CN115536914B - Composite anti-aging agent, preparation method thereof and heat-resistant rubber material - Google Patents
Composite anti-aging agent, preparation method thereof and heat-resistant rubber material Download PDFInfo
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Abstract
The invention provides a composite anti-aging agent, a preparation method thereof and a heat-resistant rubber material, and belongs to the technical field of anti-aging agents. According to the invention, the anti-aging agent is loaded in the pores of the silica aerogel by utilizing the characteristics of high porosity and strong adsorption capacity of the silica aerogel, and can be slowly released from the pores of the silica aerogel after being compounded with rubber, so that the phenomenon of migration and frosting does not occur, the consumption of the anti-aging agent in the rubber can be further improved, and the anti-aging capacity of the rubber is improved. In addition, the anti-aging agent is loaded into the pores of the silica aerogel, the obtained composite anti-aging agent has anti-aging and reinforcing functions, and meanwhile, the silane coupling agent is coated on the surface of the silica aerogel, so that the dispersibility of the silica aerogel in rubber can be improved.
Description
Technical Field
The invention belongs to the technical field of anti-aging agents, and particularly relates to a composite anti-aging agent, a preparation method thereof and a heat-resistant rubber material.
Background
Rubber materials are regarded as an important strategic material as a renewable resource, have excellent comprehensive performance and are widely applied to civil and military fields. In recent years, rubber products are increasingly widely used, the variety is more and more, the requirements on the rubber performance are higher and more, but the rubber is easy to age in the production, transportation, storage and use processes of the rubber, and the performance of the rubber is seriously affected.
Rubber aging is caused by active chemicals such as high temperature, oxygen, oil, acid, alkali, etc. This process results in deterioration of the chemical and mechanical properties of the rubber, which reduces its elasticity, hardness and mechanical properties. Among them, the thermo-oxidative aging is the most common type of rubber aging, and it is necessary to add an anti-aging agent, which prolongs the life of the product by combining with oxygen/ozone. However, the addition of a large amount of an anti-aging agent to rubber often causes the anti-aging agent to spread to the surface of a rubber product, and this phenomenon is called "blooming" which causes micro defects on the surface of rubber, loss of anti-aging protection function and environmental pollution. Because of these problems, only about 1wt% of an anti-aging agent can be added to the rubber formulation, which is insufficient to cause "blooming", but which provides very limited anti-aging capability. Therefore, how to increase the usage amount of the anti-aging agent without causing "frosting" so as to improve the anti-aging capability becomes a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a composite anti-aging agent, a preparation method thereof and a heat-resistant rubber material.
The invention provides a composite anti-aging agent which comprises silicon dioxide aerogel and an anti-aging agent loaded in the pores of the silicon dioxide aerogel, wherein the mass of the anti-aging agent is 10-20% of that of the silicon dioxide aerogel.
Preferably, the silica aerogel further comprises a silane coupling agent coated on the surface of the silica aerogel.
Preferably, the mass of the silane coupling agent is less than 5% of the mass of the silica aerogel.
Preferably, the silane coupling agent includes one or more of 3- (2, 3 glycidoxy) propyltrimethoxysilane, 3- (2, 3 glycidoxy) propyltriethoxysilane, 3- (2, 3 glycidoxy) propylmethyldiethoxysilane, 3- (3, 4 epoxycyclohexenyl) trimethoxysilane, 3-aminopropyl triethoxysilane, and bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide.
Preferably, the anti-aging agent includes at least one of anti-aging agent 4010NA, anti-aging agent RD, anti-aging agent 445, and anti-aging agent MB.
The invention also provides a preparation method of the composite anti-aging agent, which comprises the following steps:
and mixing the silicon dioxide aerogel and the anti-aging agent solution, and then carrying out cyclic loading under the negative pressure and normal pressure conditions in sequence to obtain the composite anti-aging agent.
Preferably, when the composite anti-aging agent further comprises a silane coupling agent coated on the surface of the silica aerogel, the composite anti-aging agent further comprises the step of adding the silane coupling agent to the obtained load after the loading is completed.
