A rubber oil composition capable of inhibiting multiple yellowing and a preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- PETROCHINA CO LTD
- Filing Date
- 2025-01-06
- Publication Date
- 2026-07-07
Smart Images
Figure CN122344409A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of rubber oil technology, and relates to a rubber oil composition that can inhibit multiple yellowing, its preparation method and application. Background Technology
[0002] In the application of rubber oil, it is one of the main materials for oil-extended elastomer particles and oil-extended rubber products, and it has a significant impact on the yellowing properties of colorless, light-colored, and colored rubber products. The relationship between the yellowing resistance of rubber oil and the yellowing resistance of oil-extended elastomer particles and oil-extended rubber products is quite complex. When the main chain of the rubber material contains unsaturated bonds, the rubber oil plays a protective role and delays the yellowing of the rubber composite material. However, when the main chain of the rubber material is completely saturated, although the rubber oil will protect the main chain, it will accelerate the yellowing of the rubber composite material. Generally, improving the light and heat resistance of the rubber oil itself can improve the yellowing resistance of the rubber composite material. However, when the light and heat resistance of the rubber oil is improved to a high quality level, in some cases, the oil-extended rubber material may exhibit abnormal yellowing and storage yellowing at room temperature. In this case, the excellent light and heat resistance of the rubber oil itself cannot improve the abnormal yellowing and storage yellowing of the oil-extended rubber material.
[0003] The abnormal yellowing and storage-induced yellowing of oil-extended rubber materials are related to the internal structure and deterioration process of the oil, as well as the rubber material synthesis process, resulting from the interaction of multiple materials. To suppress this abnormal yellowing, the rubber oil needs to inhibit the effects of these interactions without reducing its own resistance to light and heat yellowing. Modification of rubber oils can be achieved through the addition of additives; different types of rubber oils have different sensitivities to additives. Existing technologies typically employ a special high-pressure hydrogenation process to deeply saturate unsaturated rubber oils, resulting in zero aromatic content and almost no undesirable components, thereby improving their resistance to yellowing.
[0004] Chinese invention patent CN106520188B discloses an environmentally friendly anti-yellowing treatment process for rubber filler oil. This process uses an oxidation-extraction mixed fluid to extract and separate the rubber filler oil, removing undesirable components and improving its anti-yellowing properties. This technology targets oils containing small amounts of aromatics. By removing light- and heat-sensitive components through the process, it improves the oil's resistance to photo- and heat aging. The target oils are solvent-refined or hydrogenated products that retain a small amount of aromatics.
[0005] Chinese invention patent application CN117304976A discloses a naphthenic white oil specifically for SEBS and its preparation method. This method involves extraction, hydrogenation treatment, isomerization dewaxing, hydrogenation refining, and separation to obtain a naphthenic white oil more suitable for SEBS, improving the oil's resistance to yellowing. However, it cannot suppress abnormal yellowing during processing or yellowing during storage.
[0006] However, with the continuous improvement of high-pressure hydrogenation technology, the resulting deeply saturated rubber oils possess good anti-yellowing properties. Commercially available antioxidants such as 1010 (pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and 1076 (octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) are ineffective, or even have a negative effect, on the resistance of rubber oils and oil-extended rubber products to multiple yellowing. General-purpose antioxidants cause a rapid decline in the light and heat aging resistance of deeply saturated rubber oils to yellowing, and a decrease in the yellowing resistance of oil-extended rubber products. To inhibit multiple yellowing, the interactions between various materials need to be considered. Rubber oils produced using specific processes are formulated with special compositions to produce rubber oils that inhibit multiple yellowing.
[0007] Chinese invention patent application CN114031813A discloses an antioxidant composition and a linear low-density polyethylene resin composition, which combine hindered phenolic antioxidants, phosphite antioxidants, and acid removers to improve the gas fumigation resistance and yellowing resistance of linear low-density polyethylene. It targets the application of solid resins and inhibits various yellowing phenomena. The yellowing inhibition process differs from that used in liquid rubber oils.
