Modified petroleum resin with high softening point and high cohesiveness and preparation method thereof

Abstract

The invention relates to the technical field of modified petroleum resin, in particular to modified petroleum resin with a high softening point and high cohesiveness and a preparation method of the modified petroleum resin. The preparation method of the modified petroleum resin comprises the following steps: under the action of a Lewis acid catalyst, benzenediol and divinyl benzene are subjected to an alkylation reaction, and a product is subjected to flash evaporation at 210 DEG C and-90 kPa to remove unreacted raw materials and is recycled; and mixing the resin liquid with polyisobutylene succinic anhydride according to a mass ratio of (1-20): 1, and reacting to obtain the product. The softening point of the modified petroleum resin is 125-170 DEG C, the Gardner color number is smaller than 3, the VOC content is smaller than 0.5%, the modified petroleum resin has excellent initial viscosity, damp-heat aging resistance and high-temperature thermal stability, the compatibility with a rubber matrix is good, the Mooney viscosity of a rubber material can be effectively reduced, the mechanical property can be guaranteed, and the modified petroleum resin can be applied to the rubber industrial fields of tire production, waste tire recycling and the like.

Description

Technical Field

[0001] This invention relates to the field of modified petroleum resin technology, and more particularly to a modified petroleum resin with high softening point and high adhesion, and its preparation method. Background Technology

[0002] In the tire manufacturing process, the surface tack and initial adhesion of uncured rubber compounds, especially synthetic rubber compounds, are core fundamental properties that ensure precise bonding and stable molding of various components. If the rubber compound itself has insufficient adhesion, semi-finished products are prone to dimensional deformation and cracking at the bonding areas during storage, turnover, and molding processes, directly threatening the structural integrity of the tire and disrupting the stability of the production process. Therefore, high-performance tackifiers have become an indispensable key material in the rubber industry. Currently, non-thermally reactive alkylphenol formaldehyde resins are widely used in this field due to their good initial tack. However, these resins have significant drawbacks; their resistance to damp heat aging is poor, and the tack rapidly decreases after aeration or storage in high-temperature and high-humidity environments. In actual production, rubber compounds often need to be stored and handled under high-temperature and high-humidity conditions in summer, placing even more stringent requirements on the long-term tack retention and damp heat stability of tackifiers.

[0003] To address the insufficient resistance to damp heat in traditional alkylphenol-formaldehyde resins, the industry has undertaken numerous technological explorations. While BASF's Koresin resin (alkylphenol-acetylene resin) achieves excellent long-lasting tackification and resistance to damp heat, its production process faces several bottlenecks: high production difficulty, complex processes, extremely high equipment requirements, and the significant safety hazards posed by the raw material acetylene, resulting in high product prices and hindering large-scale adoption. Although subsequent technologies, such as the Chinese patent CN105646806B which discloses acetylene-modified alkylphenol-formaldehyde resin to simulate Koresin's performance, remain dependent on acetylene raw materials and high-pressure reaction conditions, the inherent risks of the process and environmental issues have not been fundamentally resolved. Domestically, a series of modified resins based on phenol and formaldehyde or acetaldehyde have also been developed. For example, the modified phenolic resin with bismaleimide structure and halogen-substituted unsaturated hydrocarbons disclosed in Chinese patent CN113372521B has improved the viscosity decay problem and production safety hazards under high temperature and high humidity to a certain extent, and achieved efficient thickening and low heat generation effects. However, it still requires the use of formaldehyde aqueous solution, and a large amount of formaldehyde-containing wastewater will be generated during the production process, which greatly increases the post-treatment cost and does not conform to the development trend of green production.

[0004] In light of the shortcomings of existing technologies, the tire and rubber products industry urgently needs a new type of tackifying resin that can achieve the core functions of long-lasting tackification and resistance to damp heat aging, while avoiding the use of high-risk raw materials such as acetylene in the production process, requiring no high-pressure reaction equipment, and possessing the characteristics of simple process and environmental friendliness. Summary of the Invention

[0005] To address the aforementioned technical challenges, this technology aims to develop a novel type of solid tackifying resin. Through optimized design of the synthesis pathway and molecular structure, it achieves comprehensive tackifying performance comparable to or even superior to Koresin resin without relying on acetylene or requiring high-pressure reactions. In particular, it highlights its durable adhesion under high temperature and humidity conditions, high softening point characteristics, excellent aging resistance, and high compatibility with rubber matrices.