Preferably, the negative pressure is-0.05 to-0.08 MPa, and the number of circulating loads is 3 to 5.
Preferably, the single negative pressure is maintained for 20-30 min, and the single normal pressure is maintained for 10-20 min
The invention also provides a heat-resistant rubber material which is prepared from the following raw materials in parts by weight: 100 parts of rubber matrix, 4-12 parts of compatibilizer, 4-8 parts of activator, 5-15 parts of operating oil, 20-40 parts of composite anti-aging agent, 2-6 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator and 15-45 parts of reinforcing agent; the composite anti-aging agent is the composite anti-aging agent according to the scheme or the composite anti-aging agent prepared by the preparation method according to the scheme.
The invention provides a composite anti-aging agent which comprises silicon dioxide aerogel and an anti-aging agent loaded in pores of the silicon dioxide aerogel, wherein the mass of the anti-aging agent is 10-20% of that of the silicon dioxide aerogel. According to the invention, the composite anti-aging agent loaded on the silica aerogel is prepared by utilizing the characteristics of high porosity and strong adsorption capacity of the silica aerogel, and after the composite anti-aging agent is compounded with rubber, the loaded anti-aging agent can be slowly released from the pores of the silica aerogel without a frosting phenomenon that a large amount of anti-aging agent is quickly removed, so that the use amount of the anti-aging agent in the rubber can be increased, the anti-aging capacity of the rubber is improved, and the mechanical property of the rubber is not influenced.
In addition, the anti-aging agent is loaded into the pores of the silica aerogel, and the obtained composite anti-aging agent has the functions of anti-aging and reinforcement.
Furthermore, the silane coupling agent is coated on the surface of the silicon dioxide aerogel, so that the dispersibility of the silicon dioxide aerogel in rubber can be improved, and the rubber material prepared by using the composite anti-aging agent has good mechanical property and aging resistance.
The results of the examples show that the tensile strength of the heat-resistant rubber material prepared by adding the composite anti-aging agent into rubber is 8.89-14.94 MPa, the elongation at break is 469.26-623.24%, and the hardness is 48-53A; after aging for 48 hours at 160 ℃, the tensile strength is 8.33-9.32 MPa, the elongation at break is 168.35-613.29%, and the hardness is 51-63A; after aging for 96 hours at 160 ℃, the tensile strength is 5.68-8.32 MPa, the elongation at break is 43.34-536.34%, and the hardness is 54-69A; the tensile strength is 3.67-8.05 MPa after aging for 120h at 160 ℃, the elongation at break is 40.34-396.68%, and the hardness is 60-72A.
Drawings
FIG. 1 is an infrared spectrum of a composite antioxidant, silica aerogel and an antioxidant 4010NA prepared in example 1;
fig. 2 is a thermal weight loss curve of the composite antioxidant, silica aerogel, and antioxidant 4010NA prepared in examples 1 to 4.
Detailed Description
The invention provides a composite anti-aging agent which comprises silicon dioxide aerogel and an anti-aging agent loaded in pores of the silicon dioxide aerogel, wherein the mass of the anti-aging agent is 10-20% of that of the silicon dioxide aerogel.
In the present invention, the particle diameter of the silica aerogel is preferably 20 μm or less; the specific surface area of the silica aerogel is preferably > 1500m 2 /g; the porosity of the silica aerogel is preferably 2-10 cm 3 Preferably 4 to 8cm 3 Preferably 5 to 6cm 3 /g。
In the present invention, the antioxidant is preferably one or more of an antioxidant 4010NA, an antioxidant RD, an antioxidant 445, and an antioxidant MB, and more preferably an antioxidant 4010NA.
In the present invention, the mass of the antioxidant is preferably 18 to 19% of the mass of the silica aerogel.
In the present invention, the composite anti-aging agent preferably further comprises a silane coupling agent coated on the surface of the silica aerogel. The mass of the silane coupling agent is preferably 5% or less, more preferably 3 to 4% by mass of the silica aerogel.
