A method for hydrogenating terpene resin

Abstract

The invention discloses a method for hydrogenating a terpene resin, and belongs to the technical field of terpene resin production. The method for hydrogenating a terpene resin comprises the following steps: turpentine oil is catalyzed by aluminum chloride and trimethylsilyl chloride in toluene to obtain a crude terpene resin, a magnetic catalyst is added to the crude terpene resin with stirring, nitrogen is charged to replace the gas three times, hydrogen is charged to replace the gas three times, the temperature is raised to 250-260°C, constant temperature stirring is performed for reaction for 8-10 hours, after the reaction is completed, the product is naturally cooled to room temperature to obtain a product, the magnetic supported catalyst is separated by a magnetic field to obtain a product, the product is impurity-removed by an adsorbent to obtain an impurity-removed product, the impurity-removed product is then subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin. The invention improves the selection of a catalyst for hydrogenation, and efficiently removes ruthenium ions by a self-made adsorbent, thereby ultimately improving the comprehensive performance of the prepared terpene resin.

Description

Technical Field

[0001] The invention belongs to the technical field of terpene resin production, and particularly relates to a method for hydrogenating terpene resin. 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 yellowish 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 the terpene resin is reduced by adding a composite process of catalytic hydrogenation after cationic polymerization. However, since AlCl3 is mostly used as a polymerization catalyst in cationic polymerization, chloride ions are difficult to remove, and chloride ions have a poisoning 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. In addition, the chloride ion content in the terpene resin product finally produced 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:

[0005] The invention patent with application number 200510019067.0 uses molecular sieve-supported AlCl3 as a polymerization catalyst and Pd / C as a hydrogenation catalyst. The prepared terpene resin has a Ghana color number of less than 1.

[0006] 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.

[0007] The invention patent with application number 201210130940.3 uses AlCl3 as the main catalyst in the polymerization process, and trialkylchlorosilane (trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane or tributylchlorosilane) 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.

[0008] The invention patent with application number 201711270035.7 also uses a composite catalyst system of AlCl3 and trialkylchlorosilane. By adding the main catalyst and the co-catalyst at different reaction time points, the conversion rate of the raw materials is improved and the unreacted main catalyst is reduced to further contact 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.

[0009] 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

[0010] On the basis of the prior art, the present invention improves the selection of hydrogenation catalysts, ensures the hydrogenation catalytic efficiency and effect, and reduces the production cost. The adsorbent prepared by the present invention is used to reduce the residual hydrogenation catalyst and improve the quality of the finally prepared terpene resin, thereby providing a method for hydrogenating terpene resins.

[0011] The purpose of the present invention can be achieved through the following technical solutions:

[0012] A method for hydrogenating a terpene resin comprises the following steps:

[0013] Turpentine oil is catalyzed by aluminum chloride and trimethylsilyl chloride in toluene to obtain a crude terpene resin. The crude terpene resin is transferred to a reactor, a magnetic 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 replace the gas in the reactor for the last time to 10.0 MPa. The reactor is heated to 250-260° C. and 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 magnetic supported catalyst is separated by a magnetic field to obtain a product, an adsorbent is added to the product, magnetic stirring is performed for 20-30 min, and the adsorbent is removed by filtration to obtain a de-impurity product, and the de-impurity product is subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0014] Furthermore, the crude terpene resin is prepared by the following steps:

[0015] The toluene is cooled to -5 to 5°C, and aluminum chloride is added thereto. After the addition is completed, turpentine is added thereto dropwise, and the dropping time is controlled to be 2 h. After the addition is completed, trimethylchlorosilane is added thereto. After the addition is completed, the reaction is stirred for 3 to 4 h. After the stirring reaction is completed, a mixed solution is obtained. Pure water at 80 to 90°C is added to the mixed solution with stirring, and the mixture is allowed to stand for stratification. The upper organic phase is taken, and the organic phase is washed three times with pure water at 80 to 90°C, and the mixture is allowed to stand for stratification, and the upper organic phase is collected to obtain a crude terpene resin.

