Terpene resin preparation process

Abstract

The invention discloses a terpene resin preparation process, and belongs to the technical field of terpene resin preparation, the preparation process comprises the following steps: cooling toluene to-5-5 DEG C, adding a magnetic supported catalyst into the toluene, dropwise adding turpentine into the toluene, adding heteropolyacid into the toluene after dropwise adding, stirring for reaction, separating out the magnetic supported catalyst by using a magnetic field, and separating out the terpenes by using the magnetic supported catalyst; the preparation method comprises the following steps: mixing the raw materials to obtain a mixed solution, adding pure water with the temperature of 80-90 DEG C into the mixed solution while stirring, washing for three times, standing for layering, collecting an upper organic phase to obtain a terpene resin crude product, adding an activated carbon supported palladium catalyst into the terpene resin crude product while stirring, and hydrotreating to obtain the terpene resin. According to the preparation method, a self-made magnetic supported catalyst is used as a main catalyst, heteropoly acid is used as a cocatalyst, hydrotreatment is carried out, and the transparent terpene resin with the Ghananer color number of 1 is finally prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of terpene resin preparation, and specifically relates to a terpene resin preparation process. Background Art

[0002] Terpene resin is a series of linear polymers from liquid to solid obtained by cationic polymerization of α-pinene or β-pinene in turpentine under the action of catalyst. Since terpene resin itself has not only good physical properties but also good chemical properties, it is widely used in adhesives, rubber and other fields, and plays a vital role.

[0003] However, terpene resins are easily oxidized to yellow or brown during storage or use. The reason is that terpene resin molecules contain double bonds, which are easy to absorb oxygen and turn yellow. Therefore, in the prior art, the double bond content in terpene resins is reduced by adding a composite process of catalytic hydrogenation after cationic polymerization. However, since most of the cationic polymerization uses AlCl 3 As a polymerization catalyst, chloride ions are difficult to remove and have a poisonous effect on the catalyst in the catalytic hydrogenation process. In order to ensure the hydrogenation effect, a large amount of hydrogenation catalyst is used. The commonly used hydrogenation catalyst is precious metal palladium. The increase in the amount of precious metal palladium will lead to a significant increase in cost, which is not conducive to industrial production. Moreover, the chloride ion content in the final terpene resin product is still excessive, affecting the performance and application of the terpene resin.

[0004] In order to solve the above technical problems, the existing technology has made many improvements: The invention patent with application number 200510019067.0 uses molecular sieve to support AlCl 3 As a polymerization catalyst, and then using Pd / C as a hydrogenation catalyst, the prepared terpene resin has a Gardner color number of less than 1.

[0005] The invention patent with application number 200910114077.0 adopts activated halogen-free heteropolyacids or their salts as polymerization catalysts. The halogen-free heteropolyacids can reduce the impact on the subsequent hydrogenation reaction catalyst, thereby reducing the amount of catalyst used and ultimately reducing the production cost of terpene resins.

[0006] The invention patent application number is 201210130940.3 through AlCl 3 As the main catalyst in the polymerization process, trialkylchlorosilane (trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane or tributylchlorosilane) is used as a co-catalyst to polymerize at low temperature to obtain terpene resin. After testing, the elemental chlorine content in the prepared terpene resin is less than 100 mg / kg.

[0007] The invention patent with application number 201711270035.7 also uses AlCl 3 The composite catalyst system of trialkylchlorosilane and the main catalyst and the co-catalyst are added at different reaction time points to improve the conversion rate of the raw materials and reduce the further contact of the unreacted main catalyst with the resin molecules to form combined chlorine. After testing, the elemental chlorine content in the prepared terpene resin is less than 10 mg / kg.

[0008] The invention with application number 202210452687.7 discloses an ultra-light-colored, highly stable hydrogenated terpene-phenol resin and a preparation method thereof. This invention patent points out that hydrogenated terpene-phenol resin also has the technical problem of easy oxidation and discoloration. This invention patent improves the hydrogenation process and achieves the purpose of significantly lightening the color of terpene-phenol resin by adding catalysts, catalyst carriers and stabilizers. The Ghana color number of the finally prepared terpene-phenol resin is less than 2. Summary of the invention

[0009] Based on the prior art, the present invention improves the selection of polymerization catalysts, namely, prepares magnetic catalysts, thereby improving the separation efficiency of catalysts, reducing catalyst residues, and improving the quality of the finally prepared terpene resin, and thereby provides a terpene resin preparation process.

