CN119350736B - Heat-resistant rubber composition and preparation method of synthetic rubber - Google Patents
Heat-resistant rubber composition and preparation method of synthetic rubber Download PDFInfo
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Abstract
本发明公开了一种耐热橡胶组合物及合成橡胶的制备方法，属于橡胶技术领域。所述耐热橡胶组合物的原料包括：丁腈橡胶、三元乙丙橡胶、补强剂、防老剂、活化剂、硫化剂、硫化促进剂、助交联剂、耐热改性助剂，其中，所述耐热改性助剂由纳米ZrO2掺杂八官能苯乙烯‑POSS和纳米HfO2掺杂八官能苯乙烯‑POSS组成；所述合成橡胶采用上述耐热橡胶组合物制备而成。本发明制备的合成橡胶具有优异的耐热性能和耐磨性能，力学性能稳定，使用寿命长。The invention discloses a method for preparing a heat-resistant rubber composition and a synthetic rubber, and belongs to the field of rubber technology. The raw materials of the heat-resistant rubber composition include: nitrile rubber, ethylene propylene diene rubber, a reinforcing agent, an antioxidant, an activator, a vulcanizing agent, a vulcanization accelerator, a cross-linking agent, and a heat-resistant modification auxiliary agent, wherein the heat-resistant modification auxiliary agent is composed of nano ZrO2 doped with eight-functional styrene-POSS and nano HfO2 doped with eight-functional styrene-POSS; the synthetic rubber is prepared by the above-mentioned heat-resistant rubber composition. The synthetic rubber prepared by the present invention has excellent heat resistance and wear resistance, stable mechanical properties, and long service life.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a heat-resistant rubber composition and a preparation method of synthetic rubber.
Background
The rubber product has the advantages of good insulativity, sealing property, water resistance, oil resistance, rebound resilience, plasticity and the like, can be applied to different fields of tires, rubber pads, sealing rings, conveyor belts, cables and the like, and mainly uses natural and synthetic rubber as raw materials and also comprises reclaimed rubber produced by recycling waste rubber. Common rubber products are easily softened at high temperature, and not only can lose the original functions, but also can damage articles contacted with the rubber products. Therefore, in these high-temperature special application environments, there is a higher requirement on the performance of the rubber products, and it is necessary to have good stability, high strength, high temperature resistance and heat resistance, and ensure that good performance can be maintained even under extreme temperature conditions, thereby ensuring safe operation of the equipment and safety of users. Such rubber products are required not only to be excellent in heat resistance but also to be resistant to chemical attack and thermal oxidation attack, thereby realizing a reliable function without affecting the convenience of operation.
Chinese patent CN109923154A discloses a rubber composition and a preparation method thereof, wherein the rubber composition comprises rubber wet masterbatch, rubber and carbon black which are prepared by taking rubber latex solution and slurry containing carbon black as raw materials, wherein the rubber latex solution is prepared by emulsion polymerization of at least one of Isoprene Rubber (IR), styrene-butadiene rubber (SBR), butadiene Rubber (BR), nitrile rubber (NBR) and Chloroprene Rubber (CR), the rubber component is a blend rubber component of natural rubber and synthetic diene rubber, and the combination rubber amount of the carbon black with specific DBP absorption amount and iodine absorption amount is increased, so that vulcanized rubber prepared by the rubber composition has good wear resistance and low heat resistance, but the heat resistance and mechanical stability of the obtained vulcanized rubber are limited, and cannot meet certain application scenes with higher requirements. Chinese patent CN102604172A discloses a heat-resistant nitrile rubber composition, which comprises nitrile rubber, acrylic rubber, zinc oxide, magnesium oxide, stearic acid, white carbon black, spray carbon black, sulfur, quinone oxime, dicumyl peroxide, magnesium methacrylate, an anti-aging agent OD, an anti-aging agent BPPD and gamma-aminopropyl triethoxysilane, wherein the acrylic rubber and various auxiliary agents are added into the nitrile rubber, so that the heat resistance of the nitrile rubber is improved to a certain extent, the heat resistance effect is good, but the stability of the obtained heat-resistant rubber is poor, the problem of performance reduction easily occurs along with the increase of the service time, and the wear resistance and the durability are limited.
