Rosin resin, tread rubber composition containing rosin resin, preparation method and application

Abstract

The invention relates to the technical field of preparation of rosin resin, in particular to rosin resin, a tread rubber composition containing the rosin resin as well as a preparation method and application of the tread rubber composition. The rosin resin is obtained by carrying out esterification reaction on rosin and polyhydric alcohol under the action of a catalyst, and the proportion of isopimaric acid in the rosin is not more than 5%. The rosin resin disclosed by the invention is applied to tires, and meanwhile, the performances of wet land holding force, rolling resistance and wear resistance are improved, and the effect is relatively good.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of rosin resins, and particularly relates to a rosin resin, a tread rubber composition containing the rosin resin, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of the automotive industry, especially the development of electric vehicles, the performance of tires has become increasingly important for the safety of vehicles and the economy of energy. Among them, wet grip, rolling resistance, and abrasion resistance are the three core indicators for measuring tire performance, and they restrict each other.

[0003] Wet grip refers to the grip ability of a tire on a wet road surface, which directly affects the braking performance and handling stability of a vehicle; rolling resistance is closely related to vehicle energy consumption; abrasion resistance determines the service life of a tire and the particulate emissions of the tire.

[0004] At present, anti-slip resins are widely used in tires to improve wet grip, but there will be some negative impacts on rolling resistance and abrasion resistance, and it is difficult to improve and balance the three performances simultaneously. Different resins added to improve tire performance in the prior art often have the problem that they can only improve one of the performances and cannot improve and balance the other two performances.

[0005] For example, Japanese Patent Publication No. 2012-512290 discloses a rubber composition, which improves wet grip performance and rolling resistance by adding an α-methylstyrene polymer resin as a plasticizer, but does not consider its wear resistance, and there is still room for further improvement.

[0006] The prior art (Feng Kunhao, Long Yanni, Chen Zhaohui, etc. Influence of the dosage of modified rosin resin on the properties of solution-polymerized styrene-butadiene rubber / cis-1,4-polybutadiene rubber blends [J]. Synthetic Rubber Industry, 2019, 42(3):5.) discloses that applying a modified rosin resin to a solution-polymerized styrene-butadiene rubber (SSBR) / cis-1,4-polybutadiene rubber (BR) blend can improve the wet skid resistance of the SSBR / BR blend while basically not affecting its rolling resistance. However, the rosin resin used therein needs to be modified, and it does not improve rolling resistance, and its wear resistance also needs to be further improved.

[0007] There is an urgent need to provide a rosin resin that can effectively improve the wet grip of tires, while reducing rolling resistance and enhancing abrasion resistance.

[0008] Compared with traditional petroleum resins, rosin resins, as a renewable resource, have an important impact. Therefore, it is very necessary to develop a rosin resin, a tread rubber composition containing the rosin resin, a preparation method thereof, and an application thereof that can solve the above technical problems. Summary of the Invention

[0009] The object of the present invention is to overcome the deficiencies of the prior art and provide a rosin resin, a tread rubber composition containing the rosin resin, a preparation method and an application thereof, which have remarkable effects in improving the wet grip, rolling resistance and wear resistance of tires.

[0010] The present invention is realized through the following technical solutions: The first aspect of the present invention provides a preparation method of a rosin resin, wherein the rosin resin is obtained by an esterification reaction of rosin and a polyol under the action of a catalyst, and the proportion of isopimaric acid in the rosin is not more than 5%.

[0011] The rosin in the present invention may be at least one of masson pine rosin, gum rosin, simao rosin, south asian rosin, caribbean rosin.

[0012] The rosin used in the present invention meets the requirements of "GB / T 8145-2021 Gum rosin", and the components in the rosin are measured according to "GB / T14020-2024 Hydrogenated rosin".

[0013] As an implementation manner of the present invention, the polyol includes at least one of a diol, a triol and a tetrol.

[0014] Preferably, the diol includes at least one of ethylene glycol and diethylene glycol, the triol includes at least one of glycerol and trihydroxypropane; the tetrol includes pentaerythritol.