[0008] For rubber oils containing small amounts of aromatics, anti-yellowing methods such as process treatment or additives are used, but both are less effective for rubber oils containing almost no aromatics. When additive combinations are applied to rubber oils containing almost no aromatics, they have a negative effect on multiple yellowing problems, only inhibiting some yellowing and failing to address multiple yellowing phenomena. Further improvements are needed to solve these problems. Summary of the Invention
[0009] To address the aforementioned problems in existing technologies, this invention provides a rubber oil composition that can inhibit multiple yellowing phenomena. When applied to rubber oil, this antioxidant composition effectively eliminates multiple yellowing phenomena in rubber oil and rubber products during processing and storage. It not only improves the light and heat resistance of rubber oil to yellowing but also inhibits abnormal yellowing and storage yellowing phenomena in oil-mixed and oil-extended rubber products.
[0010] To achieve the above objectives, the technical solution of the present invention is as follows:
[0011] This invention provides a rubber oil composition for inhibiting multiple yellowing, comprising the following components: a naphthenic rubber oil base oil and an antioxidant, wherein the antioxidant includes phosphite antioxidants; further comprising one or more of hindered phenolic antioxidants, organic acids and purple absorbers; wherein the antioxidant accounts for 0.1-4% of the total mass of the rubber oil.
[0012] Furthermore, the naphthenic rubber oil base oil is obtained by hydrogenating, hydroisomerizing and dewaxing the naphthenic feedstock oil, and hydrogenating supplementary refining.
[0013] This high-pressure hydrogenation combined process removes undesirable non-hydrocarbon components containing heteroatoms such as S, N, and O from naphthenic feedstocks, while also removing aromatics. This ensures that the rubber oil base oil is almost free of substances prone to yellowing, allowing the rubber oil base oil to withstand 4 hours under 160℃ thermo-oxidative conditions and 1050 μW / cm² conditions. 2 It does not change color after 12 hours under irradiation intensity. Adding 0.1%-4% of a unique composition that inhibits multiple yellowing phenomena to the refined rubber oil base oil, and allowing it to fully dissolve at a suitable temperature, yields a clear, colorless rubber oil product. The addition of this unique composition effectively removes active substances from the rubber oil, inhibits and delays the deterioration process, and improves its resistance to light and heat yellowing, while preventing abnormal yellowing of oil-extended rubber products and storage yellowing.
[0014] In some specific embodiments of the present invention, the antioxidant composition combination includes: phosphite antioxidant + hindered phenolic antioxidant, phosphite antioxidant + organic acid, phosphite antioxidant + ultraviolet absorber, phosphite antioxidant + hindered phenolic antioxidant + organic acid, phosphite antioxidant + hindered phenolic antioxidant + ultraviolet absorber, phosphite antioxidant + organic acid + ultraviolet absorber, and phosphite antioxidant + hindered phenolic antioxidant + organic acid + ultraviolet absorber.
[0015] In some embodiments of the present invention, the phosphite antioxidants include, but are not limited to, one or more of pentaerythritol diisodecyl diphosphite, poly(dipropylene glycol) phenyl phosphite, phenyl diisodecyl phosphite, tetraphenyl dipropylene glycol diphosphite, diphenyl isodecyl phosphite, diphenyl phosphite, tri(dodecyl) phosphite, phenyl diisooctyl phosphite, tri(tetranyl) phosphite, tri(nonylphenol) phosphite, tri(2-nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and pentapentetol dibis(2,4-di-tert-butylphenyl) phosphite.
[0016] In some embodiments of the present invention, the hindered phenolic antioxidant includes, but is not limited to, one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.
