CN113980157A - Low-water-content emulsion type tert-amyl peroxypivalate and preparation method thereof - Google Patents
Low-water-content emulsion type tert-amyl peroxypivalate and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title claims abstract description 52
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 31
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 15
- 239000007798 antifreeze agent Substances 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 230000002528 anti-freeze Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229920001400 block copolymer Polymers 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000010008 shearing Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 6
- 229950010765 pivalate Drugs 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 5
- 239000001593 sorbitan monooleate Substances 0.000 claims description 5
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- -1 peroxide pivalate Chemical class 0.000 claims 6
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 238000003786 synthesis reaction Methods 0.000 abstract description 24
- 239000012071 phase Substances 0.000 description 64
- 239000000047 product Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- KCHNMIKAMRQBHD-UHFFFAOYSA-N 1-hydroperoxypentane Chemical compound CCCCCOO KCHNMIKAMRQBHD-UHFFFAOYSA-N 0.000 description 10
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTGLJCSUKOLTEM-UHFFFAOYSA-N 2-ethylhexyl carbonochloridate Chemical compound CCCCC(CC)COC(Cl)=O RTGLJCSUKOLTEM-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
- C07C407/006—Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a low-water-content emulsion type tert-amyl peroxypivalate and a preparation method thereof, belonging to the technical field of initiator preparation. The initiator comprises the following components in percentage by mass: oil phase: 40% -60%; emulsifier: 0.5 to 2 percent; dispersing agent: 2% -5%; an antifreeze agent: 10-30% and the balance of deionized water; wherein the oil phase comprises tert-amyl hydroperoxide, tert-valeryl chloride, liquid caustic soda, polyoxyethylene polyoxypropylene segmented copolymer and the balance of deionized water. The preparation process comprises two steps of synthesis and configuration, wherein in the first step, the oil phase is subjected to synthesis reaction to prepare the oil phase; and the second step is mixing the oil phase obtained in the first step with emulsifier, dispersant and antifreeze deionized water, and homogenizing and emulsifying to obtain a stable emulsion product. The emulsion product which can be stabilized by adopting the technical scheme of the invention has low water content after the oil phase is synthesized, thereby further improving the stability of the emulsion, and the stability can reach more than 24 months.
Description
Technical Field
The invention belongs to the technical field of initiator preparation, and particularly relates to low-water-content emulsion type tert-amyl peroxypivalate and a preparation method thereof.
Background
At present, organic peroxy liquid initiators are mainly divided into solvent type initiators and emulsion type initiators, which are respectively applied according to different application polymerization types, the solvent type initiators are generally applied to bulk polymerization, no dispersion requirement is required, the polymerization efficiency is high, the emulsion type initiators are often applied to suspension polymerization, the particle size of the dispersed phase of the initiators in emulsion type products is small, and the initiation efficiency and the stability of the initiation polymerization process are good.
However, the oil phase of the conventional organic peroxy initiator product has high water content after synthesis, usually the water content can reach 5-15%, and the oil phase with high water content can cause a large amount of impurities in the water phase to remain and be brought into the initiator emulsion, so that the stability of the initiator finished emulsion is influenced, and the initiation efficiency of the initiator is greatly reduced. Aiming at the problems, a common solution in the industry is to add an oil phase drying section in the process and dry the product by adopting anhydrous magnesium chloride, so that the water content of the dried product can be reduced to below 1%, the effect is good, but the process equipment is relatively complex, the drying agent cannot be reused after drying, most importantly, the oil phase loss is high, and the overall production cost is greatly increased.
