A preparation method of disproportionated rosin potassium soap with a solid content of 80%

Abstract

The invention belongs to the technical field of rosin deep processing, and provides a method for preparing disproportionated rosin potassium soap with a solid content of 80%, comprising the following steps: taking raw materials of disproportionated rosin, potassium hydroxide and water and putting them into a reactor, replacing the air in the reactor with an inert gas and sealing it, and performing a saponification reaction for 5-30 minutes under a certain pressure to obtain a disproportionated rosin potassium soap with a solid content of 80%. The disproportionated rosin potassium soap with a solid content of 80% prepared by the present invention has been significantly improved in color and properties, has a light color, and has no crystallization, gel or stratification phenomenon; in addition, the reaction process is short in time, which can greatly improve production efficiency.

Description

Technical Field

[0001] The invention belongs to the field of rosin deep processing and relates to a method for preparing disproportionated rosin potassium soap with a solid content of 80%. Background Art

[0002] Disproportionated rosin potassium soap is a variety with a larger output among rosin deep-processing products. It is a widely used chemical raw material. It can be used as an emulsifier in the synthesis of artificial rubber and plastics; as a tackifier, it can be used in adhesives to increase viscosity, and improve heat resistance, wear resistance and tear resistance; as an air-entraining agent, it can be used in concrete construction.

[0003] There are three specifications of disproportionate rosin potassium soap sold on the market: disproportionate rosin potassium soap aqueous solution with a solid content of 25%, disproportionate rosin potassium soap aqueous solution with a solid content of 50%, and disproportionate rosin potassium soap aqueous solution with a solid content of 80%. The production of disproportionate rosin potassium soap aqueous solution is mainly a saponification reaction between molten disproportionate rosin and potassium hydroxide alkali solution. The main component of disproportionate rosin is dehydroabietic acid, which accounts for more than 45% of the disproportionate rosin components. Therefore, disproportionate rosin has a strong tendency to crystallize. The preparation of disproportionate rosin potassium soap aqueous solution with a solid content of 50% or less is usually carried out at normal pressure and a reaction temperature below 100°C, which is prone to crystallization, gelation or stratification. The preparation of disproportionate rosin potassium soap aqueous solution with a solid content of 80% usually requires a reaction temperature of more than 100°C. Due to the high reaction temperature, the obtained product has a darker color. If the reaction temperature is lowered, the reaction will also be incomplete, causing the product to have crystallization, gelation or stratification.

[0004] Most disproportionate rosin potassium soaps with a solid content of 80% are darker in color and fail to meet the market demand standard, thereby reducing their product grade. For the study of disproportionate rosin potassium soaps with a light solid content of 80%, Chinese patent application CN103451049A discloses a method for directly preparing disproportionate rosin potassium soaps with a solid content of 80% from solid disproportionate rosin, wherein 95-105 parts of solid disproportionate rosin and 55-80 parts of 20-25% concentration of potassium hydroxide solution are added to a saponification reactor, heated to 80-100°C while stirring evenly for 1-2 hours of saponification reaction, and after the saponification reaction stops, cooled to 70-80°C for discharging, and the finished product is lighter in color, but the saponification reaction time is long and the production efficiency is low. In addition, saponification time is also an important factor affecting the color of disproportionate rosin potassium soap aqueous solution. The longer the saponification time, the darker the color of the disproportionate rosin potassium soap aqueous solution, and the shorter the saponification time, the lighter the color of the disproportionate rosin potassium soap aqueous solution.

[0005] In addition, adding chemical additives such as decolorizing agents is also a widely used method. Chinese patent application CN103435473A discloses a preparation process of disproportionated rosin potassium soap with a solid content of 80% using peroxide K as a decolorizing agent, which improves the appearance and the grade of the product, but peroxide K has strong oxidizing properties and is flammable and explosive.

[0006] Therefore, a preparation method is provided, which ensures that the saponification reaction is completed in a short time without adding any decolorizing agent, which is a prerequisite for preparing a disproportionate rosin potassium soap aqueous solution with a solid content of 80% that is light in color and not easy to crystallize, gel or delaminate. Summary of the invention

[0007] The invention aims at the problems existing in the prior art and provides a method for preparing disproportionated rosin potassium soap with a solid content of 80%, so as to solve the technical problems that the disproportionated rosin potassium soap aqueous solution prepared in the prior art has a dark color and is prone to crystallization, gel or stratification.

[0008] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0009] (1) Put disproportionated rosin, potassium hydroxide and water into a reaction kettle;

[0010] (2) The air in the kettle is replaced with an inert gas and then sealed to carry out saponification reaction under a certain pressure;

[0011] (3) After the reaction is completed, the temperature is lowered and the material is discharged to obtain a disproportionate rosin potassium soap aqueous solution with a solid content of 80%.

