Aromatic oil composition and preparation method thereof

Abstract

The invention provides an aromatic oil composition and a preparation method thereof, and the aromatic oil composition comprises the following components by weight: 10-50 parts of petroleum asphalt; 30-70 parts of environment-friendly aromatic hydrocarbon oil; 5 to 15 parts of acenaphthylene resin; and 5-20 parts of low condensation point alkylbenzene. The acenaphthylene resin and the low-condensation-point short-chain alkylbenzene are combined and applied to the environment-friendly aromatic oil for the first time, the technical problem that traditional environment-friendly aromatic oil is poor in low-temperature performance is solved through the synergistic effect of the rigid condensed ring structure of the acenaphthylene resin and the low-temperature fluidity of the short-chain alkylbenzene, and the product keeps stable performance within the temperature range of-50 DEG C to 150 DEG C; and the high-performance tire is suitable for extreme weather conditions. The elongation at break of a rubber product at-40 DEG C is greater than or equal to 150%, and the tensile strength at 100 DEG C is greater than or equal to 15 MPa, so that the rubber product is obviously superior to a traditional product.

Description

Technical Field

[0001] This invention relates to the field of rubber processing aids, specifically to an aromatic oil composition and its preparation method. Background Technology

[0002] Aromatic oils, as important plasticizers and softeners in the rubber industry, directly affect the performance and application range of rubber products due to their temperature adaptability. Currently, mainstream environmentally friendly aromatic oil products on the market, such as TDAE (treated distilled aromatic oil) and MES (mildly extracted solvent oil), while meeting the EU REACH regulations in terms of environmental performance, have significant shortcomings in temperature adaptability. Specifically: poor low-temperature performance, with pour points typically between -15℃ and -25℃, making them prone to crystallization and precipitation in cold environments, leading to hardening and decreased elasticity in rubber products; insufficient high-temperature viscosity retention, with viscosity decreasing too rapidly at high temperatures, affecting the high-temperature performance of rubber products; and high temperature sensitivity, with unsatisfactory viscosity-temperature characteristics, making it difficult to meet the requirements for wide-temperature-range applications.

[0003] In existing technologies, to improve the low-temperature performance of aromatic oils, pour point depressants are typically added or compounded with low-viscosity oils. However, these methods often suffer from drawbacks such as limited pour point depressant effectiveness, potential impact on other oil properties, excessive addition of low-viscosity components damaging high-temperature performance, and compatibility issues leading to product instability. For example, Chinese patent CN102234188A discloses a method for preparing environmentally friendly warm-mix asphalt mixtures. This method involves adding aromatic oils to petroleum asphalt and stirring the mixture at 110–130°C for 15–20 minutes to prepare soft asphalt, which is then uniformly mixed with heated mineral aggregates, mineral powder fillers, hydrated lime, and rock asphalt. This technology primarily targets the warm-mix process of asphalt mixtures, aiming to reduce mixing, paving, and compaction temperatures to achieve energy conservation and environmental protection, but its focus is on improving the road performance of asphalt mixtures. Therefore, existing technologies require further development. Summary of the Invention

[0004] To address the shortcomings of existing technologies and solve the aforementioned problems, an aromatic oil composition and its preparation method are proposed, and the following technical solution is provided: An aromatic oil composition, by weight, comprises: 10-50 parts petroleum asphalt; 30-70 parts environmentally friendly aromatic oil; 5-15 parts acenaphthene resin; and 5-20 parts low-pour-point alkylbenzene.

[0005] The mass ratio of the acenaphthene resin to the low-pour-point alkylbenzene is 1-1.5:1.

[0006] Furthermore, by weight, it includes: 30 parts petroleum asphalt; 50 parts environmentally friendly aromatic oil; 10 parts acenaphthene resin; and 10 parts low-pour-point alkylbenzene.