[0010] The purpose of the present invention can be achieved by the following technical solutions: A terpene resin preparation process comprises the following steps: Toluene is cooled to -5 to 5°C, a magnetic supported catalyst is added thereto, and turpentine is then added dropwise thereto, and the dropping time is controlled to be 2 h. After the dropping is completed, a heteropoly acid is added thereto, and the reaction is stirred for 3 to 4 h. After the stirring reaction is completed, the magnetic supported catalyst is separated by a magnetic field to obtain a mixed solution, pure water at 80 to 90°C is added to the mixed solution with stirring, and then the mixture is allowed to stand for stratification, and the upper organic phase is taken, and the organic phase is washed three times with pure water at 80 to 90°C, and then the upper organic phase is collected after standing for stratification to obtain a crude terpene resin, and an activated carbon-supported palladium catalyst is added to the crude terpene resin with stirring, and the terpene resin is obtained after hydrogenation treatment.

[0011] Furthermore, the usage ratio of the toluene, the magnetic supported catalyst, the turpentine oil, the heteropoly acid and the activated carbon supported palladium catalyst is 100 mL: 6.5-8.0 g: 80-100 g: 1.0-1.2 g: 4-5 g.

[0012] Furthermore, the palladium content in the activated carbon-supported palladium catalyst is 5%.

[0013] Further, the hydroprocessing comprises the following steps: The crude terpene resin is transferred to a reactor, and the activated carbon-supported palladium catalyst is added to the reactor with stirring, and nitrogen is introduced to replace the air in the reactor, and the nitrogen-supported gas is introduced three times, and hydrogen is introduced to replace the nitrogen, and the hydrogen-supported gas is introduced three times. The reactor is filled with hydrogen to 10.0 MPa for the last time, and the reactor is heated to 250-260°C, and the reaction is stirred at a constant temperature for 8-10 h. After the reaction is completed, it is naturally cooled to room temperature to obtain a product, and the product is filtered to recover the activated carbon-supported palladium catalyst, and the filtrate is collected and distilled under reduced pressure to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0014] Furthermore, the magnetic supported catalyst is prepared by the following steps: A1. Add CoCl to deionized water with stirring 2 6H 2 O and FeCl 3 6H 2 O, stirring and mixing at room temperature for 10 to 20 minutes, then adding sodium citrate thereto with stirring, continuing stirring and mixing for 1 to 2 hours, then adjusting the pH of the system to 11.5 to 12.0, heating the system to 80 to 85°C, stirring at constant temperature for 2 to 3 hours, after stirring, cooling to room temperature to obtain a sol, washing the sol with deionized water to neutrality, and then drying to constant weight to obtain a dry gel, calcining the dry gel in a muffle furnace at 550 to 580°C for 5 to 6 hours, and then grinding to obtain a catalyst; A2. Add the above-prepared catalyst to anhydrous ethanol, disperse it magnetically for 10 minutes, then add 25% ammonia water by mass, stir for 30-40 minutes, then add tetraethoxysilane and p-toluenesulfonic acid. After the addition is completed, heat the system to 120-130°C, stir and react at constant temperature for 24 hours. After the reaction is completed, cool to room temperature, separate the solid component by magnetic field, wash the solid component three times with deionized water, and dry to constant weight to obtain a magnetic supported catalyst.

[0015] Furthermore, the deionized water, CoCl 2 6H 2 O, FeCl 3 6H 2 The dosage ratio of O and sodium citrate is 500 mL:0.1-0.2 mol:0.3-0.5 mol:15-20 g.

[0016] Furthermore, the dosage ratio of anhydrous ethanol, catalyst, 25% ammonia water, tetraethoxysilane and p-toluenesulfonic acid in A2 is 200 mL: 20 g: 30-40 mL: 20-30 mL: 10-15 g.