Disclosure of Invention
In view of the defects existing in the prior art, the invention provides a heat-resistant rubber composition and a preparation method of synthetic rubber, wherein the heat-resistant rubber composition further improves the heat resistance and the stability of the rubber by adding a specific heat-resistant modification auxiliary agent to act together with other components, so that the rubber maintains excellent mechanical property and wear resistance, and the service life is prolonged.
A heat-resistant rubber composition comprises the following raw materials:
The heat-resistant modified auxiliary agent consists of nano ZrO 2 doped with eight-functional styrene-POSS and nano HfO 2 doped with eight-functional styrene-POSS.
According to the invention, the heat resistance and mechanical stability of the rubber are further improved by adding the specific heat-resistant modification auxiliary agent, so that the service life is prolonged. This is due to the synergistic effect of nano ZrO 2/HfO2 and POSS structure, and in the process of synthesizing octafunctional styrene-POSS by hydrolytic polycondensation, nano zirconium dioxide/hafnium dioxide dispersion liquid is added to successfully dope nano metal oxide into cage structure, so as to form a stable modified auxiliary agent with better compatibility and dispersibility with rubber matrix.
The nanometer ZrO 2 has high melting point, excellent thermal stability and thermal shock resistance, can bear extreme temperature change without cracking or breaking, has high melting point of the nanometer HfO 2, excellent thermal stability and corrosion resistance, can keep stable at extremely high temperature, and combines the nanometer ZrO 2 with the nanometer HfO 2 to endow the rubber with excellent high-temperature stability, so that the degradation and ageing of the rubber at high temperature can be effectively inhibited, but the direct addition often has the defects of poor compatibility with a rubber matrix, easy agglomeration and the like, so that the effect is not ideal. After the nano ZrO 2/HfO2 particles are doped into the POSS structure, the interface combination between the inorganic nano particles and the organic rubber matrix is improved, the good dispersibility of the nano particles ensures the uniform distribution between the nano particles and the rubber matrix, and more effective stress transmission and energy absorption are promoted, so that the rubber can still maintain excellent mechanical properties in a high-temperature environment. Secondly, the siloxane skeleton in the POSS cage-shaped structure molecule is beneficial to improving the thermal stability and mechanical strength, while the octafunctional styrene structure can enhance the compatibility and crosslinking density with a rubber matrix, double bonds contained in the octafunctional styrene structure can carry out crosslinking reaction with unsaturated bonds in rubber to form a complex three-dimensional network structure, the crosslinking not only increases the crosslinking density of the rubber, but also improves the tensile strength and the wear resistance, and meanwhile, the crosslinking network structure can maintain more stable performance at high temperature, and prevent excessive movement and softening of a rubber molecular chain segment, so that the heat resistance and the durability of the rubber are improved; the nano ZrO 2/HfO2 doped styrene-POSS structure not only improves the glass transition temperature of rubber, but also can form a compact protective layer, and reduces the permeation of oxygen and moisture, thereby delaying the aging of rubber. Therefore, the heat-resistant modification auxiliary agent remarkably improves the heat resistance and the durability of the rubber through the synergistic effect of the above aspects, and the comprehensive improvement ensures that the rubber can keep excellent physical properties at high temperature and prolongs the service life of the rubber.
Preferably, the heat-resistant modification auxiliary agent is prepared by the following method:
Adding styrene ethyl trimethoxy silane into tetrahydrofuran, stirring and heating, then adding the nano zirconium dioxide dispersion to react with tetramethyl ammonium hydroxide aqueous solution, decompressing and distilling after the reaction is finished, and drying to obtain nano ZrO 2 doped eight-functional styrene-POSS;
Adding nano hafnium dioxide into isopropanol water solution, carrying out ultrasonic treatment to obtain nano hafnium dioxide dispersion liquid, adding styrene ethyl trimethoxy silane into tetrahydrofuran, stirring and heating, adding nano hafnium dioxide dispersion liquid to react with tetramethyl ammonium hydroxide water solution, carrying out reduced pressure distillation and drying after the reaction is finished to obtain nano HfO 2 doped with eight-functional styrene-POSS, and uniformly mixing nano ZrO 2 doped with eight-functional styrene-POSS and nano HfO 2 doped with eight-functional styrene-POSS to obtain the heat-resistant modification auxiliary agent.