[0007] Furthermore, the acenaphthene resin is an acenaphthene homopolymer or a copolymer of acenaphthene with at least one of styrene, α-methylstyrene, and indene, and the number-average molecular weight of the acenaphthene resin is from 800 g / mol to 1500 g / mol.

[0008] Furthermore, the low-pour-point alkylbenzene is an alkylbenzene with less than 10 carbon atoms in the alkyl chain and a pour point below -50°C.

[0009] Furthermore, the low-pour-point alkylbenzene is selected from one or more of butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, and nonylbenzene.

[0010] Furthermore, the softening point of the petroleum asphalt is 60℃~90℃, and the environmentally friendly aromatic oil is a distilled aromatic oil or a high-aromatic oil with a polycyclic aromatic hydrocarbon content of less than 3%.

[0011] In addition, this application also provides a method for preparing an aromatic oil composition, the method of which is as follows: the environmentally friendly aromatic oil is divided into a first part of environmentally friendly aromatic oil and a second part of environmentally friendly aromatic oil; acenaphthene resin is premixed with the first part of environmentally friendly aromatic oil to obtain a resin oil solution; petroleum asphalt is melted and stirred with the resin oil solution to obtain an asphalt resin complex; low-pour-point alkylbenzene and the second part of environmentally friendly aromatic oil are added to the asphalt resin complex and stirred again to obtain an aromatic oil composition.

[0012] Furthermore, the mass ratio of the first part of environmentally friendly aromatic oil to the second part of environmentally friendly aromatic oil is 3-5:5-8. The temperature at which the acenaphthene resin and the first part of environmentally friendly aromatic oil are premixed is 140℃-170℃, and the time is 2 to 4 hours. The temperature at which the petroleum asphalt is melted and stirred to react with the resin oil solution is 155℃ to 165℃, the stirring speed is 800 rpm to 1200 rpm, and the time is 1.5 to 2.5 hours.

[0013] Furthermore, the second part of the environmentally friendly aromatic oil is added to the asphalt resin composite and stirred again at a temperature of 130°C to 150°C for 1 to 2 hours.

[0014] Beneficial effects: 1. This invention is the first to combine acenaphthene resin with low-pour-point short-chain alkylbenzenes in environmentally friendly aromatic oils. The rigid fused ring structure of acenaphthene resin and the low-temperature fluidity of short-chain alkylbenzenes work synergistically to solve the technical problem of poor low-temperature performance of traditional environmentally friendly aromatic oils.

[0015] 2. The product of this invention maintains stable performance within a temperature range of -50℃ to 150℃, making it suitable for high-performance tires under extreme climatic conditions. The rubber product exhibits an elongation at break of ≥150% at -40℃ and a tensile strength of ≥15MPa at 100℃, significantly superior to traditional products.

[0016] 3. A step-by-step process is adopted, first allowing the acenaphthene resin to fully react with the asphalt to form a high-temperature stable structure, and then adding low-temperature components to avoid thermal decomposition, ensuring that the performance of each component is fully utilized. Inert gas protection and specific rotation speed further enhance product stability and prevent oxidation and phase separation. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the infrared spectrum structure of Embodiment 1 of the present invention. Detailed Implementation

[0018] To enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Based on the embodiments in this application, other similar embodiments obtained by those skilled in the art without creative effort should all fall within the scope of protection of this application.

[0019] According to embodiments of the present invention, an aromatic oil composition is provided, comprising, by weight: 10-50 parts petroleum asphalt; 30-70 parts environmentally friendly aromatic oil; 5-15 parts acenaphthene resin; and 5-20 parts low-pour-point alkylbenzene. This invention is the first to combine acenaphthene resin with low-pour-point short-chain alkylbenzene in an environmentally friendly aromatic oil. The rigid fused-ring structure of the acenaphthene resin and the low-temperature fluidity of the short-chain alkylbenzene work synergistically to solve the technical problem of poor low-temperature performance in traditional environmentally friendly aromatic oils. The product of this invention maintains stable performance within a temperature range of -50℃ to 150℃, making it suitable for high-performance tires under extreme climatic conditions. The rubber product exhibits an elongation at break ≥150% at -40℃ and a tensile strength ≥15MPa at 100℃, significantly superior to traditional products.

