Preparation method of bio-based material modified coumarone resin as well as obtained product and application of bio-based material modified coumarone resin

Abstract

The invention discloses a preparation method of bio-based material modified coumarone resin, an obtained product and application. The preparation method comprises the following steps: mixing a mixture containing polymerizable components indene and coumarone, styrene or a derivative thereof and a catalyst; then dropwise adding a mixture containing polymerizable components indene and coumarone and an organic solvent solution of a bio-based material to carry out polymerization reaction; and adding a quenching agent after the reaction, and performing post-treatment to obtain a final product. According to the invention, a bio-based material is adopted as a raw material, and the raw material is derived from natural plants and has the characteristics of environmental friendliness, degradability and the like, so that the cyclic utilization of resources is realized, and the generation of wastes is reduced. The bio-based modified coumarone resin is high in hydroxyl content and narrow in molecular weight distribution, the compatibility of the coumarone resin and polar resin is improved, the use performance and the application range of the coumarone resin are improved, and the bio-based modified coumarone resin has good application prospects in the fields of adhesives, rubber, coatings, ink and the like, and is particularly suitable for tire tread rubber.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of modified coumarone resin, in particular to a preparation method of bio-based material modified coumarone resin, and the product obtained by the method and the application of the product in the rubber field, belonging to the technical field of chemical synthesis. BACKGROUND

[0002] Coumarone resin, also known as coumarone-indene resin, benzofuran-indene resin, coumarone resin, oxindene resin, commonly known as coal tar resin, is a copolymer resin with indene, oxindene and styrene as main components. Coumarone resin is yellow, brown or black block liquid or solid, has good compatibility, water resistance, acid and alkali resistance, rust resistance and electrical properties. Coumarone resin is a kind of high polymer material, if it is added into rubber, it can play the role of softening, reinforcing, tackifying and dispersing, thereby improving the processing performance of rubber; after compounding, the rubber has good adhesion, including pressure-sensitive or hot-melt, so it is widely used in rubber, tire, V-belt, conveyor belt, adhesive, paint, ink, waterproof, hose and other industries. Traditional adhesives mostly use natural rosin resin or indene resin, but due to their high price and poor performance compared with coumarone resin, coumarone resin has occupied a dominant position in the adhesive industry.

[0003] The production process of coumarone resin includes six processes of distillation and cutting fraction, acid washing and removing pyridine, decolorization, polymerization, water washing, flash evaporation, solidification and granulation, and finally solid coumarone resin product is prepared. CN201110076405.X discloses a production method of coumarone resin, which utilizes coal tar to distill heavy benzene, and then utilizes heavy benzene to distill indene and oxindene, and polymerizes indene and oxindene in the same solution to obtain coumarone resin. The specific process is coal tar heavy removal, heavy benzene hydrogenation reaction to remove impurities, preliminary separation, indene and oxindene dephenol, indene and oxindene depyridine, and indene and oxindene polymerization to prepare coumarone resin.

[0004] In addition, CN201410534473.X discloses a hydroxyl coumarone resin and a preparation method thereof. In the method, the hydroxyl coumarone resin is prepared from a mixture containing polymerizable components obtained by re-distillation of heavy benzene fraction of coal tar and 4-hydroxystyrene or 4-hydroxycinnamic acid methyl ester or 4-hydroxycinnamic acid ethyl ester. CN201510947371.5 discloses a cashew nut shell oil modified coumarone resin and a preparation method thereof. In the method, a mixture containing indene is mixed with cashew nut shell oil according to a certain proportion, washed and distilled to obtain cashew nut shell oil modified coumarone resin with a hydroxyl value.

[0005] The existing coumarone resin does not have a polar group, and has poor compatibility with polar solvents and resins, which limits the use of coumarone resin. Based on the market demand for hydroxyl value coumarone resin, and the current prominent environmental protection problem, it is a feasible direction to modify coumarone resin to obtain hydroxyl value coumarone resin from the environmental protection, cheap and easily available bio-based modifier. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of a bio-based material modified coumarone resin. The present application introduces a hydroxyl group through a bio-based material and optimizes the preparation process, thereby significantly improving the hydroxyl value of the coumarone resin, improving the compatibility of the coumarone resin with polar resins, and improving the performance and application range of the coumarone resin.