[0012] Preferably, the raw materials include the following components in parts by weight: 80-120 parts of disproportionated rosin, 10-20 parts of potassium hydroxide, and 20-35 parts of water.

[0013] More preferably, the raw materials include the following components in parts by weight: 90-110 parts of disproportionated rosin, 14-16 parts of potassium hydroxide, and 25-30 parts of water.

[0014] Preferably, the replacement is performed with an inert gas for 1 to 4 times.

[0015] More preferably, the replacement is performed 4 times with an inert gas.

[0016] Preferably, the inert gas is at least one of nitrogen and carbon dioxide.

[0017] More preferably, nitrogen is used as the inert gas.

[0018] Preferably, the reactor adopts a pressure reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, wherein the pressure in the reactor is controlled by pressing an inert atmosphere through a gas conduit, that is, when the pressure of the reactor is lower than the specified pressure, an inert gas can be pressed into the reactor through the gas introduction pipe to ensure that the pressure is not lower than the specified pressure. When the pressure of the reactor is higher than the specified pressure, there is no need to pressurize inert gas to increase the pressure, and the steam pressure in the reactor can be maintained.

[0019] Preferably, the pressure in the reactor is ≥0.5Mpa.

[0020] More preferably, the pressure in the reactor is controlled at 0.5-1.15 MPa.

[0021] Preferably, the saponification reaction temperature is 100-185° C., and the reaction time is 5-30 min.

[0022] More preferably, the saponification reaction time is 5-20 min.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The sealing reaction prevents water evaporation and ensures the stability of solid content.

[0025] 2. By replacing the air in the reactor with inert gas and reacting under sealed conditions, the color darkening caused by oxidation of disproportionated rosin can be effectively avoided.

[0026] 3. Under the reaction conditions of 100-185℃ and pressure ≥0.5Mpa, the disproportionated rosin can be crystallized and the gel dissolved without stratification, and the saponification is more complete.

[0027] 4. The saponification reaction time is short, which ensures that the color change of the disproportionated rosin potassium soap aqueous solution is very small, and at the same time greatly improves the production efficiency. DETAILED DESCRIPTION

[0028] It is worth noting that the raw materials used in the present invention are all common commercially available products, and their sources are not specifically limited.

[0029] The following sources of raw materials are provided for illustrative purposes:

[0030] The selected disproportionated rosin had the following indicators: softening point 78° C., acid value 160 mg / g, color (Ghana color number) 3, purchased from Pu’er Kemao Linhua Co., Ltd.; potassium hydroxide (analytical grade) was purchased from Guangzhou Chemical Reagent Factory.

[0031] Example 1

[0032] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0033] Example 2

[0034] Compared with Example 1, the difference is that the reaction temperature and time are different;

[0035] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 120°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 0.5Mpa, the reaction time is 14min, and then cool to 50°C to release the pressure and discharge the material.

[0036] Example 3

[0037] Compared with Example 1, the difference is that the reaction temperature and time are different;

[0038] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 100°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 0.5Mpa, the reaction time is 20min, and then cool to 50°C to release the pressure and discharge the material.

[0039] Example 4

[0040] Compared with Example 1, the difference is that the reaction temperature, time and pressure are different;

[0041] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas inlet pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 155°C, the reactor pressure reaches 0.56Mpa, the reaction time is 10min, and then cool to 50°C to release the pressure and discharge the material.

[0042] Example 5

[0043] Compared with Example 1, the difference is that the reaction temperature, time and pressure are different;

[0044] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas inlet pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 175°C, the reactor pressure reaches 0.89Mpa, the reaction time is 7min, and then cool to 50°C to release the pressure and discharge the material.

[0045] Example 6

[0046] Compared with Example 1, the difference is that the reaction temperature, time and pressure are different;

[0047] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas inlet pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 185°C, the reactor pressure reaches 1.15Mpa, the reaction time is 5min, and then cool to 50°C to release the pressure and discharge the material.