[0006] Specifically, the first aspect of this invention provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, comprising the following steps: S1. Mix hydroquinone and Lewis acid catalyst, add divinylbenzene, and carry out alkylation reaction. After the reaction is completed, filter out the Lewis acid catalyst to obtain resin solution A. S2. Flash evaporate resin solution A to obtain resin solution B; S3. Add polyisobutylene succinic anhydride to resin solution B and react. After the reaction is complete, cool to obtain modified petroleum resin. The softening point of the modified petroleum resin is ≥125℃ and the color number is 1.9-3.2.

[0007] As an implementable example, the hydroquinone includes one or more of catechol, resorcinol, and hydroquinone.

[0008] As an implementable example, the Lewis acid catalyst includes one or more of ZSM-5 molecular sieves, Y-type molecular sieves, Beta molecular sieves, aluminum chloride supported molecular sieves, zinc chloride supported molecular sieves, zinc chloride supported silica, and zinc chloride supported alumina.

[0009] Furthermore, the mass of the Lewis acid catalyst is 0.1-50% of the mass of hydroquinone.

[0010] Furthermore, the mass flow ratio of hydroquinone and divinylbenzene is (1~10):1, preferably (1.2~5):1.

[0011] Furthermore, the alkylation reaction is carried out at a temperature of 100-250°C and a pressure of 0-2 atm.

[0012] Existing high-performance tackifying resins, such as Koresin resin, rely on acetylene as a raw material, posing significant safety hazards and requiring high-pressure reaction conditions. Traditional phenolic resins, on the other hand, depend on formaldehyde aqueous solutions, generating large amounts of formaldehyde-containing wastewater with high post-treatment costs. This invention selects hydroquinone and divinylbenzene as reaction raw materials, completely eliminating dependence on high-risk, highly polluting raw materials such as acetylene and formaldehyde. On one hand, the raw materials themselves are highly safe, the reaction conditions are mild, and the production process poses no safety hazards such as explosions or toxic gas leaks. On the other hand, the reaction system requires no additional solvent, and unreacted raw materials can be recovered and recycled through high-temperature flash evaporation, reducing pollutant generation at the source and controlling the VOC content of the modified petroleum resin to 0.4%.

[0013] The two phenolic hydroxyl groups in hydroquinone (ortho-, meta-, and hydroquinone and their mixtures) act as ortho- and para-activating groups, significantly enhancing the nucleophilic reactivity of the benzene ring and providing sufficient active sites for the reaction with divinylbenzene. The two carbon-carbon double bonds of divinylbenzene form carbocation active intermediates under Lewis acid catalysis, which undergo electrophilic substitution reactions with the benzene ring of hydroquinone. This reaction not only introduces long alkyl chains from divinylbenzene into the benzene ring of hydroquinone to achieve aromatic ring alkylation modification, but also utilizes the "bifunctional" characteristics of divinylbenzene to allow multiple hydroquinone molecules to be interconnected through alkyl chains, forming a polymer backbone with moderate crosslinking degree and stronger main chain rigidity. Therefore, the softening point of the resin can reach 125-170℃. At the same time, with the subsequent introduction of polyisobutylene branched structures, the high-temperature thermal stability of the resin can be further improved, meeting the requirements of high-temperature processing and harsh working conditions in tire production.

[0014] As an feasible example, the flash evaporation process is carried out at a temperature of 200-240°C and a pressure of -90 to -100 kPa.

