Polymerization production method of 10 DEG C liquid terpene resin

Abstract

The invention discloses a polymerization production method of 10 DEG C liquid terpene resin, which comprises the following steps: pumping turpentine into a head tank in two times, adding ethanol according to a mass ratio of 1%, uniformly stirring, and dropwise adding for later use; in the polymerization kettle, closing a bottom valve of an inspection kettle, a bottom valve of a turpentine metering tank and a bottom valve of a toluene metering tank; pumping the prepared turpentine and toluene into a metering tank, standing, and adding anhydrous toluene into the polymerization reaction kettle; starting the polymerization reaction kettle for stirring, opening a chilled water inlet valve and a cold brine pump, closing the brine pump when the temperature in the kettle is reduced to 10 DEG C, and continuously reducing the temperature to 0 DEG C; starting to dropwise add turpentine; the reaction temperature is controlled between 8 DEG C and 13 DEG C; after the addition of the turpentine is finished, carrying out a reaction for 2 hours at a heat preservation temperature of 12-15 DEG C; the method prevents excessive reaction from generating macromolecules during polymerization of turpentine and aluminum trichloride, destroys certain polymerization activity of the catalyst, and inhibits the problem of high polymerization degree of pentadiene due to high activity.

Description

Technical Field

[0001] The present invention specifically relates to a polymerization production method for a 10°C liquid terpene resin. Background Art

[0002] Liquid terpene resin is a low molecular weight linear polymer made from selected turpentine oil as the basic raw material. After refining, it is polymerized with Friedel-Crafts as the catalyst, and then developed through processes such as hydrolysis, washing, filtration and distillation. It is suitable for preparing EVA, SIS, SBS hot melt adhesives and other adhesives with good initial adhesion, high cold resistance and soft performance. Liquid terpene resin has always played a particularly important role in adhesives, especially its unique cold resistance and good initial adhesion performance.

[0003] The existing liquid terpene resin products have a number average molecular weight > Mn600 and a weight average molecular weight > Mw800. When used as glue at lower ambient temperatures, such as -20°C in the north, the initial viscosity may be poor or the product may become non-sticky after complete curing. This shortcoming imposes certain environmental limitations on the use of the product. Summary of the invention

[0004] In order to overcome the shortcomings and disadvantages of the prior art, the primary purpose of the present invention is to provide a polymerization production method for a 10°C liquid terpene resin, which prevents excessive reaction to generate high molecules during the polymerization of turpentine and aluminum chloride, destroys a certain polymerization activity of the catalyst by adding a certain amount of ethanol inhibitor, and controls the polymerization process temperature at 8-12°C to suppress the problem of high polymerization degree of isopentylene due to its high activity, thereby obtaining a terpene polymer liquid with a narrow molecular weight distribution and a small and uniform size.

[0005] The primary purpose of the present invention is achieved through the following technical solutions:

[0006] A polymerization production method for a 10°C liquid terpene resin comprises the following steps:

[0007] Prepare a raw material solution, the raw materials comprising:

[0008] The mass of turpentine is 6000kg±10%, the mass of toluene is 5400kg±10%, the mass of longifolene is 3600kg±5%, the mass of terpinene is 600kg±5%, the mass of isoprene is 1800kg±5%, the mass of aluminum chloride is 210kg±2%, and the mass of ethanol is 24kg±1%;

[0009] The turpentine is pumped into the high-level tank twice, 3600kg±10% is pumped into the first time, and the remaining 2400kg±10% is added to 24kg±10% of ethanol at a mass ratio of 1% in the second time, and stirred evenly and then added dropwise for later use;

[0010] In the polymerization kettle, check that the kettle bottom valve, turpentine metering tank bottom valve and toluene metering tank bottom valve are closed, and confirm that the tail gas system is unobstructed;

[0011] Pump the prepared 3600kg±10% turpentine and 5400kg±10% toluene into the metering tank and let it stand for 30 minutes. After confirming that the water is drained cleanly, open the bottom valve of the toluene metering tank and add anhydrous toluene into the polymerization reactor;

[0012] Start the polymerization reactor stirring, open the chilled water inlet valve and the cold brine pump, and when the temperature in the reactor drops to 10°C, close the brine pump and continue to cool down to 0°C;

[0013] When the temperature in the kettle drops to 0°C, add 70kg of catalyst. If the temperature of the reactor does not rise significantly, start adding turpentine. Stop adding turpentine when the reaction temperature reaches 17°C.