[0007] To achieve the above purpose, the present application is implemented by the following technical solutions:

[0008] A preparation method of a bio-based material modified coumarone resin, the method comprising the following steps:

[0009] (1) mixing a mixture containing polymerizable components indene and coumarone, styrene or its derivative and a catalyst to obtain a mixed solution A;

[0010] (2) adding an organic solvent solution containing a mixture of polymerizable components indene and coumarone, and a bio-based material to the mixed solution A at the same time, respectively, and after dropping, warming up for polymerization reaction;

[0011] (3) after reaction, adding a quenching agent to terminate the reaction, then filtering, washing with water, standing and separating the reaction liquid, taking the organic phase, removing the organic solvent from the obtained organic phase, and removing impurities at high temperature to obtain a bio-based material modified coumarone resin.

[0012] Further, in step (1), the mixture containing polymerizable components indene and coumarone mainly contains indene and coumarone which can be polymerized, the content of indene is 50-95wt%, for example, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, the content of coumarone is 0.5-2wt%, for example, 0.5wt%, 1wt%, 1.5wt%, 2wt%, and the rest is a compound which does not participate in the polymerization reaction. The mixture of polymerizable components indene and coumarone is obtained by re-distilling heavy benzene fraction of coal tar, which can be directly purchased from the market.

[0013] Further, in step (1), the styrene derivative includes alkyl-substituted styrene, such as a-methylstyrene, and the like. The mass ratio of the sum of the mixture containing the polymerizable components of indene and cumaran in steps (1) and (2) to styrene or the styrene derivative is (2%~10%): 1, such as 2%: 1, 3%: 1, 4%: 1, 5%: 1, 6%: 1, 7%: 1, 8%: 1, 9%: 1, 10%: 1.

[0014] Further, in step (1), the catalyst is a mixture of acidic ion exchange resin (such as Amberlyst 15, Amberlyst 35, Amberlyst 36, Nafion NR50 or Lewatit K2621) and metal chloride (such as aluminum trichloride, boron trichloride or antimony trichloride). Preferably, the mass ratio of the mixture of acidic ion exchange resin and metal chloride is (1~5): 1, such as 1: 1, 2: 1, 3: 1, 4: 1, 5: 1. The catalyst can improve the reaction rate and also increase the reaction yield.

[0015] Further, in step (1), the catalyst is preferably a mixture of Amberlyst 35 and aluminum trichloride, and the mass ratio of Amberlyst 35 to aluminum trichloride is preferably 4: 1.

[0016] Further, in step (1), the mass ratio of the catalyst to the mixture containing the polymerizable components of indene and cumaran in steps (1) and (2) is (3%~8%): 1, such as 3%: 1, 4%: 1, 5%: 1, 6%: 1, 7%: 1, 8%: 1, and preferably 5%: 1.

[0017] Further, in step (1), each mixture is mixed uniformly at room temperature.

[0018] Further, in step (2), the mass ratio of the mixture containing the polymerizable components of indene and cumaran in step (2) to the mixture containing the polymerizable components of indene and cumaran in step (1) is (0.5~2): 1, such as 0.5: 1, 1: 1, 1.5: 1, 2: 1, and preferably 1: 1.

[0019] Further, in step (2), the bio-based material is lignin monomer, which is one or more of guaiacylpropane (G type), syringylpropane (S type) and p-hydroxyphenylpropane (H type). Their structural formulas are shown as follows, respectively:

[0020]

[0021] Further, in step (2), the molar ratio of the bio-based material to styrene or its derivative is (1-1.5):1, for example 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, preferably 1.3:1.