[0015] This invention limits the flash evaporation treatment temperature to 200-240℃ and the pressure to -90~-100kPa, which can efficiently separate unreacted raw materials from target intermediates while ensuring resin performance and process environmental friendliness. The temperature of 200-240℃ can quickly vaporize unreacted hydroquinone and divinylbenzene with boiling points below this range, and can also avoid overheating decomposition or excessive cross-linking of target resin liquid with molecular weight of 350-3000Da, ensuring the stability of intermediate structure. The negative pressure environment of -90~-100kPa can lower the boiling point of raw materials, accelerate the volatilization of unreacted components in combination with temperature conditions, improve separation efficiency and reduce energy consumption. Moreover, the unreacted raw materials can be recycled back to the reactor after condensation, reducing raw material loss and resin VOC content, and improving the environmental safety of the product.

[0016] As an feasible example, the polyisobutylene succinic anhydride has a molecular weight of 900-2300 Da, an acid value of 70-120 mgKOH / g, and a Gardner color number <3.

[0017] Furthermore, the polyisobutylene succinic anhydride has a molecular weight of 900-1300 Da, an acid value of 80-110 mg KOH / g, and a Gardner color number <3.

[0018] As an implementable example, the mass ratio of the resin liquid B to polyisobutylene succinic anhydride is (1-20):1.

[0019] Resin B, as an intermediate in the alkylation reaction of hydroquinone and divinylbenzene, contains a rigid aromatic ring structure, which has limited compatibility with the flexible hydrocarbon chain of rubber. In contrast, the long-chain polyisobutylene structure of polyisobutylene succinic anhydride exhibits good affinity with the hydrocarbon chain structure of rubber. By reacting with the residual phenolic hydroxyl groups in resin B, polyisobutylene branches are introduced, significantly improving the compatibility between the resin and rubber, preventing resin agglomeration, and enhancing interfacial bonding. Its viscosity-reducing effect is superior to commercially available Koresin resin. Simultaneously, its long-chain structure increases the flexibility and entanglement ability of resin molecules. Combined with the rigid main chain, this gives the resin both strong adhesion and compatibility, improving the initial tack and bonding stability of the compound. Furthermore, the heat resistance and humid heat resistance of the polyisobutylene structure synergistically with the sterically hindered phenolic hydroxyl groups of the main chain, resulting in an adhesive strength of 1.1-1 after 48 hours of humid heat aging. The resin exhibits a strength of 4 kN / m and thermal aging test data of 1.34-1.54, both superior to commercially available products. Initial tack is consistently "unbreakable." Furthermore, the resin softening point can be precisely controlled by adjusting the mass ratio of polyisobutylene succinic anhydride (PSA) to 1-20:1. Increasing the amount of PSA lowers the softening point, while decreasing it maintains a high softening point, allowing for controllable adjustment within the 125-170℃ range to suit various rubber processing requirements. In addition, PSA itself has high purity and a Gardner color number <3. Its chemical bonding reaction with resin B requires no additional solvent, effectively solidifying the active groups of the resin molecules. This reduces the product's VOC content to a minimum of 0.18%, below the 0.5% limit, significantly superior to Koresin resin and meeting the rubber industry's demand for light-colored, stable-looking tackifying resins.

[0020] A second aspect of the present invention provides a modified petroleum resin prepared by the above-described preparation method.

[0021] Beneficial effects (i) This invention adopts a non-acetylene process, which completely eliminates the dependence on high-risk raw materials such as acetylene. The reaction conditions are mild and eliminate production safety hazards. At the same time, it avoids the use of formaldehyde aqueous solution, reducing the generation of formaldehyde-containing wastewater from the source. The process does not add any additional solvents, and unreacted raw materials can be recovered and recycled through flash evaporation. The operation is simple and reduces the cost of environmental treatment.

[0022] (ii) By optimizing the synthesis route and flash evaporation process, the VOC content of the prepared modified petroleum resin (120℃, 1h) can be controlled below 0.4%, with a minimum of only 0.18%, which is significantly lower than that of commercially available Koresin resin. This greatly improves the environmental safety of rubber products during use and is in line with the trend of green production.

[0023] (III) The modified petroleum resin prepared by this invention has both good initial tack and long-term adhesion. The initial tack of the rubber compound reaches the level of "unbreakable". After 48 hours of wet heat aging, the adhesion reaches 1.1-1.4 kN / m, which is better than Koresin resin. The heat aging test data is 1.34-1.54, which is significantly higher than commercial products. It can meet the needs of rubber compound storage, turnover and use under the harsh working conditions of tires in the high temperature and high humidity environment in summer.

