stabilizer to the vulcanizing agent is 1:(0.7-1.1).

[0023] Preferably, the mass ratio of the reactive hindered amine light stabilizer to the vulcanizing agent is 1:0.9.

[0024] Vulcanizing agents are often used in rubber materials and can cross-link with rubber to form a network structure. The network structure can improve the toughness, strength and elastic modulus of rubber materials. However, there are still many problems with vulcanizing agents. For example, they have certain toxicity and will produce a large amount of toxic gases when burned, polluting the environment. In addition, the dissociation energy of the vulcanization bond is lower, which is more likely to cause aging. The reactive hindered amine light stabilizer used in the present invention can cross-link with rubber to form a network structure, thereby reducing the amount of vulcanizing agent used. However, the reactive hindered amine light stabilizer is weakly alkaline and the vulcanizing agent is mostly acidic, which will make part of the reactive hindered amine light stabilizer in the system inactive. The present application controls the ratio of the reactive hindered amine light stabilizer to the vulcanizing agent, so that the reactive hindered amine light stabilizer can still play an anti-light aging role in a weakly acidic medium.

[0025] In some embodiments, the rubber is a vulcanizable petroleum rubber and / or a natural rubber.

[0026] Preferably, the rubber is polyisoprene rubber.

[0027] In some embodiments, the softening oil is one or more of fully refined paraffin, mineral oil, tall oil and vegetable oil.

[0028] Preferably, the softening oil is fully refined paraffin.

[0029] In some embodiments, the vulcanizing agent is sulfur and / or dicumyl peroxide.

[0030] Preferably, the vulcanizing agent is sulfur.

[0031] In some embodiments, the vulcanization accelerator is one or more of zinc dimethyldithiocarbamate, N-cyclohexyl-2-benzothiazole sulfenamide, and tetramethylthiuram disulfide.

[0032] Preferably, the vulcanization accelerator is tetramethylthiuram disulfide.

[0033] In some embodiments, the auxiliary agent includes the following components in mass percentage: 30-40% active agent, 3-10% coupling agent, 10-20% antioxidant, 7-13% dispersant and 25-35% plasticizer.

[0034] In some embodiments, the active agent is a mixture of stearic acid and zinc oxide, and the mass ratio is (0.8-1):1.

[0035] Preferably, the active agent is a mixture of stearic acid and zinc oxide, and the mass ratio is 0.9:1.

[0036] Zinc oxide can increase the vulcanization speed of rubber, improve the crosslinking degree between rubber and vulcanizing agent, and activate the vulcanization accelerator. In addition, zinc oxide can also improve the fluidity of rubber materials and reduce extrusion pressure. However, it is an inorganic raw material and has poor miscibility with rubber materials. Stearic acid can soften and plasticize rubber. At the same time, stearic acid can cooperate with zinc oxide to produce soluble salts that act in rubber materials to prevent zinc oxide from migrating and precipitating. The present application adjusts the mass ratio of stearic acid and zinc oxide to make zinc oxide more miscible with rubber materials.

[0037] In some embodiments, the coupling agent is a titanate coupling agent.

[0038] In some embodiments, the dispersant is one or more of fully refined paraffin wax, graphene, and sodium sulfate.

[0039] In some embodiments, the plasticizer is one or more of hydrogenated pine resin, dibutyl sebacate, and dioctyl phthalate.

[0040] In some embodiments, the antioxidant is one or more of 2-mercaptobenzimidazole, N-(4-anilinophenyl)maleimide, 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide.

[0041] In some embodiments, the antioxidant contains at least 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide, and the mass ratio of the two is 1:(0.1-0.5).

[0042] Preferably, the antioxidant contains at least 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide, and the mass ratio of the two is 1:0.3.

[0043] In some embodiments, the mass ratio of the active agent to the antioxidant is 1:(0.3-0.5).

[0044] Preferably, the mass ratio of the active agent to the antioxidant is 1:0.4.

[0045] The present application can reduce the precipitation phenomenon of rubber materials and enhance the anti-ultraviolet ability of rubber materials by adjusting the ratio of active agents to antioxidants. The titanium dioxide in the antioxidant has a large number of hydroxyl groups on its surface and has strong oleophobicity. It has poor mutual solubility in rubber materials and is easy to precipitate and discolor the rubber. Through the specific ratio of active agents and antioxidants, the stearic acid in the active agent and the titanium dioxide in the antioxidant can be modified to increase their mutual solubility and reduce the precipitation phenomenon of rubber materials.