Preferably, the heat-resistant rubber composition comprises the following raw materials in parts by weight:
70-80 parts of nitrile rubber, 25-35 parts of ethylene propylene diene monomer rubber, 15-25 parts of reinforcing agent, 2-4 parts of anti-aging agent, 4-6 parts of activating agent, 1.5-3 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, 1-2 parts of auxiliary crosslinking agent and 6-8 parts of heat-resistant modification auxiliary agent.
Preferably, the reinforcing agent is one or a mixture of more than two of N375 carbon black, N330 carbon black, N220 carbon black, N550 carbon black and N660 carbon black.
Preferably, the reinforcing agent is a mixture of N375 carbon black and N550 carbon black in a weight ratio of 1-3:3.
Preferably, the antioxidant is one or a mixture of more than two of antioxidant RD, antioxidant 6PPD and antioxidant MB.
Preferably, the anti-aging agent is an anti-aging agent RD.
Preferably, the activator is a mixture of stearic acid and zinc oxide.
Preferably, the activator is a mixture of stearic acid and zinc oxide in a weight ratio of 1:3-5.
Preferably, the vulcanizing agent is sulfur.
Preferably, the vulcanization accelerator is one or a mixture of more than two of N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazyl disulfide and zinc diethyl dithiocarbamate.
Preferably, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfenamide and zinc diethyl dithiocarbamate in a weight ratio of 1-3:1.
Preferably, the auxiliary cross-linking agent is at least one of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate and triallyl isocyanurate.
Preferably, the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
Preferably, the heat-resistant modification auxiliary agent is prepared by the following method:
Adding 0.3-0.6 weight part of nano zirconium dioxide into 25-40 weight parts of 40-50 weight percent isopropanol water solution, carrying out ultrasonic treatment for 15-30min under the conditions of 150-200W and 30-40kHz to obtain nano zirconium dioxide dispersion liquid, adding 15-30 weight parts of styrene ethyl trimethoxysilane into 200-300 weight parts of tetrahydrofuran, heating to 45-55 ℃ under the condition of 50-100r/min stirring, then adding 7-15 weight parts of nano zirconium dioxide dispersion liquid and 3-6 weight parts of 15-20 weight percent tetramethyl ammonium hydroxide water solution, reacting for 40-45h at 45-55 ℃, carrying out reduced pressure distillation to remove an organic solvent, and drying to obtain nano ZrO 2 doped eight-functional styrene-POSS;
Adding 0.3-0.6 weight part of nano hafnium dioxide into 25-40 weight parts of 40-50 weight percent isopropanol water solution, carrying out ultrasonic treatment for 15-30min under the conditions of 150-200W and 30-40kHz to obtain nano hafnium dioxide dispersion liquid, adding 15-30 weight parts of styrene ethyl trimethoxysilane into 200-300 weight parts of tetrahydrofuran, heating to 45-55 ℃ under the stirring condition of 50-100r/min, adding 7-15 weight parts of nano hafnium dioxide dispersion liquid and 3-6 weight parts of 15-20 weight percent tetramethyl ammonium hydroxide water solution, carrying out reaction for 40-45h at 45-55 ℃, carrying out reduced pressure distillation to remove an organic solvent after the completion, drying to obtain nano HfO 2 -doped eight-functional styrene-POSS, and uniformly mixing nano ZrO 2 -doped eight-functional styrene-POSS and nano HfO 2 -doped eight-functional styrene-POSS according to the weight ratio of 1:0.5-2 to obtain the heat-resistant modified auxiliary agent.
The invention also provides a preparation method of the synthetic rubber.
Preferably, a method for preparing the synthetic rubber comprises the following steps:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 8-12min at 95-110 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent into an open mill for open milling at 45-60 ℃, standing for 20-30h after open milling, and then placing the internal mixer into a flat vulcanizing machine for 15-30min at 145-160 ℃ to obtain the synthetic rubber.
