CN117534579A - Preparation method of betaine quaternary ammonium base - Google Patents
Preparation method of betaine quaternary ammonium base Download PDFInfo
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- CN117534579A CN117534579A CN202311320437.9A CN202311320437A CN117534579A CN 117534579 A CN117534579 A CN 117534579A CN 202311320437 A CN202311320437 A CN 202311320437A CN 117534579 A CN117534579 A CN 117534579A
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- betaine
- preparation
- quaternary ammonium
- ammonium base
- chlorocarboxylic acid
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229960003237 betaine Drugs 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- -1 betaine compound Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000011033 desalting Methods 0.000 claims abstract description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 39
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 24
- 239000008247 solid mixture Substances 0.000 description 14
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 13
- 229940106681 chloroacetic acid Drugs 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- ZAJNMXDBJKCCAT-RXMQYKEDSA-N ethyl (3r)-4-chloro-3-hydroxybutanoate Chemical compound CCOC(=O)C[C@@H](O)CCl ZAJNMXDBJKCCAT-RXMQYKEDSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of betaine compound preparation, and in particular relates to a preparation method of betaine quaternary ammonium base, which comprises the following steps: the preparation method comprises the steps of mixing tertiary amine and alkaline compound uniformly below 25 ℃, adding chlorocarboxylic acid or chlorocarboxylic acid ester, heating to react for 1-7 h at 0-70 ℃, concentrating reaction liquid, desalting, recrystallizing and drying to obtain the product.
Description
Technical Field
The invention belongs to the technical field of betaine compound preparation, and particularly relates to a preparation method of betaine quaternary ammonium hydroxide.
Background
Betaine compounds are one of the quaternary ammonium alkaloids in the field of fine engineering. Betaine has various characteristics of reducing blood fat, resisting aging, absorbing moisture, amphoteric activity, resisting oxidation, resisting acid and alkali, high temperature and the like, so that the betaine is widely applied to the fields of food, feed, medicine, personal care, daily chemicals, printing and dyeing and the like. Betaine can be obtained by extraction of natural products or chemical synthesis to meet market demand.
The current methods for preparing betaine mainly comprise two methods: the extraction process is mainly ion exclusion method, and the eluted betaine mother liquor is evaporated, concentrated, three-stage crystallized and filtered to obtain anhydrous or monohydrate betaine. The method is limited by seasons and regions, and the extraction process is complex. The other is prepared by a chemical synthesis method, and chloroacetic acid and trimethylamine are used as raw materials to react in alkali liquor to generate betaine and sodium chloride.
In the actual production process, in order to improve the conversion rate of chloroacetic acid, the conditions of severe excess trimethylamine exist in the process of chemically synthesizing betaine, so that the utilization rate of the trimethylamine is lower, the recovery is difficult, and the recovery cost is too high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of betaine quaternary ammonium hydroxide, which achieves the purposes of avoiding raw material hydrolysis, high raw material utilization rate and high reaction speed.
In addition, in the production, if a strong alkaline substance is used as an acid binding agent, the defects of higher reaction temperature, chloroacetic acid hydrolysis, longer reaction time and the like exist.
Meanwhile, water is difficult to evaporate in the post-treatment dehydration process; the solvent is easy to form colloid with sodium chloride during extraction, so that the solubility of sodium chloride in an extractant is increased, and the problems of higher sodium chloride content in a crystallized product and the like are solved.
The invention solves the problems in the prior art by adopting the following technical scheme:
the invention aims to provide a preparation method of betaine quaternary ammonium base, which comprises the following steps: mixing tertiary amine and alkaline compound at below 25 deg.c, adding chlorocarboxylic acid or chlorocarboxylic ester, heating to 0-70 deg.c for reaction for 1-7 hr, concentrating the reaction liquid, desalting, re-crystallizing and drying to obtain the product.
Further, the tertiary amine compound has the structural formula
In the middle of
R 1 、R 2 ＝—CH 3 or-CH 2 CH 3 ；
R 3 ＝—(CH 2 ) n CH 3 ，n＝0～17。
Further, the alkaline compound is one of alkali metal, alkaline earth metal, ammonium hydroxide, carbonate and bicarbonate.
Further preferably, the basic compound is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, barium bicarbonate, ammonia water, ammonium carbonate, and ammonium bicarbonate.
Further, the structural formula of the chlorocarboxylic acid is
The structural formula of the chlorocarboxylic acid ester is
In the middle of
m=1 or 2;
R 4 ＝—CH 3 or-CH 2 CH 3 ；
R 5 ＝H、—CH 3 、—CH 2 CH 3 or-CH 2 C 6 H 5 。
Further, the molar ratio of the chlorocarboxylic acid or the chlorocarboxylic acid ester to the monobasic basic compound is 1:1.04, the molar ratio of the chlorocarboxylic acid or the chlorocarboxylic acid ester to the dibasic basic compound is 1:0.52, the molar ratio of chlorocarboxylic acid or chlorocarboxylic acid ester to tertiary amine is 1:1.01 to 1.50.
Further, the reaction solution is concentrated, the reaction solution is distilled under reduced pressure until the solid content is 74-82%, the precipitated solid is removed by filtration under the condition of heat preservation, and the filtrate is distilled continuously until the solid content is 89-92%.