In the present invention, the silane coupling agent preferably includes one or more of 3- (2, 3-glycidoxypropyl) propyltrimethoxysilane, 3- (2, 3-glycidoxypropyl) propyltriethoxysilane, 3- (2, 3-glycidoxypropyl) propylmethyldiethoxysilane, 3- (3, 4-epoxycyclohexenyl) trimethoxysilane, 3-aminopropyl triethoxysilane, and bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, more preferably bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide. In the invention, the silane coupling agent can improve the dispersibility of the composite anti-aging agent in rubber.
According to the invention, the silica aerogel with larger pore volume and stronger physical adsorption capacity is selected as an anti-aging agent carrier, and the method has the characteristics of large loading capacity, 16% loading efficiency, difficult desorption after adsorption and the like; the composite anti-aging agent provided by the invention can be added into rubber compound in a large amount to obviously improve the anti-aging effect of rubber, and meanwhile, the quality of the rubber is not affected by frosting caused by the free of a large amount of anti-aging agents; when the surface of the composite anti-aging agent is coated with the silane coupling agent, the composite anti-aging agent has more uniform dispersibility in the rubber material, has a good reinforcing function on the rubber material, and can obviously improve the mechanical property and the thermo-oxidative aging resistance of the rubber material.
The invention also provides a preparation method of the composite anti-aging agent, which comprises the following steps:
and mixing the silicon dioxide aerogel and the anti-aging agent solution, and then carrying out cyclic loading under the negative pressure and normal pressure conditions in sequence to obtain the composite anti-aging agent.
In the present invention, the preparation of the antioxidant solution preferably includes: and mixing the anti-aging agent with an organic solvent to obtain an anti-aging agent solution. In the present invention, the organic solvent is preferably at least one of dichloromethane, acetone and ethanol, more preferably ethanol. The invention is not particularly limited to such mixing, and may be carried out using protocols well known to those skilled in the art. In the present invention, the mass concentration of the antioxidant solution is preferably 0.1 to 5%, more preferably 0.5 to 3%, and even more preferably 0.8 to 2%.
In the present invention, the mass of the antioxidant in the antioxidant solution is preferably 6 to 20 parts, more preferably 8 to 16 parts, based on 100 parts by mass of the silica aerogel.
In the present invention, the mixing of the silica aerogel with the anti-aging agent solution is preferably performed under ultrasonic conditions; the time of the ultrasonic treatment is preferably 25-35 min, more preferably 28-30 min; the frequency of the ultrasound is preferably 40 to 100kHz, more preferably 40 to 50kHz. According to the invention, the silica aerogel and the anti-aging agent solution are mixed under the ultrasonic condition, so that the dispersion performance of the silica aerogel in the anti-aging agent solution can be improved, and the subsequent loading is facilitated.
In the present invention, the negative pressure is preferably-0.5 to-0.8 MPa, more preferably-0.6 to-0.7 MPa; the holding time of the negative pressure is preferably 20 to 30 minutes, more preferably 20 to 25 minutes; the holding time of the normal pressure is preferably 10 to 20 minutes, more preferably 10 to 15 minutes; the number of the cycles is preferably 3 to 5, more preferably 3 to 4. The invention repeatedly loads under the conditions of negative pressure and normal pressure, the negative pressure can remove air in the silica aerogel, the normal pressure can be recovered, and the anti-aging agent solution is pressed into the micro holes of the aerogel under the action of the atmospheric pressure, so that the loading of the anti-aging agent is realized.
After loading is completed, the product obtained by loading is preferably separated and dried in sequence to obtain the composite anti-aging agent.
In the present invention, the separation is preferably filtration or centrifugation. The drying operation is not particularly limited in the present invention, and a drying operation well known to those skilled in the art may be employed.
In the present invention, when the composite anti-aging agent further comprises a silane coupling agent coated on the surface of the silica aerogel, the present invention preferably adds a silane coupling agent to the resultant load after the completion of the loading, more preferably adds a silane coupling agent after the completion of the drying, to obtain the composite anti-aging agent. In the present invention, the addition amount of the silane coupling agent is preferably determined according to the content of the silane coupling agent in the composite anti-aging agent. In the present invention, the silane coupling agent is preferably added under stirring; the stirring is preferably: stirring at a rotation speed of 50-100 r/min for 15-30 min, and stirring at a rotation speed of 1000-2000 r/min for 15-30 min. In the invention, the silane coupling agent is preferably added in a dropwise manner; the dropping rate is preferably 1-10 mL/min.
