Preparation method of bio-based material modified terpene resin, obtained product and application

Abstract

The invention discloses a preparation method of bio-based material modified terpene resin, an obtained product and application, the bio-based material modified terpene resin takes a bio-based material and turpentine as raw materials, and a polymerization reaction is carried out under the action of an organic solvent and a catalyst; and after the reaction, adding a quenching agent to terminate the reaction, and post-treating the reaction liquid to obtain a final product. According to the invention, the bio-based material is used as a raw material to synthesize the bio-based material modified terpene resin, 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 preparation method is mild in operation condition, high in reaction rate, few in side reaction, stable in product and easy for industrial production, and the obtained bio-based material modified terpene resin has durability, weather resistance and corrosion resistance, can improve the wet skid resistance of tread rubber when being used in the tire tread rubber, and has a good application prospect. And meanwhile, the increase of the rolling resistance of the tread rubber caused by the addition of the resin is avoided.

Description

TECHNICAL FIELD

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

[0002] The terpene resin is a resin polymer obtained by polymerization of terpene as a material with the help of a solvent and a catalyst. Since the terpene resin itself not only has good physical properties, but also has good chemical properties, it is widely used in adhesives, rubber, coatings, inks and many other fields, and plays a crucial role. In order to maximize the quality of adhesives, rubber and other products, meet the needs of consumers, and enable terpene resin to be applied in more fields, the terpene resin is improved. After combining the terpene resin with petroleum olefins, phenol, aldehyde and other chemicals, the modified terpene resin is obtained, which has more superior performance and a wider range of applications, and can effectively meet the different needs of consumers.

[0003] The terpene phenol resin is a modified terpene resin polymerized from terpene resin and phenol. The resin has good polarity and can be fused with most film-forming materials. It is an excellent tackifier for acrylic resin, styrene-butadiene rubber, natural rubber and chlorobutyl rubber, and is widely used in the industries of hot melt adhesives, pressure sensitive adhesives, coatings, inks, printed circuits, plastics, rubber products, etc. In addition, due to the special hydroxyl structure on the surface of the terpene phenol resin, the bonding force between the rubber and the water surface is improved, thereby improving the wet skid resistance of the tire tread rubber. At the same time, the softening point and glass transition temperature are also increased, so that the tire tread rubber has better comprehensive performance. Therefore, the terpene phenol resin has a very wide application in the tire industry.

[0004] At present, the common terpene phenol resin is mainly polymerized from alpha-pinene and beta-pinene in turpentine oil and phenol or bisphenol A under the action of a catalyst. In recent years, with the increasingly severe environmental protection situation, green and environmentally friendly, sustainable development of bio-based materials play an increasingly important role in industrial production and daily life. SUMMARY

[0005] The present application aims to provide a preparation method of a bio-based material modified terpene resin. The method is simple to operate, environmentally friendly in raw materials, and has few side reactions. The obtained bio-based material modified terpene resin can be applied in the industries of adhesives, rubber, etc., especially in the tire tread rubber. It not only can improve the wet skid resistance of the tread rubber, but also can inhibit the increase of the rolling resistance caused by the addition of the resin to a certain extent, so that the tire has better tread comprehensive performance.

[0006] To achieve the above-mentioned purpose, the present application is implemented by the following technical solutions:

[0007] A preparation method of a bio-based material modified terpene resin, the method comprising the following steps:

[0008] (1) mixing a bio-based material, an organic solvent and a catalyst, and then adding and polymerizing turpentine under heating;

[0009] (2) adding a quenching agent to terminate the reaction after the reaction is completed, and then filtering, washing with water, standing and separating the reaction solution to obtain an organic phase;

[0010] (3) removing the organic solvent from the organic phase, and then removing impurities under high temperature to obtain the bio-based material modified terpene resin.

