CN115353451B - Preparation method of 2-chloro-propionyl chloride - Google Patents
Preparation method of 2-chloro-propionyl chloride Download PDFInfo
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- CN115353451B CN115353451B CN202211283160.2A CN202211283160A CN115353451B CN 115353451 B CN115353451 B CN 115353451B CN 202211283160 A CN202211283160 A CN 202211283160A CN 115353451 B CN115353451 B CN 115353451B
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- trapping agent
- radical trapping
- chloride
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- JEQDSBVHLKBEIZ-REOHCLBHSA-N (2s)-2-chloropropanoyl chloride Chemical compound C[C@H](Cl)C(Cl)=O JEQDSBVHLKBEIZ-REOHCLBHSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 58
- 150000003254 radicals Chemical class 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 16
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims description 63
- 238000007790 scraping Methods 0.000 claims description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 230000010355 oscillation Effects 0.000 claims description 28
- 238000002390 rotary evaporation Methods 0.000 claims description 28
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 24
- 239000013543 active substance Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 239000000440 bentonite Substances 0.000 claims description 14
- 229910000278 bentonite Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 235000010413 sodium alginate Nutrition 0.000 claims description 14
- 239000000661 sodium alginate Substances 0.000 claims description 14
- 229940005550 sodium alginate Drugs 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001110 calcium chloride Substances 0.000 claims description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 229940123457 Free radical scavenger Drugs 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 sodium fatty alcohol Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/23—
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
- C07B61/02—Generation of organic free radicals; Organic free radicals per se
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/03—Free radicals
Abstract
The invention discloses a preparation method of 2-chloro-propionyl chloride, belonging to the technical field of 2-chloro-propionyl chloride, which comprises the following steps: preparing a catalyst, preparing a free radical trapping agent and carrying out chlorination reaction; the chlorination reaction comprises the steps of adding propionyl chloride, a catalyst and a free radical trapping agent into a reaction container, controlling the temperature of the reaction container to be 53-55 ℃, starting stirring, then introducing chlorine, stirring for 1.5-1.8h, introducing a mixed gas of oxygen and carbon dioxide at the temperature of 78-80 ℃, continuing stirring for 30-35min, stopping introducing the chlorine and the mixed gas to obtain a reaction liquid, cooling the reaction liquid, and taking out the catalyst and the free radical trapping agent to obtain 2-chloropropionyl chloride; the method can improve the purity and yield of the product, reduce the dosage of the free radical trapping agent and reduce the reaction energy consumption.
Description
Technical Field
The invention relates to the technical field of 2-chloro-propionyl chloride, in particular to a preparation method of 2-chloro-propionyl chloride.
Background
2-chloropropionyl chloride is an important intermediate for synthesizing fine chemicals such as medicines, dyes, pesticides and the like, and the industrial synthesis method mainly comprises a 2-chloropropionic acid acyl chlorination method and a propionyl chloride chlorination method; wherein, the 2-chloropropionic acid acyl chlorination method takes 2-chloropropionic acid as a raw material, and synthesizes 2-chloropropionyl chloride under the action of phosgene, thionyl chloride, phosphorus trichloride and other acyl chlorination reagents; because phosgene is a highly toxic gas and the industry admission threshold is high, and the thionyl chloride and phosphorus trichloride acyl chlorination methods can generate sulfur dioxide and phosphorus-containing wastewater, the problems of environmental pollution and equipment corrosion are caused; the propionyl chloride chlorination method has simple reaction and stable product quality, but has the defects of long reaction time, low chlorination reaction selectivity and low product purity.
In order to reduce the reaction time of the propionyl chloride chlorination method and improve the reaction selectivity, the most common method at present is to use a catalyst combined with a free radical trapping agent, wherein the catalyst is mainly used for improving the reaction speed, but the side reaction is increased while the reaction speed is improved; but the using amount of oxygen is large, the material balance partial pressure can be reduced by adding the oxygen, the material is easy to volatilize, and the material can be entrained, so that the yield is reduced, in addition, the 2-chloropropionyl chloride needs to be rectified after the reaction is finished, the energy consumption is large during the rectification, and the production cost is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of 2-chloropropionyl chloride, which can improve the purity and yield of the product, reduce the dosage of a free radical trapping agent and reduce the reaction energy consumption.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of 2-chloro propionyl chloride comprises the following steps: preparing a catalyst, preparing a free radical trapping agent and carrying out chlorination reaction.