[0017] Furthermore, the heteropoly acid is phosphotungstic acid or phosphomolybdic acid.

[0018] Beneficial effects of the present invention: The invention uses a self-made magnetic supported catalyst as a main catalyst, and then uses a heteropoly acid as a co-catalyst, and then undergoes hydrogenation treatment to finally prepare a transparent terpene resin with a Ghana color number of 1.

[0019] The magnetic supported catalyst prepared by the present invention is an iron-cobalt composite magnetic powder loaded with p-toluenesulfonic acid. Relying on the magnetism of iron and cobalt, the efficient separation of the catalyst can be achieved, and the influence of the residual catalyst on the purity of the terpene resin can be prevented. Among them, the present invention uses protonic acid p-toluenesulfonic acid as the main catalytic agent and is matched with heteropoly acid as a co-catalyst. After testing, it shows excellent catalytic performance.

[0020] In the preparation process of the magnetic supported catalyst, tetraethoxysilane is hydrolyzed to form a silica gel material with a three-dimensional network structure, and p-toluenesulfonic acid is wrapped in the silica gel material through hydrogen bonding and wrapping, and then dried to form a magnetic supported catalyst with a core-shell structure. The magnetic supported catalyst prepared by the present invention is tested to be superior to the existing catalyst AlCl 3 , which can improve the product quality of terpene resin. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Among them, the relevant information of the raw materials used in the embodiments of the present invention is as follows Table 1: Table 1 Relevant information of raw materials raw material Specification Where to buy <![CDATA[CoCl 2 ·6H 2 O]]> 99% Shanghai MacLean Biochemical Technology Co., Ltd. <![CDATA[FeCl 3 ·6H 2 O]]> 99% Shanghai MacLean Biochemical Technology Co., Ltd. Sodium Citrate 98% Shanghai Aladdin Biochemical Technology Co., Ltd. Tetraethoxysilane 98% Shanghai Aladdin Biochemical Technology Co., Ltd. p-Toluenesulfonic acid 99% Shanghai MacLean Biochemical Technology Co., Ltd. Toluene 99.5% Sinopharm Chemical Reagent Co., Ltd. turpentine Pharmaceutical grade Shanghai Aladdin Biochemical Technology Co., Ltd. Phosphotungstic acid 99% Shanghai MacLean Biochemical Technology Co., Ltd. Phosphomolybdic acid 98% Sinopharm Chemical Reagent Co., Ltd. Activated carbon supported palladium catalyst 5%Pd Sigma-Aldrich (Shanghai) Trading Co., Ltd. Example 1

[0022] Preparation of magnetic supported catalyst: A1. Take 500 mL of deionized water and add 0.1 mol of CoCl 2 6H 2 O and 0.3 mol FeCl 3 6H 2O, stirred and mixed at room temperature for 10 min, then 15 g of sodium citrate was added thereto with stirring, and the stirring and mixing was continued for 1 h, and then the pH of the system was adjusted to 11.5 with sodium hydroxide. After the pH adjustment was completed, the system was heated to 80°C and stirred at a constant temperature for 2 h. After the stirring was completed, it was cooled to room temperature to obtain a sol, and the sol was washed with deionized water to neutrality, and then dried to constant weight to obtain a dry gel, and the dry gel was calcined in a muffle furnace at 550°C for 5 h, and then ground to obtain a catalyst; A2. Take 200 mL of anhydrous ethanol, add 20 g of the catalyst prepared above, disperse magnetically for 10 min, add 30 mL of 25% ammonia water, stir for 30 min, add 20 mL of tetraethoxysilane and 10 g of p-toluenesulfonic acid, after the addition is complete, heat the system to 120 ° C, stir and react at constant temperature for 24 h, after the reaction is completed, cool to room temperature, separate the solid component by magnetic field, wash the solid component three times with deionized water, and dry to constant weight to obtain a magnetic supported catalyst.