[0016] Furthermore, the dosage ratio of the toluene, aluminum chloride, turpentine, trimethylsilyl chloride, magnetic catalyst and adsorbent is 100 mL: 5-7 g: 80-100 g: 1.5-3.0 g: 4-5 g: 10-20 g.

[0017] Furthermore, the magnetic catalyst is prepared by the following steps:

[0018] NiCl2·6H2O, RuCl3·3H2O and FeCl3·6H2O are added to deionized water with stirring, and the mixture is stirred at room temperature for 10 to 20 min. Then, sodium citrate is added thereto with stirring, and the mixture is stirred for 1 to 2 h. Then, the pH value of the system is adjusted to 11.5 to 12.0 with sodium hydroxide. After the pH value is adjusted, the system is heated to 80 to 85°C and stirred at the constant temperature for 2 to 3 h. After the stirring is completed, the system is cooled to room temperature to obtain a sol. The sol is washed with deionized water to neutrality, and then dried to constant weight to obtain a dry gel. The dry gel is calcined in a muffle furnace at 550 to 580°C for 5 to 6 h, and then ground to obtain a magnetic catalyst.

[0019] Furthermore, the usage ratio of the deionized water, NiCl2·6H2O, RuCl3·3H2O, FeCl3·6H2O and sodium citrate is 500 mL: 0.1-0.2 mol: 0.1-0.3 mol: 0.3-0.5 mol: 15-20 g.

[0020] Furthermore, the adsorbent is prepared by the following steps:

[0021] A1, adding carboxymethyl chitosan to deionized water with stirring, stirring until the solid is completely dissolved, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide thereto with stirring, then adjusting the pH of the system to 5.0-5.5 with hydrochloric acid, stirring and mixing for 2-3 hours, after the stirring and mixing is completed, completing the carboxyl activation, then stirring and adding polyethyleneimine thereto, then adjusting the pH of the system to 7.5-8.0 with sodium hydroxide, continuing to stir and mix for 24 hours to obtain a condensation product, placing the condensation product in a dialysis bag, placing it in a 0.1 mol / L Na2HPO4 aqueous solution, a 4 mol / L NaCl pure aqueous solution, and deionized water in turn for dialysis for 24 hours, after the treatment is completed, placing it in a freeze dryer for freeze drying to obtain modified carboxymethyl chitosan;

[0022] A2. Add modified carboxymethyl chitosan to deionized water with stirring until the solid is completely dissolved, then add RuCl3·3H2O thereto, stir at room temperature for 4 to 5 h, then add 5 wt% glutaraldehyde aqueous solution thereto, stir and mix for 1 to 2 h, then freeze-dry in a freeze dryer to obtain a ruthenium-loaded carboxymethyl chitosan sponge, then soak the obtained ruthenium-loaded carboxymethyl chitosan sponge in a 1 mol / L hydrochloric acid solution for 12 h, take out, and then wash three times with deionized water to obtain an adsorbent.

[0023] Furthermore, the amount ratio of deionized water, carboxymethyl chitosan, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide and polyethyleneimine in A1 is 100 mL: 1 g: 2 g: 2 g: 2-3 g.

[0024] Furthermore, the amount ratio of the deionized water, modified carboxymethyl chitosan, RuCl3·3H2O and 5 wt% glutaraldehyde aqueous solution in A2 is 100 mL:5 g:1 g:40-50 mL.

[0025] Beneficial effects of the present invention:

[0026] The present invention provides a method for hydrogenating a terpene resin. The present invention improves the selection of a hydrogenation catalyst (magnetic catalyst) and efficiently removes ruthenium (Ru) ions through a homemade adsorbent, thereby ultimately improving the comprehensive performance of the prepared terpene resin.