The preparation method comprises the steps of mixing fatty alcohol-polyoxyethylene ether sodium sulfate, p-toluenesulfonic acid, nano boron nitride and absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 30-40kHz and the time to be 35-40min, placing the mixture in a rotary evaporator after the ultrasonic oscillation is finished, carrying out rotary evaporation, controlling the temperature during the rotary evaporation to be 75-80 ℃ and the time to be 45-50min, and obtaining a catalyst active substance after the rotary evaporation is finished;
mixing polyvinyl alcohol, sodium alginate, a catalyst active substance and deionized water, stirring at 40-45 ℃ for 20-25min at a stirring speed of 100-120rpm, adding glutaraldehyde and sulfuric acid, continuously stirring for 2-2.5h to obtain a membrane scraping solution, scraping the membrane from the membrane scraping solution by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 400-450 mu m and the membrane scraping speed to be 13-14m/min, and airing at 30-35 ℃ after membrane scraping is finished to obtain a catalyst;
in the preparation of the catalyst, the weight ratio of fatty alcohol-polyoxyethylene ether sodium sulfate to p-toluenesulfonic acid to nano boron nitride to absolute ethyl alcohol is 18-7:2-3;
in the preparation of the catalyst, the weight ratio of polyvinyl alcohol, sodium alginate, catalyst active substance, deionized water, glutaraldehyde and sulfuric acid is (1.5-1.7);
in the preparation catalyst, the particle size of the nano boron nitride is 30-40nm.
Mixing 2,2,6,6-tetramethylpiperidine oxide, magnesium chloride, calcium chloride, nano bentonite and absolute ethyl alcohol, then performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 40-50kHz and the time to be 40-45min, placing the mixture in a rotary evaporator after the ultrasonic oscillation is finished, performing rotary evaporation, controlling the temperature during the rotary evaporation to be 75-80 ℃ and the time to be 45-50min, and obtaining a free radical scavenger active substance after the rotary evaporation is finished;
mixing polyvinyl alcohol, sodium alginate, a free radical trapping agent active substance and deionized water, stirring at 40-45 ℃ for 20-25min at a stirring speed of 100-120rpm, adding glutaraldehyde and sulfuric acid, continuously stirring for 2-2.5h to obtain a membrane scraping solution, scraping the membrane scraping solution by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 350-400 mu m, and the membrane scraping speed to be 14-15m/min, and airing at 30-35 ℃ after membrane scraping is finished to obtain the free radical trapping agent;
in the preparation of the free radical trapping agent, the weight ratio of 2,2,6,6-tetramethylpiperidine oxide, magnesium chloride, calcium chloride, nano bentonite to absolute ethyl alcohol is 0.5-0.7, and the weight ratio of the 2,2,6,6 to the nano bentonite to the absolute ethyl alcohol is 2-3:5-6:7-8;
in the preparation of the free radical trapping agent, the weight ratio of polyvinyl alcohol, sodium alginate, active substances of the free radical trapping agent, deionized water, glutaraldehyde and sulfuric acid is (2-2.2);
in the preparation of the free radical trapping agent, the particle size of the nano bentonite is 30-40nm.
