CN110922513B - Preparation method of emulsion type cumyl peroxyneodecanoate - Google Patents
Preparation method of emulsion type cumyl peroxyneodecanoate Download PDFInfo
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Abstract
The invention relates to the technical field of initiators, and particularly relates to a preparation method of emulsion type cumyl peroxyneodecanoate, which comprises three procedures of synthesis, purification and preparation, wherein cumyl hydroperoxide, alkali liquor and neodecanoyl chloride are used for reaction to obtain a water-in-oil emulsion, and then three treating agents are adopted to wash, stand and divide water to obtain the emulsion. The invention effectively solves the problems of reduced initiating activity and increased unit consumption of the dispersing agent caused by the fact that the cumene hydroperoxide remains in the emulsion type cumyl peroxyneodecanoate initiator, and simultaneously effectively reduces the content of a water phase, thereby reducing the content of water-soluble ions such as chloride ions, iron ions, sodium ions, potassium ions and the like, and finally preparing the emulsion type cumyl peroxyneodecanoate initiator with high purity and high activity.
Description
Technical Field
The invention relates to the technical field of initiators, and particularly relates to a preparation method of emulsion type cumyl peroxyneodecanoate.
Background
Cumyl peroxyneodecanoate (CNP) is colorless or light yellow flowable liquid and is mainly used as an initiator for PVC polymerization. The higher the activity of the initiator is, the lower the polymerization reaction temperature is, the suitable polymerization reaction temperature range of the cumyl peroxyneodecanoate is 40-60 ℃, and the content of the cumyl peroxyneodecanoate can be kept unchanged after the cumyl peroxyneodecanoate is stored for a long time below-15 ℃.
With the rapid development of the domestic polymer synthesis industry, the varieties and the demand of the initiator for polymer synthesis are rapidly improved. The emulsion type cumyl peroxyneodecanoate serving as the high-efficiency initiator for synthesizing the high polymer has the advantages of low dosage of the solvent type initiator, high initiation efficiency, uniform heat release of polymerization reaction and convenient control in the polymerization process of the high polymer compared with the solvent type initiator, particularly realizes green and environment-friendly effect after water is used as a solvent, effectively avoids the harm of flammable solvent to human bodies in the production and use processes, and has excellent performance of the obtained product, thereby being the initiator for synthesizing the high polymer with safety, environment protection, high efficiency and stable product quality.
With the rapid development of the domestic PVC industry, the variety and the demand of the initiator for PVC production are rapidly improved, and particularly the initiator is high in activity and free of hybridization and has high quality. The cumyl peroxyneodecanoate (CNP) is used as a high-efficiency initiator for PVC production, is usually compounded with di (2-ethylhexyl) peroxydicarbonate (EHP) for use, and has the advantages of small dosage, high initiation efficiency, uniform heat release of polymerization reaction, convenience in control and the like in the production process of PVC.
Chinese patent CN102584665A discloses a preparation method of solvent type cumyl peroxyneodecanoate with mass fraction of 75%, belonging to the field of preparation methods of initiators for high polymer synthesis, and the preparation method comprises the following steps: adding cumene hydroperoxide into an alkaline solution; dripping neodecanoyl chloride into the obtained solution; after the new decanoyl chloride is dripped; stopping stirring and standing for 20-40 minutes after the reaction is finished, separating mother liquor, and washing a reaction product until the pH value is 5-7; adding alkane solvent into the obtained reaction product, and stirring for 1 hour at the temperature of 0 ℃; to obtain the solvent type cumyl peroxyneodecanoate. The preparation method provided by the patent simplifies the process flow, overcomes the complex requirements on reaction equipment, enables the reaction to be carried out in a mild and safe environment, greatly improves the product quality and yield, and can reach the yield of more than 95%. The quality level of the product can reach the same level as that of the similar products abroad.