[0046] Another aspect of the present invention provides a method for preparing a high elasticity anti-oxidation rubber material, comprising the following steps:

[0047] S1. Mixing and stirring the rubber, softening oil and additives at 130-150° C. for 15-25 minutes to obtain a mixture A;

[0048] S2. Add the mixture A in step S1, the vulcanizing agent and the vulcanization accelerator into an open mill for vulcanization, set the temperature to 60-80° C., and the vulcanization time to 0.5-1.5 hours. Then add a reactive hindered amine light stabilizer, and continue stirring for 0.5-1 hour to obtain a highly elastic and antioxidant rubber material.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) The reactive hindered amine light stabilizer of a specific structure used in the present invention can undergo a cross-linking reaction with the rubber under the action of a vulcanization accelerator, thereby enhancing the toughness and light aging resistance of the rubber.

[0051] (2) The present invention adopts a reactive hindered amine light stabilizer with a specific structure to avoid the problem of precipitation and migration when the reactive hindered amine light stabilizer is blended with rubber, thereby enhancing the mutual solubility of the system. In addition, it can also improve the flame retardant effect of the rubber and improve the safety performance of the rubber material.

[0052] (3) The present invention can improve the acid and alkali resistance of the rubber material by adjusting the ratio of the reactive hindered amine light stabilizer to the vulcanizing agent, and can also prevent the reactive hindered amine light stabilizer from being deactivated in an acidic medium.

[0053] (4) The present invention can improve the mutual solubility of inorganic materials in the rubber material by regulating the mass ratio of stearic acid and zinc oxide and regulating the ratio of the active agent to the antioxidant, thereby preventing precipitation from occurring during the use of the rubber and causing rubber aging. DETAILED DESCRIPTION

[0054] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0055] The structure of the reactive hindered amine light stabilizer used in each preparation example, embodiment and comparative example is:

[0056]

[0057] Among them, R1 is R2 is R3 is ---represents the bonding position of the free radical.

[0058] The preparation method of a reactive hindered amine light stabilizer comprises the following steps:

[0059] (1) 470.85 mmol of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 114.84 mmol of hexachloro-1,3,5,2,4,6-triazatriphosphine and 137.81 mmol of sodium carbonate were added to water 8 times the mass volume of N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, the temperature was raised to 80° C., and stirred for 2 h to obtain compound A;

[0060] (2) 257.32 mmol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide was mixed with 68.62 mmol Zn(OTf)2 and 240.16 mmol Zn and added to toluene 13 times the mass volume of compound A, and then 4A molecular sieves 5 times the mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide were added, and 343 mmol compound A prepared in step (1) was added while stirring. After the addition was completed, the mixture was stirred at 35° C. for 7 h, and then 154.4 mmol 1,3-propylene glycol was slowly added dropwise to the reaction solution at a dropping rate of 2 mL / min and stirred at room temperature for 16 h to obtain compound B.

[0061] (3) 137.27 mmol of compound B prepared in step (2), 178.45 mmol of N-methyl-5-hexen-1-amine and 164.72 mmol of sodium carbonate were added to water 8 times the mass volume of compound B, the temperature was raised to 80° C., and stirred for 2 h to obtain a reactive hindered amine light stabilizer.

[0062] The raw materials in the following examples and comparative examples are as follows:

[0063] The rubber is polyisoprene rubber; the softening oil is fully refined paraffin; the vulcanizing agent is sulfur; the vulcanization accelerator is tetramethylthiuram disulfide; the activator is a mixture of stearic acid and zinc oxide; the coupling agent is a titanate coupling agent; the antioxidant is a mixture of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide; the dispersant is fully refined paraffin; and the plasticizer is hydrogenated Songjiang resin.

[0064] Among them, polyisoprene rubber was purchased from Kraton Corporation in the United States, model IR0307; fully refined paraffin was purchased from Jinan Xinyue Chemical Co., Ltd.; titanate coupling agent was purchased from Nanjing Xuanhao New Material Technology Co., Ltd., model NXH-401; fully refined paraffin was purchased from Jinan Zhuocai Chemical Co., Ltd.; hydrogenated Songjiang resin was purchased from Shangrao Sinan Resin Co., Ltd.