[0015] As an implementation manner of the present invention, the catalyst includes at least one of sulfur, sulfide, phosphoric acid, phosphorous acid, hypophosphorous acid, nano cerium oxide, nano titanium dioxide, nano lanthanum oxide, neodymium oxide, magnesium oxide, zinc oxide, lithium carbonate, calcium hydroxide and p-toluenesulfonic acid.

[0016] As an implementation manner of the present invention, the temperature of the esterification reaction is 220-300 °C, and the time is 3-20 h. Within this range, as long as the acid value of the prepared rosin resin can be below 50 mg / g, the hydroxyl value can be below 60 mg / g, and the sum of the acid value and the hydroxyl value can be below 60 mg / g.

[0017] Further preferably, the preparation method includes: adding crushed rosin to a reaction kettle, heating to 180 °C for melting under nitrogen protection, closing the nitrogen, adding a polyol and a catalyst, heating for an esterification reaction, the esterification reaction temperature is 220-300 °C, the esterification reaction time is 3-20 h, and the indexes of acid value, hydroxyl value and softening point are monitored in real time.

[0018] Index test: Acid value: Measured according to "GB / T 8146-2022 Test methods for rosin"; Hydroxyl value: measured according to the acetic anhydride method in GB / T 7383-2020 "Determination of hydroxyl value of non-ionic surfactants"; Softening point: measured according to GB / T 8146-2022 "Test method for rosin".

[0019] As an embodiment of the present invention, the raw materials for preparing the rosin resin include, by weight: Rosin 100 parts by weight Polyol 5-22 parts by weight Catalyst 0.1-1 part by weight.

[0020] The second aspect of the present invention provides a rosin resin prepared by the above-mentioned preparation method.

[0021] As an embodiment of the present invention, the acid value of the rosin resin is 50 mg / g or less, preferably not more than 30 mg / g, and more preferably not more than 15 mg / g.

[0022] The acid value determination method of the rosin resin in the present invention is tested with reference to GB / T 8146-2022 "Rosin Test Method".

[0023] As an embodiment of the present invention, the hydroxyl value of the rosin resin is 60 mg / g or less, preferably not more than 35 mg / g, more preferably not more than 30 mg / g, and particularly preferably not more than 20 mg / g.

[0024] The method for determining the hydroxyl value of the rosin resin in the present invention refers to the acetic anhydride method in GB / T 7383-2020 "Determination of the Hydroxyl Value of Non-ionic Surfactants", and the hydroxyl value means: the number of milligrams of potassium hydroxide required to neutralize the acid generated by esterifying hydroxyl groups in 1g of the sample with acetic anhydride or the number of milligrams of potassium hydroxide equivalent to the hydroxyl groups in 1g of the sample.

[0025] As an embodiment of the present invention, the sum of the acid value and the hydroxyl value of the rosin resin is less than 60 mg / g, preferably not more than 30 mg / g, and more preferably not more than 20 mg / g.

[0026] As an embodiment of the present invention, the softening point of the rosin resin is greater than 65°C.

[0027] The third aspect of the present invention provides a tread rubber composition containing rosin resin, which comprises the following components in parts by weight: Rubber 100 parts Rosin resin 1-60 parts 60-140 parts of filler.

[0028] As an embodiment of the present invention, the rubber includes at least one of natural rubber NR, styrene-butadiene rubber SBR, and butadiene rubber BR. The styrene-butadiene rubber SBR is not particularly limited and may include solution-polymerized SBR (S-SBR), unmodified emulsion-polymerized SBR (E-SBR), and their modified SBRs, etc. Preferably, the styrene-butadiene rubber includes at least one of solution-polymerized styrene-butadiene rubber SSBR and emulsion-polymerized styrene-butadiene rubber ESBR. The butadiene rubber BR is cis-1,4-polybutadiene rubber, including various BRs such as modified BR and high-cis BR, or a combination thereof.

[0029] Preferably, the rubber includes styrene-butadiene rubber SBR and butadiene rubber BR, and the mass percentage of styrene-butadiene rubber in the rubber is 80%.

[0030] As an embodiment of the present invention, the filler includes at least one of silica and carbon black.