Through search, the Chinese patent application numbers are: 201110442115.2, filing date: in 2011, 26 months 11, the invention and creation name is: a preparation method of emulsion type bis (2-ethylhexyl) peroxydicarbonate with the mass fraction of 50 percent. The initiator disclosed in the application is prepared by mixing and reacting an alkaline solution and an oxidant; dropwise adding 2-ethylhexyl chloroformate to the obtained solution; after the chloroformic acid 2-ethylhexyl ester is dripped, stirring; separating mother liquor after the reaction is finished; uniformly mixing deionized water, an antifreezing agent, an emulsifier and a dispersant to prepare an aqueous phase solution; mixing the obtained reaction product with the obtained aqueous phase solution; cooling to obtain the emulsion type bis (2-ethylhexyl) peroxydicarbonate. The prepared emulsion type bis (2-ethylhexyl) peroxydicarbonate overcomes the defects of high energy consumption, environmental pollution, easy harm to human bodies and the like of solvent type initiators. However, the stability of the obtained emulsion type bis (2-ethylhexyl) peroxydicarbonate initiator in the storage process still needs to be further improved.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defect that the storage stability of the traditional emulsion type organic peroxide initiator is relatively poor, and provides a low-water-content emulsion type tert-amyl peroxypivalate and a preparation method thereof. By adopting the technical scheme of the invention, the problems can be effectively solved, a stable emulsion product is obtained, the water content of the synthesized oil phase is low, the stability of the emulsion can be further improved, and the stability can reach more than 24 months.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a low-water-content emulsion type tert-amyl peroxypivalate which comprises the following components in percentage by mass: oil phase: 40% -60%; emulsifier: 0.5 to 2 percent; dispersing agent: 2% -5%; an antifreeze agent: 10-30% and the balance of deionized water; wherein the oil phase comprises tert-amyl hydroperoxide, tert-valeryl chloride, liquid caustic soda, polyoxyethylene polyoxypropylene segmented copolymer and the balance of deionized water.
Furthermore, the molar ratio of the liquid alkali, the tert-amyl hydroperoxide and the tert-amyl chloride is (1.2-1.4): (1.0-1.1): 1.0; the addition amount of the polyoxyethylene polyoxypropylene block copolymer is 200ppm-500ppm (based on the added water in the formula).
Furthermore, the emulsifier is at least one of nonylphenol polyoxyethylene ether OP-10, fatty alcohol polyoxyethylene ether lacto-bailing and sorbitan monooleate S-80.
Further, the emulsifier is preferably nonylphenol polyoxyethylene ether OP-10.
Furthermore, the dispersant is polyvinyl alcohol PVA 4040, and the antifreeze agent is at least one of methanol, ethanol and ethylene glycol.
Further, the antifreeze agent is preferably methanol.
The invention relates to a preparation method of the low-water-content emulsion type tert-amyl peroxypivalate, which comprises the following two steps:
firstly, synthesizing an oil phase, namely firstly adding tert-amyl hydroperoxide, tert-valeryl chloride and liquid caustic soda into a system added with a polyoxyethylene polyoxypropylene block copolymer for a synthetic reaction, and washing and purifying after the reaction is finished to obtain the oil phase;
and step two, emulsion preparation, namely mixing the oil phase synthesized in the step one with an emulsifier, a dispersant, an antifreeze and deionized water, stirring, shearing and emulsifying.
Furthermore, in the first step, firstly, mixing the liquid caustic soda, the deionized water and the polyoxyethylene polyoxypropylene block copolymer, and stirring; then, dropwise adding tert-amyl hydroperoxide and stirring; finally, pivaloyl chloride is added dropwise and stirred.
Furthermore, in the second step, the emulsifier, the dispersant, the antifreeze and the deionized water are sequentially added into the reaction kettle for mixing, the temperature is controlled below 0 ℃, and the mixture is stirred for 10-15 min to serve as auxiliary materials for later use; then, putting the auxiliary materials into an oil phase emulsifying kettle, and stirring for 10-15 min; finally, shearing and emulsifying for 25-35 min.
Furthermore, in the first step, when the liquid alkali, the deionized water and the polyoxyethylene polyoxypropylene block copolymer are mixed, the temperature is controlled to be below 30 ℃, the temperature for dripping the tert-amyl hydroperoxide is below 30 ℃, the dripping time is 3min, stirring is carried out after the dripping is finished, and the stirring time is 4-6 min; the temperature of the pivaloyl chloride is below 40 ℃, the dripping time is 10min, and the stirring time after dripping is controlled to be 80-85 min.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the low-water-content emulsion type tert-amyl peroxypivalate, the oil phase with the water content of below 1% can be synthesized by optimally designing the component composition and the proportion thereof, particularly optimizing the component and the proportion of the oil phase, so that the influence on the stability of the initiator emulsion is effectively avoided, and the initiation efficiency of the initiator is ensured. Meanwhile, the invention also controls the proportion of the oil phase, the emulsifier, the dispersant and other auxiliary agents, and utilizes the synergistic compounding among the components, thereby effectively improving the storage stability of the synthesized emulsion type peroxypivalate pivalate, and the storage time can reach more than 24 months.