The chlorination reaction comprises the steps of adding propionyl chloride, a catalyst and a free radical trapping agent into a reaction container, controlling the temperature of the reaction container to be 53-55 ℃, starting stirring, controlling the stirring speed to be 100-120rpm, then introducing chlorine and controlling the flow rate of the chlorine to be 40-45L/h, stirring for 1.5-1.8h, introducing mixed gas of oxygen and carbon dioxide at the temperature of 78-80 ℃, controlling the flow rate of the mixed gas to be 0.5-0.6L/h, continuing stirring for 30-35min, stopping introduction of the chlorine and the mixed gas to obtain reaction liquid, cooling the reaction liquid to be 28-30 ℃, taking out the catalyst and the free radical trapping agent, and obtaining 2-chloropropionyl chloride;
in the chlorination reaction, the weight ratio of propionyl chloride, a catalyst and a free radical trapping agent is 125-130;
in the chlorination reaction, the volume ratio of oxygen to carbon dioxide in the mixed gas of oxygen and carbon dioxide is 11-13.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the 2-chloropropionyl chloride, the catalyst and the free radical trapping agent are used as active ingredients to prepare the membrane, the fatty alcohol-polyoxyethylene ether sodium sulfate is added into the catalyst, the magnesium chloride and the calcium chloride are added into the free radical trapping agent, and simultaneously, the preheated mixed gas of oxygen and carbon dioxide is introduced at the later stage of the reaction, so that the purity and the yield of the prepared 2-chloropropionyl chloride can be improved, the purity of the prepared 2-chloropropionyl chloride is 96.279-97.957%, and the yield is 96.06-97.65%;
(2) According to the preparation method of the 2-chloropropionyl chloride, the free radical trapping agent is used as an active ingredient for preparing the membrane, and the magnesium chloride and the calcium chloride are added into the free radical trapping agent, so that the using amount of the free radical trapping agent can be reduced, the small-flow oxygen addition is only carried out at the later stage of the reaction, and the large amount of oxygen is prevented from being introduced from the beginning of the reaction;
(3) According to the preparation method of the 2-chloropropionyl chloride, the catalyst and the free radical trapping agent are used as active ingredients to prepare the membrane, the fatty alcohol-polyoxyethylene ether sodium sulfate is added into the catalyst, the magnesium chloride and the calcium chloride are added into the free radical trapping agent, and simultaneously, the preheated mixed gas of oxygen and carbon dioxide is introduced in the later stage of the reaction, so that the high purity of the 2-chloropropionyl chloride in the final product can be ensured, the later-stage rectification process is avoided, and the reaction energy consumption is reduced.
Drawings
FIG. 1 is a liquid chromatography analysis chart of 2-chloropropionyl chloride prepared in example 1;
FIG. 2 is a liquid chromatography analysis chart of 2-chloropropionyl chloride prepared in example 2;
FIG. 3 is a liquid chromatography analysis chart of 2-chloropropionyl chloride prepared in example 3.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of 2-chloro propionyl chloride comprises the following steps:
1. preparing a catalyst: mixing 18g of sodium fatty alcohol-polyoxyethylene ether sulfate, 6g of p-toluenesulfonic acid, 2g of nano boron nitride and 55g of absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 30kHz and the time to be 35min, placing the mixture in a rotary evaporator to carry out rotary evaporation after the ultrasonic oscillation is finished, controlling the temperature during the rotary evaporation to be 75 ℃ and the time to be 45min, and obtaining a catalyst active substance after the rotary evaporation is finished;
mixing 1.5g of polyvinyl alcohol, 1.5g of sodium alginate, 0.5g of catalyst active substance and 28g of deionized water, placing the mixture at 40 ℃ and stirring at a stirring speed of 100rpm for 20min, then adding 0.02g of glutaraldehyde and 0.022g of sulfuric acid, continuously stirring for 2h to obtain a membrane scraping solution, using an automatic membrane scraping machine to scrape the membrane from the membrane scraping solution, controlling the height of a scraper during membrane scraping to be 400 mu m, controlling the membrane scraping speed to be 13m/min, and after membrane scraping is finished, placing the mixture at 30 ℃ for airing to obtain a catalyst;
the particle size of the nano boron nitride is 30nm.
2. Preparing a free radical trapping agent: mixing 0.5g of 2, 6-tetramethylpiperidine oxide, 2g of magnesium chloride, 5g of calcium chloride, 7g of nano bentonite and 60g of absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 40kHz and the time to be 40min, placing the mixture in a rotary evaporator after the ultrasonic oscillation is finished, carrying out rotary evaporation, controlling the temperature during the rotary evaporation to be 75 ℃ and the time to be 45min, and obtaining a free radical trapping agent active substance after the rotary evaporation is finished;
mixing 2g of polyvinyl alcohol, 1.8g of sodium alginate, 1g of a free radical scavenger active substance and 35g of deionized water, stirring at a stirring speed of 100rpm at 40 ℃ for 20min, adding 0.022g of glutaraldehyde and 0.022g of sulfuric acid, continuously stirring for 2h to obtain a membrane scraping solution, scraping the membrane from the membrane scraping solution by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 350 mu m, controlling the membrane scraping speed to be 14m/min, and airing at 30 ℃ after membrane scraping is finished to obtain the free radical scavenger;
the particle size of the nano bentonite is 30nm.