[0031] Silica refers to silica or other silicate derivatives, including precipitated silica, aluminum silicate or calcium silicate, fumed silica, etc., as well as bio-based silica such as rice husk silica.

[0032] Carbon black includes furnace black, acetylene black, thermal black, channel black, graphite, etc., including models such as N110 / N220 / N234 / N330 / N345 / N472 / N550 / N660 / N650 / N770 / N772 / N774 / N880 / N990, etc. Carbon black can be used alone or in combination.

[0033] Preferably, the amount of silica used is 60 - 140 parts, and more preferably 80 - 120 parts.

[0034] As an embodiment of the present invention, the amount of rosin resin used in the tread rubber composition is 1 - 10 parts, or 10 - 20 parts, or 20 - 30 parts, or 30 - 40 parts, or 40 - 50 parts, or 50 - 60 parts.

[0035] As an embodiment of the present invention, the tread rubber composition further includes common compounding agents used in other rubbers, such as plasticizers, coupling agents, vulcanizing agents, accelerators, and anti-aging agents, etc.

[0036] Plasticizers, also known as processing oils or operating oils, include petroleum-derived processing oils (aromatic oils, paraffin oils, naphthenic oils, etc.), vegetable oils (rapeseed oil, soybean oil, etc.), and paraffin wax, etc. The preferred mass fraction is 0 - 30 parts, and more preferably 10 - 20 parts.

[0037] Coupling agents, preferably sulfide-based silane coupling agents and mercapto-based silane coupling agents, such as Si-69 and Si-75, etc., and the dosage is preferably 5 - 10 parts.

[0038] Vulcanizing agent, preferably sulfur, mainly includes vulcanizing powder, insoluble sulfur, colloidal sulfur, etc., and the dosage is preferably 1-3 parts.

[0039] Accelerator, including thiazole vulcanization accelerators such as accelerator M, DM, MZ, and MTT, etc., sulfenamide vulcanization accelerators such as CZ, NS, DZ, and NOBS, etc., thiuram vulcanization accelerators such as TMTD, TMTM, TETD, TBzTD, DPTT, TIBTD, and DDTS, etc., dithiocarbamate vulcanization accelerators such as EZ, BZ, PZ, ZBEC, TDEC, etc., guanidine vulcanization accelerators such as DPG, DOTG, etc., thiourea vulcanization accelerators such as ETU, DETU, DPTU, etc. Usually, activators such as zinc oxide and stearic acid are used to improve the vulcanization efficiency.

[0040] Preferably, the accelerator includes sulfenamide series vulcanization accelerators, thiazole series vulcanization accelerators, and guanidine series vulcanization accelerators, which can be used alone or in combination. The dosage is preferably 2-5 parts.

[0041] Antioxidant, including amine antioxidants, phenolic antioxidants, heterocyclic antioxidants, phosphite antioxidants, and other antioxidants, etc., such as TMQ, 6PPD, and IPPD, which can be used alone or in combination. The preferred dosage is 2-4 parts.

[0042] As an embodiment of the present invention, the tread rubber composition includes the following components by weight parts: Styrene-butadiene rubber 80 parts Butadiene rubber 20 parts Silica 90 parts Carbon black 6 parts Naphthenic aromatic oil 15 parts Rosin resin 20 parts Silane coupling agent 7.2 parts Zinc oxide 3.5 parts Accelerator CBS 1.8 parts Accelerator DPG 2 parts Antioxidant 6PPD 3 parts Wax 2 parts Stearic acid 2.5 parts Sulfur 2 parts.

[0043] The fourth aspect of the present invention provides a preparation method of the above-mentioned tread rubber composition, including the following steps: mixing each raw material in a mixer according to the proportion, and then it is obtained.

[0044] As an embodiment of the present invention, the mixing is carried out in stages. The first-stage mixing: 145°C × 300 s, rotation speed 65 rpm; the second-stage mixing: 155°C × 180 s, rotation speed 45 rpm.

[0045] As an embodiment of the present invention, the Mooney viscosity of the tread rubber composition is 55 ± 10 MPa·s under the conditions of ML 1+4, 125°C. "ML 1+4, 125°C" means the torque value measured when preheating for 1 min at 125°C with a large rotor and rotating for 4 min.