[0023] Example 2

[0024] Preparation of magnetic supported catalyst: A1. Take 500 mL of deionized water and add 0.2 mol of CoCl 2 6H 2 O and 0.4 mol FeCl 3 6H 2 O, stirred and mixed at room temperature for 20 min, then 18 g of sodium citrate was added thereto with stirring, and the stirring and mixing was continued for 2 h, and then the pH of the system was adjusted to 12.0 with sodium hydroxide. After the pH adjustment was completed, the system was heated to 85°C and stirred at a constant temperature for 3 h. After the stirring was completed, it was cooled to room temperature to obtain a sol, and the sol was washed with deionized water to neutrality, and then dried to constant weight to obtain a dry gel, and the dry gel was calcined in a muffle furnace at 570°C for 6 h, and then ground to obtain a catalyst; A2. Take 200 mL of anhydrous ethanol, add 20 g of the catalyst prepared above, disperse magnetically for 10 min, add 35 mL of 25% ammonia water, stir for 40 min, add 25 mL of tetraethoxysilane and 12 g of p-toluenesulfonic acid, after the addition is complete, heat the system to 130 ° C, stir and react at constant temperature for 24 h, after the reaction is completed, cool to room temperature, separate the solid component by magnetic field, wash the solid component three times with deionized water, and dry to constant weight to obtain a magnetic supported catalyst.

[0025] Example 3

[0026] Preparation of magnetic supported catalyst: A1. Take 500 mL of deionized water and add 0.2 mol of CoCl 2 6H 2 O and 0.5 mol FeCl 3 6H 2 O, stirred and mixed at room temperature for 20 min, then 20 g of sodium citrate was added thereto with stirring, and the stirring and mixing was continued for 2 h, and then the pH of the system was adjusted to 12.0 with sodium hydroxide. After the pH adjustment was completed, the system was heated to 85°C and stirred at a constant temperature for 3 h. After the stirring was completed, it was cooled to room temperature to obtain a sol, and the sol was washed with deionized water to neutrality, and then dried to constant weight to obtain a dry gel, and the dry gel was calcined in a muffle furnace at 580°C for 6 h, and then ground to obtain a catalyst; A2. Take 200 mL of anhydrous ethanol, add 20 g of the catalyst prepared above, disperse magnetically for 10 min, add 40 mL of 25% ammonia water, stir for 40 min, add 30 mL of tetraethoxysilane and 15 g of p-toluenesulfonic acid, after the addition is complete, heat the system to 130 ° C, stir and react at constant temperature for 24 h, after the reaction is completed, cool to room temperature, separate the solid component by magnetic field, wash the solid component three times with deionized water, and dry to constant weight to obtain a magnetic supported catalyst.

[0027] Example 4

[0028] A terpene resin preparation process comprises the following steps: S1. Take 100 mL of toluene, cool to 5°C, add 6.5 g of the magnetic supported catalyst prepared in Example 1, and after the addition is completed, add 80 g of turpentine oil dropwise thereto, and control the dropping time to be 2 h. After the addition is completed, add 1.0 g of phosphotungstic acid thereto, and after the addition is completed, stir and react for 3 h. After the stirring reaction is completed, separate the magnetic supported catalyst by using a magnetic field to obtain a mixed solution, stir and add 80°C pure water to the mixed solution, and then stand for stratification, take the upper organic phase, and then use 80°C pure water to wash the organic phase three times, and then stand for stratification, collect the upper organic phase, and obtain a crude terpene resin; S2. The crude terpene resin is transferred to a reactor, 4 g of activated carbon-supported palladium catalyst is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, and the nitrogen is introduced to replace the gas in the reactor three times, hydrogen is introduced to replace the nitrogen, and the hydrogen is introduced to replace the gas in the reactor three times, and hydrogen is introduced to the reactor to 10.0 MPa for the last time. The reactor is heated to 250°C and stirred at a constant temperature for 8 h. After the reaction is completed, it is naturally cooled to room temperature to obtain a product, and the product is filtered to recover the activated carbon-supported palladium catalyst, the filtrate is collected and distilled under reduced pressure to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0029] Example 5