[0017] In some embodiments of the present invention, the organic acid includes, but is not limited to, one or more of isostearic acid, stearic acid, isopramearic acid, palmitic acid, oleic acid, isononanoic acid, nonanoic acid, isooctanoic acid, octanoic acid, fruit acid, benzoic acid, citric acid, malic acid, tartaric acid, acetic acid, succinic acid, and oxalic acid.
[0018] In some embodiments of the present invention, the ultraviolet absorber includes, but is not limited to, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole.
[0019] In some embodiments of the present invention, the antioxidant, by weight, includes 50-100 parts of phosphite antioxidant; and also includes 1-50 parts of hindered phenolic antioxidant, 1-50 parts of organic acid and / or 1-20 parts of ultraviolet absorber.
[0020] In some embodiments of the present invention, the antioxidant, by weight, includes 50-80 parts of phosphite antioxidant; and also includes 10-30 parts of hindered phenolic antioxidant, 20-50 parts of organic acid and / or 10-20 parts of ultraviolet absorber.
[0021] In some embodiments of the present invention, the antioxidant, by weight, includes 50 parts of phosphite antioxidant; and also includes 20 parts of hindered phenolic antioxidant, 20 parts of organic acid and / or 10 parts of ultraviolet absorber.
[0022] The present invention also provides a method for preparing any of the above-described rubber oil compositions, characterized by comprising the following steps:
[0023] (1) Preparation of naphthenic rubber oil base oil: Naphthenic feedstock oil is subjected to hydrogenation treatment, hydrogenation isomerization dewaxing and hydrogenation supplementation refining in sequence to obtain the base oil.
[0024] (2) Preparation of antioxidants:
[0025] ① Take the liquid components of phosphite antioxidants, hindered phenolic antioxidants and / or organic acids, heat and stir until homogeneous, or add them to ultraviolet absorbers and dissolve until clear.
[0026] Alternatively, ② take the solid components of phosphite antioxidants, hindered phenolic antioxidants, and / or organic acids and dissolve them in the target rubber oil base oil to obtain the product; or add an ultraviolet absorber and mix evenly to obtain the product.
[0027] Alternatively, the antioxidants prepared in steps ① and ② can be mixed to obtain the desired product;
[0028] (3) Add the antioxidant obtained in step (2) to the naphthenic rubber base oil prepared in step (1), heat and stir to obtain the product.
[0029] It is worth noting that, in the preparation of the antioxidant, the target rubber oil base oil added during the preparation of the solid component antioxidant composition is not included in the amount of the antioxidant composition, but is included in the amount of the rubber oil base oil. Furthermore, in step ①, the heating temperature is 85-90℃; the solid components are added to the target rubber oil base oil in order of increasing dissolution temperature.
[0030] Firstly, the purpose of hydrotreating is to achieve deep desulfurization, deoxidation, saturation of polycyclic aromatic hydrocarbons, and ring-opening chemical reactions in naphthenic feedstocks, removing undesirable non-hydrocarbon components such as gums and asphaltenes, and obtaining more desirable components such as alkanes and cycloalkanes. There are no restrictions on the catalysts and specific process conditions used in hydrotreating, as long as the objectives are achieved.
[0031] Preferably, the catalyst for hydrogenation treatment uses alumina as a support and molybdenum oxide and nickel oxide as active components; wherein, molybdenum oxide accounts for 4.0-30.0 wt% of the catalyst, and nickel oxide accounts for 1.0-6.0 wt% of the catalyst;
[0032] The purpose of hydroisomerization and pour point depressing is to isomerize high-pour-point n-alkanes, converting straight-chain structures into long-chain branched structures, thereby lowering the pour point. There are no restrictions on the catalysts or specific process conditions used in hydroisomerization and pour point depressing, as long as the objective is achieved.
[0033] The specific process parameters are as follows: hydrogen partial pressure 17.0-19.0 MPa; reaction temperature 370-410℃; space velocity 1.0-1.2 h⁻¹; hydrogen-to-oil volume ratio 1500-2500:1.