[0014] The reaction temperature is controlled between 8°C and 13°C, and the remaining turpentine is gradually added dropwise, and the temperature is continuously lowered to 8°C each time the turpentine is added until all the turpentine has been added;

[0015] After the turpentine oil is added, continue to keep warm and react for 30 minutes;

[0016] The reaction was carried out at a temperature of 12°C to 15°C for 2 hours, and the material was discharged after the reaction was completed.

[0017] Preferably, the purity of the longifolene is 80%, the purity of the terpinene is 90%, the purity of the piperylene is 72%, and the ethanol is analytical grade ethanol.

[0018] Preferably, the appearance of the polymerization liquid is a wine red liquid at the end of the polymerization.

[0019] Preferably, after the polymerization reaction is completed, the reaction is cooled to room temperature and separated and purified to obtain a stable low molecular weight terpene resin.

[0020] Preferably, the catalyst is aluminum chloride, and the added amount is 210 kg ± 2%.

[0021] Preferably, the temperature in the polymerization vessel is controlled by a cold brine pump.

[0022] Preferably, the amount of ethanol added is 0.5% to 3% by weight.

[0023] Preferably, the weight ratio of turpentine to longifolene is 1:1 to 1:2, the weight ratio of turpentine to terpinene is 1:1 to 1:2, and the weight ratio of turpentine to piperylene is 1:0.1 to 1:0.3.

[0024] Preferably, the amount of aluminum trichloride added is 0.1% to 1.0% of the total mass of the polymerization reactants.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] After improvement, during the cationic polymerization of turpentine, 10% of absolute ethanol or 15% of terpineol is added as polymerization inhibitor in terms of raw materials, and the polymerization process temperature of turpentine is also adjusted to 25 - 30 °C for polymerization. Polymerization at a higher temperature can make the molecular weight distribution narrower and more uniform. Through a large number of experimental demonstrations and test data, it can be known that linear polymers with number average molecular weight <Mn 400, weight average molecular weight <Mw 400, and glass transition temperature of about -35 °C can be obtained by polymerizing at 25 - 30 °C. The liquid terpene resin product with number average molecular weight <Mn 400, weight average molecular weight <Mw 400, and glass transition temperature of -35 °C overcomes the technical problems such as poor initial adhesion or complete non - adhesion after curing when used as glue at environmental temperatures such as -20 °C in the north. Specific embodiments

[0027] The specific embodiments of the present invention are further described in detail to make the technical solutions of the present invention easier to understand and master.

[0028] Example 1

[0029] A polymerization production method of 10 °C liquid terpene resin, comprising the following steps:

[0030] Raw material dosage:

[0031] Turpentine: 6000 kg, toluene: 5400 kg, longifolene: 3600 kg, isolimonene: 600 kg, piperylene: 1800 kg, aluminum trichloride: 210 kg, ethanol: 24 kg.

[0032] Preparation before batching

[0033] Use 200 kg of longifolene to displace the pipeline from the oil depot to the blending kettle and discharge it;

[0034] The prepared turpentine needs to be subjected to water separation treatment to ensure it is clean before use;

[0035] The turpentine is added to the high - level tank in two times. After adding 3600 kg for the first time, stop pumping. For the remaining 2400 kg, add ethanol at 1% (24 kg ethanol), stir evenly and set aside.

[0036] Inspection before polymerization reaction

[0037] Check whether the bottom valve of the polymerization kettle is closed; confirm that the bottom valves of the turpentine and toluene metering tanks are closed; check whether the exhaust gas venting system is unobstructed; ensure that the configured 3600kg turpentine and 5400kg toluene are pumped into the metering tank, let it stand for 30 minutes, and confirm that the water is drained cleanly.