The preparation method provided by the invention is simple and is convenient for industrialized popularization.
According to the invention, an anti-aging agent solution is adsorbed into the pores of the silica aerogel by utilizing a vacuum adsorption principle, and a silane coupling agent is wrapped on the surface of the silica aerogel after drying, so that the functional silica aerogel of the vacuum adsorption anti-aging agent is obtained; according to the invention, the silica aerogel loaded with the anti-aging agent is compounded with the rubber matrix, and the anti-aging agent is slowly released from the holes of the silica aerogel, so that the purposes of increasing the use amount of the anti-aging agent and not causing frosting are achieved, and meanwhile, the dispersibility of the silica aerogel in rubber is improved due to hybridization of the silane coupling agent.
The invention also provides a heat-resistant rubber material which is prepared from the following raw materials in parts by weight: 100 parts of rubber matrix, 4-12 parts of compatibilizer, 4-8 parts of activator, 5-15 parts of operating oil, 20-40 parts of composite anti-aging agent, 2-6 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator and 15-45 parts of reinforcing agent;
the composite anti-aging agent is the composite anti-aging agent according to the scheme or the composite anti-aging agent prepared by the preparation method according to the scheme.
The preparation raw materials of the heat-resistant rubber material comprise 100 parts of rubber matrix. In the invention, the rubber matrix is preferably ethylene propylene diene monomer rubber and styrene butadiene rubber; the mass ratio of the ethylene propylene diene monomer rubber to the styrene-butadiene rubber is preferably 30: 70-50: 50; the content of ethylidene norbornene in the ethylene propylene diene monomer is preferably 5.0wt%; the Mooney viscosity of the ethylene propylene diene monomer at 125 ℃ is preferably 45; the styrene-butadiene rubber is preferably emulsion styrene-butadiene rubber, more preferably SBR1502.
The raw materials for preparing the heat-resistant rubber material comprise 4-12 parts of compatibilizer, preferably 6-10 parts, and more preferably 8 parts by mass of rubber matrix. In the present invention, the compatibilizer is preferably at least one of EVM, SEPS, SBS and SIBS, more preferably EVM.
The preparation raw materials of the heat-resistant rubber material also comprise 4-8 parts of an activating agent, preferably 5-6 parts, based on the mass parts of the rubber matrix. In the present invention, the activator is preferably a mixture of stearic acid and zinc oxide or a mixture of zinc stearate and zinc oxide; the mass ratio of the stearic acid to the zinc oxide is preferably 1:3 to 5; the mass ratio of the zinc stearate to the zinc oxide is preferably 1:1 to 2. In the present invention, the activator is capable of promoting the progress of the vulcanization reaction.
The preparation raw materials of the heat-resistant rubber material comprise 5-15 parts of operating oil, preferably 5-10 parts, and more preferably 6-8 parts by mass of rubber matrix. In the present invention, the operation oil is preferably at least one of aromatic hydrocarbon oil, naphthenic oil, paraffinic oil and high-temperature heat transfer oil, more preferably paraffinic oil 2280 and N4016 naphthenic oil; the mass ratio of the paraffinic oil 2280 to the N4016 naphthenic oil is preferably 1-2: 1.
the raw materials for preparing the heat-resistant rubber material comprise 20-40 parts of composite anti-aging agent, preferably 25-30 parts, based on the mass parts of the rubber matrix. In the invention, the composite anti-aging agent can be added in a large amount without causing frosting, thereby improving the heat resistance and mechanical property of the material.
