Preparation method of beta-pinene liquid resin

Abstract

The invention discloses a preparation method of beta-pinene liquid resin, which comprises the following steps: adding analytically pure AR toluene into a three-mouth reaction bottle, controlling the stirring rotation speed at 500 / min, starting a constant-temperature water bath, cooling to 30 DEG C, adding 3g of analytically pure AR aluminum trichloride into the three-mouth reaction bottle at one time, the preparation method comprises the following steps: uniformly mixing 92 g of 98% beta-pinene and 8 g of spice-grade terpilenol, putting the mixture into a 125 ml constant-pressure dropwise adding funnel, starting to dropwise add beta-pinene for polymerization when the temperature in a reaction flask is reduced to 30 DEG C, stopping dropwise adding when the temperature in the reaction flask is increased to 55 DEG C, and controlling the dropwise adding temperature in the whole process to be 55-60 DEG C until all the materials are dropwise added and the polymerization liquid becomes wine red at the moment; carrying out heat preservation for 2 hours at the constant temperature of 40 DEG C, hydrolyzing and washing, then desolventizing toluene at the temperature of 160 DEG C, vacuumizing to-0.092 Mpa at the temperature of 225 DEG C, and discharging; the beta-pinene liquid resin prepared by the method has fluidity, high cohesion, high viscosity and high peel strength.

Description

Technical Field

[0001] The invention specifically relates to a method for preparing beta-pinene liquid resin. Background Art

[0002] β-pinene is one of the main components of turpentine. Turpentine is a natural chemical made by cutting pine resin. Turpentine is a mixed chemical with multiple components. The main components of turpentine are α-pinene, β-pinene, dipentene, longifolene, etc. The resins formed by polymerization of turpentine and its monomers using a Lewis acid system as a catalyst are collectively called terpene resins (also known as pinene resins). They are classified into solid terpene (pinene) resins and liquid terpene (pinene) resins based on the shape of the products. Based on the source and use of raw materials and the application performance requirements of the products, they can be divided into ordinary terpene (pinene) resins (such products are produced using full turpentine as raw materials).

[0003] α-pinene resin and β-pinene resin (such products are produced by distilling turpentine oil into α-pinene and β-pinene and then using them separately). At present, the common production technology can only produce liquid terpene resins using ordinary turpentine α-pinene and dipentene as raw materials, while β-pinene can only produce solid terpene resins due to its own molecular structure, which is highly active and easy to polymerize.

[0004] The raw materials for producing liquid terpene (pinene) resins are mixed compounds mainly composed of α-pinene, dipentene and longifolene. The molecular structures of the above monomers are relatively stable due to their molecular structures, that is, the double bonds are in the ring structure. Even under the catalyst of Lewis acid, the double bonds in the ring structure are not easy to open and undergo polymerization. This is conducive to the formation of polymers mainly composed of low molecular weight trimers and tetramers, and the final product of such polymers is liquid terpene resins. At present, the liquid terpene resins produced from such raw materials are affected by the molecular structure of the raw material components. The polymers formed have the characteristics of good initial viscosity, good fluidity and low viscosity, but the disadvantages are low cohesion, small peeling force and low viscosity. Summary of the invention

[0005] In order to overcome the deficiencies and shortcomings of the prior art, the primary purpose of the present invention is to provide a method for preparing a β-pinene liquid resin, which has fluidity and high cohesion, high viscosity and peel strength. The polymer product produced by β-pinene has the above-mentioned characteristics due to the characteristics of its molecular structure. Therefore, according to the characteristics of β-pinene resin, it has such advantages.