[0038] Polymerization reaction operation

[0039] Open the bottom valve of the toluene metering tank, put anhydrous toluene into the polymerization reactor, and ensure that all toluene is put in; start the polymerization reactor to stir, and open the chilled water inlet valve and the cold brine pump;

[0040] When the toluene in the kettle drops to 10°C, turn off the brine pump and continue to cool down. When the temperature in the kettle drops to 0°C, add 70 kg of catalyst;

[0041] When the temperature in the reactor does not rise significantly, start adding turpentine;

[0042] First add turpentine until the temperature reaches 17°C, then continue to use cold salt water to cool down to 8°C, then add turpentine again until the temperature reaches 13°C;

[0043] Continue this process until the turpentine is used up (finally stop the temperature at 10°C);

[0044] Add 600 kg of turpentine to the ethanol in batches, and observe the temperature change in the reactor during the addition;

[0045] After the turpentine is completely added, keep the temperature at 12-15°C and continue to keep the temperature for 2 hours.

[0046] Reaction solution test

[0047] After the turpentine oil is added, the mixture is kept warm for 30 minutes, and a sample is taken to detect whether the reaction liquid is wine red; the temperature is maintained at 13-15°C for 2 hours, and the material is finally discharged.

[0048] Process indicators:

[0049] Turpentine: 6000 kg, toluene: 5400 kg, AlCl3: 210 kg, ethanol: 24 kg, initiation temperature: 17°C, dropping temperature: 8-13°C, insulation temperature: 12-15°C, insulation time: 2 hours, polymerization end point: the polymerization liquid is wine red.

[0050] Example 2

[0051] A polymerization production method for a 10°C liquid terpene resin comprises the following steps:

[0052] Raw material dosage:

[0053] Turpentine: 6600 kg, toluene: 5940 kg, longifolene: 3960 kg, terpinene: 660 kg, isoprene: 1980 kg, aluminum chloride: 231 kg, ethanol: 26.4 kg.

[0054] Steps:

[0055] Preparation of ingredients

[0056] Use 220 kg of longifolene to displace the oil tank to the blending kettle pipeline and discharge;

[0057] The prepared turpentine oil is treated with water separation to ensure that the water is removed;

[0058] Turpentine is added to the high-level tank in two batches. 3960 kg is added in the first batch, and 1% (26.4 kg ethanol) ethanol is added to the remaining 2640 kg, and stirred evenly for later use.

[0059] Pre-polymerization inspection

[0060] Check whether the bottom valve of the polymerization kettle is closed, and whether the bottom valves of the turpentine and toluene metering tanks are closed;

[0061] Confirm that the exhaust gas venting system is unobstructed;

[0062] Pump the prepared 3960kg turpentine and 5940kg toluene into the metering tank and let it stand for 30 minutes to ensure that the water is drained cleanly.

[0063] Polymerization reaction operation

[0064] Open the bottom valve of the toluene metering tank and inject anhydrous toluene into the polymerization reactor;

[0065] Start the polymerization kettle stirring, open the chilled water inlet valve and the cold brine pump;

[0066] When the temperature in the kettle drops to 10°C, turn off the brine pump, and continue to cool it down to 0°C before adding 77 kg of catalyst;

[0067] According to the temperature control requirements, add turpentine oil and control the temperature between 8-13℃ each time;

[0068] Add 600 kg of ethanol mixed with turpentine each time. When the reaction temperature rises to about 13°C, add turpentine again.

[0069] After the addition was completed, the temperature was maintained at 12-15°C for 2 hours.

[0070] Reaction solution test

[0071] After the turpentine is added, keep warm for 30 minutes and check whether the reaction solution is wine red;

[0072] The temperature was maintained between 13-15°C for 2 hours and then discharged.

[0073] Process indicators:

[0074] Turpentine: 6600 kg, toluene: 5940 kg, AlCl3: 231 kg, ethanol: 26.4 kg, initiation temperature: 17°C, dropping temperature: 8-13°C, insulation temperature: 12-15°C, insulation time: 2 hours, polymerization end point: the polymerization liquid is wine red.