Chinese patent application CN102532351A discloses a preparation method of emulsion type cumyl peroxyneodecanoate with mass fraction of 50%, belonging to the field of preparation of initiators for high polymer synthesis. The preparation method comprises the following steps: adding cumene hydroperoxide into an alkaline solution; dripping neodecanoyl chloride into the obtained solution; after the new decanoyl chloride is dripped, stirring again; stopping stirring after the reaction is finished, and separating mother liquor; uniformly mixing deionized water, an antifreezing agent, an emulsifier and a dispersant; mixing the obtained reaction product with the obtained water phase solution, and stirring at 0 ℃ for emulsion synthesis; cooling to obtain the emulsion type cumyl peroxyneodecanoate with the concentration of 49-51 percent. The patent application simplifies the process flow, overcomes the complex requirements on reaction equipment, ensures that the reaction is carried out in a mild and safe environment, and the prepared product is convenient to store and transport and can be widely applied to industrial production. And the product quality and yield are greatly improved, and the yield can reach more than 95 percent.
The two patent applications have the advantages of convenient operation, short process time and suitability for industrial application, but the two patent applications do not specify a specific purification process in the preparation process of cumyl peroxyneodecanoate, and the activity and the purity of the product are greatly influenced. Cumene hydroperoxide has initiating activity, but the half-life period is greatly increased compared with cumyl peroxyneodecanoate, the initiating effect is basically not generated under the conventional polymerization condition, and the initiating activity of the product is greatly reduced.
If the aqueous phase of the cumyl peroxyneodecanoate stock solution intermediate is more, the water-soluble impurity ions such as chloride ions, iron ions and the like in the intermediate can cause the problems of reduced initiating efficiency of an initiator, increased unit consumption of a dispersing agent, poor quality of polyvinyl chloride resin and the like in the polymerization process of vinyl chloride. The invention provides a specific purification method, which ensures the activity and purity of the emulsion type cumyl peroxyneodecanoate in the polymerization process of vinyl chloride.
Therefore, it is necessary to develop a method for preparing emulsion-type cumyl peroxyneodecanoate which can solve the above-mentioned problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a high-purity high-activity emulsion type cumyl peroxyneodecanoate initiator, which effectively solves the problems of reduced initiation activity and increased unit consumption caused by the fact that cumyl hydroperoxide remains in the emulsion type cumyl peroxyneodecanoate initiator, and simultaneously effectively reduces the content of a water phase, further reduces the content of water-soluble ions such as chloride ions, iron ions, sodium ions, potassium ions and the like, and finally prepares the high-purity high-activity emulsion type cumyl peroxyneodecanoate initiator.
The invention is realized by the following technical scheme:
a preparation method of emulsion type cumyl peroxyneodecanoate comprises three working procedures of synthesis, purification and preparation, wherein:
synthesizing:
(1) adding cumene hydroperoxide into alkali liquor to obtain solution 1;
(2) adding neodecanoyl chloride into the solution 1, standing, and dividing water to obtain a water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion by using a treating agent A, a treating agent B and a treating agent C solution in sequence, standing after each washing, and dividing water to obtain the water-in-oil emulsion;
wherein the treating agent A is alkali liquor or a sulfur-containing reducing compound, the treating agent B is a pH buffering agent, and the treating agent C is polyethylene glycol.
Preferably, the alkali liquor is 25-35% of alkali liquor prepared from sodium hydroxide or/and potassium hydroxide.
Preferably, the dry basis mass ratio of the alkali liquor to the cumene hydroperoxide is 0.4-0.6: 1.
Preferably, the dry basis mass ratio of cumene hydroperoxide to neodecanoyl chloride is 0.8-1.0: 1.
More preferably, the synthesis procedure comprises the steps of:
(1) dropwise adding cumene hydroperoxide into an alkali liquor, wherein the dry basis mass ratio of the alkali liquor to the cumene hydroperoxide is 0.4-0.6:1, the dropwise adding time is 20-30min, and stirring for 15-30min to obtain a solution 1;
(2) dripping neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of the cumyl hydroperoxide to the neodecanoyl chloride is 0.8-1.0:1, the dripping time is 45-60min, the temperature is 25-35 ℃, the reaction time is 60-90min, standing is 30-45min, and water separation is carried out to obtain the water-in-oil emulsion.