[0027] Firstly, the magnetic catalyst prepared by the present invention is a Ru / NiFe2O4 composite material, wherein the iron and nickel are magnetic, giving the catalyst a magnetic separation function; wherein the rare earth metal ruthenium has excellent adsorption properties for hydrogen, and the present invention develops it into a hydrogenation catalyst, which is applied to the hydrogenation process of terpene resin, and exhibits excellent catalytic hydrogenation efficiency, and at the same time, the price of ruthenium is relatively low, and the use cost is significantly reduced relative to the palladium-carbon catalyst; wherein, the present invention selects nickel rather than cobalt, which is also a magnetic material, because the price of nickel is relatively lower, and at the same time, nickel has hydrogen activity and abundant active sites, and the present invention improves the magnetism of the magnetic catalyst and the hydrogenation efficiency of the catalyst by adding nickel, and there is a synergistic effect between ruthenium and nickel, which can comprehensively improve the catalytic hydrogenation efficiency of the magnetic catalyst.

[0028] Then, since the iron and nickel in the magnetic catalyst belong to magnetic materials, they can be effectively separated by using a magnetic field. In order to prevent the precipitation of ruthenium ions in the magnetic catalyst from affecting the purity of the terpene resin product, the present invention prepares an adsorbent with selective adsorption. In the preparation process of the adsorbent, the present invention uses carboxymethyl chitosan as a substrate, polyethylene imine as a chelating aid, ruthenium ions as template ions, and glutaraldehyde as a cross-linking agent, and utilizes the adsorption effect between the abundant hydrophilic functional groups (hydroxyl, amino and carboxyl) on carboxymethyl chitosan and the abundant nitrogen-containing functional groups on polyethylene imine and ruthenium ions, and prepares an adsorbent with selective adsorption of ruthenium ions through an adsorption-branching cross-linking-elution process. DETAILED DESCRIPTION

[0029] 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:

[0030] Table 1 Relevant information of raw materials

[0031] raw material Specification Where to buy <![CDATA[NiCl2·6H2O]]> 99% Shanghai MacLean Biochemical Technology Co., Ltd. <![CDATA[RuCl3·3H2O]]> 99% Shanghai MacLean Biochemical Technology Co., Ltd. <![CDATA[FeCl3·6H2O]]> 99% Shanghai MacLean Biochemical Technology Co., Ltd. Sodium Citrate 98% Shanghai Aladdin Biochemical Technology Co., Ltd. Carboxymethyl chitosan Degree of substitution ≥80% Shanghai MacLean Biochemical Technology Co., Ltd. 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide ≥97% Sigma-Aldrich (Shanghai) Trading Co., Ltd. N-Hydroxysuccinimide 98% Sigma-Aldrich (Shanghai) Trading Co., Ltd. Polyethyleneimine Linear; Mw=100000 Shanghai MacLean Biochemical Technology Co., Ltd. Toluene 99.5% Sinopharm Chemical Reagent Co., Ltd. Aluminum Chloride Anhydrous; ≥98.5% Sinopharm Chemical Reagent Co., Ltd. turpentine Pharmaceutical grade Shanghai Aladdin Biochemical Technology Co., Ltd. Trimethylchlorosilane 99% Shanghai MacLean Biochemical Technology Co., Ltd. Activated carbon supported palladium catalyst 5%Pd Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0032] Example 1

[0033] Preparation of magnetic catalyst:

[0034] Take 500 mL of deionized water, add 0.1 mol of NiCl2·6H2O, 0.1 mol of RuCl3·3H2O and 0.3 mol of FeCl3·6H2O, stir and mix at room temperature for 10 min, then add 15 g of sodium citrate, continue stirring and mixing for 1 h, and then use sodium hydroxide to adjust the pH of the system to 11.5. After the pH adjustment is completed, the system is heated to 80°C and stirred at constant temperature for 2 h. After stirring, it is cooled to room temperature to obtain a sol. The sol is washed with deionized water to neutrality and then dried to constant weight to obtain a dry gel. The dry gel is calcined in a muffle furnace at 550°C for 5 h and then ground to obtain a magnetic catalyst.

[0035] Example 2

[0036] Preparation of magnetic catalyst:

[0037] Take 500 mL of deionized water, add 0.2 mol of NiCl2·6H2O, 0.2 mol of RuCl3·3H2O and 0.5 mol of FeCl3·6H2O, stir and mix at room temperature for 20 min, then add 18 g of sodium citrate, continue stirring and mixing for 2 h, and then use sodium hydroxide to adjust the pH of the system to 12.0. After the pH adjustment is completed, the system is heated to 85°C and stirred at constant temperature for 3 h. After stirring, it is cooled to room temperature to obtain a sol. The sol is washed with deionized water to neutrality and then dried to constant weight to obtain a dry gel. The dry gel is calcined in a muffle furnace at 580°C for 6 h and then ground to obtain a magnetic catalyst.