[0020] The specific raw materials used in this application are as follows: Acenamethanone Resin A: Acenamethanone-Indene copolymer, Mn=1200, softening point 135℃, manufactured by Qianyu Semiconductor Materials (Jiangsu) Co., Ltd., brand name EX resin.

[0021] Environmentally friendly aromatic oil: TDAE oil, viscosity 108 cSt at 40℃, PCA <1%, Ningbo Hansheng Chemical Co., Ltd., brand name Vivatec 500.

[0022] Petroleum asphalt: softening point 75℃, penetration 45 (0.1mm), No. 70 road petroleum asphalt from Panjin Northern Asphalt Co., Ltd.

[0023] Example 1 The formula is as follows by weight: 30 parts petroleum asphalt, 50 parts environmentally friendly aromatic oil, 10 parts acenaphthene resin, and 10 parts octylbenzene.

[0024] Preparation process: The environmentally friendly aromatic oil is divided into a first part and a second part, with a mass ratio of 4:6. Under nitrogen protection, 20% of the total amount of acenaphthene resin and environmentally friendly aromatic oil is added to a reactor, heated to 150℃, and stirred for 2 hours until completely dissolved. Petroleum asphalt is preheated to a fully fluid state at 165℃. The preheated petroleum asphalt is added to the reactor, and the temperature is maintained at 160℃, with stirring at 1000 rpm for 3 hours. Octylbenzene is preheated to 70℃ and added to the reactor, along with the remaining second part of environmentally friendly aromatic oil. The system temperature is adjusted to 130℃, and stirred for 1.5 hours until completely homogeneous. The mixture is then cooled to 65℃ and filtered through a 200-mesh filter to obtain the product. Infrared spectroscopy characterization was performed on this product, and the test results are as follows: Figure 1 As shown in the infrared spectrum, the sample at 700 cm⁻¹ -1 750 cm -1 800 cm -1 850 cm -1 Several characteristic absorption peaks appeared in the region, which are attributed to the out-of-plane bending vibration of the aromatic ring, among which the 700 cm⁻¹ peak is the most prominent. -1 The strong absorption at 750-800 cm⁻¹ is a typical characteristic of monosubstituted benzenes, originating from the octylbenzene component in the formulation, while... -1 The absorption in this region corresponds to the fused-ring aromatic hydrocarbon structure, primarily originating from the acenaphthene and naphthalene ring units of the acenaphthene resin. (1600 cm⁻¹) -1 The strong absorption peak at 2800-3000 cm⁻¹ is characteristic of the C=C skeletal vibration of aromatic rings, confirming the presence of a conjugated aromatic ring system in the sample. This also originates from the rigid fused ring structure of acenaphthene resin and the aromatic ring components in environmentally friendly aromatic oils. -1 The strong absorption peaks appearing in the region are attributed to the CH stretching vibrations of methyl and methylene groups, with the peak at 2850 cm⁻¹ being the most prominent. -1 and 2920 cm -1 The extremely significant absorption in the vicinity indicates that the sample contains abundant long-chain alkyl structures, mainly derived from alkyl side chains in petroleum asphalt, alkyl substituents in environmentally friendly aromatic oils, and octyl chains in octylbenzene. The absorption is most pronounced in the 1650-1800 cm⁻¹ region. -1 The absence of significant absorption in the region indicates the absence of carbonyl compounds, proving that the nitrogen-protected preparation process effectively prevents oxidation reactions. The infrared spectroscopy confirms that the preparation in Example 1 was successful.

