Aromatic oil composition as well as preparation method and application thereof

Abstract

The invention provides an aromatic oil composition as well as a preparation method and application thereof. The aromatic oil composition is prepared from the following components in parts by weight: 10-50 parts of petroleum asphalt; 30-80 parts of environment-friendly aromatic hydrocarbon oil; and 5-10 parts of acenaphthene resin. The acenaphthylene resin is introduced for the first time and is compounded with the petroleum asphalt and the environment-friendly aromatic hydrocarbon oil, the rubber modulus is improved, filler dispersion and hysteresis loss optimization are achieved, and when the rubber is used for new energy automobile tire tread rubber, the wet skid resistance can be remarkably improved, the rolling resistance is reduced, the wear resistance is enhanced, and breakthrough balance of magic triangle performance is achieved.

Description

Technical Field

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

[0002] With the rapid development of new energy vehicles, higher demands are being placed on tire performance. New energy vehicles are heavier, have higher instantaneous torque, and are sensitive to driving range; therefore, tires need to achieve a better balance between rolling resistance, wet grip, and wear resistance (commonly known as the "magic triangle"): reducing rolling resistance to improve range, enhancing wet grip to ensure safe handling under high torque, and improving wear resistance to cope with greater vehicle weight. Traditional aromatic oil plasticizer systems are insufficient to meet these comprehensive requirements.

[0003] In existing technologies, high-performance tires often employ a silica / silane coupling agent system combined with environmentally friendly aromatic oils (such as TDAE and NAP) to reduce rolling resistance. However, these environmentally friendly oils have low aromatic content, resulting in reduced compatibility with polar rubbers (such as solution-polymerized styrene-butadiene rubber SSBR) and a weakened effect on filler dispersion, leading to a sacrifice in abrasion resistance and wet grip. Introducing functional resins can improve specific properties, but existing resins often negatively impact rolling resistance, have poor environmental performance, or struggle to achieve multiple performance goals simultaneously. 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, its preparation method, and its applications are proposed, and the following technical solution is provided: An aromatic oil composition is made from the following components in parts by weight: 10-50 parts of petroleum asphalt; 30-80 parts of environmentally friendly aromatic oil; and 5-10 parts of acenaphthene resin.

[0005] Furthermore, the mass ratio of the petroleum asphalt to acenaphthene resin is 4-6:1.

[0006] Furthermore, there are 35 parts of petroleum asphalt; 57 parts of environmentally friendly aromatic oil; and 8 parts of acenaphthene resin.

[0007] Furthermore, the number-average molecular weight of the acenaphthene resin is between 800 g / mol and 1500 g / mol.

[0008] Furthermore, the acenaphthene resin is an acenaphthene homopolymer or an acenaphthene-indene copolymer.

[0009] Furthermore, the softening point of the petroleum asphalt is 60°C to 90°C, and the environmentally friendly aromatic oil is a distilled aromatic oil or a high-aromatic environmentally friendly oil with a polycyclic aromatic hydrocarbon content of less than 3%.

[0010] In addition, the present invention also provides a method for preparing the above-mentioned aromatic oil composition, the method being 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; the second part of environmentally friendly aromatic oil is added to the asphalt resin complex and stirred again to obtain the aromatic oil composition.

[0011] Furthermore, the mass ratio of the first part of environmentally friendly aromatic oil to the second part of environmentally friendly aromatic oil is 3-6:4-7.

[0012] Furthermore, the temperature for premixing the acenaphthene resin with 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 melted petroleum asphalt 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; the temperature for adding the second part of environmentally friendly aromatic oil to the asphalt resin composite and stirring again is 130℃ to 150℃, and the time is 1 to 2 hours.

[0013] The present invention also provides a use of an aromatic oil composition as a plasticizer in tire tread compound.

[0014] Beneficial effects: 1. This invention introduces acenaphthene resin for the first time, which is compounded with petroleum asphalt and environmentally friendly aromatic oil. Through a specific pre-dissolution and high-speed shear compounding process, π-π conjugation and polar interaction between components are achieved, which improves the modulus of the rubber compound, the dispersion of fillers and the optimization of hysteresis loss. When used in the tread compound of new energy vehicle tires, it can significantly improve wet skid resistance, reduce rolling resistance and enhance wear resistance, and achieve a breakthrough balance of the "magic triangle" performance.

[0015] 2. The aromatic oil composition of the present invention, through the combined action of the rigid aromatic ring structure of acenaphthene resin and the polar components of asphalt, can form more and stronger local interaction points in the rubber matrix, increasing the hysteresis loss of the rubber compound at low temperature and high frequency. The stable composite system formed by acenaphthene resin, base oil, and asphalt promotes more uniform dispersion and more effective silanization of fillers such as silica, significantly reducing the frictional heat generation of polymer chain segments and filler networks under high temperature and low strain. The rigid structure of acenaphthene resin, as a "reinforcing point," together with asphalt, improves the crosslinking network strength and hardness of the rubber compound, reduces material spalling during friction, and significantly improves wear resistance.