[0038] Example 3

[0039] Preparation of magnetic catalyst:

[0040] Take 500 mL of deionized water, add 0.2 mol of NiCl2·6H2O, 0.3 mol of RuCl3·3H2O and 0.5 mol of FeCl3·6H2O, stir and mix at room temperature for 20 min, then add 20 g of sodium citrate, continue stirring and mixing for 2 h, and then use sodium hydroxide to adjust the pH of the system to 12.0. After the pH adjustment is completed, the system is heated to 85°C and stirred at constant temperature for 3 h. After stirring, it is cooled to room temperature to obtain a sol. The sol is washed with deionized water to neutrality and then dried to constant weight to obtain a dry gel. The dry gel is calcined in a muffle furnace at 580°C for 6 h and then ground to obtain a magnetic catalyst.

[0041] Comparative Example 1

[0042] Comparative Example 1 is the control group of Example 2, except that the raw material NiCl2·6H2O in Example 2 is removed, and the remaining raw materials and the preparation method remain the same as those in Example 2, and finally a magnetic catalyst is obtained.

[0043] Comparative Example 2

[0044] Comparative Example 2 is the control group of Example 2, except that the raw material RuCl3·3H2O in Example 2 is removed, and the remaining raw materials and the preparation method remain the same as those in Example 2, and finally a magnetic catalyst is obtained.

[0045] Example 4

[0046] Preparation of adsorbent:

[0047] A1, take 100 mL of deionized water, stir and add 1 g of carboxymethyl chitosan thereto, stir until the solid is completely dissolved, stir and add 2 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 2 g of N-hydroxysuccinimide thereto, adjust the pH of the system to 5.0 with hydrochloric acid, stir and mix for 2 h, after stirring and mixing, complete carboxyl activation, stir and add 2 g of polyethyleneimine thereto, adjust the pH of the system to 7.5 with sodium hydroxide, continue stirring and mixing for 24 h, obtain a condensation product, place the condensation product in a dialysis bag, place it in a 0.1 mol / L Na2HPO4 aqueous solution, a 4 mol / L NaCl pure aqueous solution, and deionized water in turn for dialysis for 24 h, after treatment, place it in a freeze dryer for freeze drying to obtain modified carboxymethyl chitosan;

[0048] A2. Take 100 mL of deionized water, add 5 g of modified carboxymethyl chitosan thereto with stirring, stir until the solid is completely dissolved, then add 1 g of RuCl3·3H2O thereto, stir at room temperature for 4 h, then add 40 mL of 5 wt% glutaraldehyde aqueous solution thereto, stir and mix for 1 h, then place in a freeze dryer for freeze drying to obtain a ruthenium-loaded carboxymethyl chitosan sponge, then soak the obtained ruthenium-loaded carboxymethyl chitosan sponge in 1 mol / L hydrochloric acid solution for 12 h, take out, and then wash three times with deionized water to obtain an adsorbent.

[0049] Example 5

[0050] Preparation of adsorbent:

[0051] A1, take 100 mL of deionized water, stir and add 1 g of carboxymethyl chitosan thereto, stir until the solid is completely dissolved, stir and add 2 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 2 g of N-hydroxysuccinimide thereto, adjust the pH of the system to 5.4 with hydrochloric acid, stir and mix for 3 h, after stirring and mixing, complete carboxyl activation, stir and add 3 g of polyethyleneimine thereto, adjust the pH of the system to 7.8 with sodium hydroxide, continue stirring and mixing for 24 h, obtain a condensation product, place the condensation product in a dialysis bag, place it in a 0.1 mol / L Na2HPO4 aqueous solution, a 4 mol / L NaCl pure aqueous solution, and deionized water in turn for dialysis for 24 h, after treatment, place it in a freeze dryer for freeze drying to obtain modified carboxymethyl chitosan;