3. Chlorination reaction: adding 125g of propionyl chloride, 5g of catalyst and 6g of free radical trapping agent into a reaction vessel, controlling the temperature of the reaction vessel to 53 ℃, starting stirring, controlling the stirring speed to 100rpm, then introducing chlorine and controlling the flow of the chlorine to be 40L/h, stirring for 1.5h, introducing a mixed gas of oxygen and carbon dioxide at the temperature of 78 ℃, controlling the flow of the mixed gas to be 0.5L/h, continuing stirring for 30min, stopping introducing the chlorine and the mixed gas to obtain a reaction liquid, cooling the reaction liquid to 28 ℃, taking out the catalyst and the free radical trapping agent to obtain 171g of 2-chloropropionyl chloride, and carrying out liquid chromatographic analysis on the prepared 2-chloropropionyl chloride, wherein the liquid chromatographic analysis chart is shown in figure 1, and the liquid chromatographic analysis chart can know that the purity of the prepared 2-chloropropionyl chloride is 97.957% and the yield is 97.65%;
the volume ratio of the oxygen to the carbon dioxide in the mixed gas of the oxygen and the carbon dioxide is 11.
Example 2
A preparation method of 2-chloro propionyl chloride comprises the following steps:
1. preparing a catalyst: mixing 19g of sodium fatty alcohol-polyoxyethylene ether sulfate, 6.5g of p-toluenesulfonic acid, 2.5g of nano boron nitride and 56g of absolute ethyl alcohol, and then carrying out ultrasonic oscillation, wherein the frequency of the ultrasonic oscillation is controlled to be 35kHz and the time is 37min, placing the mixture in a rotary evaporator for rotary evaporation after the ultrasonic oscillation is finished, the temperature during the rotary evaporation is controlled to be 77 ℃ and the time is 47min, and obtaining a catalyst active substance after the rotary evaporation is finished;
mixing 1.6g of polyvinyl alcohol, 1.7g of sodium alginate, 0.6g of catalyst active substance and 29g of deionized water, stirring at a stirring speed of 110rpm at 42 ℃ for 22min, adding 0.021g of glutaraldehyde and 0.023g of sulfuric acid, continuously stirring for 2.2h to obtain a membrane scraping solution, scraping the membrane by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 420 mu m, controlling the membrane scraping speed to be 13.5m/min, and airing at 32 ℃ after membrane scraping is finished to obtain a catalyst;
the particle size of the nano boron nitride is 35nm.
2. Preparing a free radical trapping agent: mixing 0.6g of 2, 6-tetramethylpiperidine oxide, 2.5g of magnesium chloride, 5.5g of calcium chloride, 7.5g of nano-bentonite and 61g of absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 45kHz and the time to be 42min, placing the mixture in a rotary evaporator for rotary evaporation after the ultrasonic oscillation is finished, controlling the temperature during the rotary evaporation to be 77 ℃ and the time to be 47min, and obtaining a free radical scavenger active substance after the rotary evaporation is finished;
mixing 2.1g of polyvinyl alcohol, 2g of sodium alginate, 1.1g of active substance of a free radical scavenger and 37g of deionized water, stirring at a stirring speed of 110rpm at 42 ℃ for 22min, adding 0.024g of glutaraldehyde and 0.024g of sulfuric acid, continuously stirring for 2.2h to obtain a membrane scraping solution, scraping the membrane by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 370 mu m, controlling the membrane scraping speed to be 14.5m/min, and airing at 32 ℃ after membrane scraping is finished to obtain the free radical scavenger;
the particle size of the nano bentonite is 35nm.