[0034] Preferably, the total acid content of the catalyst is 0.5-1.0 mmol / g, the strong acid content is 40-45%, the medium-strong acid content is 20-25%, and the weak acid content is 35-40%.
[0035] The purpose of hydrotreating is to further hydrogenate and saturate chemically unstable hydrocarbons such as olefins and unsaturated aromatics produced in previous processes, obtaining ideal alkanes and cycloalkanes, thereby further improving the light and heat resistance of rubber oil base oils. There are no restrictions on the catalysts or specific process conditions used in hydrotreating, as long as the desired objectives are achieved.
[0036] Preferably, the hydroisomerization dewaxing catalyst uses a molecular sieve as a support and oxides of group VIII elements as active ingredients; wherein the active ingredients account for 0.1-1.0% by mass.
[0037] The specific process parameters are as follows: hydrogen partial pressure is 17-19 MPa; temperature is 330-400℃; space velocity is 0.5-0.7 h⁻¹; hydrogen-to-oil volume ratio is 1500-2000:1.
[0038] Furthermore, the hydrogenation supplemental refining catalyst uses amorphous silica-alumina as a support and oxides of group VIII elements as active components; wherein the active components account for 0.3-1.5% by mass.
[0039] The specific process parameters are as follows: hydrogen partial pressure is 17.0-19.0 MPa; reaction temperature is 280-320℃; space velocity is 2.0-2.5 h⁻¹; hydrogen-to-oil volume ratio is 1500-2000:1.
[0040] Furthermore, the preparation of naphthenic rubber oil base oil also includes: gas-liquid separation of the hydrogenated and refined naphthenic feedstock oil, fractionation of the liquid phase, and collection of fractions with temperatures above 360°C, 390°C, and 420°C as rubber oil base oil.
[0041] Compared with the prior art, the present invention has the following beneficial effects:
[0042] (1) This invention uses cycloalkanes rubber oil with zero aromatic carbon atom content as base oil and adds antioxidants of a specific composition, which can effectively remove trace active substances in rubber oil, inhibit and delay the deterioration process of rubber oil, give rubber oil better storage stability, and improve light and heat resistance yellowing performance; inhibit the abnormal yellowing of oil-extended oil and oil-extended rubber materials and the phenomenon of storage yellowing, and realize rubber oil that inhibits multiple yellowing.
[0043] (2) The naphthenic rubber oil base oil used in this invention removes undesirable components containing heteroatoms such as S, N, and O from the naphthenic feedstock oil through a high-pressure hydrogenation combined process, while also removing aromatics, ensuring that the rubber oil base oil is almost free of substances prone to yellowing. This allows the rubber oil base oil to withstand 4 hours under thermo-oxidative conditions at 160℃ and 1050 μW / cm 2 No color change after 12 hours under irradiation intensity;
[0044] (3) The preparation process of the composition of the present invention is simple, and antioxidants can be added to rubber oil as needed. It does not require complex blending equipment and has a wide range of applications. Attached Figure Description
[0045] Figure 1 Images showing the yellowing effect of different oil-filled particles after 4 months of storage. Detailed Implementation
[0046] The present invention will be further described in detail below with reference to specific embodiments. The following embodiments are not intended to limit the present invention, but only to illustrate the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are generally performed under conventional conditions. Unless otherwise specified, the materials and reagents used in the following embodiments are commercially available.