[0022] Further, in step (2), the organic solvent is one or more of diethanol methyl ether, 1,4-dioxane, diethyl ether and chloroform. The amount of the organic solvent used as a reaction medium can be selected as needed. It has been found through experiments that when the organic solvent is a mixture of diethanol methyl ether and diethyl ether, the occurrence of side reactions can be reduced and the reaction yield can be improved, so the organic solvent is preferably diethanol methyl ether and diethyl ether, and the mass ratio of diethanol methyl ether to diethyl ether is preferably (1-3):1, for example 1:1, 2:1, 3:1, preferably 3:1.

[0023] Further, in step (2), the mass ratio of the bio-based material to the organic solvent in the organic solvent solution of the bio-based material is 1:(3-8), for example 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, preferably 1:4.

[0024] Further, in step (2), the mixture containing the polymerizable components indene and cumaron, and the organic solvent solution of the bio-based material are simultaneously added dropwise into the mixed solution A of step (1) respectively, and the dropping temperature is 60-70°C, for example 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C. The temperature is controlled to be 70-75°C during the dropping process, for example 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, and the dropping time is 15-60 min, for example 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min.

[0025] Further, in step (2), after the dropping of the materials is completed, the temperature is raised to 80-90°C for polymerization, for example 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, and the reaction time is 1-3 h, for example 1 h, 2 h, 3 h.

[0026] Further, in step (3), the quenching agent is triethylamine (TEA), pyridine or 1,8-diazabicycloundec-7-ene (DBU). The mass ratio of the quenching agent to the catalyst is (0.5-3):1, for example 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, preferably 2:1.

[0027] Further, in step (3), after the reaction is terminated, the solid catalyst is removed by filtration, and then water is added to the reaction solution to wash the reaction solution. The mass ratio of the water added to the total mixture containing the polymerizable component indene and cumaran in steps (1) and (2) is (0.5-2):1, for example, 0.5:1, 1:1, 1.5:1, or 2:1. After washing with water, the mixture is allowed to stand to separate into two phases to remove water-soluble impurities such as the quenching agent, and the organic phase is used.

[0028] Further, in step (3), the organic phase obtained by separation is subjected to solvent removal. The solvent removal method can be performed by atmospheric distillation or vacuum distillation. The distillation temperature can be selected according to the type of the organic solvent, and the pressure for vacuum distillation is generally -0.08 MPa to -0.1 MPa.

[0029] Further, in step (3), after the solvent is removed, the remaining material is subjected to impurity removal at a high temperature, and then the temperature is lowered to room temperature to obtain the target product, the bio-based material modified cumaran resin. The temperature for high-temperature impurity removal is 240°C to 260°C, for example, 240°C, 245°C, 250°C, 255°C, or 260°C. The pressure for impurity removal is -0.08 MPa to -0.1 MPa. The time for impurity removal is 30 min to 2 h, for example, 30 min, 1 h, 1.5 h, 2 h, 2.5 h, or 3 h. The high-temperature impurity removal mainly removes high-boiling-point impurities in the mixture of the polymerizable components indene and cumaran.

[0030] Further, when the bio-based material is guaiacylpropane (G type), the structure of the bio-based material modified cumaran resin obtained is as follows:

[0031]

[0032]

[0033] Further, when the bio-based material is syringylpropane (S type), the structure of the bio-based material modified cumaran resin obtained is as follows:

[0034]

[0035] Further, when the bio-based material is p-hydroxyphenylpropane (H type), the structure of the bio-based material modified cumaran resin obtained is as follows:

[0036]

[0037] The present application also provides a bio-based material modified cumaran resin, which is at least one of the structures represented by the following formulas (I)-(X):

[0038]

[0039]

[0040]

[0041] Further, in the above formula (I) to formula (X), l, m, n are all integers from 1 to 100, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100.

[0042] The application further provides application of the above-mentioned bio-based material modified coumarone resin or the bio-based material modified coumarone resin prepared according to the above-mentioned method in adhesives, rubber, paint, ink.

[0043] The application further provides application of the above-mentioned bio-based material modified coumarone resin or the bio-based material modified coumarone resin prepared according to the above-mentioned method in rubber products, preferably tires, which can improve the wet skid resistance of the tire tread rubber and avoid the increase of the rolling resistance of the tire tread rubber caused by the addition of the resin.