More preferably, the purification process comprises the steps of:
(1) washing the water-in-oil emulsion by using a treating agent A solution, standing, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a treating agent B solution, standing, dividing water, and adjusting the pH value to 6.5-7.5 to obtain a solution 3;
(3) and washing the solution 3 with a solution of a treating agent C, standing, and carrying out water diversion to obtain a solution 4.
More preferably, the mass ratio of the dry basis of the treating agent A to the water-in-oil emulsion is 0.06-0.1: 1.
More preferably, the mass fraction of the treating agent a solution is 5 to 25%.
More preferably, the treating agent a is at least one of sodium hydroxide, potassium hydroxide, sodium sulfite and sodium bisulfite.
More preferably, the mass ratio of the dry basis of the treating agent B to the solution 2 is 0.02-0.04: 1.
More preferably, the mass fraction of the treating agent B solution is 5-15%.
More preferably, the treating agent B is at least one of sodium bicarbonate and sodium carbonate.
More preferably, the mass ratio of the dry basis of the treating agent C to the solution 3 is 0.001-0.01: 1.
More preferably, the mass fraction of the treating agent C solution is 0.25 to 2.5%.
More preferably, the treating agent C is at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 and polyethylene glycol 800.
More preferably, the purification process comprises the steps of:
(1) washing the water-in-oil emulsion for 1-2 times by using a treating agent A solution, standing after washing each time, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a treating agent B solution, standing, dividing water, and adjusting the pH value to 6.5-7.5 to obtain a solution 3;
(3) and washing the solution with a treating agent C solution for 31-2 times, standing after each washing, and separating water to obtain a solution 4.
The treating agent A is used for removing unreacted cumene hydroperoxide; the treating agent B adjusts the pH value of the solution 2 to provide a neutral condition for washing the treating agent C; the treating agent C is used for removing the water phase in the water-in-oil emulsion.
More preferably, the formulation procedure comprises the steps of:
(1) mixing a dispersing agent, an emulsifying agent, an antifreezing agent and desalted water to obtain a homogenized liquid;
(2) and mixing the solution 4 with the homogenized solution, and emulsifying to obtain the emulsion.
More preferably, the mass ratio of the dispersing agent, the emulsifying agent, the antifreezing agent and the desalted water is 1:0.8-1.5:12-16: 30-37.
More preferably, the mass ratio of the solution 4 to the homogenization solution is 1: 1.05-1.15.
More preferably, the dispersant is at least one of polyvinyl alcohol with a degree of alcoholysis of 80% and polyvinyl alcohol with a degree of alcoholysis of 72%.
More preferably, the emulsifier is at least one of lacto-lark having HLB of 11 to 14.
More preferably, the anti-freezing agent is at least one of methanol, ethanol and isopropanol.
More preferably, the formulation procedure comprises the steps of:
(1) mixing a dispersing agent, an emulsifying agent, an antifreezing agent and desalted water according to the mass ratio of 1:0.8-1.5:12-16:30-37 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.05-1.15, stirring for 1-3h at the temperature of-5-0 ℃, transferring to an emulsification pump, and emulsifying for 1-3 times to obtain the emulsion.
More preferably, the preparation method of the emulsion type cumyl peroxyneodecanoate comprises the following steps:
synthesizing:
(1) dropwise adding cumene hydroperoxide into an alkali liquor, wherein the dry basis mass ratio of the alkali liquor to the cumene hydroperoxide is 0.4-0.6:1, the dropwise adding time is 20-30min, and stirring for 15-30min to obtain a solution 1;
(2) dripping neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of the cumyl hydroperoxide to the neodecanoyl chloride is 0.8-1.0:1, the dripping time is 45-60min, the temperature is 25-35 ℃, the reaction time is 60-90min, standing is 30-45min, and water is separated to obtain water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion for 1-2 times by using a treating agent A solution, standing after washing each time, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a treating agent B solution, standing, dividing water, and adjusting the pH value to 6.5-7.5 to obtain a solution 3;
(3) washing the solution with a treating agent C solution for 31-2 times, standing after each washing, and dividing water to obtain a solution 4;
preparation:
(1) mixing a dispersing agent, an emulsifying agent, an antifreezing agent and desalted water according to the mass ratio of 1:0.8-1.5:12-16:30-37 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.05-1.15, stirring for 1-3h at the temperature of-5-0 ℃, transferring to an emulsification pump, and emulsifying for 1-3 times to obtain the emulsion.
