CN115536913A - Heat-resistant and aging-resistant modifier for rubber and preparation method thereof - Google Patents
Heat-resistant and aging-resistant modifier for rubber and preparation method thereof Download PDFInfo
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- CN115536913A CN115536913A CN202211245145.9A CN202211245145A CN115536913A CN 115536913 A CN115536913 A CN 115536913A CN 202211245145 A CN202211245145 A CN 202211245145A CN 115536913 A CN115536913 A CN 115536913A
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- rubber
- phenylenediamine
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 71
- 239000005060 rubber Substances 0.000 title claims abstract description 70
- 230000032683 aging Effects 0.000 title claims abstract description 44
- 239000003607 modifier Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002071 nanotube Substances 0.000 claims abstract description 68
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 33
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 120
- 238000010438 heat treatment Methods 0.000 claims description 63
- 239000000377 silicon dioxide Substances 0.000 claims description 50
- 235000012239 silicon dioxide Nutrition 0.000 claims description 48
- 238000009987 spinning Methods 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 10
- 229960004889 salicylic acid Drugs 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- -1 N- (1 Chemical compound 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a heat-resistant aging-resistant modifier for rubber and a preparation method thereof; the invention firstly modifies N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine, mixes the N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine with propylene oxide for reaction, grafts the propylene oxide to increase the molecular weight, prepares a modified titanium dioxide nanotube with a hollow structure, loads a macromolecule p-phenylenediamine anti-aging agent, achieves the purpose of slow release, reduces the mobility, maintains the anti-aging performance, and simultaneously utilizes the extremely high length-diameter ratio of the nanotube to enhance the mechanical performance of a rubber system and enhance the heat resistance performance; the addition amount of N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine and propylene oxide is limited, enough N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine with small molecular weight is reserved, the N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine is quickly released from the nanotube, and enough anti-aging agent components are provided in the rubber matrix in the earliest time.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a heat-resistant and aging-resistant modifier for rubber and a preparation method thereof.
Background
Rubber is used as a high polymer material and has high elasticity and viscoelasticity, so that the rubber has high use value and even military value, but the deterioration of physical properties and chemical properties is gradually generated due to external factors in the use, storage and processing processes of the elastomer organic high polymer material, and finally the use value is lost; therefore, in the current protection for rubber, people often add an anti-aging agent to protect the rubber and prolong the service life of the rubber, but the rubber still faces the aging problem due to consumption and migration and seepage of the anti-aging agent.
Disclosure of Invention
The invention aims to provide a heat-resistant aging-resistant modifier for rubber and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing epoxy propane and 50-60% of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine, dropwise adding 0.01-0.03 part of salicylic acid, stirring uniformly, then heating to 160-165 ℃ under the protection of nitrogen atmosphere, stirring for reacting for 8-12h, dropwise adding the rest N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10-24h;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3-4 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and carrying out vacuum drying for 12-18 hours to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing ethyl orthosilicate into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4-8 hours to obtain a silicon dioxide precursor solution, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
s22, collecting spinning fibers, heating the spinning fibers in an argon atmosphere to 180-200 ℃, keeping the temperature at a heating rate of 5-8 ℃/min, keeping the temperature for 30-45min, introducing mixed gas of argon and oxygen, heating to 600-700 ℃, keeping the temperature at a heating rate of 3-5 ℃/min, keeping the temperature for 2-3.5h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60-65%, heating to 50-60 ℃, performing ultrasonic dispersion treatment for 2-4.5 hours, performing centrifugal separation, washing with deionized water to be neutral, and performing vacuum drying to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant and aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent, preparing into a negative carrier liquid, protecting in a nitrogen atmosphere, adding the silicon dioxide nanotube prepared in the step S2, and dispersing for 1.5-3h by ultrasonic waves;
s32, vacuumizing, keeping the vacuum for 30-45min, and introducing high-pressure nitrogen for 30-45min;
s33, repeating the step S323-5 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24-36 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for rubber.