[0052] A2. Take 100 mL of deionized water, add 5 g of modified carboxymethyl chitosan thereto with stirring, stir until the solid is completely dissolved, then add 1 g of RuCl3·3H2O thereto, stir at room temperature for 5 h, then add 48 mL of 5 wt% glutaraldehyde aqueous solution thereto, stir and mix for 2 h, then place in a freeze dryer for freeze drying to obtain a ruthenium-loaded carboxymethyl chitosan sponge, then soak the obtained ruthenium-loaded carboxymethyl chitosan sponge in 1 mol / L hydrochloric acid solution for 12 h, take out, and then wash three times with deionized water to obtain an adsorbent.

[0053] Example 6

[0054] Preparation of adsorbent:

[0055] A1, take 100 mL of deionized water, stir and add 1 g of carboxymethyl chitosan thereto, stir until the solid is completely dissolved, stir and add 2 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 2 g of N-hydroxysuccinimide thereto, adjust the pH of the system to 5.5 with hydrochloric acid, stir and mix for 3 h, after stirring and mixing, complete carboxyl activation, stir and add 3 g of polyethyleneimine thereto, adjust the pH of the system to 8.0 with sodium hydroxide, continue stirring and mixing for 24 h, obtain a condensation product, place the condensation product in a dialysis bag, place it in a 0.1 mol / L Na2HPO4 aqueous solution, a 4 mol / L NaCl pure aqueous solution, and deionized water in turn for dialysis for 24 h, after treatment, place it in a freeze dryer for freeze drying to obtain modified carboxymethyl chitosan;

[0056] A2. Take 100 mL of deionized water, add 5 g of modified carboxymethyl chitosan thereto with stirring, stir until the solid is completely dissolved, then add 1 g of RuCl3·3H2O thereto, stir at room temperature for 5 h, then add 50 mL of 5 wt% glutaraldehyde aqueous solution thereto, stir and mix for 2 h, then place in a freeze dryer for freeze drying to obtain a ruthenium-loaded carboxymethyl chitosan sponge, then soak the obtained ruthenium-loaded carboxymethyl chitosan sponge in 1 mol / L hydrochloric acid solution for 12 h, take out, and then wash three times with deionized water to obtain an adsorbent.

[0057] Example 7

[0058] A method for hydrogenating a terpene resin comprises the following steps:

[0059] S1. Take 100 mL of toluene, cool it to 5°C, add 5 g of aluminum chloride thereto, and after the addition is complete, add 80 g of turpentine oil thereto dropwise, and control the dropping time to be 2 h. After the addition is complete, add 1.5 g of trimethylsilyl chloride thereto, and after the addition is complete, stir and react for 3 h. After the stirring reaction is complete, obtain a mixed solution, stir and add 80°C pure water to the mixed solution, let it stand for stratification, take the upper organic phase, and then use 80°C pure water to wash the organic phase three times, let it stand for stratification, collect the upper organic phase, and obtain a crude terpene resin;

[0060] S2. The crude terpene resin is transferred to a reactor, 4 g of the magnetic catalyst prepared in Example 1 is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, 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 magnetic supported catalyst is separated by a magnetic field to obtain a product, 10 g of the adsorbent prepared in Example 4 is added to the product, magnetic stirring is performed for 20 min, and the adsorbent is removed by filtration to obtain a decontaminated product, and the decontaminated product is subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0061] Example 8

[0062] A method for hydrogenating a terpene resin comprises the following steps:

[0063] S1. Take 100 mL of toluene, cool it to 0°C, add 7 g of aluminum chloride thereto, and after the addition is complete, add 90 g of turpentine oil dropwise thereto, and control the dropping time to be 2 h. After the addition is complete, add 3.0 g of trimethylsilyl chloride thereto, and after the addition is complete, stir and react for 4 h. After the stirring reaction is complete, obtain a mixed solution, stir and add 90°C pure water to the mixed solution, let it stand for stratification, take the upper organic phase, and then use 90°C pure water to wash the organic phase three times, let it stand for stratification, collect the upper organic phase, and obtain a crude terpene resin;