[0047] Example 1
[0048] (1) The naphthenic crude oil was fractionated under reduced pressure, and the distillate oil with a boiling range of 360-500℃ was used as the naphthenic feedstock with a total naphthenic hydrocarbon content of more than 40%. Then, catalyst 1 (with molybdenum oxide and nickel oxide as active components and alumina as the balance support) was used, and the hydrogen partial pressure was set to 18.0 MPa, the reaction temperature to 380℃, and the space velocity to 1.0 h⁻¹. -1 Hydrogenation was performed at a hydrogen-to-oil volume ratio of 1500:1; then catalyst 2 (with molecular sieve as support and platinum dioxide as the active ingredient at a mass content of 0.8%) was used, and the hydrogen partial pressure was set at 18.0 MPa, the reaction temperature at 350℃, and the space velocity at 0.5 h⁻¹. -1 Hydrogen-oil volume ratio of 1500:1 was used for hydroisomerization and pour point depressing treatment; catalyst 3 (with amorphous silica-alumina as the support, and platinum dioxide and palladium oxide as the active components by mass) was used, and the hydrogen partial pressure was set at 18.0 MPa, the reaction temperature at 300℃, and the space velocity at 2.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 2000:1; the product is then fed into a gas-liquid separator for gas-liquid separation, and the separated liquid phase is fed into a fractionation tower for fractionation. The fraction with a temperature greater than 330°C is collected to obtain naphthenic rubber oil base oil 1, which is used for later use.
[0049] (2) Take 20 parts of tridecyl phosphite, 30 parts of pentaerythritol diisodecyl phosphite and 50 parts of isostearic acid, mix them, stir at 85°C until the solution is clear, cool to room temperature, and obtain antioxidant 1 for later use.
[0050] (3) Mix the naphthenic rubber oil base oil 1 and antioxidant 1 at a mass ratio of 99.2:0.8 and stir at 80°C for 10 min to obtain a clear, uniform, and turbid rubber oil composition 1.
[0051] Example 2
[0052] (1) Same as Example 1;
[0053] (2) Take 50 parts of pentaerythritol diisodecyl diphosphite, 30 parts of tridecyl phosphite and 20 parts of isooctyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, mix them, stir at 85°C until the solution is clear, cool to room temperature, and obtain antioxidant 2 for later use.
[0054] (3) Mix the naphthenic rubber oil base oil 1 and antioxidant 2 at a mass ratio of 99.5:0.5 and stir at 80°C for 10 min to obtain a clear, uniform, and turbid rubber oil composition 2.
[0055] Example 3
[0056] (1) Same as Example 1;
[0057] (2) Take 50 parts of pentaerythritol diisodecyl phosphate, 20 parts of isooctyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 20 parts of isostearic acid, mix them, stir at 85°C, then add 10 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and dissolve until the solution is clear. Cool to room temperature to obtain antioxidant 3 for later use.
[0058] (3) Mix the naphthenic rubber oil base oil 1 and antioxidant 3 at a mass ratio of 99.5:0.5 and stir at 80°C for 10 min to obtain a clear, uniform, and turbid rubber oil composition 3.
[0059] Example 4
[0060] (1) Same as Example 1;
[0061] (2) Take naphthenic rubber base oil 1 as solvent and heat to 120°C. Add pentaerythritol di(2,4-di-tert-butylphenyl) bis(diphosphite) ester at 5% of the solvent mass. After it is fully dissolved, keep it for 5 minutes and cool to 90°C. Then add stearic acid and 1% 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole at 3% of the solvent mass. After it is fully dissolved, keep it for 5 minutes and cool to room temperature to obtain antioxidant 5 for later use.
[0062] (3) Mix the naphthenic rubber oil base oil 1 and antioxidant 4 at a mass ratio of 95:5 and stir at 80°C for 10 minutes to obtain a clear, uniform, and turbid rubber oil composition 5.
[0063] Comparative Example 1
[0064] Commercially available high-pressure hydrotreated base oil 1 (basic properties are shown in Table 1).
[0065] Comparative Example 2
[0066] Commercially available high-pressure hydrotreated base oil 2 (basic properties are shown in Table 1).
[0067] Comparative Example 3
[0068] Compared with Example 3, the only difference is that an equal amount of commercially available high-pressure hydrogenated base oil 2 (basic properties are shown in Table 1) is used instead of naphthenic rubber oil base oil 1;
[0069] A clear, uniform, and turbid rubber oil composition 5 was obtained.