The concentration of the high-purity high-activity emulsion type cumyl peroxyneodecanoate initiator (CNP) prepared by the invention is 50-52%.
The invention has the beneficial effects that:
the emulsion type cumyl peroxyneodecanoate initiator prepared by the method provided by the invention can reduce the content of cumyl hydroperoxide remained in the emulsion type cumyl peroxyneodecanoate initiator to be below 0.1% through a purification process, thereby greatly improving the activity of the initiator. Meanwhile, the water phase content of the cumyl peroxyneodecanoate oil-in-water emulsion is reduced to be below 1.5 percent, the chloride ion content of the emulsion cumyl peroxyneodecanoate initiator is reduced to be below 0.025 percent, the alkali metal ion content is reduced to be below 0.02 percent, and the iron ion content is reduced to be below 1ppm, so that the high-purity high-activity emulsion cumyl peroxyneodecanoate initiator is prepared.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
A preparation method of emulsion type cumyl peroxyneodecanoate comprises the following steps:
synthesizing:
(1) dropwise adding 600kg of cumene hydroperoxide into 25% potassium hydroxide alkaline liquor, wherein the dry basis mass ratio of the alkaline liquor to the cumene hydroperoxide is 0.4:1, the dropwise adding time is 20min, and stirring for 15min after the dropwise adding is finished to obtain a solution 1;
(2) dropwise adding neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of cumene hydroperoxide to neodecanoyl chloride is 0.8:1, the dropwise adding time is 45min, reacting at 25 ℃ for 60min after the dropwise adding is finished, standing for 30min, and dividing water to obtain a water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion for 1 time by using a 5% sodium hydroxide solution, wherein the mass ratio of a dry basis of the sodium hydroxide to the water-in-oil emulsion is 0.06:1, standing after washing, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a 5% sodium bicarbonate solution, wherein the mass ratio of the dry basis of the sodium bicarbonate to the solution 2 is 0.02:1, standing, dividing water, and adjusting the pH value to 6.5 to obtain a solution 3;
(3) washing the solution for 31 times by using 0.25% polyethylene glycol 200 solution, wherein the mass ratio of the dry basis of the polyethylene glycol 200 to the solution 3 is 0.001:1, standing after washing, and dividing water to obtain a solution 4;
preparation:
(1) mixing polyvinyl alcohol with alcoholysis degree of 80%, lacto-chlorothalonil with HLB of 11, methanol and desalted water according to the mass ratio of 1:0.8:12:30 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.05, stirring for 1h at the temperature of-5 ℃, transferring into an emulsification pump, and emulsifying for 1 time to obtain the emulsion.
Example 2
A preparation method of emulsion type cumyl peroxyneodecanoate comprises the following steps:
synthesizing:
(1) dropwise adding 600kg of cumene hydroperoxide into 35% sodium hydroxide alkaline liquor, wherein the dry basis mass ratio of the alkaline liquor to the cumene hydroperoxide is 0.6:1, the dropwise adding time is 30min, and stirring for 20min after the dropwise adding is finished to obtain solution 1;
(2) dropwise adding neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of cumene hydroperoxide to neodecanoyl chloride is 1.0:1, the dropwise adding time is 60min, reacting at 35 ℃ for 90min after the dropwise adding is finished, standing for 45min, and dividing water to obtain a water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion for 2 times by using a 25% sodium sulfite solution, wherein the mass ratio of the dry basis of the sodium sulfite to the water-in-oil emulsion is 0.1:1, standing after each washing, and dividing water to obtain a solution 2;
(2) washing the solution 2 by 15% sodium carbonate solution, wherein the mass ratio of the dry basis of the sodium carbonate to the solution 2 is 0.04:1, standing, dividing water, and adjusting the pH value to 7.5 to obtain a solution 3;
(3) washing the solution with 2.5% polyethylene glycol 800 solution for 32 times, wherein the mass ratio of the dry basis of the polyethylene glycol 800 to the solution 3 is 0.01:1, standing after each washing, and dividing water to obtain a solution 4;
preparation:
(1) mixing polyvinyl alcohol with alcoholysis degree of 72%, lacto-chlorothalonil with HLB of 14, isopropanol and desalted water according to the mass ratio of 1:1.5:16:37 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.15, stirring for 3 hours at the temperature of-2 ℃, transferring into an emulsification pump, and emulsifying for 3 times to obtain the emulsion.