[0075] Example 3

[0076] A polymerization production method for a 10°C liquid terpene resin comprises the following steps:

[0077] Raw material dosage:

[0078] Turpentine: 5400 kg, toluene: 4860 kg, longifolene: 3240 kg, terpinene: 540 kg, isoprene: 1620 kg, aluminum chloride: 189 kg, ethanol: 21.6 kg.

[0079] Steps:

[0080] Preparation of ingredients

[0081] Use 180 kg of longifolene to displace the oil tank to the blending kettle pipeline and discharge;

[0082] The prepared turpentine oil is treated to separate water and used without water;

[0083] Turpentine is added to the high-level tank in two batches, 3240 kg is added for the first time, and 1% (21.6 kg of ethanol) ethanol is added to the remaining 2160 kg, and stirred evenly for later use.

[0084] Pre-polymerization inspection

[0085] Check whether the bottom valve of the polymerization kettle is closed, and whether the bottom valves of the turpentine and toluene metering tanks are closed;

[0086] Check that the exhaust system is vented and unobstructed;

[0087] 3240kg turpentine and 4860kg toluene were pumped into the metering tank and allowed to stand for 30 minutes to ensure that the water was drained cleanly.

[0088] Polymerization reaction operation

[0089] Open the bottom valve of the toluene metering tank and inject anhydrous toluene into the polymerization reactor;

[0090] Start the polymerization kettle stirring, open the chilled water inlet valve and the cold brine pump;

[0091] When the temperature in the kettle drops to 10°C, turn off the brine pump, and continue to cool it down to 0°C before adding 63 kg of catalyst;

[0092] Add turpentine gradually according to the temperature change, making sure the temperature is controlled between 8-13℃ each time;

[0093] 600 kg of the ethanol turpentine mixture was added dropwise each time, and after the addition was completed, the temperature was maintained at 12-15° C. for 2 hours.

[0094] Reaction solution test

[0095] After the turpentine is added, keep warm for 30 minutes and check whether the reaction solution is wine red;

[0096] The reaction temperature was maintained at 13-15°C for 2 hours, and the product was discharged.

[0097] Process indicators:

[0098] Turpentine: 5400 kg, toluene: 4860 kg, AlCl3: 189 kg, ethanol: 21.6 kg, initiation temperature: 17°C, dropping temperature: 8-13°C, insulation temperature: 12-15°C, insulation time: 2 hours, polymerization end point: the polymerization liquid is wine red.

[0099] Performance test experiment

[0100] Experimental Materials:

[0101] Sample A: 10°C liquid terpene resin prepared according to Example 1;

[0102] Sample B: 10°C liquid terpene resin prepared according to Example 2;

[0103] Sample C: 10°C liquid terpene resin prepared according to Example 3;

[0104] Control sample D: existing liquid terpene resin product;

[0105] Equipment: Differential Scanning Calorimeter (DSC)

[0106] Experimental methods:

[0107] Sample preparation: Take 10 mg of each of Sample A, Sample B, Sample C, and Sample D obtained from the experiment; the samples need to be dried to remove any residual solvent.

[0108] Differential Scanning Calorimetry (DSC) Analysis:

[0109] The glass transition temperature was measured using DSC, with the temperature range set to -80°C to +100°C and the heating rate set to 10°C / min.

[0110] During the experiment, the heat flow curve of the sample was recorded to identify the glass transition temperature (T g ) position. The glass transition temperature is usually determined by the transition point on the curve (i.e., the step change that occurs in the heat flow curve).

[0111] The sample is first kept at a constant temperature at low temperature. As the temperature gradually rises, the sample will undergo a transition from glassy state to rubbery state. At this time, the glass transition temperature will appear as a step jump in the heat flow curve (T g ).

[0112] Data Analysis:

[0113] The glass transition temperature of each sample was determined by analyzing the transition temperature in the DSC curve.

[0114] Glass transition temperature (T g ) can be quantitatively analyzed by the step change of the curve (i.e. the temperature where the heat flow changes significantly).

[0115] The experimental results are shown in Table 1 below.