[0070] Comparative Example 4
[0071] Compared with Example 4, the only difference is that the antioxidant component is: 0.5% by solvent mass of B225 (equal parts of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] and tris(2,4-di-tert-butylphenyl)phosphite);
[0072] A clear, uniform, and turbid rubber oil composition 6 was obtained.
[0073] Comparative Example 5
[0074] Compared with Example 3, the only difference is that the naphthenic rubber oil base oil 1 and antioxidant 3 are in a mass ratio of 99.95:0.05;
[0075] A clear, uniform, and turbid rubber oil composition 7 was obtained.
[0076] The basic properties of the base oils in the comparative examples of this invention are shown in Table 1.
[0077] Table 1
[0078]
[0079]
[0080] Test case
[0081] The results of the investigation of the multiple yellowing properties of the rubber oil base oil (cycloalkane rubber oil base oil, commercially available high-pressure hydrogenated oil) or rubber oil composition of the above embodiments under the same conditions are shown in Table 2.
[0082] Synergistic yellowing test: Mix oil-extended particles (rubber oil base oil) or oil (rubber oil composition) with SBS or SEBS rubber particles. After the oil is completely absorbed, add calcium powder. After thorough mixing, store in the dark at room temperature for 3-7 days. Use a colorimeter to detect the reflected light of the particles and determine the yellowing index value.
[0083] Table 2
[0084]
[0085]
[0086] Note: Color codes below +25 are yellow to the naked eye, and yellowness indexes above 10 are yellow to the naked eye.
[0087] As can be seen from the table above, the rubber oil base oils of Examples 1-4 of this invention and the rubber oil compositions formed therefrom with antioxidants exhibit excellent photothermal stability, with a stability of 1050 μW / cm² under thermo-oxidative conditions at 160°C for 4 hours. 2 The product does not change color after 12 hours under irradiation intensity and effectively inhibits abnormal yellowing and storage yellowing of oil-extended oil-based materials and oil-extended rubber materials. Although commercially available high-pressure hydrogenated base oil 1 with 0% aromatic hydrocarbon content has excellent photothermal stability, its inhibitory effect on abnormal yellowing and storage yellowing of oil-extended oil-based materials and oil-extended rubber materials is limited. The effect of commercially available high-pressure hydrogenated base oil 2 with a lower aromatic hydrocarbon content (0.5%) is even worse. Even when combined with the antioxidant of the present invention (i.e., Comparative Example 3), its anti-yellowing performance is still poor. Compared with Example 4, Comparative Example 4 uses other types of antioxidants, and its photothermal resistance is reduced, and its inhibitory effect on multiple yellowing is significantly reduced. Compared with Example 3, the amount of antioxidant in Comparative Example 5 is lower, and the inhibitory effect on multiple yellowing is also affected. It can be seen that the presence of antioxidants does not necessarily achieve the effect of multiple anti-yellowing, and it also depends on the amount used.
[0088] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.
Claims
1. A rubber oil composition capable of inhibiting multiple yellowing processes, characterized in that, It comprises the following components: naphthenic rubber oil base oil and antioxidants, wherein the antioxidants include phosphite antioxidants; it also comprises one or more of hindered phenolic antioxidants, organic acids and purple absorbers; wherein the antioxidants account for 0.1-4% of the total mass of the rubber oil.
2. The rubber oil composition according to claim 1, characterized in that, The naphthenic rubber oil base oil is obtained by hydrogenation treatment, hydroisomerization dewaxing, and hydrorefining of naphthenic feedstock oil.