Example 3
A preparation method of emulsion type cumyl peroxyneodecanoate comprises the following steps:
synthesizing:
(1) dropwise adding 600kg of cumene hydroperoxide into 30% potassium hydroxide alkaline liquor, wherein the dry basis mass ratio of the alkaline liquor to the cumene hydroperoxide is 0.5:1, the dropwise adding time is 25min, and stirring for 30min after the dropwise adding is finished to obtain solution 1;
(2) dropwise adding neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of cumene hydroperoxide to neodecanoyl chloride is 0.9:1, the dropwise adding time is 50min, reacting at 30 ℃ for 75min after the dropwise adding is finished, standing for 36min, and dividing water to obtain a water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion for 2 times by using 15% sodium bisulfite solution, wherein the mass ratio of the dry basis of the sodium bisulfite to the water-in-oil emulsion is 0.08:1, standing after each washing, and dividing water to obtain solution 2;
(2) washing the solution 2 with a 10% sodium bicarbonate solution, wherein the mass ratio of the dry basis of the sodium bicarbonate to the solution 2 is 0.03:1, standing, dividing water, and adjusting the pH value to 7.0 to obtain a solution 3;
(3) washing the solution with 1.25% polyethylene glycol 600 solution for 32 times, wherein the mass ratio of the dry basis of the polyethylene glycol 600 to the solution 3 is 0.005:1, standing after each washing, and dividing water to obtain a solution 4;
preparation:
(1) mixing polyvinyl alcohol with alcoholysis degree of 80%, lacto-chlorothalonil with HLB of 12, absolute ethyl alcohol and desalted water according to the mass ratio of 1:1.2:14:33 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.1, stirring for 2h at 0 ℃, transferring to an emulsification pump, and emulsifying for 2 times to obtain the emulsion.
Comparative example 1
The only difference from example 3 is that no purification step is used, and the other conditions are the same, as follows:
synthesizing:
(1) dropwise adding 600kg of cumene hydroperoxide into 30% potassium hydroxide alkaline liquor, wherein the dry basis mass ratio of the alkaline liquor to the cumene hydroperoxide is 0.5:1, the dropwise adding time is 25min, and stirring for 30min after the dropwise adding is finished to obtain solution 1;
(2) dropwise adding neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of cumene hydroperoxide to neodecanoyl chloride is 0.9:1, the dropwise adding time is 50min, reacting at 30 ℃ for 75min after the dropwise adding is finished, standing for 36min, and dividing water to obtain a water-in-oil emulsion;
preparation:
(1) mixing polyvinyl alcohol with alcoholysis degree of 80%, lacto-chlorothalonil with HLB of 12, absolute ethyl alcohol and desalted water according to the mass ratio of 1:1.2:14:33 to obtain a homogenized liquid;
(2) mixing the water-in-oil emulsion and the homogenizing solution according to the mass ratio of 1:1.1, stirring for 2 hours at the temperature of 0 ℃, transferring to an emulsification pump, and emulsifying for 2 times to obtain the water-in-oil emulsion.