[0064] S2. The crude terpene resin is transferred to a reactor, 4.5 g of the magnetic catalyst prepared in Example 2 is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, 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 255° 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 magnetic supported catalyst is separated by a magnetic field to obtain a product, 15 g of the adsorbent prepared in Example 5 is added to the product, magnetic stirring is performed for 30 min, and the adsorbent is removed by filtration to obtain a decontaminated product, and the decontaminated product is then subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0065] Example 9

[0066] A method for hydrogenating a terpene resin comprises the following steps:

[0067] S1. Take 100 mL of toluene, cool it to -5°C, add 7 g of aluminum chloride thereto, and after the addition is complete, add 100 g of turpentine oil thereto dropwise, control the dropping time to be 2 h, and after the addition is complete, add 3.0 g of trimethylsilyl chloride thereto, and after the addition is complete, stir and react for 4 h. After the stirring reaction is complete, obtain a mixed solution, stir and add 90°C pure water to the mixed solution, let it stand for stratification, take the upper organic phase, and then use 90°C pure water to wash the organic phase three times, let it stand for stratification, collect the upper organic phase, and obtain a crude terpene resin;

[0068] S2. The crude terpene resin is transferred to a reactor, 5 g of the magnetic catalyst prepared in Example 3 is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, 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 magnetic supported catalyst is separated by a magnetic field to obtain a product, 20 g of the adsorbent prepared in Example 6 is added to the product, magnetic stirring is performed for 30 min, and the adsorbent is removed by filtration to obtain a decontaminated product, and the decontaminated product is subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0069] Comparative Example 3

[0070] Comparative Example 3 is the control group of Example 8, in which the raw material Example 2 in Example 8 is replaced with the magnetic catalyst prepared in Comparative Example 1, and the other raw materials and hydrogenation method remain the same as in Example 8, and finally a terpene resin is obtained.

[0071] Comparative Example 4

[0072] Comparative Example 4 is the control group of Example 8, in which the raw material Example 2 in Example 8 is used to replace the magnetic catalyst prepared by Comparative Example 2, and the other raw materials and hydrogenation method remain the same as those in Example 8, and finally a terpene resin is obtained.

[0073] Comparative Example 5

[0074] Comparative Example 5 is the control group of Example 8, in which the magnetic catalyst prepared in Example 2 is replaced by an activated carbon-supported palladium catalyst, and the other raw materials and hydrogenation method remain the same as in Example 8, and finally a terpene resin is obtained.

[0075] Specifically, Comparative Example 5 discloses a method for hydrogenating a terpene resin, comprising the following steps:

[0076] S1. Take 100 mL of toluene, cool it to 0°C, add 7 g of aluminum chloride thereto, and after the addition is complete, add 90 g of turpentine oil dropwise thereto, and control the dropping time to be 2 h. After the addition is complete, add 3.0 g of trimethylsilyl chloride thereto, and after the addition is complete, stir and react for 4 h. After the stirring reaction is complete, obtain a mixed solution, stir and add 90°C pure water to the mixed solution, let it stand for stratification, take the upper organic phase, and then use 90°C pure water to wash the organic phase three times, let it stand for stratification, collect the upper organic phase, and obtain a crude terpene resin;

[0077] 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 255° 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 magnetic supported catalyst is separated by a magnetic field to obtain a product, 15 g of the adsorbent prepared in Example 5 is added to the product, magnetic stirring is performed for 30 min, and the adsorbent is removed by filtration to obtain a decontaminated product, and the decontaminated product is then subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0078] Comparative Example 6

[0079] Comparative Example 6 is the control group of Example 8, in which the raw material adsorbent in Example 8 is removed, and the remaining raw materials and hydrogenation method remain unchanged from Example 8, and finally a terpene resin is obtained.