[0006] The primary purpose of the present invention is achieved through the following technical solutions:

[0007] A method for preparing a β-pinene liquid resin comprises the following steps:

[0008] Take a three-necked reaction bottle with a capacity of 250 ml, add analytical grade AR toluene, the amount of toluene is 100 g ± 10%, and adjust the stirring speed of the reaction bottle to 500 r / min ± 10%;

[0009] Add analytical pure AR aluminum chloride into the above reaction bottle at once, the amount of aluminum chloride used is 3g±0.5g, start the constant temperature water bath to adjust the temperature of the reaction system to 30℃±5℃;

[0010] Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 92g±2g and the amount of terpineol is 8g±2g, and then pour into a constant pressure dropping funnel with a capacity of 125ml;

[0011] When the temperature in the reaction bottle drops to 30°C ± 5°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction bottle to be maintained between 55°C and 60°C during the dripping process;

[0012] When the temperature in the reaction flask rises to 55°C, stop adding dropwise;

[0013] After the addition was completed, the reaction system was maintained at a constant temperature of 40°C ± 5°C for 2 hours;

[0014] Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 160°C ± 10°C;

[0015] Evacuate to -0.092Mpa±0.02Mpa at 225℃±10℃ and discharge.

[0016] As a preference, the method comprises the following steps:

[0017] Take a three-necked reaction bottle with a capacity of 250 ml, add 90 g of analytical grade AR toluene into it, and adjust the stirring speed of the reaction bottle to 450 r / min;

[0018] Add 2.5 g of analytically pure AR aluminum chloride into the above reaction bottle at once, and start a constant temperature water bath to adjust the temperature of the reaction system to 25°C;

[0019] Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 90 g and the amount of terpineol is 10 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml;

[0020] When the temperature in the reaction flask drops to 25°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process;

[0021] When the temperature in the reaction flask rises to 55°C, stop adding dropwise;

[0022] After the addition was completed, the reaction system was maintained at a constant temperature of 35°C for 2 hours;

[0023] Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 150°C;

[0024] Evacuate to -0.090 MPa at 215°C and discharge.

[0025] Preferably, the method comprises the following steps: taking a three-necked reaction bottle with a capacity of 250 ml, adding analytically pure AR toluene therein, the amount of toluene used being 110 g, and adjusting the stirring speed of the reaction bottle to 550 r / min%;

[0026] Add 3.5 g of analytically pure AR aluminum chloride into the above reaction bottle at once, and start a constant temperature water bath to adjust the temperature of the reaction system to 35°C;

[0027] Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 94 g and the amount of terpineol is 6 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml;

[0028] When the temperature in the reaction flask drops to 35°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process;

[0029] When the temperature in the reaction flask rises to 55°C, stop adding dropwise;

[0030] After the addition was completed, the reaction system was maintained at a constant temperature of 45°C for 2 hours;

[0031] Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 170°C;

[0032] Evacuate to -0.094 MPa at 235°C and discharge.

[0033] Preferably, the method comprises the following steps: taking a three-necked reaction bottle with a capacity of 250 ml, adding analytically pure AR toluene therein, wherein the amount of toluene is 100 g, and adjusting the stirring speed of the reaction bottle to 500 r / min;

[0034] Add 3 g of analytically pure AR aluminum chloride into the above reaction bottle at once, start a constant temperature water bath and adjust the temperature of the reaction system to 30°C;

[0035] Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 92 g and the amount of terpineol is 8 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml;

[0036] When the temperature in the reaction flask drops to 30°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process;

[0037] When the temperature in the reaction flask rises to 55°C, stop adding dropwise;

[0038] After the addition was completed, the reaction system was maintained at a constant temperature of 40°C for 2 hours;

[0039] Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 160°C;

[0040] Evacuate to -0.092 MPa at 225°C and discharge.

[0041] Preferably, the method for hydrolysis and washing treatment is: heat the pre-used hot water to 95°C for standby use, open four washing kettles for stirring; use 95°C hot water for the first washing, add 1 kg of demulsifier to each kettle, stir for 25 minutes and let stand for 30 minutes; for the second, third and fourth washings, the hot water temperature is 80-85°C, stir for 15 minutes, and let stand for 25 minutes to separate.

[0042] Preferably, during the fourth water washing, the pH value of the aqueous phase is set to 7-8.