[0044] The technical features and beneficial effects of the application are as follows:

[0045] (1) The application uses bio-based materials as raw materials to synthesize bio-based coumarone resin, which is derived from plants in nature and has the characteristics of environmental friendliness and biodegradability, realizes the recycling of resources and reduces the generation of waste.

[0046] (2) The application grafts bio-based materials onto the benzene ring of coumarone resin, thereby endowing the coumarone resin with a polar hydroxyl group, making the coumarone resin have better compatibility with polar materials. In addition, the introduction of the hydroxyl group can also crosslink the coumarone resin with other components in the application formula, further improving the performance of adhesives, rubber, paint, ink, etc. When used in tire tread rubber, it not only improves the wet skid resistance of the tread rubber, but also avoids the increase of the rolling resistance of the tread rubber caused by the addition of the resin.

[0047] (3) The application uses at least one of diethylene glycol methyl ether, 1,4-dioxane, diethyl ether and chloroform as an organic solvent for bio-based raw materials, improves the dispersibility of bio-based materials, and makes the bio-based material modified coumarone resin obtained by polymerization have durability, weather resistance and corrosion resistance. In the application of tire tread rubber, the hydroxyl group endowed by bio-based modification increases the bonding force between rubber and water, which helps to further improve the wet skid resistance of the tread rubber.

[0048] (4) The present application selects a mixture of acidic ion exchange resin (such as Amberlyst 15, Amberlyst 35, Amberlyst 36, Nafion NR50 or Lewatit K2621) and metal chloride (aluminum trichloride, boron trichloride or antimony trichloride) as the catalyst for the polymerization reaction, and the mixed catalyst has the advantages of fast reaction speed, high conversion rate, good polymerization uniformity, narrow product molecular weight distribution, etc.

[0049] (5) The present application uses triethylamine (TEA), pyridine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the quenching agent for quenching reaction, and the H + ions in the adsorption catalyst are reduced, so as to achieve the purpose of stopping the reaction. The quenching agent can quench the high-activity catalyst, and has the advantage of completely terminating the reaction. +

[0050] (6) The preparation method provided by the present application has the advantages of mild operation condition, simple process, high reaction rate, few side reactions, stable product and easy industrial production.

[0051] (7) The bio-based modified coumarone resin has high hydroxyl content and narrow molecular weight distribution, improves the compatibility of coumarone resin and polar resin, improves the use performance and application range of coumarone resin, and has good application prospect in the fields of adhesives, rubber, coatings, inks and the like, and is especially suitable for use in tire tread rubber. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 Loss factor (tan delta) - temperature (T) curves of tread rubber 1-tread rubber 11. DETAILED DESCRIPTION

[0053] The present application will be further described below in combination with specific examples, but is not limited thereto.

[0054] Meanwhile, the methods described in the following examples are all conventional methods unless otherwise specified, and the materials described are all commercially available unless otherwise specified.

[0055] In the following examples and comparative examples, the mixture containing polymerizable components indene and coumarone used is a commercially available product, wherein the indene content is 81.32%, and the coumarone content is 1.77%.

[0056] Example 1

[0057] A preparation method of a bio-based material modified coumarone resin, comprising the following steps performed in sequence:

[0058] ​(1) At room temperature, 50 g of a mixture containing polymerizable components of indene and coumarone, 5 g of styrene, and 5 g of a catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum chloride at a mass ratio of 4:1) were added to a reaction kettle and stirred to obtain a reaction mixture solution A.

[0059] (2) The temperature was raised to 65°C, and 50 g of a mixture containing polymerizable components of indene and coumarone and 51.88 g of a 20% mass fraction guaiacyl propane (type G) organic solvent solution (the organic solvent was a mixture of diethylene glycol dimethyl ether and diethyl ether at a mass ratio of 3:1) were simultaneously added dropwise to the reaction mixture solution A. The temperature was controlled at 65-70°C during the dropwise addition, and the dropwise addition time was 30 min. After the dropwise addition was completed, the reaction temperature was controlled at 85-90°C, and the reaction was performed for 2 h. After the reaction was completed, 10 g of triethylamine was added to quench the reaction, and then the solid catalyst was removed by filtration. Then, 150 g of water was added to wash the reaction solution, and the organic phase was obtained by standing and liquid separation. A mixed solution B was obtained.