[0025] Example 2 The formula, by weight, is as follows: 25 parts petroleum asphalt, 55 parts environmentally friendly aromatic oil, 12 parts acenaphthene resin, and 8 parts hexylbenzene.

[0026] Preparation process: The environmentally friendly aromatic oil is divided into a first part and a second part, with a mass ratio of 4:6. Under nitrogen protection, 20% of the total amount of acenaphthene resin and environmentally friendly aromatic oil is added to the reactor, heated to 150°C, and stirred for 2 hours until completely dissolved. Petroleum asphalt is preheated to a fully fluid state at 165°C. The preheated petroleum asphalt is added to the reactor, and the temperature is maintained at 160°C. The mixture is stirred at 1000 rpm for 3 hours. Octylbenzene is preheated to 70°C and added to the reactor, along with the remaining second part of environmentally friendly aromatic oil. The system temperature is adjusted to 130°C, and the mixture is stirred for 1.5 hours until completely homogeneous. The mixture is then cooled to 65°C and filtered through a 200-mesh filter to obtain the product.

[0027] Example 3 The formula is as follows by weight: 50 parts petroleum asphalt, 30 parts environmentally friendly aromatic oil, 15 parts acenaphthene resin, and 5 parts hexylbenzene.

[0028] The preparation process is the same as in Example 1.

[0029] Example 4 The formula is as follows by weight: 10 parts petroleum asphalt, 70 parts environmentally friendly aromatic oil, 5 parts acenaphthene resin, and 20 parts hexylbenzene.

[0030] The preparation process is the same as in Example 1.

[0031] Example 5 The formula is as follows by weight: 30 parts petroleum asphalt, 50 parts environmentally friendly aromatic oil, 10 parts acenaphthene resin, and 10 parts octylbenzene.

[0032] Preparation process: The environmentally friendly aromatic oil is divided into a first part and a second part, with a mass ratio of 3:8. Under nitrogen protection, acenaphthene resin and the first part of the environmentally friendly aromatic oil are added to a reactor, heated to 150°C, and stirred for 2 hours until completely dissolved. Petroleum asphalt is preheated to a fully fluid state at 165°C. The preheated petroleum asphalt is added to the reactor, and the temperature is maintained at 160°C. The mixture is stirred at 1000 rpm for 3 hours. Octylbenzene is preheated to 70°C and added to the reactor, along with the remaining second part of the environmentally friendly aromatic oil. The mixture is then cooled to 65°C and filtered through a 200-mesh filter to obtain the product.

[0033] The preparation process is the same as in Example 1.

[0034] Adjust the system temperature to 130℃ and stir for 1.5 hours until completely homogeneous. Example 6 The formula is as follows by weight: 30 parts petroleum asphalt, 50 parts environmentally friendly aromatic oil, 10 parts acenaphthene resin, and 10 parts octylbenzene.

[0035] Preparation process: The environmentally friendly aromatic oil is divided into a first part and a second part, with a mass ratio of 1:1. Under nitrogen protection, acenaphthene resin and the first part of the environmentally friendly aromatic oil are added to a reactor, heated to 150°C, and stirred for 2 hours until completely dissolved. Petroleum asphalt is preheated to a fully fluid state at 165°C. The preheated petroleum asphalt is added to the reactor, and the temperature is maintained at 160°C. The mixture is stirred at 1000 rpm for 3 hours. Octylbenzene is preheated to 70°C and added to the reactor, along with the remaining second part of the environmentally friendly aromatic oil. The system temperature is adjusted to 130°C, and the mixture is stirred for 1.5 hours until completely homogeneous. The mixture is then cooled to 65°C and filtered through a 200-mesh filter to obtain the product.

[0036] Comparative Example 1 The formula is as follows, by weight: 30 parts petroleum asphalt, 60 parts environmentally friendly aromatic oil, and 10 parts acenaphthene resin; Preparation: Refer to Example 1, without adding low-pour-point alkylbenzene.