Thermal oxidation aging is the most common aging mode of rubber materials, under the influence of external oxygen and high temperature, autocatalytic chain type free radical reaction can occur in the rubber materials, oxygen molecules are combined with reactive active sites in the rubber to generate ROO & structure, and then are combined with macromolecules in the rubber to generate new free radicals to be combined with the oxygen continuously, so that the molecular chains in the rubber materials are broken, the performance is deteriorated, and the performance of the rubber materials is reduced.
The antioxidant 4020, namely N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine, is a p-phenylenediamine antioxidant, and can effectively react with free radicals in rubber, so that the free radicals are prevented from causing chain reaction in a rubber system. However, the anti-aging agent 4020 has a small molecular weight and good anti-aging performance, but gradually migrates out of the rubber during use and accumulates on the surface of the rubber, resulting in degradation of anti-aging performance and change in color of the rubber.
According to the invention, propylene oxide and an anti-aging agent 4020 are firstly used for reaction, epoxy groups in the propylene oxide react with amino groups in N- (1, 3-dimethyl) butyl-N '-phenyl-p-phenylenediamine, the propylene oxide is grafted to the N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine, the molecular weight of the propylene oxide is increased, and the mobility of the propylene oxide is reduced;
on the basis, the invention further prepares the nanotube taking silicon dioxide as the raw material, and the silicon dioxide nanotube has extremely high length-diameter ratio and can be used as nanofiber to be dispersed in a rubber matrix, thereby enhancing the mechanical property and the high temperature resistance of the nanotube and improving the tensile resistance of the nanotube;
meanwhile, the silicon dioxide nanotube is used as a hollow structure, has extremely high specific surface area, can contain a large amount of high-molecular p-phenylenediamine anti-aging agent, and achieves the purpose of slow release by virtue of a tubular structure, so that the anti-aging agent with sufficient concentration can be maintained in the rubber matrix for a long time, and the deterioration of the rubber matrix is prevented.
Further, in step S11, the molar ratio of the propylene oxide, N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine and salicylic acid is (0.9-1.1): (1-1.8): (0.01-0.03).
In the invention, when preparing the high molecular weight p-phenylenediamine anti-aging agent, the amounts of propylene oxide and N- (1, 3-dimethyl) butyl-N '-phenyl-p-phenylenediamine are strictly limited, so that the amount of the N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine exceeds the amount of propylene oxide capable of reacting, thus the prepared high molecular weight p-phenylenediamine anti-aging agent still contains a part of N- (1, 3-dimethyl) butyl-N '-phenyl-p-phenylenediamine with small molecular weight, in the using process, the N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine with small molecular weight can be released from titanium dioxide nanotubes in a limited way and diffused into a rubber matrix in the shortest time to have enough anti-aging performance, as time goes by, the part of the anti-aging agent with small molecular weight can be consumed, while the anti-aging agent with high molecular weight in the nanotubes can be released, and the rubber can be enabled to have anti-aging performance again, thereby the anti-aging performance of the rubber can be maintained for a long time.
Further, in step S21, each 100mL of the silica precursor contains 12 to 18g of tetraethoxysilane, 1.5 to 3g of polyvinylpyrrolidone, and the balance of absolute ethanol.
Further, in step S21, the spinning voltage is 12-15kV, the spinning speed is 1.2-1.8mL/h, and the spinning receiving distance is 15-25cm during electrostatic spinning.
Further, in step S22, in the mixed gas of argon and oxygen, the volume ratio of argon to oxygen is (60-70): (30-40).
Further, in step S31, the concentration of the high molecular p-phenylenediamine antioxidant in the loading liquid is 12.5wt% -20wt%.
Further, in step S32, the high-pressure nitrogen gas pressure is 2-4MPa.
In order to enhance the loading capacity of the titanium dioxide nanotube, the nanotube is treated by repeatedly using vacuum and high-pressure environment, so that more loading liquid can enter the hollow structure of the nanotube and be combined with hydroxyl groups on the surface of the nanotube so as to be loaded in the nanotube.