[0048] Example 7

[0049] Compared with Example 1, the difference is that the number of replacements is changed to 1;

[0050] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace once with nitrogen, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0051] Embodiment 8:

[0052] Compared with Example 1, the difference is that the raw material ratio is different;

[0053] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 20g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 90g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0054] Embodiment 9:

[0055] Compared with Example 1, the difference is that the raw material ratio is different;

[0056] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 20g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 80g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0057] Embodiment 10:

[0058] Compared with Example 1, the difference is that the raw material ratio is different;

[0059] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 25g of deionized water and 16g of potassium hydroxide, stir evenly, add 110g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0060] Embodiment 11:

[0061] Compared with Example 1, the difference is that the raw material ratio is different;

[0062] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 25g of deionized water and 16g of potassium hydroxide, stir evenly, add 120g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0063] Comparative Example 1

[0064] Compared with Example 1, the difference is that the pressure of the reactor is changed to 1.2Mpa;

[0065] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 1.2Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0066] Comparative Example 2

[0067] Compared with Example 1, the difference is that the reaction time is changed from 12 min to 40 min;

[0068] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 0.5Mpa, the reaction time is 40min, and then cool to 50°C to release the pressure and discharge the material.

[0069] Comparative Example 3

[0070] Compared with Example 1, the difference is that the nitrogen replacement is changed from 4 times to 0 times;

[0071] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, close the temperature and heat it, the reaction temperature is controlled at 140°C, and nitrogen is pressed into the reactor through the gas introduction pipe to make the pressure reach 0.5Mpa. The reaction time is 12min, and then the temperature is reduced to 50°C to release the pressure and discharge the material.

[0072] Comparative Example 4

[0073] Compared with Example 1, the difference is that the pressure of the reactor is changed to 0.36Mpa;

[0074] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, 28g of deionized water and 14.7g of potassium hydroxide were added, stirred evenly, 100g of disproportionate rosin was added, replaced with nitrogen 4 times, and the temperature was raised in a sealed manner. The reaction temperature was controlled at 140°C, and nitrogen was pressed into the reactor through the gas introduction pipe to make the pressure of the reactor reach 0.36Mpa. The reaction time was 12min, and then the temperature was reduced to 50°C, the pressure was released and the material was discharged to obtain a disproportionate rosin potassium soap aqueous solution.

[0075] Comparative Example 5

[0076] Compared with Example 11, the difference is that 125g of disproportionated rosin is added instead of 120g of disproportionated rosin;

[0077] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 25g of deionized water and 16g of potassium hydroxide, stir evenly, add 125g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 140°C, pressurize nitrogen through the gas introduction pipe to make the pressure of the autoclave reach 0.5Mpa, the reaction time is 12min, and then cool to 50°C to release the pressure and discharge the material.

[0078] Comparative Example 6

[0079] Compared with Example 5, the difference is that the reaction temperature is controlled at 90°C;

[0080] In a reactor equipped with a stirring device, a thermometer, a pressure gauge and a gas introduction pipe, add 28g of deionized water and 14.7g of potassium hydroxide, stir evenly, add 100g of disproportionated rosin, replace with nitrogen 4 times, close the temperature, control the reaction temperature at 90°C, pressurize nitrogen through the gas introduction pipe to make the reactor pressure reach 0.89Mpa, the reaction time is 7min, and then cool to 50°C to release the pressure and discharge the material.

[0081] The various indicators of the disproportionate rosin potassium soap aqueous solution prepared under different conditions are measured according to LY / T 1358-2014, and the test results are shown in Table 1. It can be seen from Table 1 that the technical indicators of the disproportionate rosin potassium soap aqueous solution with a solid content of 80% prepared by the technical scheme of the present invention are as follows: solid content 80.1%, Ghana color number ≤2, pH value 9.20-10.20, potassium abietic acid content 0%, potassium dehydroabietic acid content 49.51%, unsaponifiable matter content 6.3%, chloride (in terms of KCl) content 0%, no crystallization, gel and stratification phenomenon.

[0082] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

[0083]

Claims

1. A method for preparing disproportionated rosin potassium soap with a solid content of 80%, characterized in that: The following steps are involved: Take the raw materials of disproportionated rosin, potassium hydroxide and water and put them into a reaction kettle. Replace the air in the kettle with an inert gas and then seal it. Perform saponification reaction at 0.5-1.15Mpa and 100-185℃ for 5-30min to obtain the product.

2. The preparation method according to claim 1, characterized in that: The raw materials include the following components in parts by weight: 80-120 parts of disproportionated rosin, 10-20 parts of potassium hydroxide and 20-35 parts of water.

3. The preparation method according to claim 1, characterized in that: The inert gas is at least one of nitrogen and carbon dioxide.

4. The preparation method according to claim 3, characterized in that: The inert gas is nitrogen.

5. The preparation method according to claim 1, characterized in that: The reactor is equipped with a gas introduction pipe, through which gas is pressed into the reactor to control the pressure inside the reactor.

6. The preparation method according to claim 1, characterized in that: The number of inert gas replacements is 1-4 times.

7. Disproportionated rosin potassium soap with a solid content of 80% prepared according to the preparation method described in any one of claims 1 to 6.

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