The raw materials for preparing the heat-resistant rubber material comprise 2-6 parts, preferably 3-5 parts, of vulcanizing agent based on the mass parts of the rubber matrix. In the present invention, the vulcanizing agent is preferably sulfur and peroxide; the peroxide is preferably at least one of benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide (bis-di-tetra), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (bis-di-penta) and triallyl isocyanurate, more preferably dicumyl peroxide and triallyl isocyanurate; the mass ratio of the sulfur to the peroxide is preferably (1-2): 1, a step of; the mass ratio of the dicumyl peroxide to the triallyl isocyanurate is preferably 1:1.
the raw materials for preparing the heat-resistant rubber material comprise 1-3 parts of vulcanization accelerator, preferably 1-2 parts of vulcanization accelerator based on the mass parts of the rubber matrix. In the present invention, the vulcanization accelerator is preferably at least one of benzothiazole disulfide, zinc diethyldithiocarbamate, N-cyclohexyl-2-benzothiazole sulfenamide, N- (diethyleneglycol) -2-benzothiazole sulfenamide, zinc dibutyldithiocarbamate, and zinc diethyldithiocarbamate. In the present invention, the vulcanization accelerator is capable of accelerating vulcanization of rubber.
The raw materials for preparing the heat-resistant rubber material comprise 15-45 parts of reinforcing agent, more preferably 20-40 parts of reinforcing agent by taking the mass parts of the rubber matrix as the reference. The reinforcing agent preferably comprises high reinforcing carbon black N330 and/or white carbon black. In the invention, the reinforcing agent has a reinforcing effect, and can improve the mechanical property of the material.
In the present invention, the method for producing a heat-resistant rubber material preferably comprises the steps of:
mixing a rubber matrix, a compatibilizer, an activator, operating oil, a composite anti-aging agent, a vulcanizing agent, a vulcanization accelerator and a reinforcing agent to obtain a mixed rubber;
and vulcanizing the rubber compound to obtain the heat-resistant rubber material.
In the invention, rubber, a compatibilizer, an activator, operating oil, a composite anti-aging agent, a vulcanizing agent, a vulcanization accelerator and a reinforcing agent are preferably mixed to obtain a mixed rubber.
In the present invention, kneading the rubber, the compatibilizer, the activator, the process oil, the composite antioxidant, the vulcanizing agent, the vulcanization accelerator and the reinforcing agent preferably comprises: and (3) carrying out first mixing on the rubber matrix, adding a compatibilizer to carry out second mixing, adding an activating agent to carry out third mixing, then adding a composite anti-aging agent, a reinforcing agent and operating oil to carry out fourth mixing, and finally adding a vulcanizing agent and a vulcanization accelerator to carry out fifth mixing.
In the present invention, the kneading is preferably performed in a two-roll mill; the roll gap of the double-roll open mill is preferably 0.5-1.2 mm; the temperature of the kneading is preferably 60 to 70 ℃.
In the present invention, the first kneading is preferably a roll-in-roll and a thin-pass which are sequentially performed; the rotating speed of the wrapping roller is preferably 15-20 r/min; the number of thin passes is preferably 6 to 10.
In the present invention, the second kneading is preferably a thin-pass; the number of thin passes is preferably 6 to 10.
In the present invention, the third kneading, the fourth kneading and the fifth kneading are independently preferably a thin-pass kneading and a triangle-packing which are sequentially performed; the number of thin-pass times is preferably 4-8; the number of times of triangulating is preferably 5-10 times.
In the present invention, the thickness of the rubber compound is preferably 1.0 to 2.0mm.
After the rubber compound is obtained, the rubber compound is vulcanized to obtain the heat-resistant rubber material.
In the present invention, the vulcanization is preferably carried out on a press vulcanizer; the temperature of the vulcanization is preferably 165-175 ℃; the vulcanization time is preferably 15 to 30 minutes.