3. Chlorination reaction: adding 127g of propionyl chloride, 5.5g of catalyst and 6.5g of radical trapping agent into a reaction vessel, controlling the temperature of the reaction vessel to 54 ℃, starting stirring, controlling the stirring speed to 110rpm, then introducing chlorine and controlling the flow of the chlorine to 42L/h, stirring for 1.7h, introducing mixed gas of oxygen and carbon dioxide at the temperature of 79 ℃, controlling the flow of the mixed gas to 0.55L/h, continuing stirring for 32min, stopping introducing the chlorine and the mixed gas to obtain reaction liquid, cooling the reaction liquid to 29 ℃, taking out the catalyst and the radical trapping agent to obtain 173g of 2-chloropropionyl chloride, and carrying out liquid chromatography analysis on the prepared 2-chloropropionyl chloride, wherein the liquid chromatography analysis figure is shown in figure 2, and the liquid chromatography analysis figure shows that the purity of the prepared 2-chloropropionyl chloride is 97.185% and the yield is 96.47%;
the volume ratio of the oxygen to the carbon dioxide in the mixed gas of the oxygen and the carbon dioxide is 12.
Example 3
A preparation method of 2-chloro propionyl chloride comprises the following steps:
1. preparing a catalyst: mixing 20g of sodium alcohol ether sulphate, 7g of p-toluenesulfonic acid, 3g of nano boron nitride and 58g of absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 40kHz and the time to be 40min, placing the mixture in a rotary evaporator to carry out rotary evaporation after the ultrasonic oscillation is finished, controlling the temperature during the rotary evaporation to be 80 ℃ and the time to be 50min, and obtaining a catalyst active substance after the rotary evaporation is finished;
mixing 1.7g of polyvinyl alcohol, 2g of sodium alginate, 0.7g of catalyst active substances and 30g of deionized water, stirring at a stirring speed of 120rpm at 45 ℃ for 25min, adding 0.022g of glutaraldehyde and 0.025g of sulfuric acid, continuously stirring for 2.5h to obtain a membrane scraping solution, scraping the membrane scraping solution by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 450 mu m, controlling the membrane scraping speed to be 14m/min, and airing at 35 ℃ after membrane scraping is finished to obtain a catalyst;
the particle size of the nano boron nitride is 40nm.
2. Preparing a free radical trapping agent: mixing 0.7g of 2, 6-tetramethylpiperidine oxide, 3g of magnesium chloride, 6g of calcium chloride, 8g of nano bentonite and 63g of absolute ethyl alcohol, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 50kHz and the time to be 45min, placing the mixture in a rotary evaporator for rotary evaporation after the ultrasonic oscillation is finished, controlling the temperature during the rotary evaporation to be 80 ℃ and the time to be 50min, and obtaining a free radical trapping agent active substance after the rotary evaporation is finished;
mixing 2.2g of polyvinyl alcohol, 2.2g of sodium alginate, 1.2g of a free radical scavenger active substance and 38g of deionized water, stirring at a stirring speed of 120rpm at 45 ℃ for 25min, adding 0.025g of glutaraldehyde and 0.025g of sulfuric acid, continuously stirring for 2.5h to obtain a membrane scraping solution, scraping the membrane scraping solution by using an automatic membrane scraping machine, controlling the height of a scraper during membrane scraping to be 400 mu m, controlling the membrane scraping speed to be 15m/min, and airing at 35 ℃ after membrane scraping is finished to obtain the free radical scavenger;
the particle size of the nano bentonite is 40nm.
3. Chlorination reaction: adding 130g of propionyl chloride, 6g of catalyst and 7g of radical trapping agent into a reaction vessel, controlling the temperature of the reaction vessel to 55 ℃, starting stirring, controlling the stirring speed to 120rpm, then introducing chlorine and controlling the flow of the chlorine to 45L/h, stirring for 1.8h, introducing a mixed gas of oxygen and carbon dioxide at the temperature of 80 ℃, controlling the flow of the mixed gas to 0.6L/h, continuing stirring for 35min, stopping introducing the chlorine and the mixed gas to obtain a reaction liquid, cooling the reaction liquid to 30 ℃, taking out the catalyst and the radical trapping agent to obtain 178g of 2-chloropropionyl chloride, and carrying out liquid chromatographic analysis on the prepared 2-chloropropionyl chloride, wherein the liquid chromatographic analysis chart is shown in figure 3, and the purity of the prepared 2-chloropropionyl chloride is 96.279% and the yield is 96.06%;
the volume ratio of the oxygen to the carbon dioxide in the mixed gas of the oxygen and the carbon dioxide is 13.