[0043] Preferably, the method of vacuuming to -0.092Mpa±0.02Mpa at 225°C±10°C to discharge the material is:

[0044] Pump the terpene mother liquor into the terpene mother liquor high-level tank, and start the heat transfer oil to slowly heat it;

[0045] When heated to 100℃ and toluene begins to distill out, pay attention to the boiling situation in the kettle to prevent the material from rushing out. When the kettle temperature rises to 125℃, start to add dropwise until all the mother liquor has dripped into the kettle.

[0046] Start to increase the temperature, turn off the heat transfer oil when it reaches 210℃, and completely shut off the heat transfer oil when the kettle temperature reaches 225℃±10℃, and evacuate to -0.092Mpa±0.02Mpa.

[0047] Preferably, when discharging the material, nitrogen is used to de-vacuum sample and test, and if the softening point is 22-28°C, the material is discharged as qualified.

[0048] Compared with the prior art, the present invention has the following advantages:

[0049] Since the double bond structure of β-pinene is on the side chain of cycloalkane, it is highly active during the reaction, and the grafting between β-pinene molecules is easy, that is, it is easy to form a large polymer. Therefore, in the current production technology, β-pinene resin can only be used to produce high softening point terpene resin, and the softening point is usually between 110℃ and 140℃. The polymerization is achieved by adding a certain amount of terpineol to prevent the polymerization activity from forming large molecules, so that the desired molecular size product softening point is between 22-28℃. DETAILED DESCRIPTION

[0050] The specific implementation modes of the present invention are further described in detail to make the technical solutions of the present invention easier to understand and grasp.

[0051] Example

[0052] This example describes in detail the polymerization, washing and distillation processes in the process of preparing β-pinene liquid resin, and how to strictly follow the operating procedures to perform production operations to ensure the quality of the final product.

[0053] Aggregation operation steps

[0054] Before the polymerization reaction begins, first prepare the required raw materials: 5700kg toluene, 5520kg β-pinene, 180kg aluminum chloride (60kg per pot), and 480kg pinene alcohol.

[0055] Before batching, use 200kg of imported β-pinene to replace the oil tank, release it from the mixing kettle pipeline, and stir the prepared turpentine for 30 minutes, then let it stand for 30 minutes to separate the water until the water is completely removed.

[0056] Pump the processed turpentine into the high-level tank at one time for standby use.

[0057] Before starting the operation, check whether the bottom valve of the polymerization kettle is in the closed state, whether the bottom valves of the turpentine and toluene metering tanks are closed, and confirm that the tail gas venting system is unobstructed.

[0058] Pump 6000kg of turpentine (added in three times, 2000kg each time) and 5700kg of toluene into the high-level tank metering tank and let it stand for 30 minutes to ensure clean drainage.

[0059] Open the bottom valve of the toluene metering tank and let anhydrous toluene flow into the polymerization reactor, ensuring that the toluene is fully introduced to avoid affecting the subsequent reaction process.

[0060] Start the polymerization kettle stirring, and open the chilled water inlet valve and cold brine pump according to the weather conditions. When the toluene temperature in the kettle drops to 35°C, turn off the brine pump and continue to cool naturally. If the outdoor temperature is low, the cooling system may not be started.

[0061] Add 70kg of catalyst (in each kettle), and make sure that the catalyst is weighed accurately before adding it all at once. If the temperature of the reactor does not rise significantly, add turpentine to initiate the reaction. The first drop of turpentine will raise the reaction temperature to 60°C. Continue to add turpentine, and each time the temperature rises to 55°C, cool it down to 45°C until the remaining turpentine is completely added.

[0062] After the turpentine is added, keep the reactor at 40°C for 2 hours. During this period, the temperature change of the reactor needs to be checked regularly to prevent the temperature from rising too fast. After the turpentine is added, continue to keep the temperature for 30 minutes and take a sample to observe the color of the reaction liquid.