[0024] (iv) By introducing long alkyl chains and polyisobutylene branched structures, this invention significantly improves the compatibility between the resin and the rubber matrix, effectively reduces the Mooney viscosity of the rubber compound, and has a viscosity reduction effect that is better than that of Koresin resin and SL-1805. At the same time, it ensures the core properties of the rubber such as tensile strength and elongation at break. The Mooney scorch characteristics are comparable to those of Koresin resin, making it suitable for rubber mixing, molding and other processing technologies.

[0025] (v) Due to the rigid structure of the resin main chain and the introduction of heat-resistant polyisobutylene side chains, the softening point can be flexibly adjusted within the range of 125-170℃, which can adapt to the processing temperature requirements of different rubber products; good high-temperature thermal stability can avoid the performance degradation of the rubber compound due to temperature changes during processing and use, and further ensure the structural integrity and service life of products such as tires. Detailed Implementation

[0026] Example 1 The first aspect of this example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, comprising the following steps: S1. Mix 800g of catechol and 20g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 150℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Turn on the stirrer and add 400g of divinylbenzene (a mixture of o-divinylbenzene, m-divinylbenzene and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 5g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-1.

[0027] The second aspect of this example provides a modified petroleum resin prepared by the above-described preparation method.

[0028] Example 2 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of catechol and 20g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 150℃. The three-necked flask is equipped with an electric stirrer, a thermometer and a constant pressure dropping funnel. Turn on the stirrer and add 400g of divinylbenzene (a mixture of o-divinylbenzene, m-divinylbenzene and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 5g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-2.

[0029] Example 3 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 510g of catechol and 20g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 150℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Turn on the stirrer and add 400g of divinylbenzene (a mixture of o-divinylbenzene, m-divinylbenzene and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 5g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-3.

[0030] Example 4 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 510g hydroquinone and 20g Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Turn on the stirrer and add 400g divinylbenzene (a mixture of o-divinylbenzene, m-divinylbenzene and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 5g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-4.

[0031] Example 5 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) and 20g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Start the stirrer and add 400g of divinylbenzene (a mixture of ortho-, m-, and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 5g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-5.

[0032] Example 6 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) and 20g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Start the stirrer and add 400g of divinylbenzene (a mixture of ortho-, m-, and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 15g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-6.

[0033] Example 7 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) and 40g of Y-type molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Turn on the stirrer and add 400g of divinylbenzene (a mixture of ortho-, m-, and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 15g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-7.

[0034] Example 8 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) and 15g of ZSM-5 molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Start the stirrer and add 400g of divinylbenzene (a mixture of ortho-, m-, and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the ZSM-5 molecular sieve to obtain resin solution A. S2. Resin solution A is subjected to flash evaporation at 210℃ and -90kPa to obtain resin solution B. S3. Add 50g of resin solution B to a 100mL three-necked flask, add 15g of polyisobutylene succinic anhydride, and react at 210℃ for 20min. After the reaction is complete, pour the resin solution into a cooling pan while it is still hot. After cooling, a light yellow transparent blocky modified petroleum resin with high softening point and high adhesion is obtained, which is designated as PR-8.

[0035] Comparative Example 1 This example provides a commercially available tackifying resin, specifically Koresin resin, purchased from BASF Chemicals in Germany.

[0036] Comparative Example 2 This example provides a commercially available tackifying resin, which is p-tert-butylphenol formaldehyde resin purchased from Huachi Chemical Co., Ltd., model number SL-1805.