[0060] (3) The mixed solution B obtained in step (2) was heated to 100°C under -0.09 MPa to evaporate the organic solvent, and then heated to 255°C under this pressure and kept for 1 h to remove the remaining impurities, thereby obtaining a final bio-based material modified coumarone resin.

[0061] Example 2

[0062] The bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “50 g of a mixture containing polymerizable components of indene and coumarone” was replaced by “66.7 g of a mixture containing polymerizable components of indene and coumarone”; in step (2), “50 g of a mixture containing polymerizable components of indene and coumarone was added dropwise to the reaction mixture solution A” was replaced by “33.3 g of a mixture containing polymerizable components of indene and coumarone was added dropwise to the reaction mixture solution A”; and the other steps and conditions were the same as in Example 1.

[0063] Example 3

[0064] The bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “50 g of a mixture containing polymerizable components of indene and coumarone” was replaced by “33.3 g of a mixture containing polymerizable components of indene and coumarone”; in step (2), “50 g of a mixture containing polymerizable components of indene and coumarone was added dropwise to the reaction mixture solution A” was replaced by “66.7 g of a mixture containing polymerizable components of indene and coumarone was added dropwise to the reaction mixture solution A”; and the other steps and conditions were the same as in Example 1.

[0065] Example 4

[0066] A bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 4:1)” was replaced by “5 g of catalyst (a mixture of acidic ion exchange resin Lewatit K2621 and antimony trichloride at a mass ratio of 4:1)”; other steps and conditions were the same as in Example 1.

[0067] Example 5

[0068] A bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 4:1)” was replaced by “5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 2:1)”; other steps and conditions were the same as in Example 1.

[0069] Example 6

[0070] A bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 4:1)” was replaced by “3 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 4:1)”; other steps and conditions were the same as in Example 1.

[0071] Example 7

[0072] A bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (1), “5 g of styrene” was replaced by “10 g of styrene”; in step (2), “50 g of a mixture containing polymerizable components indene and coumarone and 51.88 g of a 20% mass fraction guaiacyl propane (type G) organic solvent solution (the organic solvent was a mixture of diethylene glycol dimethyl ether and diethyl ether at a mass ratio of 3:1)” was replaced by “50 g of a mixture containing polymerizable components indene and coumarone and 103.75 g of a 20% mass fraction guaiacyl propane (type G) organic solvent solution (the organic solvent was a mixture of diethylene glycol dimethyl ether and diethyl ether at a mass ratio of 3:1)”; other steps and conditions were the same as in Example 1.

[0073] Example 8

[0074] The bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 51.88 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)", was replaced by "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 59.86 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)"; other steps and conditions are the same as Example 1.

[0075] Example 9

[0076] The bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 51.88 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)", was replaced by "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 59.86 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)"; other steps and conditions are the same as Example 1.

[0077] Example 10

[0078] The bio-based material modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 51.88 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)", was replaced by "to the reaction mixed solution A, while respectively adding 50 g of mixture containing polymerizable components of indene and coumarone and 59.86 g of 20% by mass of guaiacyl propane (G type) organic solvent solution (organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1)"; other steps and conditions are the same as Example 1.

[0079] Example 11

[0080] A bio-based material-modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the phrase "50 g of a mixture containing polymerizable components indene and coumarone and 51.88 g of a 20% by mass guaiacylpropane (type G) organic solvent solution (the organic solvent was a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether was 3:1)" was replaced with "50 g of a mixture containing polymerizable components indene and coumarone and 51.88 g of a 20% by mass guaiacylpropane (type G) diethylene glycol dimethyl ether solution". The other steps and conditions were the same as in Example 1.