[0037] Comparative Example 2 The formula is as follows, by weight: 30 parts petroleum asphalt, 55 parts environmentally friendly aromatic oil, and 15 parts octylbenzene; Preparation: Refer to Example 1, but omit the acenaphthene resin dissolution step and mix directly.

[0038] Comparative Example 3 The formula is as follows by weight: 30 parts petroleum asphalt, 58 parts environmentally friendly aromatic oil, 10 parts acenaphthene resin, and 2 parts polymethyl methacrylate pour point depressant.

[0039] Preparation: Referring to Example 1, polymethacrylate, a pour point depressant, was used instead of octylbenzene.

[0040] The products prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to physicochemical property tests. The test methods are as follows: Physicochemical property tests: Kinematic viscosity: This refers to the ratio of the dynamic viscosity of a liquid to its density at the same temperature and pressure, reflecting the resistance to flow of the liquid under gravity. Its unit is millimeters per second (mm² / s). Kinematic viscosity at 40℃ and 100℃ is tested according to GB / T 265 standard. Flash point: Under specified test conditions, the lowest temperature at which a mixture of petroleum product vapor and surrounding air ignites momentarily upon contact with an ignition source (the flame spreads to the liquid surface but does not continue to burn). The higher the flash point, the lower the fire risk. According to GB / T 3536-2008 "Determination of Flash Point and Ignition Point of Petroleum Products - Cleveland Open Cup Method"; Low-temperature dynamic viscosity: The dynamic viscosity at -30℃ was tested according to NB / SH / T 0562-2013 "Determination of Yield Stress and Actual Viscosity of Engine Oil at Low Temperature"; High and low temperature storage stability: After refrigerating at -30℃ for 7 days, place in a 100℃ oven for 7 days. Observe the changes in appearance.

[0041] The specific test results are shown in Table 1.

[0042] Table 1. Test results of the physicochemical properties of the products prepared in Examples 1-6 and Comparative Examples 1-3 The products prepared in Examples 1-6 and Comparative Examples 1-3 were added to rubber compounds, and the mechanical properties of the rubber were tested.

[0043] Rubber compound formulation (parts by weight): 80 parts styrene-butadiene rubber, 20 parts butadiene rubber, 15 parts carbon black, 80 parts silica, 4 parts zinc oxide, 2 parts stearic acid, 2 parts antioxidant, 1.8 parts accelerator, 1.5 parts sulfur, and 30 parts of the product prepared in the examples or comparative examples.

[0044] The vulcanization temperature was 150℃ for 30 minutes. The resulting tread compound was then subjected to performance testing.

[0045] Processability: Mooney viscosity.

[0046] Vulcanization characteristics: T90 @ 150℃.

[0047] Mechanical properties: tensile strength, elongation at break, stress at 300% elongation, tear strength.

[0048] Dynamic mechanical properties (DMA): Temperature scan (-30℃-80℃, 10Hz, strain 0.1%-2%), recording tanδ (wet slip index) at 0℃ and tanδ (rolling resistance index) at 60℃.

[0049] Abrasion resistance: DIN abrasion tester, volume loss (mm³).

[0050] Environmental friendliness: Tested for 8 types of PCA according to REACH regulations.

[0051] The test results are shown in Table 2.