[0011] Further, in step (1), the bio-based material is a lignin monomer, for example, one or more of guaiacyl propane (G type), syringyl propane (S type) and p-hydroxyphenyl propane (H type). Their structural formulas are shown as follows, respectively:

[0012]

[0013] Further, in step (1), the organic solvent is one or more of diethanol methyl ether, 1,4-dioxane, diethyl ether and chloroform. The amount of the organic solvent as a reaction medium can be selected as needed. It is 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 or 3:1.

[0014] Further, in step (1), the mass ratio of the bio-based material to the organic solvent is preferably 1:(3-8), for example, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.

[0015] Further, in step (1), the catalyst is a mixture of an acidic ion exchange resin (such as Amberlyst 15, Amberlyst 35, Amberlyst 36, Nafion NR50 or Lewatit K2621) and a metal chloride (such as aluminum chloride, boron trichloride or antimony trichloride), and the mass ratio of the acidic ion exchange resin to the metal chloride is (1-5):1, for example, 1:1, 2:1, 3:1, 4:1 or 5:1. The catalyst can improve the reaction rate and also improve the reaction yield. Preferably, the catalyst is a mixture of Amberlyst 35 and aluminum trichloride, and preferably, the mass ratio of Amberlyst 35 to aluminum trichloride is 3:1.

[0016] Further, in step (1), the mass ratio of catalyst to turpentine is (1%~3%):1, for example, 1%:1, 1.5%:1, 2%:1, 2.5%:1, 3%:1.

[0017] Further, in step (1), the mass ratio of turpentine to bio-based material is (3~6):1, for example, 3:1, 4:1, 5:1, 6:1.

[0018] Further, in step (1), the starting dropping temperature of turpentine is 65℃~70℃, for example, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃. The temperature is controlled at 70℃~75℃ during the dropping process, for example, 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, and the dropping time is 15min~60min, for example, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min.

[0019] Further, in step (1), after the dropping of turpentine is completed, the temperature is maintained at 70℃~75℃ for the polymerization reaction, for example, 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, and the reaction time is 2h~3h.

[0020] Further, in step (1), the reaction is carried out under gas protection, and the protective gas is an inert gas such as nitrogen or argon.

[0021] Further, in step (2), the quenching agent is triethylamine (TEA), pyridine or 1,8-diazabicycloundec-7-ene (DBU), and the mass ratio of quenching agent to catalyst is (0.5~3):1, for example, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1.

[0022] Further, in step (2), after the reaction is terminated, the solid catalyst is removed by filtration, and then water is added to the reaction liquid to wash the reaction liquid. The mass ratio of added water to turpentine is (0.5~2):1, for example, 0.5:1, 1:1, 1.5:1, 2:1. After washing with water, the mixture is left to stand to separate the liquid, so as to remove water-soluble impurities such as quenching agent, and the organic phase is taken for standby.

[0023] Further, in step (3), the organic phase obtained by separation is removed of organic solvent, and the desolventization method can adopt normal pressure distillation, reduced pressure distillation and the like. The distillation temperature can be selected according to the type of organic solvent, and the pressure of reduced pressure distillation is generally -0.08 MPa~ -0.1Mpa.

[0024] Further, in step (3), after removing the solvent, the residue is removed of impurities at high temperature, and then reduced to room temperature, to obtain the target product, the bio-based material modified terpene resin. The temperature for removing impurities at high temperature is 240℃-260℃, for example, 240℃, 245℃, 250℃, 255℃, 260℃, the pressure for removing impurities is -0.08 MPa--0.1Mpa, the time for removing impurities is 30min-2h, for example, 30min, 1h, 1.5h, 2h, 2.5h, 3h. The high-temperature impurity removal mainly removes high-boiling-point impurities in turpentine oil.

[0025] Further, when the bio-based material is guaiacyl propane (G type), the structural formula of the obtained bio-based modified terpene resin is:

[0026]

[0027] Further, when the bio-based material is syringyl propane (S type), the structural formula of the obtained bio-based modified terpene resin is:

[0028]

[0029] Further, when the bio-based material is p-hydroxyphenyl propane (H type), the structural formula of the obtained bio-based modified terpene resin is:

[0030]

[0031] The present application also provides a bio-based material modified terpene resin, which is at least one of the structures shown in the following formula (I)-formula (V):

[0032]

[0033] Further, in the above formula (I)-formula (V), m is an integer of 0-100, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, n is an integer of 1-100, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100.