[0065] Example 1

[0066] A high-elasticity anti-oxidation rubber material comprises the following raw materials in percentage by mass: 70% of rubber, 6% of softening oil, 2.1% of vulcanizing agent, 3% of vulcanization accelerator, 9.9% of auxiliary agent and 4% of reactive hindered amine light stabilizer.

[0067] The auxiliary agents include 35 wt% of active agent, 7 wt% of coupling agent, 14 wt% of antioxidant, 12 wt% of dispersant and 32 wt% of plasticizer.

[0068] The antioxidant includes 77.9 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 23.1 wt % of titanium dioxide.

[0069] The active agents included 47 wt% stearic acid and 53 wt% zinc oxide.

[0070] This embodiment provides a method for preparing a high elasticity anti-oxidation rubber material, comprising the following steps:

[0071] S1. Mixing and stirring the rubber, softening oil and additives at 140° C. for 20 minutes to obtain a mixture A;

[0072] S2. Add the mixture A in step S1, the vulcanizing agent and the vulcanization accelerator into an open mill for vulcanization. Set the temperature to 70° C. and the vulcanization time to 1 hour. Then add the reactive hindered amine light stabilizer and continue stirring for 0.8 hours to obtain a highly elastic and antioxidant rubber material.

[0073] Example 2

[0074] A high-elasticity anti-oxidation rubber material comprises the following raw materials in percentage by mass: 75% of rubber, 6% of softening oil, 2.1% of vulcanizing agent, 3% of vulcanization accelerator, 9.9% of auxiliary agent and 4% of reactive hindered amine light stabilizer.

[0075] The auxiliary agents include 40 wt% of active agent, 7 wt% of coupling agent, 20 wt% of antioxidant, 8 wt% of dispersant and 25 wt% of plasticizer.

[0076] The antioxidant includes 91 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 9 wt % of titanium dioxide.

[0077] The active agent includes 50 wt% stearic acid and 50 wt% zinc oxide.

[0078] This embodiment provides a method for preparing a high elasticity anti-oxidation rubber material, comprising the following steps:

[0079] S1. Mixing and stirring the rubber, softening oil and additive at 130° C. for 15 minutes to obtain a mixture A;

[0080] S2. Add the mixture A in step S1, the vulcanizing agent and the vulcanization accelerator into an open mill for vulcanization. Set the temperature to 60° C. and the vulcanization time to 0.5 hour. Then add the reactive hindered amine light stabilizer and continue stirring for 0.5 hour to obtain a highly elastic and antioxidant rubber material.

[0081] Example 3

[0082] A high-elasticity anti-oxidation rubber material comprises the following raw materials in percentage by mass: 85% of rubber, 4.36% of softening oil, 0.7% of vulcanizing agent, 1% of vulcanization accelerator, 7% of auxiliary agent and 2% of reactive hindered amine light stabilizer.

[0083] The auxiliary agents include 40 wt% of active agent, 7 wt% of coupling agent, 12 wt% of antioxidant, 13 wt% of dispersant and 28 wt% of plasticizer.

[0084] The antioxidant includes 71 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 29 wt % of titanium dioxide.

[0085] The active agents included 46 wt% stearic acid and 54 wt% zinc oxide.

[0086] This embodiment provides a method for preparing a high elasticity anti-oxidation rubber material, comprising the following steps:

[0087] S1. Mixing and stirring the rubber, softening oil and additive at 150° C. for 25 minutes to obtain a mixture A;

[0088] S2. Add the mixture A in step S1, the vulcanizing agent and the vulcanization accelerator into an open mill for vulcanization. Set the temperature to 80° C. and the vulcanization time to 1.5 hours. Then add a reactive hindered amine light stabilizer and continue stirring for 1 hour to obtain a highly elastic and antioxidant rubber material.

[0089] Example 4

[0090] A high-elasticity anti-oxidation rubber material comprises the following raw materials in percentage by mass: 75% of rubber, 2% of softening oil, 2% of vulcanizing agent, 2% of vulcanization accelerator, 13% of auxiliary agent and 6% of reactive hindered amine light stabilizer.

[0091] The auxiliary agents include 30 wt% of active agent, 7 wt% of coupling agent, 15 wt% of antioxidant, 13 wt% of dispersant and 35 wt% of plasticizer.