Comparative example 1
A preparation method of 2-chloro propionyl chloride comprises the following steps: adding 125g of propionyl chloride, 0.19g of p-toluenesulfonic acid, 0.04g of 2, 6-tetramethylpiperidine oxide into a reaction vessel, controlling the temperature of the reaction vessel to 53 ℃, starting stirring, controlling the stirring speed to 100rpm, then introducing chlorine gas, controlling the flow of the chlorine gas to be 40L/h, stirring for 1.5h, introducing a mixed gas of oxygen and carbon dioxide at the temperature of 78 ℃, controlling the flow of the mixed gas to be 5L/h, continuing stirring for 30min, stopping introduction of the chlorine gas and the mixed gas to obtain a reaction liquid, cooling the reaction liquid to 28 ℃, and rectifying to obtain 147g of 2-chloropropionyl chloride with the purity of 85.371% and the yield of 73.16%;
the volume ratio of the oxygen to the carbon dioxide in the mixed gas of the oxygen and the carbon dioxide is 11.
Comparative example 2
The same process for the preparation of 2-chloropropionyl chloride as in example 1, except that: the chlorination reaction in the step 3 is changed into the following steps: adding 125g of propionyl chloride, 5g of catalyst and 6g of radical trapping agent into a reaction vessel, controlling the temperature of the reaction vessel to 53 ℃, starting stirring, controlling the stirring speed to 100rpm, then introducing chlorine and controlling the flow of the chlorine to be 40L/h, stirring for 1.5h, introducing oxygen with the temperature of 53 ℃, controlling the flow of the oxygen to be 0.46L/h, continuing stirring for 30min, stopping introducing the chlorine and the oxygen to obtain a reaction liquid, cooling the reaction liquid to 28 ℃, taking out the catalyst and the radical trapping agent to obtain 155g of 2-chloropropionyl chloride, wherein the purity is 94.082%, and the yield is 85.01%.
As can be seen from examples 1 to 3 and comparative examples 1 to 2, in comparative example 1, the catalyst and the radical scavenger are not used as active ingredients to prepare a membrane, the fatty alcohol-polyoxyethylene ether sodium sulfate is not added to the catalyst, and the magnesium chloride and the calcium chloride are not added to the radical scavenger, so that the purity and the yield of the prepared 2-chloropropionyl chloride are low compared with example 1; the purpose of the membrane preparation is to fix the catalyst and the free radical trapping agent under the condition of not changing active ingredients of the catalyst and the free radical trapping agent, so that the influence of the catalyst and the free radical trapping agent on the purity of a product is avoided, and meanwhile, the contact area between the catalyst and a reactant is increased; the sodium fatty alcohol polyoxyethylene ether sulfate is a common surfactant, wherein a sulfonate group can promote the reaction, and magnesium chloride and calcium chloride in a free radical trapping agent can cooperate with 2,2,6,6-tetramethylpiperidine oxide, so that the occurrence of side reaction is avoided;
in comparative example 2, the mixed gas of oxygen and carbon dioxide is not introduced, and the mixed gas is not preheated, so that the purity and the yield of the prepared 2-chloropropionyl chloride are influenced; the oxygen can promote the capture of free radicals in the later reaction stage, because the residual reactant propionyl chloride is less and less in the later reaction stage, and chlorine is continuously introduced, at the moment, the capture capability of the pre-added free radical capture agent is not enough, oxygen needs to be supplemented additionally, the reaction temperature needs to be increased in order to improve the capture speed of the free radicals, in order to reduce energy consumption, the invention only preheats the mixed gas, and the carbon dioxide is added in order to better promote the residual propionyl chloride to carry out the substitution of hydrogen on the alpha position, thereby promoting the generation of the 2-chloropropionyl chloride.
All percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A method for preparing 2-chloro-propionyl chloride is characterized by comprising the following steps: preparing a catalyst, preparing a free radical trapping agent and carrying out chlorination reaction;
the preparation method comprises the steps of mixing fatty alcohol-polyoxyethylene ether sodium sulfate, p-toluenesulfonic acid, nano boron nitride and absolute ethyl alcohol, then carrying out ultrasonic oscillation, placing the mixture in a rotary evaporator after the ultrasonic oscillation is finished, carrying out rotary evaporation, and obtaining a catalyst active substance after the rotary evaporation is finished;
mixing polyvinyl alcohol, sodium alginate, a catalyst active substance and deionized water, stirring at 40-45 ℃, adding glutaraldehyde and sulfuric acid, continuously stirring to obtain a membrane scraping solution, scraping the membrane by using an automatic membrane scraping machine, and airing after the membrane scraping is finished to obtain a catalyst;
in the preparation of the catalyst, the weight ratio of fatty alcohol-polyoxyethylene ether sodium sulfate to p-toluenesulfonic acid to nano boron nitride to absolute ethyl alcohol is 18-7:2-3;
in the preparation of the catalyst, the weight ratio of polyvinyl alcohol, sodium alginate, catalyst active substances, deionized water, glutaraldehyde and sulfuric acid is 1.5-1.7;
mixing 2,2,6,6-tetramethylpiperidine oxide, magnesium chloride, calcium chloride, nano bentonite and absolute ethyl alcohol, then carrying out ultrasonic oscillation, placing the mixture in a rotary evaporator after the ultrasonic oscillation is finished, carrying out rotary evaporation, and obtaining an active substance of the free radical trapping agent after the rotary evaporation is finished;
mixing polyvinyl alcohol, sodium alginate, a free radical trapping agent active substance and deionized water, stirring at 40-45 ℃, adding glutaraldehyde and sulfuric acid, continuously stirring for 2-2.5h to obtain a membrane scraping solution, and scraping the membrane scraping solution by using an automatic membrane scraping machine to obtain a free radical trapping agent;
in the preparation of the free radical trapping agent, the weight ratio of 2,2,6,6-tetramethylpiperidine oxide, magnesium chloride, calcium chloride, nano bentonite to absolute ethyl alcohol is 0.5-0.7, and the weight ratio of the 2,2,6,6 to the nano bentonite to the absolute ethyl alcohol is 2-3:5-6:7-8;
in the preparation of the free radical trapping agent, the weight ratio of polyvinyl alcohol, sodium alginate, active substances of the free radical trapping agent, deionized water, glutaraldehyde and sulfuric acid is (2-2.2);
the chlorination reaction comprises the steps of adding propionyl chloride, a catalyst and a free radical trapping agent into a reaction container, controlling the temperature of the reaction container to be 53-55 ℃, starting stirring, introducing chlorine and controlling the flow of the chlorine to be 40-45L/h, stirring for 1.5-1.8h, introducing mixed gas of oxygen and carbon dioxide at the temperature of 78-80 ℃, controlling the flow of the mixed gas to be 0.5-0.6L/h, continuing stirring for 30-35min, stopping introduction of the chlorine and the mixed gas to obtain reaction liquid, cooling the reaction liquid, and taking out the catalyst and the free radical trapping agent to obtain 2-chloropropionyl chloride;
in the chlorination reaction, the weight ratio of propionyl chloride, a catalyst and a free radical trapping agent is 125-130, and the weight ratio of propionyl chloride, the catalyst and the free radical trapping agent is 5-6:6-7;
in the chlorination reaction, the volume ratio of oxygen to carbon dioxide in the mixed gas of oxygen and carbon dioxide is 11-13.
2. The method for preparing 2-chloropropionyl chloride as claimed in claim 1, wherein the nano boron nitride in the catalyst is 30-40nm in particle size.
3. The method for preparing 2-chloropropionyl chloride as claimed in claim 1, wherein the nano-bentonite in the preparation of the radical scavenger has a particle size of 30-40nm.
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