(2) In the oil phase synthesis process of the low-water-content emulsion type tert-amyl peroxypivalate, the polyoxyethylene polyoxypropylene block copolymer F127 is added into the system, and the addition amount of the polyoxyethylene polyoxypropylene block copolymer F127 is controlled, so that the water content of the synthesized oil phase system can be effectively reduced, the stability of the emulsion of the product is improved, and the components of the low-water-content emulsion type tert-amyl peroxypivalate can also effectively ensure that the yield of the oil phase is over 95 percent and the content of the oil phase is over 99 percent.
(3) According to the low-water-content emulsion-type tert-amyl peroxypivalate, due to the addition of the antifreeze agent (preferably methanol), on one hand, the emulsion-type tert-amyl peroxypivalate has good antifreeze performance and excellent solubility, can be well dissolved with other components, enables the performances of the components not to be influenced mutually, has good effect, and on the other hand, the antifreeze agent does not cause any side reaction in the polymerization reaction process and can be well compatible with a polymerization system. In addition, the invention also adopts specific emulsifier and dispersant for compounding, and designs the specific type of the emulsifier, and the emulsifier can be well compatible with the dispersant, thereby being beneficial to further ensuring the use effect of the emulsifier.
(4) The preparation method of the low-water-content emulsion-type tert-amyl peroxypivalate, disclosed by the invention, has the advantages that the types, the proportions and the specific process parameters of the components are optimized, so that the components are mutually cooperated and matched, the stability of the obtained emulsion-type initiator can be effectively improved, the initiation efficiency in the polymerization process is improved, the raw material residual value (below 0.1 percent) in an emulsion finished product is reduced, the initiator induced decomposition effect caused by the tert-amyl hydroperoxide residue can be greatly reduced when the polymerization is initiated, the initiation efficiency is further improved, and the initiator addition amount and the polymerization reaction time are effectively reduced.
(5) The preparation method of the low-water-content emulsion type tert-amyl peroxypivalate comprises the steps of synthesizing an oil phase and preparing an emulsion, specifically, adopting the formula disclosed by the invention to synthesize the oil phase in the first step, mixing the oil phase with a certain amount of auxiliary materials such as an emulsifier, a dispersing agent and the like in the second step, and then homogenizing and emulsifying to obtain a stable emulsion product.
Drawings
FIG. 1 shows the results of performance test indexes of products obtained in examples of the present invention and comparative examples.
Detailed Description
The invention relates to a low-water-content emulsion type tert-amyl peroxypivalate which comprises the following components in percentage by mass: oil phase: 40% -60%; emulsifier: 0.5 to 2 percent; dispersing agent: 2% -5%; an antifreeze agent: 10 to 30 percent, and the balance of deionized water. Wherein the oil phase comprises tert-amyl hydroperoxide, tert-valeryl chloride, liquid caustic soda, polyoxyethylene polyoxypropylene segmented copolymer and the balance of deionized water. Furthermore, the molar ratio of the liquid alkali, the tert-amyl hydroperoxide and the tert-amyl chloride is (1.2-1.4): (1.0-1.1): 1.0, wherein the addition amount of the polyoxyethylene polyoxypropylene block copolymer (F127) is 200ppm to 500ppm (based on the water added in the formula).
The emulsifier is at least one of nonylphenol polyoxyethylene ether OP-10, fatty alcohol polyoxyethylene ether lacto-lark and sorbitan monooleate S-80, and preferably nonylphenol polyoxyethylene ether OP-10. The dispersing agent is preferably polyvinyl alcohol PVA 4040. The antifreeze agent adopts at least one of methanol, ethanol and glycol, preferably methanol.
The invention also provides a preparation method of the product, and the process mainly comprises two steps of oil phase synthesis and emulsion preparation:
(1) oil phase synthesis process
Firstly, mixing liquid caustic soda, deionized water and polyoxyethylene polyoxypropylene segmented copolymer, starting stirring, and controlling the temperature below 30 ℃; then, dropwise adding the formula amount of the tert-amyl hydroperoxide, wherein the dropwise adding temperature is below 30 ℃, the dropwise adding time is 3min, and stirring is carried out after the dropwise adding is finished, and the stirring time is 4-6 min; finally, pivaloyl chloride is dripped, the dripping temperature is below 40 ℃, the dripping time is 10min, and the stirring time after dripping is controlled to be 80-85 min.