[0030] A terpene resin preparation process comprises the following steps: S1, take 100 mL of toluene, cool to 0 ° C, add 7.0 g of the magnetic supported catalyst prepared in Example 2 thereto, after the addition is complete, add 90 g of turpentine oil thereto dropwise, control the dropping time to be 2 h, after the dropwise addition is complete, add 1.2 g of phosphomolybdic acid thereto, after the addition is complete, stir and react for 4 h, after the stirring reaction is complete, separate the magnetic supported catalyst by using a magnetic field to obtain a mixed solution, stir and add 90 ° C pure water to the mixed solution, let stand for stratification, take the upper organic phase, wash the organic phase three times with 90 ° C pure water, let stand for stratification, collect the upper organic phase, and obtain a crude terpene resin; S2. The crude terpene resin is transferred to a reactor, 4.5 g of activated carbon-supported palladium catalyst is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, and the nitrogen is introduced to replace the gas in the reactor three times, hydrogen is introduced to replace the nitrogen, and the hydrogen is introduced to replace the gas in the reactor three times, and hydrogen is introduced to the reactor to 10.0 MPa for the last time. The reactor is heated to 260° C. and stirred at a constant temperature for 10 h. After the reaction is completed, it is naturally cooled to room temperature to obtain a product, and the product is filtered to recover the activated carbon-supported palladium catalyst, the filtrate is collected and distilled under reduced pressure to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0031] Example 6

[0032] A terpene resin preparation process comprises the following steps: S1, take 100 mL of toluene, cool to -5 ° C, add 8.0 g of the magnetic supported catalyst prepared in Example 3, add 100 g of turpentine oil dropwise thereto after the addition is complete, control the dropping time to be 2 h, add 1.2 g of phosphomolybdic acid thereto after the addition is complete, stir and react for 4 h, after the stirring reaction is complete, separate the magnetic supported catalyst by using a magnetic field to obtain a mixed solution, stir and add 90 ° C pure water to the mixed solution, let stand for stratification, take the upper organic phase, wash the organic phase three times with 90 ° C pure water, let stand for stratification, collect the upper organic phase, and obtain a crude terpene resin; S2. The crude terpene resin is transferred to a reactor, 5 g of activated carbon-supported palladium catalyst is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, and the nitrogen is introduced to replace the gas in the reactor three times, hydrogen is introduced to replace the nitrogen, and the hydrogen is introduced to replace the gas in the reactor three times, and hydrogen is introduced to the reactor to 10.0 MPa for the last time. The reactor is heated to 260° C. and stirred at a constant temperature for 10 h. After the reaction is completed, it is naturally cooled to room temperature to obtain a product, and the product is filtered to recover the activated carbon-supported palladium catalyst, the filtrate is collected and distilled under reduced pressure to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0033] Comparative Example 1 Comparative Example 1 is the control group of Example 5, in which the magnetic supported catalyst prepared in Example 2 in Example 5 is replaced with p-toluenesulfonic acid, and the other raw materials and preparation process remain unchanged from Example 5, and finally a terpene resin is obtained.

[0034] Comparative Example 2 Comparative Example 2 is the control group of Example 5, in which the magnetic supported catalyst prepared in Example 2 is replaced by AlCl 3 The remaining raw materials and preparation process remain unchanged with those in Example 5, and terpene resin is finally obtained.

[0035] The terpene resins prepared in Examples 4 to 6 and Comparative Examples 1 to 2 were subjected to performance tests. The performance test process is as follows, and the test results are shown in Table 2: The color, softening point (ring and ball method), acid value and saponification value of the terpene resins prepared in Examples 4 to 6 and Comparative Examples 1 to 2 were determined according to the experimental methods in the forestry industry standard LY / T 1453-2010 "Terpene Resins".

[0036] Table 2 Performance test results project Industry Standards Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Color / Ghana Color ≤5 (special grade) 1 1 1 2 2 Softening point (Ring and ball method) / ℃ ≥80 95 100 99 89 95 Acid value / (mg / g) ≤1.0 0.86 0.82 0.84 1.22 1.10 Saponification value / (mg / g) ≤1.5 1.21 1.13 1.10 1.64 1.45 It can be concluded from Table 2 that the Ghana color number of the terpene resin prepared in Examples 4 to 6 of the present invention is 1, and the comprehensive performance reaches the industry's special grade standard.