[0046] The fifth aspect of the present invention provides an application of the above-mentioned rosin resin or the above-mentioned tread rubber composition or the tread rubber composition prepared by the above-mentioned preparation method in the preparation of tires.

[0047] The beneficial effects of the present invention are as follows: The present invention adds a rosin resin containing a specific content of isopimaric acid to the tread rubber composition, and by adjusting the preparation process of the rosin resin to make its softening point within a specific range, it can significantly improve the wet grip, effectively reduce the rolling resistance, and enhance the wear resistance. By improving the wet grip of the tire, the braking distance is reduced, and the safety of the vehicle on a wet road surface is improved. By reducing the rolling resistance of the tire, the energy efficiency of the vehicle is improved, and carbon dioxide emissions are reduced.

[0048] The rosin resin of the present invention is derived from natural plants and has the characteristics of renewability and environmental friendliness.

[0049] The present invention can further improve the wet grip, reduce the rolling resistance, and enhance the wear resistance by adjusting the acid value, hydroxyl value, and the sum of the two of the rosin resin within a specific range.

[0050] Compared with commercially available tread modification resins, the tread rubber composition of the present invention can significantly improve the wet grip, effectively reduce the rolling resistance, and enhance the wear resistance. Specific Embodiments

[0051] The present invention will be further described below in conjunction with specific embodiments, and the advantages and characteristics of the present invention will become clearer with the description. However, these embodiments are only exemplary and do not constitute any limitation to the scope of the present invention. Those skilled in the art should understand that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the protection scope of the present invention.

[0052] The rosin used in the following examples meets the requirements of "GB / T 8145-2021 Gum rosin".

[0053] According to GB / T 14020-2024 Hydrogenated Rosin, the content of isopimaric acid in each rosin component is as follows: Horsetail rosin 1.1%; Wetland rosin 13.9%; Caribbean rosin 10.1%; Simao rosin 4%; Nan Ya rosin 14.3%.

[0054] Example 1 A rosin resin, calculated by weight, comprising the following components: 100 parts of horsetail rosin Pentaerythritol 12 parts 0.8 parts of nano zinc oxide The preparation method of rosin resin is as follows: horsetail rosin is crushed and added into a reactor, and the temperature is raised to 180°C for melting under nitrogen protection, the nitrogen is turned off, pentaerythritol and nano zinc oxide catalyst are added, and the temperature is raised for esterification reaction, the esterification reaction temperature is 280°C, the esterification reaction time is 11 hours, and the acid value, hydroxyl value and softening point are monitored in real time. The product indicators are shown in Table 1.

[0055] Example 2 A rosin resin, calculated by weight, comprising the following components: 100 parts of horsetail rosin 12 parts glycerin 0.8 parts of p-toluenesulfonic acid The preparation method of rosin resin is as follows: horsetail rosin is crushed and added into a reactor, and the temperature is raised to 180°C for melting under nitrogen protection, the nitrogen is turned off, glycerol and p-toluenesulfonic acid catalyst are added, and the temperature is raised for esterification reaction. The esterification reaction temperature is 275°C, the esterification reaction time is 8 hours, and the acid value, hydroxyl value and softening point are monitored in real time. The product indicators are shown in Table 1.

[0056] Example 3 A rosin resin, calculated by weight, comprising the following components: 30 parts of wetland rosin 70 parts of horsetail rosin Pentaerythritol 12 parts 0.8 parts of hypophosphorous acid The preparation method of rosin resin is as follows: wetland rosin and horsetail rosin are crushed and added into a reactor, and the temperature is raised to 180°C for melting under nitrogen protection, the nitrogen is turned off, pentaerythritol and hypophosphorous acid catalyst are added, and the temperature is raised for esterification reaction. The esterification reaction temperature is 280°C, the esterification reaction time is 11 hours, and the acid value, hydroxyl value and softening point are monitored in real time. The product indicators are shown in Table 1.