[0080] Specifically, Comparative Example 6 discloses a method for hydrogenating a terpene resin, comprising the following steps:

[0081] S1. Take 100 mL of toluene, cool it to 0°C, add 7 g of aluminum chloride thereto, and after the addition is complete, add 90 g of turpentine oil dropwise thereto, and control the dropping time to be 2 h. After the addition is complete, add 3.0 g of trimethylsilyl chloride thereto, and after the addition is complete, stir and react for 4 h. After the stirring reaction is complete, obtain a mixed solution, stir and add 90°C pure water to the mixed solution, let it stand for stratification, take the upper organic phase, and then use 90°C pure water to wash the organic phase three times, let it stand for stratification, collect the upper organic phase, and obtain a crude terpene resin;

[0082] S2. The crude terpene resin is transferred to a reactor, 4.5 g of the magnetic catalyst prepared in Example 2 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 replace the nitrogen for the last time to 10.0 MPa. The reactor is heated to 255° C. and stirred at a constant temperature for 10 h. After the reaction is completed, the reactor is naturally cooled to room temperature to obtain a product, and the magnetic supported catalyst is separated by a magnetic field to obtain a product, and the product is then subjected to reduced pressure distillation to remove low-boiling impurities, and then cooled to room temperature to obtain a terpene resin.

[0083] Test Example 1

[0084] The performance test was performed on the terpene resin prepared by the hydrogenation method described in Examples 7 to 9 and Comparative Examples 3 to 6. The performance test process is as follows, and the test results are shown in Table 2:

[0085] The color, softening point (ring and ball method), acid value and saponification value of the terpene resins in Examples 7 to 9 and Comparative Examples 3 to 6 were determined according to the experimental methods in the forestry industry standard LY / T 1453-2010 "Terpene Resin". At the same time, the ruthenium content (%) in the terpene resin was determined by spectrophotometry.

[0086] Table 2 Performance test results

[0087] project Industry Standards Example 7 Example 8 Example 9 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Color / Ghana Color ≤5 (special grade) 1 1 1 2 3 1 1 Softening point (ring and ball method) / ℃ ≥80 130 133 132 130 131 134 133 Acid value / (mg / g) ≤1.0 0.48 0.44 0.45 0.45 0.47 0.50 0.45 Saponification value / (mg / g) ≤1.5 0.55 0.51 0.51 0.54 0.52 0.51 0.51 Ruthenium content / % - 0.02 0.01 0.01 0.02 0 0 0.23

[0088] It can be concluded from Table 2 that for the hydrogenation process of terpene resin, the magnetic catalyst prepared by the present invention has a catalytic effect similar to that of the activated carbon-supported palladium catalyst, but the raw materials used for the magnetic catalyst of the present application are cheaper, and the cost of the overall hydrogenation process is lower. At the same time, after adsorption treatment by the adsorbent prepared by the present invention, the residual amount of the magnetic catalyst is significantly reduced.

[0089] 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.

[0090] 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 method for hydrogenating a terpene resin, characterized in that: The following steps are involved: Turpentine oil is catalyzed by aluminum chloride and trimethylsilyl chloride in toluene to obtain a crude terpene resin, the crude terpene resin is transferred to a reactor, a magnetic catalyst is added to the reactor with stirring, nitrogen is introduced to replace the air in the reactor, nitrogen is introduced to replace the gas in the reactor three times, hydrogen is introduced to replace nitrogen, hydrogen is introduced to replace the gas in the reactor three times, hydrogen is introduced to replace the gas in the reactor for the last time to 10.0 MPa, the reactor is heated to 250-260°C, the reaction is stirred at a constant temperature for 8-10 h, after the reaction is completed, the reaction is naturally cooled to room temperature to obtain a product, the magnetic supported catalyst is separated by a magnetic field to obtain a product, an adsorbent is added to the product, magnetic stirring is performed for 20-30 min, the adsorbent is removed by filtration to obtain a decontaminated product, the decontaminated product is subjected to reduced pressure distillation to remove low-boiling impurities, and the terpene resin is obtained after cooling to room temperature; The magnetic catalyst is a Ru / NiFe2O4 composite material; The adsorbent is prepared by the following steps: A1, adding carboxymethyl chitosan to deionized water with stirring, stirring until the solid is completely dissolved, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide thereto with stirring, then adjusting the pH of the system to 5.0-5.5 with hydrochloric acid, stirring and mixing for 2-3 hours, after the stirring and mixing is completed, completing the carboxyl activation, then stirring and adding polyethyleneimine thereto, then adjusting the pH of the system to 7.5-8.0 with sodium hydroxide, continuing to stir and mix for 24 hours to obtain a condensation product, placing the condensation product in a dialysis bag, placing it in a 0.1 mol / L Na2HPO4 aqueous solution, a 4 mol / L NaCl pure aqueous solution, and deionized water in turn for dialysis for 24 hours, after the treatment is completed, placing it in a freeze dryer for freeze drying to obtain modified carboxymethyl chitosan; A2. Add modified carboxymethyl chitosan to deionized water with stirring until the solid is completely dissolved, then add RuCl3·3H2O thereto, stir at room temperature for 4 to 5 h, then add 5 wt% glutaraldehyde aqueous solution thereto, stir and mix for 1 to 2 h, then freeze-dry in a freeze dryer to obtain a ruthenium-loaded carboxymethyl chitosan sponge, then soak the obtained ruthenium-loaded carboxymethyl chitosan sponge in a 1 mol / L hydrochloric acid solution for 12 h, take out, and then wash three times with deionized water to obtain an adsorbent.