[0063] After keeping the temperature at 40°C for 2 hours, the material was discharged, and the polymerization process was completed.

[0064] Water washing steps

[0065] Transfer the materials in the polymerization kettle to water washing kettles 1#, 2#, and 3#, and heat the hot water to 95°C in advance. Turn on the stirring system of the water washing kettle and start the first water washing.

[0066] First water washing: Use 95℃ hot water, add 1kg of demulsifier to each kettle, stir for 25 minutes, and let stand for 30 minutes before starting to separate.

[0067] Second washing: Use 90℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate into layers.

[0068] The third water wash: use 85℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate into layers.

[0069] Fourth wash: Use 80℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate into layers.

[0070] After the fourth water wash, check the pH of the aqueous phase to ensure it is in the range of 7-8.

[0071] Pay special attention to the turbidity of oily alcohol substances in the water during the first stratification, and strictly control the observation of the stratification interface.

[0072] After the first water wash, samples were taken and tested in time to calculate the reaction yield.

[0073] After the fourth water wash, take a sample and perform a colorimetric test to ensure that the mother liquor meets the color standard.

[0074] Product distillation operation steps

[0075] Before distillation operation, check the bottom valve and discharge valve of the distillation kettle to ensure that they are in the closed state.

[0076] Open the feed valve and the condenser circulating water inlet valve, open the condenser exhaust valve, and close the exhaust valve after the condenser is full of water.

[0077] Pump 2900 kg of terpene mother liquor into the terpene mother liquor high level tank and record the volume of the solution.

[0078] Start the thermal oil heating system and slowly heat the distillation kettle.

[0079] When the temperature rises to 100°C, start observing the distillation of toluene to avoid violent boiling in the reactor and prevent the solution from splashing.

[0080] When the temperature rises to 125°C, the remaining mother liquor begins to be gradually added dropwise until all 11,000 kg of mother liquor has been added.

[0081] When the temperature subsequently rises to 210°C, the heat transfer oil system is turned off and the heating is continued to 230°C.

[0082] Completely turn off the heat transfer oil at 230℃ and evacuate to -0.092MPa after heating to ensure a smooth distillation process.

[0083] Use nitrogen to release the vacuum and take samples for testing during the decompression process to ensure that the softening point of the product is 22-28℃.

[0084] Adjust the color of the product as needed to ensure that the color of the final product is within the specified range (<5 colors). If the color is not up to standard, add an appropriate amount of decolorizer for treatment.

[0085] Polymerization process: Ensure that the reaction temperature is kept stable at 55°C to ensure that each batch of products reacts completely.

[0086] Washing process: The temperature and stirring time of each washing are strictly controlled to ensure that the washing effect meets the requirements, the pH value of the product is between 7-8, and the color of the final water phase meets the standards.

[0087] Distillation process: During the distillation process, the final temperature is controlled not to exceed 240°C and the softening point is ensured to be at 25°C. The quality of the final product is ensured by vacuum control and color colorimetry.

[0088] Example 2

[0089] A method for preparing a β-pinene liquid resin comprises the following steps:

[0090] Raw material preparation: 5700kg toluene, 5520kg β-pinene, 180kg aluminum chloride (60kg per pot), 480kg terpineol;

[0091] Turpentine pretreatment: Use 200kg of imported β-pinene to replace the oil tank, stir the turpentine for 30 minutes, let it stand for 30 minutes to separate the water, and ensure that the water is completely removed.

[0092] After treatment, the turpentine is pumped into a high-level tank for standby use.

[0093] Pre-operation inspection: Check whether the bottom valve of the polymerization reactor and the bottom valve of the toluene metering tank are closed, and confirm that the tail gas venting system is unobstructed. Pump 6000kg of turpentine (added three times, 2000kg each time) and 5700kg of toluene into the high-level tank metering tank and let it stand for 30 minutes to drain the water.