Comparative example 2
The difference from example 3 is only that the order of using the treating agents in the purification process is different, and the rest conditions are the same, specifically as follows:
(1) washing the water-in-oil emulsion for 2 times by using 15% sodium bisulfite solution, wherein the mass ratio of the dry basis of the sodium bisulfite to the water-in-oil emulsion is 0.08:1, standing after each washing, and dividing water to obtain solution 2;
(2) washing the solution for 22 times by using 1.25% polyethylene glycol 600 solution, wherein the mass ratio of the dry basis of the polyethylene glycol 600 to the solution 2 is 0.005:1, standing after each washing, and dividing water to obtain a solution 3;
(3) and (3) washing the solution 3 by using a 10% sodium bicarbonate solution, wherein the mass ratio of the dry basis of the sodium bicarbonate to the solution 3 is 0.03:1, standing, dividing water, and adjusting the pH value to 7.0 to obtain a solution 4.
Test example 1
Examples 1-3 and comparative examples 1-2 comparison of emulsion-type cumyl peroxyneodecanoate in appearance, active oxygen content of cumyl peroxyneodecanoate, CNP reduced value, cumyl hydroperoxide content, water-soluble ion content, time to initiate PVC polymerization. The results are shown in Table 1.
The specific method for initiating PVC polymerization is as follows:
1) at 105m3Steam is introduced into the polymerization kettle and a kettle top condenser, circulating water is introduced into a jacket, 12kg of Italian yellow anti-sticking agent (produced by Vast Bokejiu Co., Ltd. of Ordos) is added, the anti-sticking agent is atomized and adhered to the inner wall of the polymerization kettle and the lower part of the kettle top condenser, and a high-pressure water pump is started to flush until the discharged water is clean.
2) At 105m3Adding 0.7kg of sodium bicarbonate in a polymerization kettle in a dry basis amount for buffering the change of the pH value in the polymerization process; adding deionized water into the polymerization kettle, and adding deionized water when addingThe amount reaches 3m3Then, monomer addition and water injection are carried out synchronously, deionized water is injected for 41t, and 39 tons of monomer are added.
3) After the monomer and the deionized water are mixed for 180s, 7kg of polyvinyl alcohol dispersant dry base with alcoholysis degree of 72%, 28kg of polyvinyl alcohol dispersant dry base with alcoholysis degree of 80% and 8kg of polyvinyl alcohol dispersant with alcoholysis degree of 50% and mass concentration of 40% are respectively injected, the mixing is delayed for 180s, 20kg of initiator dry base (15 kg of EHP dry base and 5kg of CNP dry base) is added, the reaction temperature in the kettle is controlled to be 56.5 ℃ in the whole process, the reaction water injection rate is 4.6t/h, when the pressure in the kettle is reduced by 0.08Mpa, 18.5kg of HB-101 terminator (produced by Hanboke technology Limited company in Orchikun city, Ore) is added into the kettle to terminate the reaction, and the SG-5 type polyvinyl chloride resin is obtained.
4) And (3) carrying out steam stripping, drying, sampling detection on the product, and packaging and forming to obtain the product.
TABLE 1 comparison of Properties of isopropyl peroxyneodecanoate emulsion type cumene hydroperoxide esters in examples 1-3 and comparative examples 1-2
The following conclusions can be drawn by comparing examples 1 to 3 with comparative examples 1 to 2:
1. comparison of examples 1-3 yields: the emulsion type CNP initiator obtained by the invention has excellent performances in the aspects of purity, impurity content and initiation effect, and the performance of the initiator is improved and the impurity content is reduced along with the increase of the washing times of the treating agent A and the treating agent C;
2. comparison of comparative example 1 with example 3 gives: the emulsion type CNP initiator obtained without purification step has greatly reduced purity, and reduced initiating performance due to residual cumene hydroperoxide;
3. comparison of comparative example 2 with example 3 gives: the treatment agent C and the treatment agent B are adjusted in sequence, so that the water removal effect of the CNP oily product is poor, the purity of the solvent-type CNP initiator is reduced to a certain degree, and the sequence of the treatment agent A is unchanged, so that the initiation performance is not greatly influenced.