For further explanation of the present invention, the present invention provides a composite antioxidant, a method for preparing the same, and a heat-resistant rubber material, which are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The composite anti-aging agent consists of the following components: 50g of silica aerogel, 5g of anti-aging agent 4010NA and 692g of silane coupling agent Si; wherein the particle size of the silica aerogel is 14 mu m, and the specific surface area is more than 2200m 2 Per g, porosity of 8cm 3 /g; the silicon dioxide aerogel is purchased from Huayang new material technology group limited company, the anti-aging agent 4010NA is purchased from Shandong instant chemical industry company, the ethanol is purchased from Jinchen Fangzheng reagent factory, and the silane coupling agent Si-69 is purchased from Nanjing Neodd new material technology limited company;
the preparation method of the composite anti-aging agent comprises the following steps:
mixing an anti-aging agent 4010NA with 500mL of ethanol to obtain an anti-aging agent solution with the mass concentration of 0.8 wt%;
placing silicon dioxide aerogel into an anti-aging agent solution, performing ultrasonic dispersion for 30min at 40kHz, mixing, placing under negative pressure-0.6 MPa for 20min, keeping under normal pressure for 10min, repeatedly circulating for 3 times, separating and drying, placing into a high-speed stirrer, dropwise adding a silane coupling agent Si-69 at a speed of 5mL/min under a rotating speed of 100r/min, stirring for 15min, and stirring for 15min at a rotating speed of 2000r/min to obtain the composite anti-aging agent. In the composite anti-aging agent, the mass of the anti-aging agent 4010NA is 10 percent of that of the silica aerogel.
Example 2
The only differences from example 1 are: the amount of the antioxidant 4010NA is 6g. In the composite anti-aging agent, the mass of the anti-aging agent 4010NA is 12 percent of that of the silica aerogel.
Example 3
The only differences from example 1 are: the amount of the antioxidant 4010NA is 7g. In the composite anti-aging agent, the mass of the anti-aging agent 4010NA is 14 percent of that of the silica aerogel.
Example 4
The only differences from example 1 are: the amount of the antioxidant 4010NA is 8g. In the composite anti-aging agent, the mass of the anti-aging agent 4010NA is 16% of the mass of the silica aerogel.
Example 5
The only differences from example 1 are: the composite antioxidant is not modified with Si-69. In the composite anti-aging agent, the mass of the anti-aging agent 4010NA is 10 percent of the mass of the silicon dioxide aerogel
Comparative example 1
The composite anti-aging agent (functional mesoporous silica nanoparticle (MS-s-RT) with anti-aging effect) is prepared by adopting a comparative document CN107337809A 'a functional mesoporous silica nanoparticle with anti-aging effect, a preparation method thereof and a preparation method of the composite anti-aging agent in application'. The preparation method comprises the following steps:
3.5g of surfactant (CTAB) and 30g of ammonia water (concentration of 25 wt%) were dissolved in 1400mL of deionized water, stirred at 80 ℃ for 0.5h, then 30g of Tetraethylorthosilicate (TEOS) was added dropwise to the obtained solution, stirred for 2h, centrifugally dried, and then placed in a muffle furnace at 700 ℃ for 3h to remove residual surfactant (CTAB) and obtain mesoporous silica nanoparticles (MS).
80g of the prepared mesoporous silica nanoparticle (MS) and 24g of a silane coupling agent (KH 560) are added into a three-necked flask filled with 1500mL of absolute ethyl alcohol, the mixture is reacted at 90 ℃ for 12 hours to obtain a modified mesoporous silica intermediate (m-MS), and then 40g of an anti-aging agent intermediate (p-aminodiphenylamine, RT) and the obtained mesoporous silica intermediate are reacted at 90 ℃ for 12 hours to obtain the functional mesoporous silica nanoparticle (MS-s-RT) with an anti-aging effect.
The composite antioxidant, silica aerogel and antioxidant 4010NA prepared in example 1 were subjected to infrared tests, and the results are shown in FIG. 1. As can be seen from FIG. 1, 1518cm -1 The position is a stretching vibration peak of benzene ring group, 1306cm -1 The telescopic vibration peaks of carbon-nitrogen bonds are formed, the characteristic peaks are not formed on the silica aerogel originally, and after the silica aerogel is loaded with the anti-aging agent 4010NA, the novel product, namely the composite anti-aging agent, has the characteristic peaks, which indicates that the anti-aging agent 4010NA is successfully loaded into the gaps of the silica aerogel.