Compared with the prior art, the invention has the following beneficial effects: the invention firstly modifies N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine, mixes the N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine with propylene oxide for reaction, grafts the propylene oxide to increase the molecular weight of the propylene oxide, and also prepares a modified titanium dioxide nanotube with a hollow structure to load a high molecular p-phenylenediamine anti-aging agent, thereby achieving the purpose of slow release and reducing the mobility of the titanium dioxide nanotube, so as to keep the titanium dioxide nanotube retained in a rubber system for a long time, maintain the anti-aging performance of the titanium dioxide nanotube, and simultaneously utilize the extremely high length-diameter ratio of the nanotube to crosslink in the titanium dioxide nanotube, thereby enhancing the mechanical performance of the rubber system and simultaneously enhancing the heat resistance of the rubber system; the invention also strictly limits the addition amount of N- (1, 3-dimethyl) butyl-N '-phenyl-p-phenylenediamine and propylene oxide, ensures that enough N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine with small molecular weight is still remained after the reaction is finished, can be quickly released from the nano tube, enables the rubber matrix to have enough anti-aging agent components in the earliest time, and ensures that the rubber system has enough anti-aging performance in the service cycle by utilizing the difference of the release time of the high molecular weight anti-aging agent and the low molecular weight anti-aging agent. The heat-resistant aging-resistant modifier prepared by the invention has excellent aging resistance, can effectively improve the mechanical property and the heat resistance of rubber, and has excellent market prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1.
A preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 0.9 part of propylene oxide and 0.5 part of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine in parts by mole, dropwise adding 0.01 part of salicylic acid, uniformly stirring, then heating to 160 ℃, stirring for reacting for 8 hours under the protection of nitrogen atmosphere, dropwise adding 0.5 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4 hours to obtain a silicon dioxide precursor solution containing 12g of tetraethoxysilane and 1.5g of polyvinylpyrrolidone in each 100mL, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 12kV, the spinning speed is 1.2mL/h, and the spinning receiving distance is 15cm;
s22, collecting spinning fibers, heating the spinning fibers in an argon atmosphere to 180 ℃, wherein the heating rate is 5 ℃/min, keeping the temperature for 30min, then introducing argon-oxygen mixed gas, wherein the volume ratio of argon to oxygen in the mixed gas is 60, heating the mixed gas again, heating to 600 ℃, the heating rate is 3 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60%, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at 60 ℃ in vacuum for 12 hours to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant and aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent to prepare a negative carrier liquid with the concentration of 12.5wt%, adding the silicon dioxide nanotube prepared in the step S2 under the protection of a nitrogen atmosphere, completely immersing the silicon dioxide nanotube in a load liquid, and performing ultrasonic dispersion for 1.5h;
s32, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30min;
s33, repeating the operation of the step S32 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
Example 2.
Compared with example 1, this example increases the amount of N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine added in step S11;
a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 0.9 part of propylene oxide and 0.9 part of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine in parts by mole, dropwise adding 0.01 part of salicylic acid, stirring uniformly, then heating to 160 ℃, stirring for reacting for 8 hours under the protection of nitrogen atmosphere, dropwise adding 0.9 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4 hours to obtain a silicon dioxide precursor solution containing 12g of tetraethoxysilane and 1.5g of polyvinylpyrrolidone in each 100mL, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 12kV, the spinning speed is 1.2mL/h, and the spinning receiving distance is 15cm;
s22, collecting spinning fibers, heating the spinning fibers in an argon atmosphere to 180 ℃, wherein the heating rate is 5 ℃/min, keeping the temperature for 30min, then introducing argon-oxygen mixed gas, wherein the volume ratio of argon to oxygen in the mixed gas is 60, heating the mixed gas again, heating to 600 ℃, the heating rate is 3 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60%, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ for 12 hours in vacuum to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant and aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 into an acetone solvent to prepare a negative carrier liquid with the concentration of 12.5wt%, adding the silicon dioxide nano tube prepared in the step S2 under the protection of nitrogen atmosphere, completely immersing the silicon dioxide nano tube in a load liquid, and performing ultrasonic dispersion for 1.5 hours;
s32, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30min;
s33, repeating the operation of the step S32 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for rubber.
Example 3.