It is noted that the oil phase synthesis of the traditional organic peroxy initiator product has high water content, and no better solution exists in the industry for reducing the water content. And the traditional drying section is increased, so that the defects of complex process equipment, high oil phase loss, incapability of recycling after the drying agent is consumed and the like exist, the production cost is greatly increased, and the economic benefit of enterprises is not favorably improved. In order to solve the above problems, the present invention can effectively solve the above problems by introducing a polyoxyethylene polyoxypropylene block copolymer into the system at the stage of oil phase synthesis, and the mechanism of action is as follows: during the synthesis of the traditional initiator oil phase, the oil phase begins to generate slowly along with the dropwise addition of acyl chloride, at the moment, due to the dropwise addition reaction, in order to ensure the mixing effect after the dropwise addition liquid is added into a kettle, the stirring frequency is higher than 300 r/min, and a small amount of oil phase is emulsified in water and a small amount of water is emulsified in oil along with the slow generation of the oil phase at the rotating speed. The invention adds the polyoxyethylene polyoxypropylene segmented copolymer during synthesis, firstly, under the condition of not influencing normal peroxidation substitution reaction, in the stage of dropwise adding emulsification formation, because the surface tension of the polyoxyethylene polyoxypropylene segmented copolymer is lower, when emulsion is just formed, the polyoxyethylene polyoxypropylene segmented copolymer is contacted with emulsion liquid drops and acts with an interfacial film to replace an original oil-water interfacial film to form a new interfacial film, the interfacial film has lower elasticity, tension and service life, and the interfacial film can be cracked under the action of extrusion and other external forces during stirring to release oil or water, thereby effectively reducing the problem of high water content of an oil phase. The oil phase with the water content of less than 1 percent can be obtained after subsequent washing. By adding the drying agent, the invention can ensure that the obtained oil phase can reach the moisture content consistent with that of the oil phase dried by the traditional drying agent on the premise of not increasing the production process, and the process control is simpler, the cost is lower, and the invention is suitable for industrial popularization. In addition, due to the reduction of the water content in the oil phase, the stability of the emulsion can be further improved and the storage time of the emulsion can be prolonged during the subsequent emulsion preparation. On the other hand, the residual quantity of raw materials in the emulsion finished product is effectively reduced (the residual value is below 0.1 percent), and the induced decomposition effect of the initiator caused by the residue of the tert-amyl hydroperoxide can be greatly reduced when the polymerization is initiated, so that the initiation efficiency is greatly improved, and the addition amount of the initiator and the polymerization reaction time are reduced.
(2) Emulsion preparation process
Firstly, sequentially adding an emulsifier, a dispersant, an antifreeze and deionized water into a reaction kettle for mixing, controlling the temperature below 0 ℃, and stirring for 10-15 min to serve as auxiliary materials for later use; then, putting the auxiliary materials into an oil phase emulsifying kettle, and stirring for 10-15 min; finally, shearing and emulsifying for 25-35 min to obtain the product. Compared with the existing preparation process, the preparation method disclosed by the invention is simple in process, convenient to operate, short in synthesis time and beneficial to reduction of production cost.
The invention is further described with reference to specific examples.
Example 1
And (3) a synthesis stage: 60g of special amyl hydroperoxide (with the purity of 90 percent), 86g of liquid alkali (with the purity of 30 percent), 60g of special valeryl chloride (with the purity of 99 percent) (the molar ratio of the liquid alkali, the special amyl hydroperoxide and the special valeryl chloride is 1.3: 1.05: 1.0), 0.3g of polyoxyethylene polyoxypropylene block copolymer and the balance of deionized water.
The preparation method comprises the steps of firstly adding the polyoxyethylene polyoxypropylene block copolymer, liquid caustic soda and deionized water into a reaction kettle, starting stirring, controlling the temperature to be below 30 ℃, starting dropwise adding the formula amount of the tert-amyl hydroperoxide, dropwise adding for 3min, controlling the temperature to be below 30 ℃, stirring for 5min after the dropwise adding is finished, then starting dropwise adding the tert-valeryl chloride, dropwise adding for 10min, controlling the temperature to be below 40 ℃, stirring for 80min after the dropwise adding is finished, standing, and carrying out water diversion to finish the preparation of the oil phase.
Preparing an emulsion: OP-101%, PVA-40403%, methanol 20%, oil phase 52% and the balance of deionized water.
The preparation method comprises the steps of adding OP-10, PVA-4040, methanol and deionized water into a reaction kettle, mixing, starting stirring, controlling the temperature below 0 ℃, stirring for 10min, then transferring into an oil phase emulsifying kettle, stirring for 10min, then starting shearing, and shearing for 30min to finish the preparation.