The thermal weight loss curves of the composite antioxidants, silica aerogel and the antioxidant 4010NA prepared in examples 1 to 4 are shown in FIG. 2. As can be seen from fig. 2, the loading efficiency of the silica aerogel can reach 16% when the anti-aging agent 4010NA is successfully loaded into the voids of the silica aerogel and the mass concentration of the anti-aging agent solution is 1.6 wt%.
The maximum load efficiency of the composite antioxidant prepared in the comparative example 1 is only 9.54%, which is less than 10-16% of the load efficiency achieved in the invention.
Application example 1
The heat-resistant rubber material is prepared from the following raw materials: 60g of ethylene propylene diene monomer, 140g of styrene-butadiene rubber, 40g of composite antioxidant of example 4, 70016g of compatibilizer EVM, 4g of stearic acid, 10g of zinc oxide, 228030g of paraffin oil, 2g of benzothiazole Disulfide (DM), 6g of sulfur, 2g of dicumyl peroxide (DCP), 2g of triallyl isocyanurate (TAIC) and 70g of high-reinforcing carbon black N330; wherein ethylene propylene diene monomer is purchased from three-well company of petrochemical industry in China, styrene-butadiene rubber is purchased from Qilu company, zinc oxide is purchased from zinc product company in Liuzhou, paraffin oil 2280 is purchased from solar oil company in China, stearic acid is purchased from Feng Yi oil and technology company, DM is purchased from Tianjin organic chemical industry factory, DCP is purchased from Shandong Ruohui chemical industry Co., TAIC is purchased from Jiangsu Huaxing new material company, sulfur is purchased from Shandong instant chemical industry Co., EVM700 is purchased from Langmuir, and high reinforcing carbon black N330 is purchased from De Gusai;
the preparation method of the heat-resistant rubber material comprises the following steps:
setting the temperature of two rollers on an open mill to 65 ℃ and the rotating speed of 20r/min, regulating the two rollers to 0.5mm, firstly wrapping the ethylene propylene diene monomer rubber, then thinning and passing the ethylene propylene diene monomer rubber for 8 times, adding styrene butadiene rubber for 8 times, adding compatibilizer EVM700 for 8 times, then adding stearic acid and zinc oxide for 6 times, and triangulating for 8 times, then adding paraffin oil 2280, a composite antioxidant and high reinforcing carbon black N330 for 6 times, and triangulating for 8 times, and finally adding DM, sulfur, DCP and TAIC for 6 times, and triangulating for 8 times to obtain the rubber compound with the thickness of 1.5 mm;
vulcanizing the mixed rubber on a plate vulcanizing machine to obtain a heat-resistant rubber material; wherein the temperature of vulcanization is 165 ℃ and the time is 15min.
Application example 2
The only differences from application example 1 are: 50g of composite anti-aging agent and 60g of high-reinforcement carbon black N330.
Application example 3
The only differences from application example 1 are: 60g of composite anti-aging agent and 50g of high-reinforcing carbon black N330.
Application example 4
The only differences from application example 1 are: 70g of composite anti-aging agent and 40g of high-reinforcement carbon black N330.
Application example 5
The only differences from application example 1 are: the composite antioxidant of example 5 was used.
Comparative application example 1
The only differences from application example 4 are: the composite antioxidant is omitted, and the high reinforcing carbon black N330 is 110g.
Comparative application example 2
The only differences from application example 4 are: the composite anti-aging agent is omitted, and the high-reinforcement carbon black N330 is replaced by 110g of white carbon black.
Comparative application example 3
The only differences from application example 4 are: the composite antioxidant is the functional mesoporous silica nano-supported antioxidant (MS-s-RT) prepared in comparative example 1.
The heat-resistant rubber materials prepared in application examples 1 to 5 and comparative application examples 1 to 3 were subjected to performance mechanical properties and thermo-oxidative aging resistance tests, and the test methods were as follows: tensile strength and elongation at break were measured according to GB/T528-2009 and GB/T529-2009, and the results are shown in Table 1.