[0057] Example 4 A rosin resin, by weight parts, the components are as follows: 90 parts of Simao rosin 10 parts of wetland rosin 7.5 parts of glycerol 5 parts of ethylene glycol 0.8 part of lithium carbonate The preparation method of the rosin resin is as follows: Simao rosin and wetland rosin are crushed and added to the reaction kettle, heated to 180°C for melting under nitrogen protection, the nitrogen is turned off, glycerol, ethylene glycol and lithium carbonate catalyst are added, and the temperature is raised for esterification reaction. The esterification reaction temperature is 276°C, and the esterification reaction time is 15 h. The indexes of acid value, hydroxyl value and softening point are monitored in real time, and the product indexes are shown in Table 1.

[0058] Example 5 A rosin resin, by weight parts, the components are as follows: 85 parts of masson pine rosin 15 parts of wetland rosin 0.8 part of sulfur The preparation method of the rosin resin is as follows: Masson pine rosin and wetland rosin are crushed and added to the reaction kettle, heated to 180°C for melting under nitrogen protection, the nitrogen is turned off, glycerol and sulfur catalyst are added, and the temperature is raised for esterification reaction. The esterification reaction temperature is 275°C, and the esterification reaction time is 8 h. The indexes of acid value, hydroxyl value and softening point are monitored in real time, and the product indexes are shown in Table 1.

[0059] Example 6 A rosin resin, by weight parts, the components are as follows: 100 parts of masson pine rosin 2 parts of pentaerythritol 10 parts of ethylene glycol 0.8 part of nano-zinc oxide The preparation method of the rosin resin is as follows: Masson pine rosin is crushed and added to the reaction kettle, heated to 180°C for melting under nitrogen protection, the nitrogen is turned off, pentaerythritol, ethylene glycol and nano-zinc oxide catalyst are added, and the temperature is raised for esterification reaction. The esterification reaction temperature is 278°C, and the esterification reaction time is 15 h. The indexes of acid value, hydroxyl value and softening point are monitored in real time, and the product indexes are shown in Table 1.

[0060] Example 7 A rosin resin, by weight parts, the components are as follows: 100 parts of Simao rosin 13 parts of pentaerythritol 0.8 part of nano-zinc oxide The preparation method of rosin resin is as follows: Simao rosin is crushed and added to a reaction kettle. It is heated to 180°C for melting under nitrogen protection. Then nitrogen is turned off, and pentaerythritol and nano-zinc oxide catalyst are added. The temperature is raised for esterification reaction. The esterification reaction temperature is 280°C, and the esterification reaction time is 11h. The indexes of acid value, hydroxyl value and softening point are monitored in real time, and the product indexes are shown in Table 1.

[0061] Example 8 A kind of rosin resin, calculated by weight parts, the components are as follows: 92 parts of Simao rosin 8 parts of Caribbean rosin 15.5 parts of trimethylolpropane 0.8 part of nano-zinc oxide The preparation method of rosin resin is as follows: Simao rosin and Caribbean rosin are crushed and added to a reaction kettle. It is heated to 180°C for melting under nitrogen protection. Then nitrogen is turned off, and trimethylolpropane and nano-zinc oxide catalyst are added. The temperature is raised for esterification reaction. The esterification reaction temperature is 275°C, and the esterification reaction time is 8h. The indexes of acid value, hydroxyl value and softening point are monitored in real time, and the product indexes are shown in Table 1.

[0062] Table 1 Product indexes of each example

[0063] Comparative Example 1 - Comparative Example 7 The differences between Comparative Example 1 - Comparative Example 4 and Example 1 lie in the type and ratio of rosin, the type and dosage of polyol, and the temperature and time of esterification reaction. Among them, when pentaerythritol is used as the polyol, the esterification reaction temperature is 280°C and the esterification reaction time is 11h; when glycerol or trimethylolpropane is used as the polyol, the esterification reaction temperature is 275°C and the esterification reaction time is 8h; when ethylene glycol is used as the polyol, the esterification reaction temperature is 275°C and the esterification reaction time is 15h; Comparative Example 2 contains both pentaerythritol and ethylene glycol, the esterification reaction temperature is 278°C, and the esterification reaction time is 13h. The type and dosage of polyol in each comparative example are shown in Table 2, and the product indexes are shown in Table 3.