Example 2
And (3) a synthesis stage: 64g of special amyl hydroperoxide (purity 90%), 86g of liquid alkali (purity 30%), 60g of special valeryl chloride (purity 99%) (the molar ratio of the liquid alkali, the special amyl hydroperoxide and the special valeryl chloride is 1.3: 1.1: 1.0), 0.5g of polyoxyethylene polyoxypropylene block copolymer and the balance of deionized water.
The preparation method comprises the steps of firstly adding the polyoxyethylene polyoxypropylene block copolymer, liquid caustic soda and deionized water into a reaction kettle, starting stirring, controlling the temperature to be below 30 ℃, starting dropwise adding the formula amount of the tert-amyl hydroperoxide, dropwise adding for 3min, controlling the temperature to be below 30 ℃, stirring for 4min after the dropwise adding is finished, then starting dropwise adding the tert-valeryl chloride, dropwise adding for 10min, controlling the temperature to be below 40 ℃, stirring for 82min after the dropwise adding is finished, standing, and carrying out water diversion to finish the preparation of the oil phase.
Preparing an emulsion: OP-100.5%, PVA-40402%, ethanol 30%, oil phase 40%, and the balance of deionized water.
The preparation method comprises the steps of adding OP-10, PVA-4040, ethanol and deionized water into a reaction kettle, mixing, starting stirring, controlling the temperature below 0 ℃, stirring for 13min, then transferring into an oil phase emulsifying kettle, stirring for 15min, then starting shearing, and finishing the preparation after shearing for 35 min.
Example 3
And (3) a synthesis stage: 57g of special amyl hydroperoxide (with the purity of 90 percent), 86g of liquid alkali (with the purity of 30 percent), 60g of special valeryl chloride (with the purity of 99 percent) (the molar ratio of the liquid alkali, the special amyl hydroperoxide and the special valeryl chloride is 1.3: 1.0: 1.0), 0.3g of polyoxyethylene polyoxypropylene block copolymer and the balance of deionized water.
The preparation method comprises the steps of firstly adding the polyoxyethylene polyoxypropylene block copolymer, liquid caustic soda and deionized water into a reaction kettle, starting stirring, controlling the temperature to be below 30 ℃, starting dropwise adding the formula amount of the tert-amyl hydroperoxide, dropwise adding for 3min, controlling the temperature to be below 30 ℃, stirring for 5min after the dropwise adding is finished, then starting dropwise adding the tert-valeryl chloride, dropwise adding for 10min, controlling the temperature to be below 40 ℃, stirring for 80min after the dropwise adding is finished, standing, and carrying out water diversion to finish the preparation of the oil phase.
Preparing an emulsion: OP-101.5%, PVA-40403.5%, ethanol 20%, oil phase 52% and the balance of deionized water.
The preparation method comprises the steps of adding OP-10, PVA-4040, ethanol and deionized water into a reaction kettle, mixing, starting stirring, controlling the temperature below 0 ℃, stirring for 10min, then transferring into an oil phase emulsifying kettle, stirring for 10min, then starting shearing, and shearing for 30min to finish the preparation.
Example 4
And (3) a synthesis stage: 60g of special amyl hydroperoxide (purity 90%), 80g of liquid alkali (purity 30%), 60g of special valeryl chloride (purity 99%) (the molar ratio of the liquid alkali, the special amyl hydroperoxide and the special valeryl chloride is 1.2: 1.05: 1.0), 0.2g of polyoxyethylene polyoxypropylene block copolymer and the balance of deionized water.
The preparation method comprises the steps of firstly adding the polyoxyethylene polyoxypropylene block copolymer, liquid caustic soda and deionized water into a reaction kettle, starting stirring, controlling the temperature to be below 30 ℃, starting dropwise adding the formula amount of the tert-amyl hydroperoxide, dropwise adding for 3min, controlling the temperature to be below 30 ℃, stirring for 6min after the dropwise adding is finished, then starting dropwise adding the tert-valeryl chloride, dropwise adding for 10min, controlling the temperature to be below 40 ℃, stirring for 85min after the dropwise adding is finished, standing, and carrying out water diversion to finish the preparation of the oil phase.
Preparing an emulsion: sorbitan monooleate S-802%, PVA-40405%, ethylene glycol 10%, oil phase 52%, and the balance of deionized water.