TABLE 1 Performance data of heat-resistant rubber materials prepared by application examples 1 to 4 and comparative application examples 1 to 2
As can be seen from Table 1, the mechanical properties of comparative application examples 1 to 2 are all remarkably reduced after thermal oxidation aging, while the long-acting aging resistance of the composite materials prepared in application examples 1 to 4 is gradually increased along with the increase of the amount of the composite anti-aging agent, especially application example 4 only slightly reduces the mechanical properties at the initial stage of aging, because the anti-aging agent needs a certain time to be released from the silica aerogel in the rubber matrix, and the rubber maintains good elasticity and mechanical properties at the later stage of aging along with the continuous release of the anti-aging agent, which means that the slow release effect of the silica aerogel loaded with the anti-aging agent can endow the rubber material with long-acting aging resistance, and the amount of the anti-aging agent can be increased on the premise of not causing frosting by the use of the free anti-aging agent (the free anti-aging agent plays a role at the initial stage of aging).
The comparative application example 3 used the functional mesoporous silica nano-supported anti-aging agent (MS-s-RT) prepared in the comparative example 1, and the supported anti-aging agent content was lower than that of application example 4, so that under the same amount, the non-aged tensile strength and the tensile strength after aging for different times were both lower than those of application example 4, and the rate of decrease in tensile strength after aging of the material (the rate of change in tensile strength= (16.85-5.85) ×100/16.85=65.3 after aging of comparative application example 3 at 160 ℃ for 120 hours; and the rate of change in tensile strength= (18.39-9.05) ×100/16.85=50.7%;) after aging of application example 4 at 160 ℃ for 120 hours) was also greater than that of application example 4.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The composite anti-aging agent is characterized by comprising silica aerogel and an anti-aging agent loaded in pores of the silica aerogel, wherein the mass of the anti-aging agent is 10-20% of that of the silica aerogel.
2. The composite antioxidant according to claim 1, further comprising a silane coupling agent coated on the surface of the silica aerogel.
3. The composite antioxidant according to claim 2, wherein the mass of the silane coupling agent is 5% or less of the mass of the silica aerogel.
4. A composite anti-aging agent according to claim 2 or 3, wherein the silane coupling agent comprises one or more of 3- (2, 3 glycidoxy) propyltrimethoxysilane, 3- (2, 3 glycidoxy) propyltriethoxysilane, 3- (2, 3 glycidoxy) propylmethyldiethoxysilane, 3- (3, 4 epoxycyclohexenyl) trimethoxysilane, 3-aminopropyl triethoxysilane and bis- [ γ - (triethoxysilane) propyl ] tetrasulfide.
5. The composite antioxidant according to claim 1 or 2, wherein the antioxidant comprises at least one of an antioxidant 4010NA, an antioxidant RD, an antioxidant 445, and an antioxidant MB.
6. The method for preparing the composite antioxidant according to any one of claims 1 to 5, comprising the steps of:
and mixing the silicon dioxide aerogel and the anti-aging agent solution, and then carrying out cyclic loading under the negative pressure and normal pressure conditions in sequence to obtain the composite anti-aging agent.
7. The method according to claim 6, wherein when the composite age resistor further comprises a silane coupling agent coated on the surface of the silica aerogel, further comprising adding a silane coupling agent to the resultant load after the loading is completed.
8. The method according to claim 6 or 7, wherein the negative pressure is-0.05 to-0.08 MPa, and the number of cyclic loads is 3 to 5.
9. The method according to claim 8, wherein the single negative pressure is maintained for 20 to 30 minutes and the single normal pressure is maintained for 10 to 20 minutes.
10. The heat-resistant rubber material is characterized by being prepared from the following raw materials in parts by weight: 100 parts of rubber matrix, 4-12 parts of compatibilizer, 4-8 parts of activator, 5-15 parts of operating oil, 20-40 parts of composite anti-aging agent, 2-6 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator and 15-45 parts of reinforcing agent; the composite anti-aging agent is the composite anti-aging agent according to any one of claims 1 to 5 or the composite anti-aging agent prepared by the preparation method according to any one of claims 6 to 9.
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