The invention has the beneficial effects that:
The invention provides a heat-resistant rubber composition and a preparation method of synthetic rubber, wherein a heat-resistant modification auxiliary agent consisting of nano ZrO 2 doped with octafunctional styrene-POSS and nano HfO 2 doped with octafunctional styrene-POSS is added to act together with other components, so that the heat resistance and stability of the rubber are further improved, the rubber maintains excellent mechanical property and wear resistance, and the service life is prolonged. The invention also discloses a method for preparing the synthetic rubber by adopting the heat-resistant rubber composition, which has simple and convenient process and easy operation.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Some of the raw materials used in the following examples are described below:
nitrile butadiene rubber, NBR, model 3305E, acrylonitrile content 33.7wt%, manufacturer Lanzhou petrochemical.
Ethylene propylene diene monomer rubber, EPDM, model 3092PM, ethylene content 67wt%, manufacturer, shanghai petrochemical triple well.
The average grain diameter of the nanometer zirconium dioxide is 200nm.
The average grain diameter of nano hafnium oxide is 50nm.
Styrene ethyl trimethoxysilane, CAS 134000-44-5.
Octaphenyl-POSS, CAS 5256-79-1.
Example 1
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
75 parts of nitrile rubber, 30 parts of ethylene propylene diene monomer rubber, 20 parts of reinforcing agent, 3 parts of anti-aging agent, 5 parts of activating agent, 2 parts of vulcanizing agent, 1.5 parts of vulcanization accelerator, 1.5 parts of auxiliary crosslinking agent and 7 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 2:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:4, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 2:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modified additive is prepared by the following method:
Adding 0.45 weight part of nano zirconium dioxide into 30 weight part of 45 weight percent isopropanol water solution, carrying out ultrasonic treatment for 20min under the conditions of 180W and 35kHz to obtain nano zirconium dioxide dispersion liquid, adding 20 weight part of styrene ethyl trimethoxy silane into 250 weight part of tetrahydrofuran, heating to 50 ℃ under the stirring condition of 80r/min, adding 10 weight parts of nano zirconium dioxide dispersion liquid and 4.5 weight parts of 18 weight percent tetramethyl ammonium hydroxide water solution, reacting for 42h at 50 ℃, carrying out reduced pressure distillation to remove an organic solvent after the completion, and drying to obtain nano ZrO 2 doped eight-functional styrene-POSS;
Adding 0.45 weight part of nano hafnium oxide into 30 weight part of 45 weight percent isopropanol water solution, carrying out ultrasonic treatment for 20min under the conditions of 180W and 35kHz to obtain nano hafnium oxide dispersion liquid, adding 20 weight part of styrene ethyl trimethoxy silane into 250 weight part of tetrahydrofuran, heating to 50 ℃ under the stirring condition of 80r/min, adding 10 weight parts of nano hafnium oxide dispersion liquid and 4.5 weight parts of 18 weight percent tetramethyl ammonium hydroxide water solution, reacting for 42h at 50 ℃, carrying out reduced pressure distillation to remove an organic solvent after the reaction is finished, drying to obtain nano HfO 2 doped octafunctional styrene-POSS, and uniformly mixing nano ZrO 2 doped octafunctional styrene-POSS and nano HfO 2 doped octafunctional styrene-POSS according to the weight ratio of 1:1 to obtain the heat-resistant modified additive.
A preparation method of synthetic rubber comprises the following steps:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 10min at 100 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 24h after open mill completion, and vulcanizing for 20min at 150 ℃ to obtain the synthetic rubber.
Example 2
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
70 parts of nitrile rubber, 25 parts of ethylene propylene diene monomer rubber, 15 parts of reinforcing agent, 2 parts of anti-aging agent, 4 parts of activating agent, 1.5 parts of vulcanizing agent, 1 part of vulcanization accelerator, 1 part of auxiliary crosslinking agent and 6 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 1:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:3, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 1:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modifying assistant was the same as in example 1.
A preparation method of synthetic rubber comprises the following steps:
adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 12min at 95 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 20h after open mill completion, and vulcanizing for 30min at 145 ℃ to obtain the synthetic rubber.