[0037] Comparative Example 3 This example provides a method for preparing a modified petroleum resin with a high softening point and high adhesion, including the following steps: S1. Mix 600g of hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) and 15g of ZSM-5 molecular sieve, pour into a 2000mL three-necked flask, heat to 210℃. The three-necked flask is equipped with an electric stirrer, thermometer and constant pressure dropping funnel. Start the stirrer and add 400g of divinylbenzene (a mixture of ortho-, m-, and p-divinylbenzene) within 60min. Carry out the alkylation reaction for 60min. After the reaction is completed, filter to remove the Y-type molecular sieve to obtain resin solution A. S2. Resin liquid A is flash-evaporated at 210℃ and -90kPa to obtain resin liquid B. Resin liquid B is poured into a cooling pan and cooled to obtain a light yellow, transparent, blocky modified petroleum resin with high softening point and high adhesion, denoted as PR-03.

[0038] In the above implementation case, the polyisobutylene succinic anhydride was graded PIBSA1000 and purchased from Yangzi Petrochemical; catechol, hydroquinone, resorcinol and divinylbenzene were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0039] Performance testing The softening point and color number of the resins in Examples 1-8 and Comparative Examples 1-3 were determined according to the methods specified in the national standard GB / T 24138-2022 "Petroleum Resins". The softening point was determined according to GB / T 2294, and the Gardner color number was determined according to the method specified in GB / T 22295. The VOC content was determined by placing the resin in a 120℃ forced-air drying oven for 1 hour and measuring the thermal weight loss ratio; the test results are detailed in Table 1.

[0040] Table 1

[0041] As can be seen from Examples 1-3, the ratio of hydroquinone to divinylbenzene is very important in the preparation of modified petroleum resin, and it will significantly affect the softening point of the resin, but has a relatively small impact on the color number and VOC content.

[0042] In Example 4, hydroquinone was used as a raw material. Considering the melting point, a higher reaction temperature was required to obtain a modified petroleum resin with a softening point of 164°C.

[0043] Compared with Example 4, Example 5 differs in that the reaction temperature is increased from 150°C to 210°C and hydroquinone (catechol:resorcinol:hydroquinone = 5:3:2) is used instead of catechol, resulting in a significant decrease in the softening point of the modified petroleum resin.

[0044] Compared to Example 5, Example 6 used more polyisobutylene succinic anhydride, which significantly reduced the softening point of the resin. At the same time, more polyisobutylene branched structures were introduced into the molecular chain, which is beneficial to improving the compatibility between the resin and the rubber.

[0045] Compared to Example 5, Example 7 used twice the amount of catalyst, resulting in a resin with a higher softening point, but the color number increased.

[0046] In Example 8, 15g of ZSM-5 molecular sieve catalyst can be used to prepare a resin with similar performance to that in Example 5, indicating that the ZSM-5 molecular sieve catalyst has higher activity than the Y-type molecular sieve.

[0047] As can be seen from Comparative Examples 1-3 and Examples 1-6, the VOC content of the modified petroleum resins prepared by the scheme of the present invention is significantly lower than that of Koresin and SL-1805 resins, making them more environmentally friendly and safer.

[0048] Application examples 100 parts by weight of butadiene rubber (purchased from Sinopec, grade BR9100), 64 parts by weight of carbon black N990, 2.5 parts by weight of sulfur, 2 parts by weight of zinc oxide (3000 mesh, purchased from Hebei Jindu Zinc Oxide Plant), 0.2 parts by weight of scorching inhibitor N-cyclohexylthiophthalimide (purchased from Henan Longji Chemical Co., Ltd.), 1.5 parts by weight of microcrystalline wax (80#, purchased from Shandong Liangzhuo New Material Technology Co., Ltd.), and 4.5 parts by weight of the resin of Examples 1-6 or Comparative Examples 1-3 of this invention were mixed according to the normal rubber mixing process and tested.

[0049] Comparative Application Examples 1-3 were prepared using Koresin resin, SL-1805, and PR-03 from Comparative Examples 1-3, respectively, according to the above formulations; while Comparative Application Example 4 served as a blank control, without the addition of any petroleum (tackifying) resin.

[0050] 1. Basic performance testing of rubber compound Application Examples 1-6 were prepared using PR-1 to PR-6 prepared in Examples 1-6 according to the above formula. The basic performance data of the products are shown in Table 2.