[0092] The antioxidant includes 83 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 17 wt % of titanium dioxide.

[0093] The active agents included 46 wt% stearic acid and 54 wt% zinc oxide.

[0094] The preparation method of a high elasticity anti-oxidation rubber material in this embodiment is the same as that in embodiment 1.

[0095] Example 5

[0096] A high-elasticity anti-oxidation rubber material comprises the following raw materials in percentage by mass: 78.7% of rubber, 6% of softening oil, 3.3% of vulcanizing agent, 3% of vulcanization accelerator, 7% of auxiliary agent and 2% of reactive hindered amine light stabilizer.

[0097] The auxiliary agents include 39 wt% of active agent, 3 wt% of coupling agent, 19.5 wt% of antioxidant, 13 wt% of dispersant and 25.5 wt% of plasticizer.

[0098] The antioxidant includes 77.9 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 23.1 wt % of titanium dioxide.

[0099] The active agents included 47 wt% stearic acid and 53 wt% zinc oxide.

[0100] The preparation method of a high elasticity anti-oxidation rubber material in this embodiment is the same as that in embodiment 1.

[0101] Example 6

[0102] This embodiment provides a rubber material, and the specific implementation manner is the same as that of Embodiment 1, except that the activator includes 33 wt % of stearic acid and 67 wt % of zinc oxide.

[0103] Example 7

[0104] This embodiment provides a rubber material, and the specific implementation manner is the same as that of Embodiment 1, except that the activator includes 57 wt % of stearic acid and 43 wt % of zinc oxide.

[0105] Example 8

[0106] This embodiment provides a rubber material, and the specific implementation is the same as that of Embodiment 1, except that the antioxidant includes 53 wt % of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 47 wt % of titanium dioxide.

[0107] Example 9

[0108] This embodiment provides a rubber material, and the specific implementation method is the same as that of Example 1, except that the additives include 32wt% of an active agent, 3wt% of a coupling agent, 28.8wt% of an antioxidant, 11.2wt% of a dispersant and 25wt% of a plasticizer.

[0109] Example 10

[0110] This embodiment provides a rubber material, and the specific implementation manner is the same as that of Embodiment 1, except that a method for preparing the rubber material of this embodiment includes the following steps:

[0111] S1. Mixing and stirring the rubber, softening oil and additives at 140° C. for 20 minutes to obtain a mixture A;

[0112] S2. Add the mixture A in step S1, the vulcanizing agent, the vulcanization accelerator and the reactive hindered amine light stabilizer into an open mill for vulcanization. Set the temperature to 70° C. and the vulcanization time to 1 hour to obtain the rubber material.

[0113] Embodiment 11

[0114] This comparative example provides a rubber material, and the specific implementation method is the same as that of Example 1, except that it includes the following raw materials in mass percentage: 80% rubber, 6% softening oil, 3% vulcanizing agent, 2% vulcanization accelerator, 7% auxiliary agent and 2% reactive hindered amine light stabilizer.

[0115] Performance Test:

[0116] The embodiments and comparative examples were compared with commercially available vulcanized rubber:

[0117] (1) Tensile strength test: Tested according to GB / T528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber" standard;

[0118] (2) Anti-aging performance test: The rubber materials prepared in each embodiment and comparative example were placed in a xenon lamp aging test chamber for aging test, and then subjected to tensile strength test after aging for 500 hours;

[0119] (3) Corrosion resistance test: Place the rubber material in a 5% mass concentration sodium hydroxide solution for 24 hours, observe whether its surface is cracked or sticky, and then perform a tensile strength test;

[0120] (4) Precipitation test: Precipitation test is performed by observing the surface morphology. The presence of fogging, discoloration, and bubbles is considered precipitation.

[0121] The test results are shown in Table 1.