Example 3
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
80 parts of nitrile rubber, 35 parts of ethylene propylene diene monomer rubber, 25 parts of reinforcing agent, 4 parts of anti-aging agent, 6 parts of activating agent, 3 parts of vulcanizing agent, 2 parts of vulcanization accelerator, 2 parts of auxiliary crosslinking agent and 8 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 3:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:5, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 3:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modifying assistant was the same as in example 1.
A preparation method of synthetic rubber comprises the following steps:
adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 8min at 110 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 30h after open mill completion, and vulcanizing for 15min at 160 ℃ to obtain the synthetic rubber.
Example 4
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
75 parts of nitrile rubber, 30 parts of ethylene propylene diene monomer rubber, 20 parts of reinforcing agent, 3 parts of anti-aging agent, 5 parts of activating agent, 2 parts of vulcanizing agent, 1.5 parts of vulcanization accelerator, 1.5 parts of auxiliary crosslinking agent and 7 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 2:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:4, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 2:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modified additive is prepared by the following method:
adding 0.45 weight part of nano zirconium dioxide into 30 weight part of 45 weight percent isopropanol water solution, carrying out ultrasonic treatment for 20min under the conditions of 180W and 35kHz to obtain nano zirconium dioxide dispersion liquid, adding 20 weight part of styrene ethyl trimethoxy silane into 250 weight part of tetrahydrofuran, heating to 50 ℃ under the condition of 80r/min stirring, adding 10 weight parts of nano zirconium dioxide dispersion liquid and 4.5 weight parts of 18 weight percent tetramethyl ammonium hydroxide water solution, reacting for 42h at 50 ℃, carrying out reduced pressure distillation to remove an organic solvent after the completion, and drying to obtain the heat-resistant modification auxiliary agent.
A preparation method of synthetic rubber comprises the following steps:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 10min at 100 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 24h after open mill completion, and vulcanizing for 20min at 150 ℃ to obtain the synthetic rubber.
Example 5
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
75 parts of nitrile rubber, 30 parts of ethylene propylene diene monomer rubber, 20 parts of reinforcing agent, 3 parts of anti-aging agent, 5 parts of activating agent, 2 parts of vulcanizing agent, 1.5 parts of vulcanization accelerator, 1.5 parts of auxiliary crosslinking agent and 7 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 2:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:4, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 2:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modified additive is prepared by the following method:
Adding 0.45 weight part of nano hafnium oxide into 30 weight part of 45 weight percent isopropanol water solution, carrying out ultrasonic treatment for 20min under the conditions of 180W and 35kHz to obtain nano hafnium oxide dispersion liquid, adding 20 weight part of styrene ethyl trimethoxy silane into 250 weight part of tetrahydrofuran, heating to 50 ℃ under the condition of 80r/min stirring, adding 10 weight parts of nano hafnium oxide dispersion liquid and 4.5 weight parts of 18 weight percent tetramethyl ammonium hydroxide water solution, reacting for 42h at 50 ℃, carrying out reduced pressure distillation to remove organic solvent after the completion, and drying to obtain the heat-resistant modification auxiliary agent.
A preparation method of synthetic rubber comprises the following steps:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 10min at 100 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 24h after open mill completion, and vulcanizing for 20min at 150 ℃ to obtain the synthetic rubber.
Example 6
A heat-resistant rubber composition consists of the following raw materials in parts by weight:
75 parts of nitrile rubber, 30 parts of ethylene propylene diene monomer rubber, 20 parts of reinforcing agent, 3 parts of anti-aging agent, 5 parts of activating agent, 2 parts of vulcanizing agent, 1.5 parts of vulcanization accelerator, 1.5 parts of auxiliary crosslinking agent and 7 parts of heat-resistant modification auxiliary agent. The reinforcing agent is a mixture of N375 carbon black and N550 carbon black according to a weight ratio of 2:3, the anti-aging agent is an anti-aging agent RD, the activating agent is a mixture of stearic acid and zinc oxide according to a weight ratio of 1:4, the vulcanizing agent is sulfur, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazole sulfinamide and zinc diethyl dithiocarbamate according to a weight ratio of 2:1, and the auxiliary crosslinking agent is trimethylolpropane trimethacrylate.
The heat-resistant modification auxiliary agent consists of octaphenyl-POSS, nano zirconium dioxide and nano hafnium dioxide according to the weight ratio of 5:0.3:0.3.