[0016] 3. This invention employs pre-dissolution and high-speed shear compounding to ensure uniform dispersion of acenaphthene resin and prevent precipitation. Compared to existing stirring methods, this process promotes the full interaction between polar groups and asphaltene, forming "reinforcing points," optimizing filler (such as silica) dispersion, reducing abrasion, ensuring the product meets PCA content standards, and the pre-dissolution process ensures product storage stability, ease of pumping, and mixing dispersion. Attached Figure Description

[0017] Figure 1 This is a product diagram of product S1 obtained in 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 the following components in parts by weight: 10-50 parts petroleum asphalt; 30-80 parts environmentally friendly aromatic oil; and 5-10 parts acenaphthene resin. The present invention forms a novel environmentally friendly aromatic oil composition by compounding petroleum asphalt, environmentally friendly aromatic oil, and acenaphthene resin in specific proportions. Petroleum asphalt, as the gum component, provides adhesion and cohesive strength; the environmentally friendly aromatic oil, as the base carrier, ensures low PCA content and plasticizing effect; the acenaphthene resin introduces a rigid aromatic ring structure, utilizing its moderate polarity and thermal stability to form a π-π conjugated system with other components, promoting filler dispersion and rubber compatibility. Compared to existing simple aromatic oils, this composition significantly improves the "magic triangle" performance when applied to tire tread rubber.

[0020] The mass ratio of acenaphthene resin to petroleum asphalt is 4-6:1. This invention reveals a synergistic effect between acenaphthene resin and petroleum asphalt. This ratio is optimized based on the interaction between the rigid aromatic ring of the acenaphthene resin and the asphaltenes in petroleum asphalt, ensuring that the acenaphthene resin is fully embedded in the asphalt to form a stable complex. This promotes hydrogen bonding and van der Waals forces between polar groups, resulting in more "reinforcing points" in the composition and preventing insufficient rigidity due to too little acenaphthene or phase separation due to too much.

[0021] The number-average molecular weight of the acenaphthene resin is 800 g / mol to 1500 g / mol. The molecular weight of 800-1500 g / mol ensures a moderate chain length, and the rigid aromatic ring is compatible with the rubber chain segment, avoiding the volatilization of low molecular weight or the difficulty of dispersion of high molecular weight.

[0022] The acenaphthene resin is an acenaphthene homopolymer or an acenaphthene-indene copolymer. The acenaphthene homopolymer or acenaphthene-indene copolymer provides a polyaromatic backbone, while indene introduces additional rigidity, improving compatibility with asphalt and forming a stable π-π system.

[0023] The preparation method of the aromatic oil composition is as follows: Environmentally friendly aromatic oil is divided into a first part and a second part. Acenamethanone resin is premixed with the first part of the environmentally friendly aromatic oil to obtain a resin oil solution, ensuring full resin activity and preventing later precipitation. Petroleum asphalt is melted and reacted with the resin oil solution to obtain an asphalt-resin complex, allowing the polar groups of the acenamethanone resin to fully interact with the asphalt's resinous-asphaltenite components. The second part of the environmentally friendly aromatic oil is added to the asphalt-resin complex and stirred again to obtain the aromatic oil composition. This application uses stepwise compounding, pre-dissolution to ensure uniform dispersion of the acenamethanone resin, high-speed shearing to promote compounding with asphalt, and final adjustment to reduce viscosity and prevent precipitation. This method makes the product stable during storage, easy to pump, and improves performance consistency by 20%. Compared with simple stirring, the filler dispersion is optimized.

[0024] The specific raw materials used in this application are as follows: Petroleum asphalt: softening point 75℃, penetration 45 (0.1mm), No. 70 road petroleum asphalt from Panjin Northern Asphalt Co., Ltd.

[0025] Environmentally friendly aromatic oil E1: TDAE oil, viscosity 108 cSt at 40℃, PCA <1%, Ningbo Hansheng Chemical Co., Ltd., brand name Vivatec 500.

[0026] Environmentally friendly aromatic oil E2: High aromatic environmentally friendly oil (HAE), viscosity at 40℃ 95 cSt, PCA < 2.5ppm, aromatic carbon content CA > 30%, produced by Jinan Refining & Chemical Branch of China Petroleum & Chemical Corporation, grade JN200.

[0027] Acenamethanone Resin A: Acenamethanone-Indene copolymer, Mn=1200, softening point 135℃, manufactured by Qianyu Semiconductor Materials (Jiangsu) Co., Ltd., brand name EX resin.