Compared with the embodiment 1, the embodiment increases the addition amount of the tetraethoxysilane in the step S21;
a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 0.9 part of propylene oxide and 0.5 part of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine in parts by mole, dropwise adding 0.01 part of salicylic acid, uniformly stirring, then heating to 160 ℃, stirring for reacting for 8 hours under the protection of nitrogen atmosphere, dropwise adding 0.5 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4 hours to obtain a silicon dioxide precursor solution containing 18g of tetraethoxysilane and 1.5g of polyvinylpyrrolidone in each 100mL, and performing electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 12kV, the spinning speed is 1.2mL/h, and the spinning receiving distance is 15cm;
s22, collecting spinning fibers, placing the spinning fibers in an argon atmosphere, heating to 180 ℃, heating at a heating rate of 5 ℃/min, keeping the temperature for 30min, then introducing a mixed gas of argon and oxygen, wherein the volume ratio of the argon to the oxygen in the mixed gas is 60, heating again to 600 ℃, heating at a heating rate of 3 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60%, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ for 12 hours in vacuum to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent to prepare a negative carrier liquid with the concentration of 12.5wt%, adding the silicon dioxide nanotube prepared in the step S2 under the protection of a nitrogen atmosphere, completely immersing the silicon dioxide nanotube in a load liquid, and performing ultrasonic dispersion for 1.5h;
s32, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30min;
s33, repeating the operation of the step S32 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
Example 4.
Compared with the embodiment 1, the embodiment increases the concentration of the negative carrier liquid in the step S31;
a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 0.9 part of propylene oxide and 0.5 part of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine in parts by mole, dropwise adding 0.01 part of salicylic acid, stirring uniformly, then heating to 160 ℃, stirring for reacting for 8 hours under the protection of nitrogen atmosphere, dropwise adding 0.5 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4 hours to obtain a silicon dioxide precursor solution containing 12g of tetraethoxysilane and 1.5g of polyvinylpyrrolidone in each 100mL, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 12kV, the spinning speed is 1.2mL/h, and the spinning receiving distance is 15cm;
s22, collecting spinning fibers, heating the spinning fibers in an argon atmosphere to 180 ℃, wherein the heating rate is 5 ℃/min, keeping the temperature for 30min, then introducing argon-oxygen mixed gas, wherein the volume ratio of argon to oxygen in the mixed gas is 60, heating the mixed gas again, heating to 600 ℃, the heating rate is 3 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60%, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ for 12 hours in vacuum to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant and aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent to prepare a negative carrier liquid with the concentration of 20wt%, adding the silicon dioxide nanotube prepared in the step S2 under the protection of a nitrogen atmosphere, completely immersing the silicon dioxide nanotube in a load liquid, and performing ultrasonic dispersion for 1.5h;
s32, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30min;
s33, repeating the operation of the step S32 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
Example 5.
A preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 1.1 parts of propylene oxide and 1.08 parts of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine by mole, dropwise adding 0.03 part of salicylic acid, uniformly stirring, then heating to 160 ℃, stirring for reacting for 12 hours under the protection of nitrogen atmosphere, dropwise adding 0.72 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 24 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 5 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 8 hours to obtain a silicon dioxide precursor solution containing 18g of tetraethoxysilane and 3g of polyvinylpyrrolidone in each 100mL, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 15kV, the spinning speed is 1.8mL/h, and the spinning receiving distance is 25cm;
s22, collecting spinning fibers, heating the spinning fibers in an argon atmosphere to 200 ℃, wherein the heating rate is 8 ℃/min, keeping the temperature for 345min, then introducing mixed gas of argon and oxygen, wherein the volume ratio of the argon to the oxygen in the mixed gas is 70, reheating the spinning fibers, heating the spinning fibers to 700 ℃, the heating rate is 5 ℃/min, keeping the temperature for 3.5h, stopping heating, and cooling the spinning fibers to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into 65% nitric acid solution, heating to 60 ℃, performing ultrasonic dispersion treatment for 4.5 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at 60 ℃ in vacuum for 12 hours to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent to prepare a negative carrier liquid with the concentration of 20wt%, adding the silicon dioxide nanotube prepared in the step S2 under the protection of a nitrogen atmosphere, completely immersing the silicon dioxide nanotube in a load liquid, and performing ultrasonic dispersion for 3 hours;
s32, vacuumizing, keeping the vacuum for 45min, introducing high-pressure nitrogen, keeping the air pressure at 4MPa, and keeping the air pressure for 45min;
s33, repeating the operation of the step S32 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
Comparative example 1.