2. The method for hydrogenating a terpene resin according to claim 1, characterized in that: The crude terpene resin is prepared by the following steps: The toluene is cooled to -5 to 5°C, and aluminum chloride is added thereto. After the addition is completed, turpentine is added dropwise thereto, and the dropping time is controlled to be 2 h. After the addition is completed, trimethylsilyl chloride is added thereto. After the addition is completed, the reaction is stirred for 3 to 4 h. After the stirring reaction is completed, a mixed solution is obtained. Pure water at 80 to 90°C is added to the mixed solution with stirring, and the mixture is allowed to stand for stratification. The upper organic phase is taken, and the organic phase is washed three times with pure water at 80 to 90°C, and the mixture is allowed to stand for stratification, and the upper organic phase is collected to obtain a crude terpene resin.

3. The method for hydrogenating a terpene resin according to claim 1, characterized in that: The dosage ratio of the toluene, aluminum chloride, turpentine, trimethylsilyl chloride, magnetic catalyst and adsorbent is 100 mL: 5-7 g: 80-100 g: 1.5-3.0 g: 4-5 g: 10-20 g.

4. The method for hydrogenating a terpene resin according to claim 1, characterized in that: The magnetic catalyst is prepared by the following steps: NiCl2·6H2O, RuCl3·3H2O and FeCl3·6H2O are added to deionized water with stirring, and the mixture is stirred at room temperature for 10 to 20 minutes. Then, sodium citrate is added thereto with stirring, and the mixture is stirred for 1 to 2 hours. Then, the pH value of the system is adjusted to 11.5 to 12.0 with sodium hydroxide. After the pH value is adjusted, the system is heated to 80 to 85°C and stirred at the constant temperature for 2 to 3 hours. After the stirring is completed, the system is cooled to room temperature to obtain a sol. The sol is washed with deionized water to neutrality, and then dried to constant weight to obtain a dry gel. The dry gel is calcined in a muffle furnace at 550 to 580°C for 5 to 6 hours, and then ground to obtain a magnetic catalyst.

5. The method for hydrogenating a terpene resin according to claim 4, characterized in that: The usage ratio of the deionized water, NiCl2·6H2O, RuCl3·3H2O, FeCl3·6H2O and sodium citrate is 500 mL: 0.1-0.2 mol: 0.1-0.3 mol: 0.3-0.5 mol: 15-20 g.

6. The method for hydrogenating a terpene resin according to claim 1, characterized in that: The amount ratio of deionized water, carboxymethyl chitosan, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide and polyethyleneimine in A1 is 100 mL: 1 g: 2 g: 2 g: 2-3 g.

7. The method for hydrogenating a terpene resin according to claim 1, characterized in that: The amount ratio of deionized water, modified carboxymethyl chitosan, RuCl3·3H2O and 5 wt% glutaraldehyde aqueous solution described in A2 is 100 mL:5 g:1 g:40-50 mL.