[0028] Acenamethane homopolymer, Lüttger (Shanghai) Trading Co., Ltd., brand name Novales® CA 100.

[0029] Example 1 Formula: 35 parts petroleum asphalt, 57 parts environmentally friendly aromatic oil E1, and 8 parts acenaphthene resin A.

[0030] Preparation method: Premixing: Dissolve and premix 8 parts of acenaphthene resin A and 28 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0031] Stirring reaction: 35 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0032] Final adjustment: Add 29 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0033] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product S1, as shown. Figure 1 As shown.

[0034] Example 2 Formula: 25 parts petroleum asphalt, 67 parts environmentally friendly aromatic oil E2, and 8 parts acenaphthene resin A.

[0035] Preparation method: Premixing: Dissolve and premix 8 parts of acenaphthene resin A and 33 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 150°C for 3 hours to obtain solution A.

[0036] Stirring reaction: 25 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 155℃ and 1000 rpm for 2 hours to obtain complex B.

[0037] Final adjustment: Add 34 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0038] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product S2.

[0039] Example 3 Formula: 10 parts petroleum asphalt, 80 parts environmentally friendly aromatic oil E1, and 10 parts acenaphthene resin A.

[0040] Preparation method: Premixing: Dissolve and premix 10 parts of acenaphthene resin A and 24 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0041] Stirring reaction: 10 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0042] Final adjustment: Add 56 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0043] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product S3.

[0044] Example 4 Formula: 50 parts petroleum asphalt, 30 parts environmentally friendly aromatic oil E1, and 5 parts acenaphthene resin A.

[0045] Preparation method: Premixing: Dissolve and premix 5 parts of acenaphthene resin A and 18 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0046] Stirring reaction: 50 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0047] Final adjustment: Add 12 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0048] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product S4.

[0049] Example 5 Formula: 40 parts petroleum asphalt, 50 parts environmentally friendly aromatic oil E1, and 8 parts acenaphthene resin A.

[0050] Preparation method: Premixing: Dissolve and premix 8 parts of acenaphthene resin A and 28 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0051] Stirring reaction: 35 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0052] Final adjustment: Add 29 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0053] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product S5.

[0054] Comparative Example 1 Formula: Contains only environmentally friendly aromatic oil E1, which is D1.

[0055] Comparative Example 2 Formula: 35 parts petroleum asphalt, 65 parts environmentally friendly aromatic oil E1.

[0056] Preparation method: 35 parts of petroleum asphalt were melted at 165℃, and 32 parts of environmentally friendly aromatic oil E1 were added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours. Then, 33 parts of the remaining environmentally friendly aromatic oil E1 were added, and the mixture was stirred at 140℃ for 1.5 hours. The mixture was then cooled to 70℃ and filtered through a 200-mesh filter to obtain product D2.

[0057] Comparative Example 3 Formula: 35 parts petroleum asphalt, 57 parts environmentally friendly aromatic oil E1, and 8 parts C9 petroleum resin.

[0058] Preparation method: Premixing: Dissolve and premix 8 parts of C9 petroleum resin and 28 parts of environmentally friendly aromatic oil E1 by stirring at 160°C under nitrogen for 3 hours to obtain solution A.

[0059] Stirring reaction: 35 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0060] Final adjustment: Add 29 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0061] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product D3.

[0062] Comparative Example 4 Formula: 35 parts petroleum asphalt, 62 parts environmentally friendly aromatic oil E1, and 3 parts acenaphthene resin A.

[0063] Preparation method: Premixing: Dissolve and premix 3 parts of acenaphthene resin A and 28 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0064] Stirring reaction: 35 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0065] Final adjustment: Add 29 parts of the remaining environmentally friendly aromatic oil E1 to the B complex and stir at 140°C for 1.5 hours.

[0066] Cooling and filtration: Cool to 70℃, filter through a 200-mesh filter to obtain product D4.

[0067] Comparative Example 5 Formula: 35 parts petroleum asphalt, 57 parts environmentally friendly aromatic oil E1, and 8 parts acenaphthene resin A.

[0068] Preparation method: Premixing: Dissolve and premix 8 parts of acenaphthene resin A and 57 parts of environmentally friendly aromatic oil E1 by stirring under nitrogen at 160°C for 3 hours to obtain solution A.

[0069] Stirring reaction: 35 parts of petroleum asphalt were melted at 165℃, and liquid A was added. The mixture was sheared and mixed at 160℃ and 1000 rpm for 2 hours to obtain complex B.

[0070] Cooling and filtration: Cool to 70℃, filter with 200 mesh to obtain product D5.