The preparation method comprises the steps of adding sorbitan monooleate S-80, PVA-4040, ethylene glycol and deionized water into a reaction kettle, mixing, starting stirring, controlling the temperature below 0 ℃, stirring for 15min, then transferring into an oil phase emulsifying kettle, stirring for 12min, then starting shearing, and shearing for 25min to finish the preparation.
Example 5
And (3) a synthesis stage: 60g of special amyl hydroperoxide (with the purity of 90 percent), 94g of liquid alkali (with the purity of 30 percent), 60g of special valeryl chloride (with the purity of 99 percent) (the molar ratio of the liquid alkali, the special amyl hydroperoxide and the special valeryl chloride is 1.4: 1.05: 1.0), 0.4g of polyoxyethylene polyoxypropylene block copolymer and the balance of deionized water.
The preparation method comprises the steps of firstly adding the polyoxyethylene polyoxypropylene block copolymer, liquid caustic soda and deionized water into a reaction kettle, starting stirring, controlling the temperature to be below 30 ℃, starting dropwise adding the formula amount of the tert-amyl hydroperoxide, dropwise adding for 3min, controlling the temperature to be below 30 ℃, stirring for 6min after the dropwise adding is finished, then starting dropwise adding the tert-valeryl chloride, dropwise adding for 10min, controlling the temperature to be below 40 ℃, stirring for 85min after the dropwise adding is finished, standing, and carrying out water diversion to finish the preparation of the oil phase.
Preparing an emulsion: 2% of fatty alcohol-polyoxyethylene ether lacto-lark, 10% of PVA-40405% of ethylene glycol, 60% of oil phase and the balance of deionized water.
The preparation method comprises the steps of adding fatty alcohol-polyoxyethylene ether lacto-lark, PVA-4040, ethylene glycol and deionized water into a reaction kettle, mixing, starting stirring, controlling the temperature below 0 ℃, stirring for 15min, then transferring into an oil phase emulsifying kettle, stirring for 12min, then starting shearing, and shearing for 25min to finish the preparation.
Comparative example 1
The oil phase of the product of this comparative example was synthesized without the addition of the polyoxyethylene polyoxypropylene block copolymer, and the remaining components and preparation process were consistent with those of example 1.
Comparative example 2
The product of the comparative example has the advantages that the addition amount of the tert-amyl hydroperoxide is higher than that of the example 1 and higher than the range required by the invention during oil phase synthesis, the formula requirement is not met, and the other components and the preparation process are consistent with those of the example 1.
Comparative example 3
The product of the comparative example has the advantages that the addition amount of the tert-amyl hydroperoxide is lower than that of the example 1 and lower than the range required by the invention during oil phase synthesis, the formula requirement is not met, and the rest components and the preparation process are consistent with those of the example 1.
Comparative example 4
In the product of the comparative example, the addition amount of the pivaloyl chloride during oil phase synthesis is higher than that in example 1 and higher than the range required by the invention, the formula requirement is not met, and the other components and the preparation process are consistent with those in example 1.
Comparative example 5
In the product of the comparative example, the addition amount of pivaloyl chloride during oil phase synthesis is lower than that in example 1 and lower than the range required by the invention, so that the formula requirement is not met, and the other components and the preparation process are consistent with those in example 1.
Comparative example 6
The oil phase synthesis process of the product of the comparative example is consistent with that of example 1, no emulsifier is added during the preparation of the emulsion, and the rest components and the preparation process are consistent with those of example 1.
Comparative example 7
The oil phase synthesis process of the product of the comparative example is consistent with that of example 1, no dispersant is added during the preparation of the emulsion, and the rest components and the preparation process are consistent with those of example 1.
Comparative example 8
In the comparative example, the temperature for dropping pivaloyl chloride during oil phase synthesis is below 30 ℃, which is lower than the requirement of the invention, and the other components and the preparation method are consistent with those in example 1.
Comparative example 9
In the comparative example, the temperature for dropping pivaloyl chloride during oil phase synthesis is below 50 ℃, which is higher than the requirement of the invention, and the other components and the preparation method are consistent with those in example 1.
The products obtained in the above examples and comparative examples were tested, including (1) testing the content of the oil product obtained by the preparation, the content of chlorine in the oil product, the residual amount and the water content; (2) the stability of the final emulsion product was tested and the results are shown in figure 1. According to the data in fig. 1, the components and the proportion thereof can effectively reduce the water content of the synthetic oil product and improve the stability of the emulsion of the product, and the stability can reach more than 24 months and is stable and not layered.