The comparative example does not prepare a macromolecular p-phenylenediamine anti-aging agent, but directly uses the anti-aging agent 4020 for replacement in equal quantity;
a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a modified silicon dioxide nanotube;
s11, dispersing tetraethoxysilane into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4 hours to obtain a silicon dioxide precursor solution containing 12g of tetraethoxysilane and 1.5g of polyvinylpyrrolidone in each 100mL, and performing electrostatic spinning on the silicon dioxide precursor solution;
during electrostatic spinning, the spinning voltage is 12kV, the spinning speed is 1.2mL/h, and the spinning receiving distance is 15cm;
s12, collecting spinning fibers, placing the spinning fibers in an argon atmosphere, heating to 180 ℃, heating at a heating rate of 5 ℃/min, keeping the temperature for 30min, then introducing a mixed gas of argon and oxygen, wherein the volume ratio of the argon to the oxygen in the mixed gas is 60, heating again to 600 ℃, heating at a heating rate of 3 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s13, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60%, heating to 50 ℃, performing ultrasonic dispersion treatment for 2 hours, performing centrifugal separation, washing to be neutral by using deionized water, and drying at the temperature of 60 ℃ for 12 hours in vacuum to obtain a modified silicon dioxide nanotube;
s2, preparing a heat-resistant aging-resistant modifier for rubber;
s21, dispersing an anti-aging agent 4020 in an acetone solvent to prepare a negative carrier liquid with the concentration of 12.5wt%, adding the silicon dioxide nanotube prepared in the step S1 under the protection of a nitrogen atmosphere, completely immersing in the load liquid, and performing ultrasonic dispersion for 1.5h;
s22, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30min;
s23, repeating the operation of the step S22 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
Comparative example 2.
Compared with the embodiment 1, the comparative example is to prepare the modified silicon dioxide nanotube, and directly uses white carbon black for equivalent substitution;
a preparation method of a heat-resistant aging-resistant modifier for rubber comprises the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing 0.9 part of propylene oxide and 0.5 part of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine in parts by mole, dropwise adding 0.01 part of salicylic acid, stirring uniformly, then heating to 160 ℃, stirring for reacting for 8 hours under the protection of nitrogen atmosphere, dropwise adding 0.5 part of N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10 hours;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and drying for 12 hours at the temperature of 80 ℃ in vacuum to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a heat-resistant aging-resistant modifier for rubber;
s21, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 in an acetone solvent to prepare a negative carrier liquid with the concentration of 12.5wt%, protecting in a nitrogen atmosphere, adding white carbon black, and performing ultrasonic dispersion for 1.5-3h;
s22, vacuumizing, keeping the vacuum for 30min, introducing high-pressure nitrogen, keeping the air pressure at 2MPa, and keeping the air pressure for 30-45min;
s23, repeating the operation of the step S22 for 3 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
And (3) detection: according to parts by weight, 10 parts of the anti-aging agent prepared in the examples 1-5 and the comparative examples 1-2 are respectively mixed with 100 parts of styrene butadiene rubber, 2 parts of sulfur, 5 parts of zinc oxide, 1 part of stearic acid, 20 parts of white carbon black and 20 parts of carbon black at 150 ℃ multiplied by T 90 Vulcanizing;
placing the sample in an environment at 100 ℃, and detecting the tensile strength and the elongation at break of the sample according to GB/T528-2009 at a specified time; the detection results are shown in the following table;
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the heat-resistant aging-resistant modifier for rubber is characterized by comprising the following steps:
s1, preparing a high-molecular p-phenylenediamine anti-aging agent;