[0081] Example 12

[0082] A bio-based material-modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the phrase "50 g of a mixture containing polymerizable components indene and coumarone and 51.88 g of a 20% by mass guaiacylpropane (type G) organic solvent solution (the organic solvent was a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether was 3:1)" was replaced with "50 g of a mixture containing polymerizable components indene and coumarone and 51.88 g of a 20% by mass guaiacylpropane (type G) organic solvent solution (the organic solvent was a mixture of 1,4-dioxane and chloroform, and the mass ratio of 1,4-dioxane to chloroform was 3:1)". The other steps and conditions were the same as in Example 1.

[0083] Example 13

[0084] A bio-based material-modified coumarone resin was prepared according to the method of Example 1, except that in step (2), the phrase "after the reaction was completed, 10 g of triethylamine was added to quench the reaction" was replaced with "after the reaction was completed, 10 g of pyridine was added to quench the reaction". The other steps and conditions were the same as in Example 1.

[0085] Comparative Example 1

[0086] A method for preparing a coumarone resin, comprising the following steps performed in sequence:

[0087] (1) 100 g of a mixture containing polymerizable components indene and coumarone, 5 g of styrene, and 5 g of a catalyst (a mixture of an acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 4:1) were added together into a reaction kettle, and the mixture was stirred at 70°C for 2 h. After the reaction was completed, 10 g of triethylamine was added to quench the reaction, to obtain a mixed solution A.

[0088] (2) 150 g of water was added to the mixed solution A obtained in step (1) for washing. After standing and separating the liquids, the organic phase was heated to 255° C. at −0.09 MPa and kept warm for 1 h to remove residual impurities to obtain the final coumarone resin.

[0089] Comparative Example 2

[0090] Bio-based material modified coumarone resin was prepared according to the method of Example 1, except that: in step (1), "5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum chloride in a mass ratio of 4:1)" was replaced by "5 g of aluminum chloride"; the other steps and conditions were the same as in Example 1.

[0091] Comparative Example 3

[0092] Bio-based material modified coumarone resin was prepared according to the method of Example 1, except that: in step (1), "5 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum chloride in a mass ratio of 4:1)" was replaced by "5 g of acidic ion exchange resin Amberlyst 35"; the other steps and conditions were the same as in Example 1.

[0093] Comparative Example 4

[0094] A bio-based material modified coumarone resin was prepared according to the method of Example 1, except that: in step (2), "50 g of a mixture containing polymerizable components of indene and coumarone and 51.88 g of an organic solvent solution of guaiacylpropane (type G) with a mass fraction of 20% (the organic solvent is a mixture of diethanol methyl ether and ethyl ether, and the mass ratio of diethanol methyl ether to ethyl ether is 3:1) are simultaneously added dropwise to the reaction mixed solution A" is replaced by "50 g of a mixture containing polymerizable components of indene and coumarone and 51.88 g of a toluene solution of guaiacylpropane (type G) with a mass fraction of 20% are simultaneously added dropwise to the reaction mixed solution A"; the other steps and conditions are the same as in Example 1.

[0095] Comparative Example 5

[0096] Bio-based material modified coumarone resin was prepared according to the method of Example 1, except that: in step (2), "after the reaction is completed, 10 g of triethylamine is added to quench the reaction" is replaced by "after the reaction is completed, 10 g of sodium carbonate is added to quench the reaction"; other steps and conditions are the same as in Example 1.

[0097] Comparative Example 6

[0098] A method for preparing a bio-based material modified coumarone resin comprises the following steps performed in sequence:

[0099] (1) 100 g of a mixture containing polymerizable components indene and cumaran, 5 g of styrene, 51.88 g of a 20% mass fraction guaiacylpropane (type G) organic solvent solution (the organic solvent is a mixture of diethylene glycol dimethyl ether and diethyl ether, and the mass ratio of diethylene glycol dimethyl ether to diethyl ether is 3:1), and 5 g of a catalyst (a mixture of an acidic ion exchange resin Amberlyst 35 and aluminum chloride in a mass ratio of 4:1) were added into a reaction kettle at room temperature and stirred and mixed to obtain a reaction mixture solution A.