[0064] The difference between Comparative Example 1 and Example 1 is mainly that the softening point is not within the protection range, the difference between Comparative Example 2 and Example 2 is mainly that the sum of the acid value and the hydroxyl value is not within the protection range, the difference between Comparative Example 3 and Example 4 is mainly that the acid value is not within the protection range, the difference between Comparative Example 4 and Example 3 is mainly that the acid value and the sum of the acid value and the hydroxyl value are not within the protection range, the difference between Comparative Example 5 and Example 3 is mainly that the ratio of masson rosin and wetland rosin is changed to an equal weight ratio, and the content of isopimaric acid is not within the protection range, Comparative Example 6 replaces the rosin resin with α-methylstyrene resin purchased from the market, and the difference between Comparative Example 7 and Example 1 is that the type of rosin is different and is changed to South Asia rosin, and the other conditions are the same.

[0065] Table 2 Comparative Example Formulas

[0066] Table 3 Product indicators of each comparative example

[0067] Application Example 1 A tread rubber composition, comprising the following components in parts by weight: Styrene butadiene rubber 80 parts Butadiene rubber 20 parts 90 parts of silicon dioxide 6 parts carbon black 15 parts of naphthenic aromatic oil 20 parts of rosin resin Silane coupling agent Si-697.2 parts 3.5 parts of zinc oxide Accelerator CBS 1.8 parts Accelerator DPG 2 parts Anti-aging agent 6PPD 3 parts 2 parts wax 2.5 parts of stearic acid 2 parts of sulfur.

[0068] Description of main materials: (1) Styrene butadiene rubber (SBR) brand SL 4602, sourced from TRINSEO; (2) Butadiene rubber (BR) brand CB25, sourced from LANXESS; (3) White carbon black (silicon dioxide) brand HD 165MP, sourced from QUECHEM; (4) Carbon black brand N330, sourced from BlackCat; (5) Cycloparaffin aromatic oil brand Norman346, sourced from Orgkhim; (6) Rosin resin is the rosin resin prepared in each example or comparative example; the remaining additives are conventional commercially available products.

[0069] Preparation of tread rubber composition: Mix each raw material in a kneader in stages according to the proportion. The first-stage mixing: 145°C × 300 s, rotation speed 65 rpm; the second-stage mixing: 155°C × 180 s, rotation speed 45 rpm. The Mooney viscosity of the tread rubber composition is controlled at ML(1+4), 55 ± 10 MPa·s under the condition of 125°C, thus obtained.

[0070] Test Example 1 Performance Test and Evaluation of Tread Rubber Composition tanδ value test: Through DMA dynamic mechanical property test, using the tensile mode from -60°C to +100°C, heating rate 5 K / min, 10 Hz, dynamic strain 0.25%.

[0071] Wet grip: Represented by the tanδ value at 0°C. The larger the tanδ value, the better the wet grip.

[0072] Rolling resistance: Represented by the tanδ value at 60°C. The smaller the tanδ value, the smaller the rolling resistance.

[0073] Abrasion resistance: Determined according to GB / T 9867-2008 "Rubber, vulcanized or thermoplastic - Determination of abrasion resistance (rotary roller mill method)", represented by the relative volume loss amount mm 3 of the tire under specific conditions. The smaller the relative volume loss amount, the better the abrasion resistance.

[0074] The performance determination and evaluation of the tread rubber composition are shown in Table 4.

[0075] Table 4 Test Indexes of Tread Rubber Composition

[0076] It can be seen from the data in Table 4 that the rosin resin indexes of Examples 1 to 8 all meet the rosin resin preparation characteristics described in the present invention. In contrast, the rosin resins of Comparative Examples 1 to 5 do not meet or only partially meet the characteristics of the present invention in some aspects. Particularly noteworthy is that the α-methylstyrene resin used in Comparative Example 6 is the best-performing tread modification resin on the market. The test results show that Examples 1 to 8 are superior to Comparative Example 6 in terms of wet grip, rolling resistance, and abrasion resistance. On the other hand, further analyzing Comparative Examples 1 to 5 and Comparative Example 6, it is found that the performance differences between them are not significant, indicating that the resin prepared by the present invention has significant advantages in wet grip, rolling resistance, and abrasion resistance at the same time.