[0122] Table 1

[0123]

[0124]

[0125] It can be seen from Table 1 that the high elasticity and antioxidant rubber materials prepared in Examples 1 to 5 have a high initial tensile strength, good anti-aging performance and corrosion resistance, and strong mutual solubility between the components; in Example 6, due to the change in the ratio of stearic acid and zinc oxide, the mutual solubility of zinc oxide in the system becomes poor, and the tensile strength of the rubber material decreases; in Example 7, due to the change in the ratio of stearic acid and zinc oxide, the aging resistance of the rubber material is slightly reduced due to the reduction of zinc oxide components; in Example 8, due to the change in the ratio of 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide, the mutual solubility of titanium dioxide and the rubber system is poor, resulting in precipitation; in Example 9, due to the change in the ratio of antioxidant to activator, on the one hand, the activator cannot promote vulcanization and reduce the crosslinking degree of the rubber In addition, the stearic acid content in the active agent is reduced, and it is not possible to effectively modify the inorganic oxide to enhance its mutual solubility, resulting in precipitation; Example 10 Since the reactive hindered amine light stabilizer and the vulcanizing agent are added simultaneously for vulcanization during the preparation process, a part of the reactive hindered amine light stabilizer reacts with the vulcanizing agent and is inactivated, resulting in a reduction in the content of the vulcanizing agent, a decrease in the crosslinking degree of the rubber, a decrease in the initial tensile strength, and the inactivation of the reactive hindered amine light stabilizer leads to a decrease in the anti-aging performance of the rubber material, and cracking and sticking phenomena; Example 11 Since the ratio of the reactive hindered amine light stabilizer to the vulcanizing agent is changed, the content of the reactive hindered amine light stabilizer is reduced, resulting in a decrease in the anti-aging performance of the rubber material, and in addition, the acidity of the rubber system is enhanced, and cracking and sticking phenomena occur in the corrosion resistance test. The test results show that the high elasticity and antioxidant rubber material prepared by the present invention has a higher initial tensile strength, indicating that the rubber material of the present invention has good elasticity. In addition, the rubber material has good antioxidant and corrosion resistance, and the components have high mutual solubility and are not easy to precipitate and age.

[0126] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.

Claims

1. A highly elastic and anti-oxidation rubber material, characterized in that: The raw materials include the following mass percentages: 75-85% rubber, 2-6% softening oil, 2-6% vulcanizing agent, 1-3% vulcanization accelerator, 7-13% auxiliary agent and 2-6% reactive hindered amine light stabilizer. The structure of the reactive hindered amine light stabilizer is: ； Among them, R1 is , R2 is , R3 is , Represents the bonding position of the free radical; The mass ratio of the reactive hindered amine light stabilizer to the vulcanizing agent is 1:(0.7-1.1); The auxiliary agent includes the following components by mass percentage: 30-40% active agent, 3-10% coupling agent, 10-20% antioxidant, 7-13% dispersant and 25-35% plasticizer; The active agent is a mixture of stearic acid and zinc oxide, and the mass ratio is (0.8-1):1; The antioxidant contains at least 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and titanium dioxide, and the mass ratio of the two is 1:(0.1-0.5); The mass ratio of the active agent to the antioxidant is 1:(0.3-0.5); The method for preparing the highly elastic and anti-oxidation rubber material comprises the following steps: S1. Mix and stir the rubber, softening oil and additives at 130-150° C. for 15-25 minutes to obtain a mixture A; S2. Add the mixture A in step S1, the vulcanizing agent and the vulcanization accelerator into an open mill for vulcanization, set the temperature to 60-80° C., and the vulcanization time to 0.5-1.5 hours, then add the reactive hindered amine light stabilizer, and continue stirring for 0.5-1 hour to obtain a highly elastic antioxidant rubber material.

2. A high elasticity anti-oxidation rubber material according to claim 1, characterized in that: The preparation method of the reactive hindered amine light stabilizer comprises the following steps: (1) Add N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, hexachloro-1,3,5,2,4,6-triazatriphosphine and sodium carbonate to water, heat and stir to obtain compound A; (2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ethanol 10-oxide is mixed with Zn(OTf)2 and Zn and added to toluene, and then 4A molecular sieve is added, and the compound A prepared in step (1) is added while stirring. After the addition is completed, 1,3-propylene glycol is slowly added dropwise to the reaction solution, and the dropping rate is controlled and stirred at room temperature to obtain compound B; (3) Compound B prepared in step (2), N-methyl-5-hexen-1-amine and sodium carbonate are added to water, heated and stirred to obtain a reactive hindered amine light stabilizer.

3. The high elasticity and oxidation resistant rubber material according to claim 1, characterized in that: The rubber is petroleum rubber and / or natural rubber that can undergo vulcanization.

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