A preparation method of synthetic rubber comprises the following steps:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer, banburying for 10min at 100 ℃, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent for open mill, standing for 24h after open mill completion, and vulcanizing for 20min at 150 ℃ to obtain the synthetic rubber.
Test example 1
The synthetic rubber prepared in the above examples was subjected to a low temperature brittleness test with reference to standard GB/T15256-2014. The synthetic rubber prepared in the above example was used as a rubber damper block for fatigue test, and a cycle endurance test was performed in a damper disc, and the parameters of one cycle test were 1200N pre-load, 1600N load, 3Hz frequency, 1min test, 15S force-release stop, and 6000 or more endurance cycles, to see whether cracking/wear occurred. The results are shown in Table 1.
TABLE 1 results of Low temperature brittleness and durability test of rubber
Test example 2
The synthetic rubber prepared in the above examples was subjected to a thermo-oxidative aging test, specifically by aging the synthetic rubber under air conditions at 120℃for 168 hours. The mechanical properties of the synthetic rubber before and after the aging test were tested with reference to standard GB/T528-2009. Wherein the change rate= (value before aging test-value after aging test)/value before aging test×100%, and the results are shown in table 2.
TABLE 2 results of Heat stability test of rubber
As is clear from the comparison of examples 1 to 6, the synthetic rubbers (heat-resistant rubber compositions) prepared in examples 1 to 3 are excellent in heat resistance and durability and stable in mechanical properties, because the specific heat-resistant modifying auxiliary agent is added to the raw material formulation of the heat-resistant rubber composition to act together with other components, thereby remarkably improving the heat resistance and stability of the rubber. Compared with examples 1-3, the heat-resistant modification auxiliary agent consisting of nano ZrO 2 doped with octafunctional styrene-POSS and nano HfO 2 doped with octafunctional styrene-POSS is not used in examples 4-6, and it can be seen from Table 2 that the heat resistance (mechanical stability) of the rubber is reduced to different extents, which indicates that examples 4-6 are obviously deteriorated in the aspect of corresponding performance tests due to the fact that the necessary technical scheme of the invention is not adopted, and further demonstrates the importance of the necessary technical scheme defined by the invention on the technical effects thereof.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (9)
1. The heat-resistant rubber composition is characterized by comprising the following raw materials of nitrile rubber, ethylene propylene diene monomer rubber, a reinforcing agent, an anti-aging agent, an activating agent, a vulcanizing agent, a vulcanization accelerator, a crosslinking assistant and a heat-resistant modification auxiliary agent, wherein the heat-resistant modification auxiliary agent consists of nano ZrO 2 doped with eight-functional styrene-POSS and nano HfO 2 doped with eight-functional styrene-POSS;
the heat-resistant modified additive is prepared by the following method:
Adding styrene ethyl trimethoxy silane into tetrahydrofuran, stirring and heating, then adding the nano zirconium dioxide dispersion to react with tetramethyl ammonium hydroxide aqueous solution, decompressing and distilling after the reaction is finished, and drying to obtain nano ZrO 2 doped eight-functional styrene-POSS;
Adding nano hafnium dioxide into isopropanol water solution, carrying out ultrasonic treatment to obtain nano hafnium dioxide dispersion liquid, adding styrene ethyl trimethoxy silane into tetrahydrofuran, stirring and heating, adding nano hafnium dioxide dispersion liquid to react with tetramethyl ammonium hydroxide water solution, carrying out reduced pressure distillation and drying after the reaction is finished to obtain nano HfO 2 doped with eight-functional styrene-POSS, and uniformly mixing nano ZrO 2 doped with eight-functional styrene-POSS and nano HfO 2 doped with eight-functional styrene-POSS to obtain the heat-resistant modification auxiliary agent.
2. The heat-resistant rubber composition according to claim 1, wherein the reinforcing agent is one or a mixture of two or more of N375 carbon black, N330 carbon black, N220 carbon black, N550 carbon black and N660 carbon black.
3. The heat-resistant rubber composition according to claim 1, wherein the antioxidant is one or a mixture of two or more of an antioxidant RD, an antioxidant 6PPD and an antioxidant MB.