[0077] The above detailed description is a specific description of one feasible embodiment of the present invention. This embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or modification without departing from the present invention should be included within the scope of the technical solution of the present invention.

Claims

1. A preparation method of rosin resin, characterized in that, The rosin resin is obtained by esterification reaction of rosin and polyol under the action of a catalyst, and the proportion of isopimaric acid in the rosin is no more than 5%.

2. The preparation method according to claim 1, characterized in that, The polyol includes at least one of a diol, a triol, and a tetraol.

3. The preparation method according to claim 2, characterized in that, The diol includes at least one of ethylene glycol and diethylene glycol, the triol includes at least one of glycerol and trihydroxypropane, and the tetraol includes pentaerythritol.

4. The preparation method according to claim 1, wherein, The catalyst comprises at least one of sulfur, sulfide, phosphoric acid, phosphorous acid, hypophosphorous acid, nano cerium oxide, nano titanium dioxide, nano lanthanum oxide, neodymium oxide, magnesium oxide, zinc oxide, lithium carbonate, calcium hydroxide and p-toluenesulfonic acid.

5. The preparation method according to claim 1, wherein The temperature of the esterification reaction is 220-300° C., and the time is 3-20 hours.

6. The preparation method according to claim 1, wherein The raw materials for preparing the rosin resin include, by weight: Rosin 100 parts by weight Polyol 5-22 parts by weight Catalyst 0.1-1 part by weight.

7. A rosin resin, characterized in that, The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. The rosin resin according to claim 7, characterized in that, The acid value of the rosin resin is 50 mg / g or less, and / or the hydroxyl value of the rosin resin is 60 mg / g or less, and / or the sum of the acid value and the hydroxyl value of the rosin resin is 60 mg / g or less, and / or the softening point of the rosin resin is greater than 65°C.

9. A tread rubber composition containing rosin resin, characterized in that, According to parts by weight, it includes the following components: Rubber 100 parts Rosin resin 1-60 parts 60-140 parts of filler; The rosin resin is the rosin resin according to claim 7 or 8.

10. The tread rubber composition according to claim 9, characterized in that, The rubber includes at least one of natural rubber, styrene-butadiene rubber and butadiene rubber; the filler includes at least one of silicon dioxide and carbon black.

11. The tread rubber composition according to claim 9, characterized in that, The tread rubber composition further comprises a plasticizer, a coupling agent, a vulcanizing agent, an accelerator and an antioxidant.

12. The tread rubber composition according to claim 10, wherein The rubber comprises styrene butadiene rubber and butadiene rubber, and the mass percentage of the styrene butadiene rubber in the rubber is 80%.

13. The tread rubber composition according to claim 11, characterized in that, According to parts by weight, it includes the following components: Styrene butadiene rubber 80 parts Butadiene rubber 20 parts 90 parts of silicon dioxide 6 parts carbon black 15 parts of naphthenic aromatic oil 20 parts of rosin resin Silane coupling agent 7.2 parts 3.5 parts of zinc oxide Accelerator CBS 1.8 parts Accelerator DPG 2 parts Anti-aging agent 6PPD 3 parts 2 parts wax 2.5 parts of stearic acid 2 parts of sulfur.

14. A method for preparing a tread rubber composition according to any one of claims 9-13, characterized in that, The method comprises the following steps: mixing the raw materials in a mixing machine according to proportion to obtain the product.

15. The preparation method according to claim 14, wherein, The mixing is carried out in stages: the first stage mixing is at 145° C.×300 s and the rotation speed is 65 rpm; the second stage mixing is at 155° C.×180 s and the rotation speed is 45 rpm.

16. The preparation method according to claim 14, wherein, The Mooney viscosity of the tread rubber composition is 55±10 MPa·s under the condition of ML 1+4, 125° C.

17. Use of the rosin resin according to any one of claims 7 to 8, the tread rubber composition according to any one of claims 9 to 13, or the tread rubber composition prepared by the preparation method according to any one of claims 14 to 16 in preparing tires.

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