[0051] Table 2

[0052] As can be seen from the table, in Comparative Application Example 4, without the addition of any petroleum resin, the system viscosity is very high. In Comparative Application Example 3, with the addition of non-polyisobutylene succinic anhydride modified petroleum resin, the Mooney viscosity is still as high as 62.2. Comparative Application Example 1 demonstrates that Koresin resin significantly reduces viscosity, and the comparative application examples also show lower viscosity.

[0053] Application Examples 1-8 show excellent viscosity-reducing effects, Application Example 5 is comparable to Koresin resin, and Application Example 6 has a viscosity-reducing effect superior to Koresin resin and Huachi Chemical's SL-1805.

[0054] The modified petroleum resins prepared under different conditions in Examples 5 and 8 have similar properties and also show similar properties in the application examples.

[0055] The resin prepared in Example 7 has a higher viscosity than koresin resin, but performs similarly in terms of initial tack and thermal aging properties.

[0056] In terms of Mooney scorch, the modified petroleum resin and Koresin resin provided in this example are not significantly different; however, the tensile strength is superior to that in comparative application examples 4 and 3.

[0057] 2. Initial tack, damp heat aging test, and thermal aging test of the rubber compound. The initial tack, damp heat aging and thermal aging tests were then conducted on the above-mentioned adhesive materials, and the data results are shown in Table 3.

[0058] Table 3

[0059] As can be seen from the experimental results in Table 3, in terms of initial viscosity, the effect of adding petroleum resin is significantly better than that of the comparative application example 4.

[0060] In the damp heat aging test, the performance of PR-1 to PR-6 prepared by this invention after 24 hours was comparable to that of Koresin, and the adhesion after 48 hours was slightly better than that of Koresin. In application example 6, the effect of Koresin resin was significantly better.

[0061] The results of the thermal aging test show that the PR-1 to PR-6 prepared by the present invention are superior to Koresin resin and Huachi Chemical's SL-1805. The significant improvement in application example 4 may be related to the high softening point of PR-4 prepared in example 4. The excellent results of the thermal aging test in application example 6 may be related to the fact that more polyisobutylene chains improve the compatibility with rubber / fillers, etc.

Claims

1. A method for preparing a modified petroleum resin with high softening point and high adhesion, characterized in that, Includes the following steps: S1. Mix hydroquinone and Lewis acid catalyst, add divinylbenzene, and carry out alkylation reaction. After the reaction is completed, filter out the Lewis acid catalyst to obtain resin solution A. S2. Flash evaporate resin solution A to obtain resin solution B; S3. Add polyisobutylene succinic anhydride to resin solution B and react. After the reaction is complete, cool to obtain modified petroleum resin. The modified petroleum resin has a softening point ≥125℃ and a color number of 1.9-3.

2.

2. The preparation method according to claim 1, characterized in that, The hydroquinone mentioned includes one or more of catechol, resorcinol, and hydroquinone.

3. The preparation method according to claim 1, characterized in that, The Lewis acid catalyst includes one or more of the following: ZSM-5 molecular sieve, Y-type molecular sieve, Beta molecular sieve, aluminum chloride supported molecular sieve, zinc chloride supported molecular sieve, zinc chloride supported silica, and zinc chloride supported alumina.

4. The preparation method according to claim 1, characterized in that, The mass of the Lewis acid catalyst is 0.1-50% of the mass of hydroquinone.

5. The preparation method according to claim 1, characterized in that, The mass ratio of hydroquinone to divinylbenzene is (1~10):

1.

6. The preparation method according to claim 1, characterized in that, The alkylation reaction is carried out at a temperature of 100-250℃ and a pressure of 0-2 atm.

7. The preparation method according to claim 1, characterized in that, The flash evaporation process is carried out at a temperature of 200-240℃ and a pressure of -90 to -100 kPa.

8. The preparation method according to any one of claims 1-7, characterized in that, The polyisobutylene succinic anhydride has a molecular weight of 900-2300 Da and an acid value of 70-120 mg KOH / g.

9. The preparation method according to claim 1, characterized in that, The mass ratio of the resin solution B to polyisobutylene succinic anhydride is (1-20):

1.

10. A modified petroleum resin with high softening point and high adhesion prepared by a method according to any one of claims 1-9.

Images