[0034] The present application also provides the use of the above-mentioned bio-based material modified terpene resin or the bio-based material modified terpene resin prepared according to the above-mentioned method in adhesives, rubber.

[0035] The application also provides the application of the above-mentioned bio-based material modified terpene resin or the bio-based material modified terpene resin prepared according to the above-mentioned method in a rubber product, preferably a tire, 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.

[0036] The application has the following beneficial effects:

[0037] (1) The application uses bio-based materials as modifiers to synthesize terpene resins, and the raw materials are derived from plants in nature, which has the characteristics of environmental friendliness and biodegradability, realizes the recycling of resources, and reduces the generation of waste.

[0038] (2) The bio-based material modified terpene resin synthesized by the application has a narrow molecular weight distribution, has durability, weather resistance and corrosion resistance, and can improve the wet skid resistance of the tire tread rubber when used in the tire tread rubber, while avoiding the increase of the rolling resistance of the tire tread rubber caused by the addition of the resin.

[0039] (3) The application uses at least one of diethylene glycol methyl ether, 1,4-dioxane, diethyl ether and chloroform as an organic solvent of the bio-based raw material, which improves the dispersibility of the bio-based material, makes the bio-based material modified terpene resin obtained by polymerization contain more hydroxyl groups, increases the bonding force between the rubber and water, and helps to further improve the wet skid resistance of the tire tread rubber.

[0040] (4) The application selects a mixture of acidic ion exchange resin and metal chloride as a catalyst for 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.

[0041] (5) The application uses triethylamine (TEA), pyridine and 1,8-diazabicycloundec-7-ene (DBU) as a quenching agent for quenching reaction, which can adsorb H+ ions in the catalyst and reduce the concentration of H+, so as to stop the reaction. The quenching agent can quench the high-activity catalyst and has the advantage of complete termination of the reaction.

[0042] (6) The preparation method has mild operating conditions, high reaction rate, few side reactions, stable product and easy industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 The loss factor (tan delta) - temperature (T) curves of the tire tread rubbers 1-8. DETAILED DESCRIPTION

[0044] The application will be further described below in combination with specific examples, but is not limited thereto.

[0045] The methods described in the following examples and comparative examples are conventional methods unless otherwise specified; the materials described are commercially available unless otherwise specified.

[0046] Example 1

[0047] A method for preparing a bio-based material modified terpene resin, comprising the following steps in sequence:

[0048] (1) At room temperature, 25 g guaiacylpropane (G type), 100 g mixture of diethylene glycol methyl ether and ether (mass ratio of diethylene glycol methyl ether to ether is 3:1) and 2 g catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride with a mass ratio of 3:1) are added into a reaction kettle at the same time, and then nitrogen is introduced. When the temperature of the reaction system rises to 65℃, the polymerization reaction is started by adding 100 g of turpentine oil containing 81.52% of a-pinene and 12.41% of β-pinene into the reaction kettle dropwise, and the dropwise addition time is 25 min. After the dropwise addition is completed, the reaction temperature is controlled at 70-75℃, and the reaction is carried out for 2 h. After the reaction is completed, 3 g of triethylamine is added to quench the reaction, and the solid catalyst is removed by filtration. Then, 150 g of water is added to wash the mixed solution, and the organic phase is obtained by standing and liquid separation of the mixed solution to obtain mixed solution A.

[0049] (2) The mixed solution A obtained in step (1) is heated to 100℃ under-0.09 MPa to evaporate the organic solvent, and then heated to 255℃ under this pressure and kept for 1 h to remove the remaining impurities to obtain the final bio-based material modified terpene resin.