[0100] (2) The reaction temperature was controlled at 85-90°C, and the reaction was carried out for 2 h. After the reaction was completed, 10 g of triethylamine was added to quench the reaction, and then the solid catalyst was removed by filtration. Then, 150 g of water was added to wash the reaction solution, and the organic phase was obtained by standing and liquid separation, to obtain a mixed solution B.

[0101] (3) The mixed solution B obtained in step (2) was heated to 100°C under -0.09 MPa to evaporate the organic solvent, and then heated to 255°C under this pressure and kept for 1 h to remove the remaining impurities, to obtain the final bio-based material modified cumaran resin.

[0102] The corresponding indexes of the products obtained in the above examples and comparative examples were detected, wherein the softening point of the resin was measured by the ring and ball method, the molecular weight was measured by the GPC method, the color was measured by visual colorimetry of a benzene solution of the resin with iron, cobalt, and copper standard colorimetric solution, the hydroxyl content was measured by titration, and PDI=Mw / Mn.

[0103] The results are shown in Table 1 below:

[0104] Table 1

[0105]

[0106] Performance experiment

[0107] 1, Tire tread rubber formula (parts by weight):

[0108] SSBR 96.25 parts; BR 30 parts; white carbon black 100 parts; carbon black 5 parts; Si69 10 parts; stearic acid 1 part; protective wax 1 part; antioxidant 4020 2 parts; antioxidant RD 1 part; accelerator DPG 2.5 parts; zinc oxide 3 parts; sulfur 2 parts; accelerator CBS 2 parts, and resin 30 parts. The resins were resins prepared in Example 1, Example 3, Example 4, Example 11, Example 13, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, and Comparative Example 6, respectively, and the tire tread rubbers obtained from different resins were tire tread rubber 1, tire tread rubber 2, tire tread rubber 3, tire tread rubber 4, tire tread rubber 5, tire tread rubber 6, tire tread rubber 7, tire tread rubber 8, tire tread rubber 9, tire tread rubber 10, and tire tread rubber 11, respectively.

[0109] 2. Tread rubber preparation process:

[0110] (1) One-stage mixing (internal mixer): mix raw rubber SSBR and BR for 60 s, add stearic acid, protective wax, antioxidant 4020, antioxidant RD, 1 / 2 resin, 1 / 2 white carbon black, carbon black, Si69, press the ladle and mix for 60 s, add the remaining white carbon black and the remaining resin, mix for 60 s, clean the ladle for 15 s, press the ladle and mix for 70 s, add zinc oxide, press the ladle and mix for 40 s, keep warm for 180 s, and discharge the rubber (temperature is 150±5℃).

[0111] Two-stage mixing (open mill): hot roller mixing (front roller 80℃, back roller 85℃) 1.4mm roller gap mixing rubber 1 minute, cutting rubber 4 times; add material (sulfur, accelerator DPG and accelerator CBS), eat material for two minutes, cut rubber 4 times; 0mm roller gap to make 4 triangular packs, 1.2mm roller gap to make 6 rolls, and down sheet.

[0112] 3. Test method

[0113] The anti-wet skid resistance and rolling resistance of the obtained tread rubber were determined by DMA method. Test conditions: nitrogen atmosphere, fixed frequency of 1 Hz, heating rate of 5℃ / min, and temperature range of -40℃-80℃.

[0114] 4. Experimental results

[0115] The loss factor (tan δ) - temperature (T) curves of the tread rubber 1-tread rubber 11 are shown in Figure 1 The loss factor (tan δ) - temperature (T) curve can represent the anti-wet skid resistance and rolling resistance of the rubber, generally, the larger the loss factor (tan δ) value at 0℃ indicates the better the anti-wet skid resistance of the rubber, and vice versa; while the smaller the loss factor (tan δ) value at 60℃ indicates the lower the rolling resistance of the rubber, and vice versa. Figure 1 It can be seen that the anti-wet skid resistance of the tread rubber added with the bio-based material modified coumarone resin of Example 1 is better than that of the tread rubber added with the resins of other examples and comparative examples; and the rolling resistance of the tread rubber added with the resin of Example 1 is also lower than that of the tread rubber added with the resins of other examples and comparative examples, and the application performance of the resin of Example 1 to the tread rubber is best improved.