s11, mixing epoxy propane and 50-60% of N- (1, 3-dimethyl) butyl-N '-phenyl p-phenylenediamine, dropwise adding 0.01-0.03 part of salicylic acid, stirring uniformly, then heating to 160-165 ℃ under the protection of nitrogen atmosphere, stirring for reacting for 8-12h, dropwise adding the rest N- (1, 3-dimethyl) butyl-N' -phenyl p-phenylenediamine again, and continuing to react for 10-24h;
s12, after the reaction is finished, carrying out ice-water bath treatment, dissolving a reaction product by using dichloromethane, washing for 3-4 times by using a saturated sodium carbonate solution, separating an organic phase, continuously washing the organic phase by using deionized water until the pH value is not changed, separating the organic phase again, and carrying out vacuum drying for 12-18 hours to obtain the high-molecular p-phenylenediamine anti-aging agent;
s2, preparing a modified silicon dioxide nanotube;
s21, dispersing ethyl orthosilicate into absolute ethyl alcohol, adding polyvinylpyrrolidone, stirring and mixing for 4-8 hours to obtain a silicon dioxide precursor solution, and carrying out electrostatic spinning on the silicon dioxide precursor solution;
s22, collecting spinning fibers, placing the spinning fibers in an argon atmosphere, heating to 180-200 ℃, keeping the temperature at the heating rate of 5-8 ℃/min, keeping the temperature for 30-45min, introducing mixed gas of argon and oxygen, heating to 600-700 ℃, keeping the temperature at the heating rate of 3-5 ℃/min, keeping the temperature for 2-3.5h, stopping heating, and cooling to room temperature along with a furnace to obtain a silicon dioxide nanotube;
s23, dispersing the silicon dioxide nanotube into a nitric acid solution with the concentration of 60-65%, heating to 50-60 ℃, performing ultrasonic dispersion treatment for 2-4.5 hours, performing centrifugal separation, washing to be neutral by using deionized water, and performing vacuum drying to obtain a modified silicon dioxide nanotube;
s3, preparing a heat-resistant and aging-resistant modifier for rubber;
s31, dispersing the high-molecular p-phenylenediamine anti-aging agent prepared in the step S1 into an acetone solvent, preparing into a negative carrier liquid, protecting in a nitrogen atmosphere, adding the silicon dioxide nano tube prepared in the step S2, and dispersing for 1.5-3h by ultrasonic waves;
s32, vacuumizing, keeping the vacuum for 30-45min, and introducing high-pressure nitrogen for 30-45min;
s33, repeating the step S323-5 times, recovering the atmospheric pressure, centrifugally separating the lower-layer precipitate, and drying at 60 ℃ for 24-36 hours in a nitrogen atmosphere to obtain the heat-resistant and aging-resistant modifier for the rubber.
2. The method for preparing the heat-resistant aging-resistant modifier for rubber as claimed in claim 1, wherein: in step S11, the molar ratio of the propylene oxide, the N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine and the salicylic acid is (0.9-1.1) in terms of molar parts: (1-1.8): (0.01-0.03).
3. The method for preparing the heat-resistant aging-resistant modifier for rubber as claimed in claim 1, wherein: in step S21, each 100mL of silica precursor contains 12-18g of tetraethoxysilane, 1.5-3g of polyvinylpyrrolidone, and the balance of absolute ethanol.
4. The method for preparing the heat-resistant aging-resistant modifier for rubber as claimed in claim 1, wherein: in the step S21, during electrostatic spinning, the spinning voltage is 12-15kV, the spinning speed is 1.2-1.8mL/h, and the spinning receiving distance is 15-25cm.
5. The method for preparing the heat-resistant aging-resistant modifier for rubber as claimed in claim 1, wherein: in step S22, in the mixed gas of argon and oxygen, the volume ratio of argon to oxygen is (60-70): (30-40).
6. The method for preparing the heat-resistant aging-resistant modifier for rubber as claimed in claim 1, wherein: in step S31, the concentration of the high molecular p-phenylenediamine anti-aging agent in the loading liquid is 12.5wt% -20wt%.
7. The method for preparing the heat-resistant aging-resistant modifier for rubber according to claim 1, characterized in that: in step S32, the high-pressure nitrogen gas pressure is 2-4MPa.
8. The heat and aging resistant modifier for rubber prepared by the preparation method as described in claim 1 to 7.
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