[0052] Table 2. Test results of rubber compounds prepared from the products obtained in Examples 1-6 and Comparative Examples 1-3. The performance of Examples 1-6 was compared with that of Comparative Examples 1-3. The results show that the present invention significantly improves the wide-temperature-range performance of the aromatic oil composition through the synergistic effect of acenaphthene resin and low-pour-point alkylbenzenes. Specifically, the dynamic viscosity of Examples 1-6 at -30℃ was significantly lower than that of Comparative Examples 1 and 2, and their low-temperature storage stability was satisfactory, while the comparative examples all showed precipitation or stratification. This indicates that the combination of acenaphthene resin and short-chain alkylbenzenes effectively solves the problem of poor low-temperature fluidity of traditional environmentally friendly aromatic oils. Regarding high-temperature stability, the examples remained homogeneous after heat storage at 100℃, while the comparative examples showed stratification, indicating that the composite structure formed by acenaphthene resin and petroleum asphalt has good high-temperature compatibility. In rubber compound applications, the tread rubber obtained from the examples is superior to the comparative examples in terms of tensile strength, tear strength, wet skid resistance, and rolling resistance, while also exhibiting better abrasion performance, demonstrating a superior balance between comprehensive mechanical and dynamic properties. The above results demonstrate that the present invention, through the combination of component synergy and stepwise preparation process, has successfully achieved stable application of aromatic oil compositions in a wide temperature range of -50℃ to 150℃, making them suitable for rubber products under extreme working conditions such as high-performance tires.

[0053] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An aromatic oil composition, characterized in that, By weight, it includes: 10-50 parts petroleum asphalt; 30-70 parts environmentally friendly aromatic oil; 5-15 parts acenaphthene resin; and 5-20 parts low-pour-point alkylbenzene.

2. The aromatic oil composition according to claim 1, characterized in that, The mass ratio of the acenaphthene resin to the low-pour-point alkylbenzene is 1-1.5:

1.

3. The aromatic oil composition according to claim 1, characterized in that, By weight, it includes: 30 parts petroleum asphalt; 50 parts environmentally friendly aromatic oil; 10 parts acenaphthene resin; and 10 parts low-pour-point alkylbenzene.

4. The aromatic oil composition according to claim 1, characterized in that, The acenaphthene resin is a homopolymer of acenaphthene or a copolymer of acenaphthene with at least one of styrene, α-methylstyrene, and indene, and the number-average molecular weight of the acenaphthene resin is from 800 g / mol to 1500 g / mol.

5. The aromatic oil composition according to claim 2, characterized in that, The low-pour-point alkylbenzene is an alkylbenzene with less than 10 carbon atoms in its alkyl chain and a pour point below -50°C.

6. The aromatic oil composition according to claim 1, characterized in that, The low-pour-point alkylbenzene is selected from one or more of butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, and nonylbenzene.

7. The aromatic oil composition according to claim 1, characterized in that, The softening point of the petroleum asphalt is 60℃~90℃, and the environmentally friendly aromatic oil is an aromatic oil with a polycyclic aromatic hydrocarbon content of less than 3%.

8. A method for preparing an aromatic oil composition according to any one of claims 1-7, characterized in that, The preparation method is as follows: the environmentally friendly aromatic oil is divided into a first part of environmentally friendly aromatic oil and a second part of environmentally friendly aromatic oil. Acenamel resin is premixed with the first part of environmentally friendly aromatic oil to obtain a resin oil solution. Petroleum asphalt is melted and stirred with the resin oil solution to obtain an asphalt resin complex. Low-pour-point alkylbenzene and the second part of environmentally friendly aromatic oil are added to the asphalt resin complex and stirred again to obtain an aromatic oil composition.

9. The method for preparing the aromatic oil composition according to claim 8, characterized in that, The mass ratio of the first part of environmentally friendly aromatic oil to the second part of environmentally friendly aromatic oil is 3-5:5-8. The temperature for premixing the acenaphthene resin and the first part of environmentally friendly aromatic oil is 140℃-170℃, and the time is 2 to 4 hours. The temperature for stirring and reacting the petroleum asphalt with the resin oil solution after melting is 155℃ to 165℃, the stirring speed is 800 rpm to 1200 rpm, and the time is 1.5 to 2.5 hours.

10. The method for preparing the aromatic oil composition according to claim 8, characterized in that, The second part of the environmentally friendly aromatic oil is added to the asphalt resin composite and stirred again at a temperature of 130°C to 150°C for 1 to 2 hours.

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