The technical scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (9)
1. The preparation method of the emulsion type cumyl peroxyneodecanoate is characterized by comprising three working procedures of synthesis, purification and preparation, wherein:
synthesizing:
(1) adding cumene hydroperoxide into alkali liquor to obtain solution 1;
(2) adding neodecanoyl chloride into the solution 1, standing, and dividing water to obtain a water-in-oil emulsion;
and (3) purification:
(1) washing the water-in-oil emulsion by using a treating agent A solution, standing, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a treating agent B solution, standing, dividing water, and adjusting the pH value to 6.5-7.5 to obtain a solution 3;
(3) washing the solution 3 with a solution of a treating agent C, standing, and carrying out water diversion to obtain a solution 4;
wherein the treating agent A is alkali liquor or a sulfur-containing reducing compound, the treating agent B is a pH buffering agent, and the treating agent C is polyethylene glycol.
2. The method according to claim 1, wherein the dry basis mass ratio of the alkali solution to cumene hydroperoxide in the synthesis process is 0.4-0.6: 1; the dry basis mass ratio of the cumene hydroperoxide to the neodecanoyl chloride is 0.8-1.0: 1.
3. The method of claim 2, wherein the synthesis process comprises the steps of:
(1) dropwise adding cumene hydroperoxide into an alkali liquor, wherein the dry basis mass ratio of the alkali liquor to the cumene hydroperoxide is 0.4-0.6:1, the dropwise adding time is 20-30min, and stirring for 15-30min to obtain a solution 1;
(2) dripping neodecanoyl chloride into the solution 1, wherein the dry basis mass ratio of the cumyl hydroperoxide to the neodecanoyl chloride is 0.8-1.0:1, the dripping time is 45-60min, the temperature is 25-35 ℃, the reaction time is 60-90min, standing is 30-45min, and water separation is carried out to obtain the water-in-oil emulsion.
4. The method according to claim 1, wherein the treating agent A has a mass ratio of dry basis to water-in-oil emulsion of 0.06-0.1: 1; the mass ratio of the dry basis of the treating agent B to the solution 2 is 0.02-0.04: 1; the mass ratio of the dry basis of the treating agent C to the solution 3 is 0.001-0.01: 1.
5. The production method according to claim 1, wherein the treating agent a is at least one of sodium hydroxide, potassium hydroxide, sodium sulfite, and sodium bisulfite; the treating agent B is at least one of sodium bicarbonate and sodium carbonate; the treating agent C is at least one of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 and polyethylene glycol 800.
6. The method according to claim 1, wherein the purification process comprises the steps of:
(1) washing the water-in-oil emulsion for 1-2 times by using a treating agent A solution, standing after washing each time, and dividing water to obtain a solution 2;
(2) washing the solution 2 with a treating agent B solution, standing, dividing water, and adjusting the pH value to 6.5-7.5 to obtain a solution 3;
(3) and washing the solution with a treating agent C solution for 31-2 times, standing after each washing, and separating water to obtain a solution 4.
7. The method of claim 1, wherein the formulating step comprises the steps of:
(1) mixing a dispersing agent, an emulsifying agent, an antifreezing agent and desalted water to obtain a homogenized liquid;
(2) and mixing the solution 4 with the homogenized solution, and emulsifying to obtain the emulsion.
8. The preparation method according to claim 7, wherein the mass ratio of the dispersing agent, the emulsifying agent, the antifreezing agent and the desalted water is 1:0.8-1.5:12-16: 30-37; the mass ratio of the solution 4 to the homogenizing liquid is 1: 1.05-1.15; the dispersing agent is at least one of polyvinyl alcohol with alcoholysis degree of 80% and polyvinyl alcohol with alcoholysis degree of 72%; the emulsifier is at least one of lacteal with HLB of 11-14; the antifreeze is at least one of methanol, ethanol and isopropanol.
9. The method of claim 7, wherein the formulating step comprises the steps of:
(1) mixing a dispersing agent, an emulsifying agent, an antifreezing agent and desalted water according to the mass ratio of 1:0.8-1.5:12-16:30-37 to obtain a homogenized liquid;
(2) mixing the solution 4 and the homogenized solution according to the mass ratio of 1:1.05-1.15, stirring for 1-3h at-5-0 ℃, transferring into an emulsification pump, and emulsifying for 1-3 times to obtain the product.
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