4. The heat-resistant rubber composition according to claim 1, wherein the activator is a mixture of stearic acid and zinc oxide.
5. The heat-resistant rubber composition according to claim 1, wherein the vulcanizing agent is sulfur, and the vulcanization accelerator is one or a mixture of two or more of N-cyclohexyl-2-benzothiazole sulfenamide, dibenzothiazyl disulfide and zinc diethyldithiocarbamate.
6. The heat-resistant rubber composition according to claim 1, wherein the auxiliary crosslinking agent is at least one of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate and triallyl isocyanurate.
7. The heat-resistant rubber composition according to claim 1, which comprises the following raw materials in parts by weight:
70-80 parts of nitrile rubber, 25-35 parts of ethylene propylene diene monomer rubber, 15-25 parts of reinforcing agent, 2-4 parts of anti-aging agent, 4-6 parts of activating agent, 1.5-3 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, 1-2 parts of auxiliary crosslinking agent and 6-8 parts of heat-resistant modification auxiliary agent.
8. The heat-resistant rubber composition according to claim 7, wherein the heat-resistant modifying auxiliary agent is prepared by the following method:
Adding 0.3-0.6 weight part of nano zirconium dioxide into 25-40 weight parts of isopropanol water solution, carrying out ultrasonic treatment for 15-30min to obtain nano zirconium dioxide dispersion liquid, adding 15-30 weight parts of styrene ethyl trimethoxy silane into 200-300 weight parts of tetrahydrofuran, heating to 45-55 ℃ under stirring, adding 7-15 weight parts of nano zirconium dioxide dispersion liquid and 3-6 weight parts of tetramethyl ammonium hydroxide water solution, reacting for 40-45h at 45-55 ℃, carrying out reduced pressure distillation after the completion, and drying to obtain nano ZrO 2 doped eight-functional styrene-POSS;
Adding 0.3-0.6 weight part of nano hafnium dioxide into 25-40 weight parts of isopropanol water solution, carrying out ultrasonic treatment for 15-30min to obtain nano hafnium dioxide dispersion liquid, adding 15-30 weight parts of styrene ethyl trimethoxy silane into 200-300 weight parts of tetrahydrofuran, heating to 45-55 ℃ under stirring, adding 7-15 weight parts of nano hafnium dioxide dispersion liquid and 3-6 weight parts of tetramethyl ammonium hydroxide water solution, reacting for 40-45h at 45-55 ℃, carrying out reduced pressure distillation after finishing, drying to obtain nano HfO 2 doped octafunctional styrene-POSS, and uniformly mixing nano ZrO 2 doped octafunctional styrene-POSS and nano HfO 2 doped octafunctional styrene-POSS according to the weight ratio of 1:0.5-2 to obtain the heat-resistant modification auxiliary agent.
9. A process for producing a synthetic rubber, characterized in that the synthetic rubber is produced by using the heat-resistant rubber composition according to any one of claims 1 to 8, comprising the steps of:
Adding nitrile rubber, ethylene propylene diene monomer, a reinforcing agent, an anti-aging agent and a heat-resistant modification auxiliary agent into an internal mixer for banburying, adding the internal mixer with an activating agent, a vulcanizing agent, a vulcanization accelerator and an auxiliary crosslinking agent into an open mill for open scouring, standing after the open scouring is finished, and vulcanizing in a vulcanizing machine to obtain the synthetic rubber.
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| CN109679104A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of eight amino pyrene propyl cage-type silsesquioxane silicon rubber heat-resisting auxiliary agents |
| CN117024139A (en) * | 2023-08-15 | 2023-11-10 | 宁波博莱特光电科技股份有限公司 | Optical fiber ceramic ferrule and preparation method thereof |
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| US6852794B2 (en) * | 2001-09-07 | 2005-02-08 | The Goodyear Tire & Rubber Company | Rubber compound containing a polyhedral oligomeric silsesquioxanes |
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| CN109679104A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of eight amino pyrene propyl cage-type silsesquioxane silicon rubber heat-resisting auxiliary agents |
| CN117024139A (en) * | 2023-08-15 | 2023-11-10 | 宁波博莱特光电科技股份有限公司 | Optical fiber ceramic ferrule and preparation method thereof |
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