[0094] Polymerization process: Open the bottom valve of the toluene metering tank and flow anhydrous toluene into the polymerization kettle to ensure that it is fully added. Start stirring and start the chilled water and cold brine systems according to weather conditions to keep the temperature in the kettle at around 35°C. Add 70kg of aluminum trichloride catalyst to ensure that the reaction temperature gradually increases. If the reaction temperature does not rise, turpentine can be gradually added to initiate the reaction. The first drop of turpentine is 60°C, and the temperature is maintained between 55°C and 45°C after each drop until the remaining turpentine is completely added. After the turpentine is added, keep the reactor at 40°C for 2 hours and check the temperature regularly to prevent it from heating up too quickly.

[0095] Discharging: After the reaction is completed, discharging begins to complete the polymerization process.

[0096] Water washing steps

[0097] Preparation before water washing: transfer the materials in the polymerization reactor to water washing reactors 1#, 2#, and 3#, and heat the hot water to 95°C in advance.

[0098] Washing process: First wash: Use 95℃ hot water, add 1kg of demulsifier to each kettle, stir for 25 minutes, let stand for 30 minutes and then separate. Second wash: Use 90℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate. Third wash: Use 85℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate. Fourth wash: Use 80℃ hot water, stir for 15 minutes, let stand for 25 minutes and then separate.

[0099] Quality control: Check the pH value of the water phase after the fourth water wash to ensure that it is between 7 and 8. Pay special attention to the turbidity of the oil-alcohol substance during the first layering, and strictly control the layering interface. Take samples for testing in time after the first round of water washing, and calculate the reaction yield.

[0100] Chroma and conformity: Take a sample after the fourth wash and perform a colorimetric test to ensure that the mother liquor meets the chroma standards.

[0101] Product distillation operation steps

[0102] Preparation before distillation: Check the bottom valve and discharge valve of the distillation kettle to ensure that they are in a closed state. Open the feed valve and the condenser circulating water inlet valve, open the condenser exhaust valve, and close the exhaust valve after the condenser is full of water.

[0103] Mother liquor addition: Pump 2900 kg of terpene mother liquor into the terpene mother liquor high level tank and record the volume of the solution.

[0104] Heating process: Start the thermal oil heating system and slowly heat up the distillation kettle. When the temperature reaches 100°C, start observing the distillation of toluene to avoid violent boiling. When the temperature rises to 125°C, gradually add the remaining mother liquor until 11,000 kg of mother liquor is completely added.

[0105] Distillation control: When the temperature rises to 210°C, turn off the heat transfer oil system and continue heating to 230°C. At 230°C, completely turn off the heat transfer oil, stop heating and evacuate to -0.092MPa.

[0106] Vacuum treatment and testing: Use nitrogen to release the vacuum, and take samples for testing during the decompression process to ensure that the product softening point is between 22-28°C. Adjust the product color as needed to ensure that the final product color meets the standard (<5 colors). If there is a color difference, add an appropriate amount of decolorizer for treatment.

[0107] During the polymerization process, the reaction temperature should be kept at around 55°C and the reaction time should be sufficient to ensure that each batch of products reacts completely and avoid temperature fluctuations. If the weather is cold, the cooling system operation can be appropriately adjusted or the flow of cold brine can be reduced.

[0108] The temperature and stirring time of each water washing must be controlled accurately to avoid the effect being affected by too low or too high temperature, and ensure that the pH value and color standard of the water phase are within the specified range.

[0109] During the distillation process, the final temperature should be strictly controlled not to exceed 240℃ to avoid affecting the product quality. Ensure that the softening point is controlled at around 25℃, and optimize the final product by adjusting the vacuum degree and color colorimetry.

[0110] Example 3

[0111] A method for preparing a β-pinene liquid resin comprises the following steps:

[0112] Raw material preparation: toluene: 5700kg, β-pinene: 5520kg, aluminum chloride catalyst: 180kg (60kg per pot), pineneol: 480kg.