Claims (10)
1. The low-water-content emulsion-type tert-amyl peroxypivalate is characterized by comprising the following components in percentage by mass: oil phase: 40% -60%; emulsifier: 0.5 to 2 percent; dispersing agent: 2% -5%; an antifreeze agent: 10-30% and the balance of deionized water; wherein the oil phase comprises tert-amyl hydroperoxide, tert-valeryl chloride, liquid caustic soda, polyoxyethylene polyoxypropylene segmented copolymer and the balance of deionized water.
2. The low water content emulsion-type pivalic peroxide pivalate of claim 1, wherein: the molar ratio of the liquid caustic soda to the tert-amyl hydroperoxide to the tert-amyl acyl chloride is (1.2-1.4): (1.0-1.1): 1.0, wherein the addition amount of the polyoxyethylene polyoxypropylene block copolymer is 200ppm to 500 ppm.
3. The low water content emulsion-type pivalic peroxide pivalate of claim 1, wherein: the emulsifier is at least one of nonylphenol polyoxyethylene ether OP-10, fatty alcohol polyoxyethylene ether lacto-lark and sorbitan monooleate S-80.
4. The low water content emulsion-type pivalic peroxide pivalate of claim 3, wherein: the emulsifier is preferably nonylphenol polyoxyethylene ether OP-10.
5. A low water content emulsion-type pivalic peroxide pivalate according to any one of claims 1 to 4, wherein: the dispersant is polyvinyl alcohol PVA 4040, and the antifreeze agent is at least one of methanol, ethanol and glycol.
6. The low water content emulsion-type pivalic peroxide pivalate of claim 5, wherein: the antifreeze agent is preferably methanol.
7. A process for the preparation of a low water content emulsion-type pivaloyl peroxypivalate according to any one of claims 1 to 6, which comprises two steps:
firstly, synthesizing an oil phase, namely adding tert-amyl hydroperoxide, tert-valeryl chloride and liquid alkali into a system in which a polyoxyethylene polyoxypropylene block copolymer is added for a synthetic reaction;
and step two, emulsion preparation, namely mixing the oil phase synthesized in the step one with an emulsifier, a dispersant, an antifreeze and deionized water, stirring, shearing and emulsifying.
8. The method for preparing a low water content emulsion-type pivalic peroxypivalate according to claim 7, wherein: in the first step, firstly, mixing liquid caustic soda, deionized water and polyoxyethylene polyoxypropylene segmented copolymer, and stirring; then, dropwise adding tert-amyl hydroperoxide and stirring; finally, pivaloyl chloride is added dropwise and stirred.
9. The method for preparing a low water content emulsion-type pivalic peroxypivalate according to claim 7, wherein: in the second step, firstly, sequentially adding an emulsifier, a dispersant, an antifreeze and deionized water into a reaction kettle for mixing, controlling the temperature below 0 ℃, and stirring for 10-15 min to serve as auxiliary materials for later use; then, putting the auxiliary materials into an oil phase emulsifying kettle, and stirring for 10-15 min; finally, shearing and emulsifying for 25-35 min.
10. The method for preparing a low water content emulsion-type pivalic peroxypivalate according to claim 8, wherein: in the first step, when mixing liquid caustic soda, deionized water and a polyoxyethylene polyoxypropylene segmented copolymer, controlling the temperature below 30 ℃, dropwise adding tert-amyl hydroperoxide at the temperature below 30 ℃, wherein the dropwise adding time is 3min, and stirring is carried out after the dropwise adding is finished, wherein the stirring time is 4-6 min; the temperature of the pivaloyl chloride is below 40 ℃, the dripping time is 10min, and the stirring time after dripping is controlled to be 80-85 min.
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| CN102532352A (en) * | 2011-12-26 | 2012-07-04 | 淄博正华助剂股份有限公司 | Preparation method of emulsion-type 50wt% bis-(3,5,5-trimethyl caproyl) peroxide |
| CN102585050A (en) * | 2011-12-28 | 2012-07-18 | 淄博正华助剂股份有限公司 | Preparation method of emulsion type tert-butyl peroxyneo-caprate with 50% mass fraction |
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| CN110922513A (en) * | 2019-10-22 | 2020-03-27 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of emulsion type cumyl peroxyneodecanoate |
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