[0116] Table 1

[0117] sample <![CDATA[Glass transition temperature (T g )]]> Sample A -35℃ Sample B -33℃ Sample C -32℃ Sample D -20℃

[0118] The glass transition temperatures of samples A, B and C are significantly lower than those of sample D, which indicates that a liquid terpene resin having a glass transition temperature lower than that of conventional products is successfully prepared by the formulation and process of the present invention.

[0119] The glass transition temperatures of samples B and C are close to -35 °C, proving that the process adjustments made according to the above scheme have a significant effect on the properties of the final polymer, which may be due to different molecular structures or increased flexibility of the polymer chains, resulting in a glass transition temperature lower than that of conventional products.

[0120] 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 polymerization production method for a 10°C liquid terpene resin, characterized in that , including the following steps: Prepare a raw material solution, the raw materials comprising: The mass of turpentine is 6000kg±10%, the mass of toluene is 5400kg±10%, the mass of longifolene is 3600kg±5%, the mass of terpinene is 600kg±5%, the mass of isoprene is 1800kg±5%, the mass of aluminum chloride is 210kg±2%, and the mass of ethanol is 24kg±1%; The turpentine is pumped into the high-level tank twice, 3600kg±10% is pumped into the first time, and the remaining 2400kg±10% is added to 24kg±10% of ethanol at a mass ratio of 1% in the second time, and stirred evenly and then added dropwise for later use; In the polymerization kettle, check that the kettle bottom valve, turpentine metering tank bottom valve and toluene metering tank bottom valve are closed, and confirm that the tail gas system is unobstructed; Pump the prepared 3600kg±10% turpentine and 5400kg±10% toluene into the metering tank and let it stand for 30 minutes. After confirming that the water is drained cleanly, open the bottom valve of the toluene metering tank and add anhydrous toluene into the polymerization reactor; Start the polymerization reactor stirring, open the chilled water inlet valve and the cold brine pump, and when the temperature in the reactor drops to 10°C, close the brine pump and continue to cool down to 0°C; When the temperature in the kettle drops to 0°C, add 70kg of catalyst. If the temperature of the reactor does not rise significantly, start adding turpentine. Stop adding turpentine when the reaction temperature reaches 17°C. The reaction temperature is controlled between 8°C and 13°C, and the remaining turpentine is gradually added dropwise, and the temperature is continuously lowered to 8°C each time the turpentine is added until all the turpentine has been added; After the turpentine oil is added, continue to keep warm and react for 30 minutes; The reaction was carried out at a temperature of 12°C to 15°C for 2 hours, and the material was discharged after the reaction was completed.

2. The polymerization production method of 10°C liquid terpene resin according to claim 1, characterized in that The purity of the longifolene is 80%, the purity of the terpinene is 90%, the purity of the isopentylene is 72%, and the ethanol is analytical grade ethanol.

3. The polymerization production method of 10°C liquid terpene resin according to claim 1, characterized in that , where the appearance of the polymerization liquid is a wine red liquid at the end of the polymerization.

4. The method for producing a 10°C liquid terpene resin by polymerization as claimed in claim 3, characterized in that After the polymerization reaction is completed, a stable low molecular weight terpene resin is obtained by cooling to room temperature and separating and purifying.

5. The polymerization production method of 10°C liquid terpene resin according to claim 1, characterized in that , where the catalyst is aluminum chloride, and the added amount is 210kg±2%.

6. The polymerization production method of 10°C liquid terpene resin according to claim 1, characterized in that , where the temperature in the polymerization reactor is controlled by a cold brine pump.

7. The method for producing a 10°C liquid terpene resin by polymerization according to claim 1, characterized in that , wherein the amount of ethanol added is 0.5% to 3% by weight.

8. The method for producing a 10°C liquid terpene resin by polymerization according to claim 1, characterized in that , the weight ratio of turpentine to longifolene is 1:1 to 1:2, the weight ratio of turpentine to terpinene is 1:1 to 1:2, and the weight ratio of turpentine to isoprene is 1:0.1 to 1:0.

3.

9. The method for producing a 10°C liquid terpene resin by polymerization according to claim 1, characterized in that , wherein the amount of aluminum chloride added is 0.1% to 1.0% of the total mass of the polymerization reactants.