[0113] Turpentine pretreatment: Use 200kg of imported β-pinene to replace the oil tank, stir for 30 minutes, let stand for 30 minutes to separate the water, and ensure that the water is removed. The treated turpentine is pumped into the high-level tank for standby use.

[0114] Inspection before operation: Check whether the bottom valve of the polymerization kettle is closed, whether the bottom valves of the toluene and turpentine metering tanks are closed, and confirm that the tail gas venting system is unobstructed.

[0115] Polymerization process: Add turpentine and toluene: Pump 6000kg turpentine (added three times, 2000kg each time) and 5700kg toluene into the high-level tank and let it stand for 40 minutes to ensure that the water is drained cleanly. Open the bottom valve of the toluene metering tank and flow anhydrous toluene into the polymerization kettle to ensure that it is fully added. Start stirring and adjust the cooling system according to the outside weather temperature to keep the temperature in the kettle at 30℃-35℃.

[0116] Catalyst input: 60kg aluminum chloride catalyst (per pot) is added, ensuring accurate weighing and all input at once. If the temperature does not rise significantly, add an appropriate amount of turpentine to stimulate the reaction. The temperature of the first drop of turpentine is 65°C, and after each drop of turpentine, the temperature is gradually raised to 60°C, and then maintained at 45°C-55°C until the turpentine is completely added.

[0117] Insulation stage: After the turpentine is added, keep the temperature at 45°C for 1 hour to prevent the temperature from rising too quickly.

[0118] End and discharge: After the reaction is completed, keep the temperature at 40°C for 1 hour. After the temperature stabilizes, discharge begins to complete the polymerization process.

[0119] Water washing steps

[0120] Preparation before water washing: transfer the materials in the polymerization kettle to water washing kettles 1#, 2#, and 3#, and heat the hot water to 90°C in advance.

[0121] Washing process: First wash: Use 90℃ hot water, add 1.5kg of demulsifier to each kettle, stir for 20 minutes, let stand for 35 minutes and then separate. Second wash: Use 85℃ hot water, stir for 20 minutes, let stand for 30 minutes and then separate. Third wash: Use 80℃ hot water, stir for 20 minutes, let stand for 30 minutes and then separate. Fourth wash: Use 75℃ hot water, stir for 20 minutes, let stand for 30 minutes and then separate.

[0122] Quality control: Check the pH value of the water phase to ensure it is between 7 and 8. Pay attention to the turbidity of the oily alcohol substances during the first layering to ensure the stability of the layering interface. Take samples after each water wash and calculate the reaction yield by analysis.

[0123] Final inspection: After the fourth water wash, a colorimetric test is performed to ensure that the color of the mother liquor meets the standard and the chromaticity value is within the specified range.

[0124] Product distillation operation steps

[0125] Preparation before distillation: Check the bottom valve and discharge valve of the distillation kettle to ensure that they are in a closed state. Start the condenser circulating water system and check the exhaust valve to ensure that the condenser system is operating normally.

[0126] Mother liquor addition: Pump 2900 kg of terpene mother liquor into the terpene mother liquor high level tank and record the volume of the solution.

[0127] Heating process: Start the thermal oil heating system and slowly heat the distillation kettle to avoid sudden temperature rise. When the temperature rises to 110°C, observe the distillation of toluene to avoid violent boiling in the reactor. When the temperature rises to 130°C, gradually add the remaining mother liquor until 11,000 kg of mother liquor is completely added.

[0128] Distillation control: When the temperature rises to 215°C, turn off the heat transfer oil system and continue heating to 230°C. At 230°C, completely turn off the heat transfer oil system, stop heating and evacuate to -0.09MPa to ensure the smooth progress of the distillation process.

[0129] Vacuum treatment and product testing: Use nitrogen to release the vacuum and ensure that the softening point of the product is between 22℃-30℃ during the decompression process. Adjust the product color as needed to ensure that the final product color meets the color standard (<5 colors). If the color is not up to standard, add an appropriate amount of decolorizer.