Claims

1. A method for preparing a bio-based material modified coumarone resin, characterized in that The following steps are involved: (1) mixing a mixture containing polymerizable components of indene and coumarone, styrene or its derivatives, and a catalyst to obtain a mixed solution A; (2) simultaneously adding a mixture of polymerizable components, indene and coumarone, and an organic solvent solution of a bio-based material to the mixed solution A, and then heating the solution to carry out a polymerization reaction after the addition is complete; (3) After the reaction, a quenching agent is added to terminate the reaction, and then the reaction solution is filtered, washed with water, and allowed to stand for separation. The organic phase is taken, and the organic solvent is removed from the obtained organic phase and impurities are removed at high temperature to obtain a bio-based material modified coumarone resin.

2. The preparation method according to claim 1, wherein: In step (1), the mixture containing the polymerizable components indene and coumarone contains indene and coumarone, the content of indene is 50-95wt%, and the content of coumarone is 0.5-2wt%.

3. The preparation method according to claim 1, wherein: In step (1), the styrene derivative is α-methylstyrene; preferably, in step (1), the mass ratio of styrene or its derivative to the total mixture containing the polymerizable components indene and coumarone in steps (1) and (2) is (2% to 10%):

1.

4. The preparation method according to claim 1, wherein: In step (1), the catalyst is a mixture of an acidic ion exchange resin and a metal chloride; preferably, the acidic ion exchange resin is Amberlyst 15, Amberlyst 35, Amberlyst 36, Nafion NR50 or Lewatit K2621, and the metal chloride is aluminum trichloride, boron trichloride or antimony trichloride; preferably, the mass ratio of the acidic ion exchange resin to the metal chloride is (1-5):

1.

5. The preparation method according to claim 1 or 4, characterized in that: In step (1), the mass ratio of the catalyst to the total mixture containing the polymerizable components indene and coumarone in steps (1) and (2) is (3% to 8%):1; preferably, the mass ratio of the mixture containing the polymerizable components indene and coumarone in step (2) to the mixture containing the polymerizable components indene and coumarone in step (1) is (0.5 to 2):

1.

6. The preparation method according to claim 1, wherein: In step (2), the bio-based material is one or more of guaiacyl propane, syringyl propane and p-hydroxyphenyl propane; preferably, the molar ratio of the bio-based material to styrene or its derivatives is (1 to 1.5):

1.

7. The preparation method according to claim 1, wherein: In step (2), the organic solvent is one or more of diethanol methyl ether, 1,4-dioxane, ether and chloroform, preferably a mixture of diethanol methyl ether and ether; preferably, in step (2), the mass ratio of the bio-based material to the organic solvent is 1: (3 to 8).

8. The preparation method according to claim 1, wherein: In step (2), the temperature for adding the mixture containing the polymerizable components indene and coumarone to the organic solvent solution of the bio-based material is 60°C to 70°C, the temperature is controlled at 70°C to 75°C during the addition process, and the addition time is 15min to 60min; preferably, in step (2), after the addition is completed, the temperature is raised to 80°C to 90°C for polymerization reaction, and the reaction time is 1h to 3h.

9. The preparation method according to claim 1, wherein: In step (3), the quencher is triethylamine, pyridine or 1,8-diazabicycloundec-7-ene; preferably, the mass ratio of the quencher to the catalyst is (0.5-3):1; Preferably, in step (3), the mass ratio of the water used for washing to the total mixture containing the polymerizable components indene and coumarone in steps (1) and (2) is (0.5-2):1; Preferably, in step (3), impurity removal is carried out at 240° C. to 260° C., the impurity removal pressure is -0.08 MPa to -0.1 MPa, and the impurity removal time is 30 min to 2 h.

10. A bio-based material modified coumarone resin prepared by the preparation method according to any one of claims 1 to 9, and use of the bio-based material modified coumarone resin in rubber products, preferably in tires; preferably, the bio-based material modified coumarone resin is used to improve the wet skid resistance of tires and reduce the rolling resistance of tires.

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