[0050] Example 2

[0051] The bio-based material modified terpene resin is prepared according to the method of Example 1, except that in step (1), "25 g guaiacylpropane (G type)" is replaced by "25 g p-hydroxyphenylpropane (H type)", and the other steps and conditions are the same as those of Example 1.

[0052] Example 3

[0053] The bio-based material modified terpene resin is prepared according to the method of Example 1, except that in step (1), "25 g guaiacylpropane (G type)" is replaced by "25 g syringylpropane (S type)", and the other steps and conditions are the same as those of Example 1.

[0054] Example 4

[0055] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “2 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 3:1)” was replaced with “2 g of catalyst (a mixture of acidic ion exchange resin Lewatit K2621 and boron trichloride at a mass ratio of 3:1)”; other steps and conditions were the same as Example 1.

[0056] Example 5

[0057] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “2 g of catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum trichloride at a mass ratio of 3:1)” was replaced with “2 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 Example 1.

[0058] Example 6

[0059] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “after the reaction was completed, 3 g of triethylamine was added to quench the reaction” was replaced with “after the reaction was completed, 3 g of pyridine was added to quench the reaction”; other steps and conditions were the same as Example 1.

[0060] Example 7

[0061] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “after the reaction was completed, 3 g of triethylamine was added to quench the reaction” was replaced with “after the reaction was completed, 6 g of triethylamine was added to quench the reaction”; other steps and conditions were the same as Example 1.

[0062] Example 8

[0063] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “100 g of a mixture of diethylene glycol methyl ether and diethyl ether (mass ratio of diethylene glycol methyl ether to diethyl ether was 3:1)” was replaced with “100 g of a mixture of 1,4-dioxane and chloroform (mass ratio of 1,4-dioxane to chloroform was 3:1)”; other steps and conditions were the same as Example 1.

[0064] Example 9

[0065] A bio-based material modified terpene resin was prepared according to the method of Example 1, except that in step (1), “100 g of a mixture of diethylene glycol methyl ether and diethyl ether (mass ratio of diethylene glycol methyl ether to diethyl ether was 3:1)” was replaced with “100 g of diethylene glycol methyl ether”; other steps and conditions were the same as Example 1.

[0066] Example 10

[0067] The bio-based material-modified terpene resin was prepared according to the method of Example 1, except that in step (1), "100 g of a mixture of diethylene glycol methyl ether and diethyl ether (mass ratio of diethylene glycol methyl ether to diethyl ether was 3:1)" was replaced with "100 g of diethylene glycol methyl ether", and other steps and conditions were the same as in Example 1.

[0068] Comparative Example 1

[0069] The terpene resin was prepared according to the method of Example 1, except that in step (1), no guaiacylpropane (G type) was added, and other steps and conditions were the same as in Example 1.

[0070] Comparative Example 2

[0071] The bio-based material-modified terpene resin was prepared according to the method of Example 1, except that in step (1), "2 g of a catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum chloride with a mass ratio of 3:1)" was replaced with "2 g of aluminum oxide", and other steps and conditions were the same as in Example 1.

[0072] Comparative Example 3

[0073] The bio-based material-modified terpene resin was prepared according to the method of Example 1, except that in step (1), "2 g of a catalyst (a mixture of acidic ion exchange resin Amberlyst 35 and aluminum chloride with a mass ratio of 3:1)" was replaced with "2 g of acidic ion exchange resin Amberlyst 35", and other steps and conditions were the same as in Example 1.

[0074] Comparative Example 4

[0075] The bio-based material-modified terpene resin was prepared according to the method of Example 1, except that in step (1), "100 g of a mixture of diethylene glycol methyl ether and diethyl ether (mass ratio of diethylene glycol methyl ether to diethyl ether was 3:1)" was replaced with "100 g of toluene", and other steps and conditions were the same as in Example 1.

[0076] Comparative Example 5

[0077] The bio-based material-modified terpene resin was prepared according to the method of Example 1, except that in step (1), "after the reaction was completed, 3 g of triethylamine was added to quench the reaction" was replaced with "after the reaction was completed, 3 g of sodium carbonate was added to quench the reaction".