[0130] Performance test experiment

[0131] Experimental steps:

[0132] Take a sample of the β-pinene liquid resin of the above example to ensure its purity and uniformity.

[0133] Place the resin sample in the sample slot of the softening point tester, or use a glass tube method device for measurement.

[0134] A temperature control device is set to gradually increase the temperature of the sample during the heating process.

[0135] The state of the sample was recorded every 1°C to observe the temperature at which it changed from a solid state to a softened state.

[0136] When the sample begins to show signs of softening (such as deformation or becoming sticky), record the temperature value immediately.

[0137] Repeat the experiment three times, record the softening point temperature each time and calculate the average value. The results are shown in Table 1 below

[0138] Table 1 Experimental data record table

[0139] Experiment number Heating temperature(℃) Sample status Remark 1 22.0 Start to soften Initial deformation 2 22.5 Continue to soften Slightly sticky 3 23.0 Completely softened No obvious hardness 4 23.5 Slightly soft Slight surface flow 5 24.0 Soften completely The sample becomes completely soft 6 24.5 Slightly liquid The sample is obviously deformed 7 25.0 Completely softened No hardness visible 8 25.5 No significant changes Softening completed 9 26.0 Completely softened Keep flowing 10 26.5 Completely softened High temperature changes 11 27.0 Completely softened Sample has no hardness 12 27.5 Completely softened Sample has no hardness

[0140] It can be seen from the experimental data that the β-pinene liquid resin begins to soften and completely softens between 22.0°C and 27.5°C, which is consistent with the expected softening point range (22°C-28°C).

[0141] Average softening point: According to experimental results, the softening point of β-pinene liquid resin is 24.0°C (this value is the average value of multiple experiments).

[0142] Conclusion: The experiment verifies that the softening point of β-pinene liquid resin is between 22℃ and 28℃, which is consistent with theoretical expectations. The experimental data supports that the softening point of the resin material is within the expected range and is suitable for related application requirements.

[0143] Of course, the above are only typical examples of the present invention. In addition to these, the present invention may also have many other specific implementations. Any technical solutions formed by equivalent replacement or equivalent transformation fall within the scope of protection required by the present invention. Of course, the above are only typical examples of the present invention. In addition to these, the present invention may also have many other specific implementations. Any technical solutions formed by equivalent replacement or equivalent transformation fall within the scope of protection required by the present invention.

Claims

1. A method for preparing β-pinene liquid resin, characterized in that , including the following steps: Take a three-necked reaction bottle with a capacity of 250 ml, add analytical grade AR toluene, the amount of toluene is 100 g ± 10%, and adjust the stirring speed of the reaction bottle to 500 r / min ± 10%; Add analytical pure AR aluminum chloride into the above reaction bottle at once, the amount of aluminum chloride used is 3g±0.5g, start the constant temperature water bath to adjust the temperature of the reaction system to 30℃±5℃; Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 92g±2g and the amount of terpineol is 8g±2g, and then pour into a constant pressure dropping funnel with a capacity of 125ml; When the temperature in the reaction bottle drops to 30°C ± 5°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction bottle to be maintained between 55°C and 60°C during the dripping process; When the temperature in the reaction flask rises to 55°C, stop adding dropwise; After the addition was completed, the reaction system was maintained at a constant temperature of 40°C ± 5°C for 2 hours; Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 160°C ± 10°C; Evacuate to -0.092Mpa±0.02Mpa at 225℃±10℃ and discharge.

2. The method for preparing the β-pinene liquid resin according to claim 1, characterized in that , including the following steps: Take a three-necked reaction bottle with a capacity of 250 ml, add 90 g of analytical grade AR toluene into it, and adjust the stirring speed of the reaction bottle to 450 r / min; Add 2.5 g of analytically pure AR aluminum chloride into the above reaction bottle at once, start a constant temperature water bath and adjust the temperature of the reaction system to 25°C; Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 90 g and the amount of terpineol is 10 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml; When the temperature in the reaction flask drops to 25°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process; When the temperature in the reaction flask rises to 55°C, stop adding dropwise; After the addition was completed, the reaction system was maintained at a constant temperature of 35°C for 2 hours; Performing hydrolysis and water washing treatment, and desolventizing toluene from the reaction solution at 150°C; Evacuate to -0.090 MPa at 215°C and discharge.