3. The rubber oil composition according to claim 1, characterized in that, The phosphite antioxidants are selected from one or more of the following: pentaerythritol diisodecyl phosphite, poly(dipropylene glycol) phenyl phosphite, phenyl diisodecyl phosphite, tetraphenyl dipropylene glycol diphosphite, diphenyl isodecyl phosphite, diphenyl phosphite, tri(dodecyl) phosphite, phenyl diisooctyl phosphite, tri(tetranyl) phosphite, tri(nonylphenol) phosphite, tri(2-nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and pentapentetol dibis(2,4-di-tert-butylphenyl) phosphite. The hindered phenolic antioxidant is selected from one or more of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, and 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane; The organic acid is selected from one or more of isostearic acid, stearic acid, isopalactic acid, palmitic acid, oleic acid, isononanoic acid, nonanoic acid, isooctanoic acid, octanoic acid, fruit acid, benzoic acid, citric acid, malic acid, tartaric acid, acetic acid, succinic acid, and oxalic acid; The ultraviolet absorber is selected from 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole.
4. The method for preparing the rubber oil composition according to any one of claims 1-3, characterized in that, Includes the following steps: (1) Preparation of naphthenic rubber oil base oil: Naphthenic feedstock oil is subjected to hydrogenation treatment, hydrogenation isomerization dewaxing and hydrogenation supplementation refining in sequence to obtain the base oil. (2) Preparation of antioxidants: ① Take the liquid components of phosphite antioxidants, hindered phenolic antioxidants and / or organic acids, heat and stir until homogeneous to obtain the product, or add them to ultraviolet absorbers and dissolve until clear. Alternatively, ② take the solid components of phosphite antioxidants, hindered phenolic antioxidants, and / or organic acids and dissolve them in the target rubber oil base oil to obtain the product; or add an ultraviolet absorber and mix evenly to obtain the product. Alternatively, the antioxidants prepared in steps ① and ② can be mixed to obtain the desired product; (3) Add the antioxidant obtained in step (2) to the naphthenic rubber base oil prepared in step (1), heat and stir to obtain the product.
5. The preparation method according to claim 4, characterized in that, The catalyst for hydrogenation treatment uses alumina as a support and molybdenum oxide and nickel oxide as active components; wherein, molybdenum oxide accounts for 4.0-30.0 wt% of the catalyst and nickel oxide accounts for 1.0-6.0 wt% of the catalyst. The specific process parameters are as follows: hydrogen partial pressure 17.0-19.0 MPa; reaction temperature 370-410℃; space velocity 1.0-1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 1500-2500:
1.
6. The preparation method according to claim 5, characterized in that, The catalyst has a total acid content of 0.5-1.0 mmol / g, with a strong acid content of 40-45%, a medium-strong acid content of 20-25%, and a weak acid content of 35-40%.
7. The preparation method according to claim 4, characterized in that, The hydroisomerization dewaxing catalyst uses molecular sieves as a support and oxides of group VIII elements as active components; wherein the mass percentage of the active components is 0.1-1.0%. The specific process parameters are as follows: hydrogen partial pressure 17-19 MPa; temperature 330-400℃; space velocity 0.5-0.7 h⁻¹ -1 The hydrogen-to-oil volume ratio is 1500-2000:
1.
8. The preparation method according to claim 4, characterized in that, The hydrogenation supplemental refining catalyst uses amorphous silica-alumina as a support and oxides of group VIII elements as active components; wherein the active components account for 0.3-1.5% by mass. The specific process parameters are as follows: hydrogen partial pressure is 17.0-19.0 MPa; reaction temperature is 280-320℃; space velocity is 2.0-2.5 h⁻¹; hydrogen-to-oil volume ratio is 1500-2000:
1.
9. The preparation method according to claim 4, characterized in that, Also includes: The hydrotreated naphthenic feedstock oil is subjected to gas-liquid separation, and the liquid phase is fractionated to collect fractions with temperatures above 360°C, 390°C, and 420°C, which are used as rubber oil base oils.
10. The application of the rubber oil composition prepared by the method of any one of claims 1-3 or any one of claims 4-9 in oil-extended elastomer particles and oil-extended rubber products.