[0078] The corresponding indicators 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 GPC method, the hydroxyl content was measured by titration method, and PDI = Mw / Mn.

[0079] The results are shown in Table 1 below:

[0080] Table 1

[0081]

[0082]

[0083] Performance experiment

[0084] 1, Tread rubber formula (parts by weight):

[0085]

[0086]

[0087] 2, Tread rubber preparation process:

[0088] (1) First stage mixing (internal mixer): mix raw rubber SSBR and BR for 60 s, add stearic acid, protective wax, antioxidant, 1 / 2 resin sample (prepared in the example or the comparative example), 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 sample to the ladle and mix for 60 s, clean the ladle for 15 s, press the ladle and mix for 70 s, add zinc oxide to the ladle, press the ladle and mix for 40 s, keep mixing for 180 s, and take out the rubber (temperature is 150±5℃).

[0089] Second stage mixing (open mill): hot roller open mixing (front roller 80℃, back roller 85℃) 1.4mm roller gap open mixing rubber 1 minute, cut rubber 4 times; add material (sulfur and accelerator), 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.

[0090] 3, Test method

[0091] 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 1Hz, heating rate of 5℃ / min, and heating range of -40℃-80℃.

[0092] 4, Experimental results

[0093] The loss factor (tan δ)-temperature (T) curve of the tread rubber 1-8 is 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, and 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. From Figure 1It can be seen that the wet skid resistance of the tread rubber added with the modified terpene resin of Example 1 is similar to that of the tread rubber added with Example 4, but is better than that of the tread rubber added with Example 9, and is better than that of the tread rubber added with Comparative Examples 1-5; and the rolling resistance of the tread rubber added with Example 1 is obviously lower than that of the tread rubber added with other examples and comparative examples, and the application performance of the resin of Example 1 to the tread rubber is the best.

Claims

1. A method for preparing a bio-based material modified terpene resin, characterized in that The following steps are involved: (1) mixing the bio-based material, the organic solvent and the catalyst, then heating and adding turpentine dropwise to carry out polymerization reaction; (2) After the reaction is completed, a quenching agent is added to terminate the reaction, and the reaction solution is then filtered, washed with water, allowed to stand for separation, and the organic phase is taken; (3) removing the organic solvent from the organic phase and then removing impurities at high temperature to obtain a bio-based material modified terpene resin.

2. The preparation method according to claim 1, wherein: In step (1), the bio-based material is one or more of guaiacyl propane, syringyl propane and p-hydroxyphenyl propane; preferably, in step (1), the mass ratio of turpentine oil to the bio-based material is (3-6):

1.

3. 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.

4. The preparation method according to claim 1 or 3, wherein: In step (1), the mass ratio of the catalyst to the turpentine oil is (1% to 3%):

1.

5. The preparation method according to claim 1, wherein: In step (1), the organic solvent is one or more of diethanol methyl ether, 1,4-dioxane, diethyl ether and chloroform, preferably a mixture of diethanol methyl ether and diethyl ether.

6. The preparation method according to claim 1, 2 or 5, characterized in that: In step (1), the mass ratio of the bio-based material to the organic solvent is 1:(3-8).

7. The preparation method according to claim 1, wherein: In step (1), turpentine is added dropwise at 65°C to 70°C, the temperature is controlled to be 70°C to 75°C during the addition process, the addition time is 15min to 60min, and after the addition is completed, the temperature is controlled to be 70°C to 75°C and the reaction is carried out for 2h to 3h; preferably, in step (1), the reaction is carried out under gas protection.

8. The preparation method according to claim 1, wherein: In step (2), 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.

9. The preparation method according to claim 1, wherein: In step (2), the mass ratio of water used for washing to turpentine 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 terpene resin prepared according to the preparation method of any one of claims 1 to 9, and use of the bio-based material modified terpene resin in rubber products, preferably in tires; preferably, the bio-based material modified terpene resin is used to improve the wet skid resistance of tires and reduce the rolling resistance of tires.

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