3. The method for preparing the β-pinene liquid resin according to claim 1, characterized in that , including the following steps: Take a three-necked reaction bottle with a capacity of 250 ml, add analytical grade AR toluene, the amount of toluene is 110 g, and adjust the stirring speed of the reaction bottle to 550 r / min%; Add 3.5 g of analytically pure AR aluminum chloride into the above reaction bottle at once, and start a constant temperature water bath to adjust the temperature of the reaction system to 35°C; Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 94 g and the amount of terpineol is 6 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml; When the temperature in the reaction flask drops to 35°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process; When the temperature in the reaction flask rises to 55°C, stop adding dropwise; After the addition was completed, the reaction system was maintained at a constant temperature of 45°C for 2 hours; Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 170°C; Evacuate to -0.094 MPa at 235°C and discharge.

4. The method for preparing the β-pinene liquid resin according to claim 1, characterized in that , including the following steps: Take a three-necked reaction bottle with a capacity of 250 ml, add 100 g of analytical grade AR toluene into it, and adjust the stirring speed of the reaction bottle to 500 r / min; Add 3 g of analytically pure AR aluminum chloride into the above reaction bottle at once, start a constant temperature water bath and adjust the temperature of the reaction system to 30°C; Mix 98% β-pinene and fragrance-grade terpineol, wherein the amount of β-pinene is 92 g and the amount of terpineol is 8 g, and then pour into a constant pressure dropping funnel with a capacity of 125 ml; When the temperature in the reaction flask drops to 30°C, start dripping the mixture of β-pinene and terpineol at a constant rate, and control the temperature in the reaction flask to be maintained between 55°C and 60°C during the dripping process; When the temperature in the reaction flask rises to 55°C, stop adding dropwise; After the addition was completed, the reaction system was maintained at a constant temperature of 40°C for 2 hours; Perform hydrolysis and water washing treatment, and desolventize toluene from the reaction solution at 160°C; Evacuate to -0.092 MPa at 225°C and discharge.

5. The method for preparing β-pinene liquid resin according to claim 1, characterized in that: The method for hydrolysis and washing treatment is: heat the pre-used hot water to 95°C for standby use, open four water washing kettles for stirring; use 95°C hot water for the first water washing, add 1 kg of demulsifier to each kettle, stir for 25 minutes and let stand for 30 minutes; for the second, third and fourth water washings, the hot water temperature is 80-85°C, stir for 15 minutes, and let stand for 25 minutes to separate.

6. The method for preparing β-pinene liquid resin according to claim 5, characterized in that: During the fourth water wash, the pH value of the aqueous phase was adjusted to 7-8.

7. The method for preparing β-pinene liquid resin according to claim 1, characterized in that: The method of discharging the material at 225℃±10℃ and vacuuming to -0.092Mpa±0.02Mpa is: Pump the terpene mother liquor into the terpene mother liquor high-level tank, and start the heat transfer oil to slowly heat it; When heated to 100℃ and toluene begins to distill out, pay attention to the boiling situation in the kettle to prevent the material from rushing out. When the kettle temperature rises to 125℃, start to add dropwise until all the mother liquor has dripped into the kettle. Start to increase the temperature, turn off the heat transfer oil when it reaches 210℃, and completely shut off the heat transfer oil when the kettle temperature reaches 225℃±10℃, and evacuate to -0.092Mpa±0.02Mpa.

8. The method for preparing β-pinene liquid resin according to claim 7, characterized in that: When discharging, nitrogen is used to de-vacuum sample and test. If the softening point is 22-28℃, the material is qualified.