[0037] It should be noted that, in this article, terms such as "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or equipment that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment.

[0038] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A process for preparing a terpene resin, characterized in that: The following steps are involved: Toluene is cooled to -5 to 5°C, a magnetic supported catalyst is added thereto, and turpentine is then added dropwise thereto, and the dropping time is controlled to be 2 h. After the dropping is completed, a heteropoly acid is added thereto, and the reaction is stirred for 3 to 4 h. After the stirring reaction is completed, the magnetic supported catalyst is separated by a magnetic field to obtain a mixed solution, pure water at 80 to 90°C is added to the mixed solution with stirring, and then the mixture is allowed to stand for stratification, and the upper organic phase is taken, and the organic phase is washed three times with pure water at 80 to 90°C, and then the upper organic phase is collected after standing for stratification to obtain a crude terpene resin, and an activated carbon-supported palladium catalyst is added to the crude terpene resin with stirring, and the terpene resin is obtained after hydrogenation treatment.

2. A terpene resin preparation process according to claim 1, characterized in that: The dosage ratio of the toluene, the magnetic supported catalyst, the turpentine oil, the heteropoly acid and the activated carbon supported palladium catalyst is 100 mL: 6.5-8.0 g: 80-100 g: 1.0-1.2 g: 4-5 g.

3. A terpene resin preparation process according to claim 1, characterized in that: The palladium content in the activated carbon-supported palladium catalyst is 5%.

4. A process for preparing a terpene resin according to claim 1, characterized in that: The hydroprocessing comprises the following steps: The crude terpene resin is transferred to a reactor, and the activated carbon-supported palladium catalyst is added to the reactor with stirring, and nitrogen is introduced to replace the air in the reactor, and the nitrogen-supported gas is introduced three times, and hydrogen is introduced to replace the nitrogen, and the hydrogen-supported gas is introduced three times. The reactor is filled with hydrogen to 10.0 MPa for the last time, and the reactor is heated to 250-260°C, and the reaction is stirred at a constant temperature for 8-10 h. After the reaction is completed, it is naturally cooled to room temperature to obtain a product, and the product is filtered to recover the activated carbon-supported palladium catalyst, and the filtrate is collected and distilled under reduced pressure to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

5. A process for preparing a terpene resin according to claim 1, characterized in that: The magnetic supported catalyst is prepared by the following steps: A1. Add CoCl2·6H2O and FeCl3·6H2O to deionized water with stirring, stir and mix at room temperature for 10-20 min, then add sodium citrate with stirring, continue to stir and mix for 1-2 h, then adjust the pH of the system to 11.5-12.0, heat the system to 80-85°C, stir at constant temperature for 2-3 h, and after stirring, cool to room temperature to obtain a sol, wash the sol with deionized water to neutrality, and then dry to constant weight to obtain a dry gel, calcine the dry gel in a muffle furnace at 550-580°C for 5-6 h, and then grind to obtain a catalyst; A2. Add the above-prepared catalyst to anhydrous ethanol, disperse it magnetically for 10 minutes, then add 25% ammonia water by mass, stir for 30-40 minutes, then add tetraethoxysilane and p-toluenesulfonic acid. After the addition is completed, heat the system to 120-130°C, stir and react at constant temperature for 24 hours. After the reaction is completed, cool to room temperature, separate the solid component by magnetic field, wash the solid component three times with deionized water, and dry to constant weight to obtain a magnetic supported catalyst.

6. A process for preparing a terpene resin according to claim 5, characterized in that: The usage ratio of deionized water, CoCl2·6H2O, FeCl3·6H2O and sodium citrate in A1 is 500 mL: 0.1-0.2 mol: 0.3-0.5 mol: 15-20 g.

7. A process for preparing a terpene resin according to claim 5, characterized in that: The dosage ratio of anhydrous ethanol, catalyst, 25% ammonia water, tetraethoxysilane and p-toluenesulfonic acid in A2 is 200 mL: 20 g: 30-40 mL: 20-30 mL: 10-15 g.

8. A process for preparing a terpene resin according to claim 1, characterized in that: The heteropoly acid is phosphotungstic acid or phosphomolybdic acid.