[0071] Tire tread compounds were prepared using the products obtained in Examples 1-5 and Comparative Examples 1-5, respectively. The specific formulations are shown in Table 1.

[0072] Table 1 Tire tread compound formulation The vulcanization temperature was 150℃ for 30 minutes. The resulting tread compound was then subjected to performance testing.

[0073] Processability: Mooney viscosity.

[0074] Vulcanization characteristics: T90 @ 150℃.

[0075] Mechanical properties: tensile strength, elongation at break, stress at 300% elongation, tear strength.

[0076] 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℃.

[0077] Abrasion resistance: DIN abrasion tester, volume loss (mm³).

[0078] Environmental friendliness: Tested for 8 types of PCA according to REACH regulations.

[0079] The test results are shown in Table 2.

[0080] Table 2. Test results of tire tread compounds prepared from the products obtained in Examples 1-5 and Comparative Examples 1-5. Anti-slip properties: The 0°C tanδ values ​​of Examples 1 and 2 are significantly higher than all comparative examples, especially about 16%-20% higher than the benchmark environmentally friendly oil in Comparative Example 1, proving that the product of the present invention can significantly improve wet grip safety. Rolling resistance: The 60°C tanδ value of the examples is significantly lower than all comparative examples, about 17%-20% lower than Comparative Example 1, which means better endurance performance.

[0081] Abrasion resistance: The DIN wear volume of the example was much lower than that of the comparative example, and was improved by about 23% compared with the comparative example 1, which verifies the outstanding contribution of the rigid structure of acenaphthene to abrasion resistance.

[0082] In traditional technologies, improving one aspect often comes at the expense of another. However, this invention simultaneously achieves high 0°C tanδ, low 60°C tanδ, and low wear, truly breaking the trade-off dilemma of the "magic triangle."

[0083] Comprehensive enhancement of mechanical properties: The example demonstrates superior tensile strength, modulus (300% tensile stress), and tear strength, indicating that the acenaphthene resin-asphalt composite system effectively enhances the rigidity and toughness of the compound.

[0084] Key aspects of composition and process: Comparative Example 2 (without resin) and Comparative Example 3 (using C9 resin) are significantly inferior to the embodiments of the present invention in all aspects, especially in the balance of dynamic properties and abrasion resistance. This strongly demonstrates the irreplaceable nature of acenaphthene resin in the specific system of the present invention, and the necessity of the dissolution-then-composite process for maximizing its performance.

[0085] In summary, the environmentally friendly aromatic oil based on acenaphthene structure provided by this invention, through innovative component design and preparation process, has been successfully applied to tire rubber compounds for new energy vehicles. Under the premise of strictly complying with environmental standards, it has achieved a significant simultaneous improvement in the three core properties of rolling resistance, wet skid resistance, and wear resistance, meeting the special needs of new energy vehicles for tire technology and having significant industrial application value.

[0086] 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, It is made from the following components in parts by weight: 10-50 parts petroleum asphalt; 30-80 parts environmentally friendly aromatic oil; and 5-10 parts acenaphthene resin.

2. The aromatic oil composition according to claim 1, characterized in that, The mass ratio of petroleum asphalt to acenaphthene resin is 4-6:

1.

3. The aromatic oil composition according to claim 1, characterized in that, 35 parts of petroleum asphalt; 57 parts of environmentally friendly aromatic oil; and 8 parts of acenaphthene resin.

4. The aromatic oil composition according to claim 2, characterized in that, The number-average molecular weight of the acenaphthene resin is between 800 g / mol and 1500 g / mol.

5. The aromatic oil composition according to claim 3, characterized in that, The acenaphthene resin is an acenaphthene homopolymer or an acenaphthene-indene copolymer.

6. The aromatic oil composition according to claim 2, characterized in that, The softening point of the petroleum asphalt is 60°C to 90°C, and the environmentally friendly aromatic oil is a distilled aromatic oil or a high-aromatic environmentally friendly oil with a polycyclic aromatic hydrocarbon content of less than 3%.

7. The method for preparing the aromatic oil composition according to claim 1, 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. The second part of environmentally friendly aromatic oil is added to the asphalt resin complex and stirred again to obtain an aromatic oil composition.

8. The preparation method according to claim 7, 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 3-6:4-7.

9. The preparation method according to claim 7, characterized in that, The temperature for premixing the acenaphthene resin with 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 melted petroleum asphalt 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; the temperature for adding the second part of environmentally friendly aromatic oil to the asphalt resin composite and stirring again is 130℃ to 150℃, and the time is 1 to 2 hours.

10. The use of the aromatic oil composition according to any one of claims 1-6, characterized in that, The aromatic oil composition is used as a plasticizer in tire tread compound.

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