Further, the desalting process is to add an organic solvent to the concentrated product, dissolve betaine sufficiently and filter to remove insoluble substances.
And the recrystallization process is to heat the desalted filtrate to 70 ℃, decompress and distill until the betaine starts to precipitate, slowly cool to room temperature, precipitate the betaine, slowly add a poor solvent into the filtrate after filtration to ensure that the betaine continues to precipitate, and filter and collect a filter cake.
Further, fluidized bed drying is adopted for drying, and the drying temperature is 160 ℃.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the preparation method of betaine quaternary ammonium base of the invention firstly mixes tertiary amine with alkaline compound raw material at low temperature, then adds chlorocarboxylic acid or chlorocarboxylic ester and then heats up in a stage, compared with the preparation method in the prior art, the utilization rate of the raw material is high, the prepared betaine content is 97.7-99.5%, and the yield is 94.5-98.5%, which are higher than that of betaine prepared by the prior preparation method.
2. The preparation method controls the reaction temperature, avoids raw material hydrolysis, has high reaction speed and obviously improves the synthetic reaction efficiency.
3. The invention optimizes the defects of the post-treatment process, and is difficult to form colloid with sodium chloride during solvent extraction through concentration, desalination, recrystallization and drying treatment, so that the sodium chloride content in the crystallized product is reduced, and the product quality is provided.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the technical means thereof may be more clearly understood, and in order that the present invention may be more readily understood, its objects, features and advantages be more particularly described below.
Detailed Description
It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
In addition, unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present invention may be obtained commercially or prepared by existing methods.
A method for preparing betaine quaternary ammonium base, comprising the following steps:
tertiary amine and alkaline compound are used as raw materials, after being uniformly mixed at a low temperature below 25 ℃, chlorocarboxylic acid or chlorocarboxylic acid ester is added, and the molar ratio of the added chlorocarboxylic acid or chlorocarboxylic acid ester to the monobasic alkaline compound is 1:1.04, the molar ratio of the chlorocarboxylic acid or the chlorocarboxylic acid ester to the dibasic basic compound is 1:0.52, the molar ratio of chlorocarboxylic acid or chlorocarboxylic acid ester to tertiary amine is 1:1.01 to 1.50, after reacting for 2 hours at 0 to 10 ℃, heating to 30 to 40 ℃ to continue reacting for 1 hour, and finally heating to 70 ℃ to react for 1 hour.
When the solid content of the reaction liquid is 74-82%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 89-92%; the filter cake is leached by an equal volume of extractant, preferably methanol or ethanol, and the leaching solution is used for dissolving and distilling the obtained solid mixture after being supplemented with new liquid, the solvent dosage is 2.5-12 times of that of the solid mixture, and insoluble substances are removed by filtration after full stirring. Concentrating the extractive solution to 70deg.C saturated state by distillation, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a speed, and precipitating betaine; filtering to remove betaine, slowly adding betaine poor solvent, preferably petroleum ether or diethyl ether, which is 5 times of the volume of the extractant, dropwise adding the poor solvent for 5-12 hr, filtering after betaine precipitation, rectifying the filtrate for recycling, drying the betaine with fluidized bed,the drying temperature was 160 ℃.
Example 1
Uniformly mixing trimethylamine solution and sodium hydroxide solution at the temperature of-5 to 0 ℃, and then adding chloroacetic acid solution, wherein the mole ratio of the added chloroacetic acid solution to the sodium hydroxide solution is 1:1.04, the molar ratio of chloroacetic acid solution to trimethylamine solution is 1:1.01, after reacting for 2 hours at 0-10 ℃, heating to 30-40 ℃ to continue reacting for 1 hour, and finally heating to 70 ℃ to react for 1 hour. When the solid content of the reaction liquid is 74-76%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 90-91%; the filter cake is leached by methanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 2.5 times of that of the solid mixture, and insoluble matters are removed by filtration after full stirring. Concentrating methanol extractive solution by distillation to 70deg.C saturated state, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a speed, and precipitating betaine; filtering to remove betaine, slowly adding diethyl ether serving as a poor solvent of the betaine into the filtrate, wherein the diethyl ether is 5 times of the volume of methanol, the dropwise adding time of the poor solvent is 5-12 h, filtering after the betaine is separated out, rectifying the filtrate, recycling, and drying the betaine by adopting a fluidized bed at the drying temperature of 160 ℃. Betaine content 99.23% and yield 97.11%.
Example two
Uniformly mixing trimethylamine solution and ammonia water solution at the temperature of-5 to 0 ℃, adding chloroacetic acid solution, and adding the molar ratio of chloroacetic acid solution to ammonia water is 1:1.04, the molar ratio of chloroacetic acid solution to trimethylamine solution is 1:1.50, after reacting for 2 hours at 0-10 ℃, heating to 30-40 ℃ to continue reacting for 1 hour, and finally heating to 70 ℃ to react for 1 hour. When the solid content of the reaction liquid is 79-80%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 89-90%; the filter cake is leached by the ethanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 12 times of that of the solid mixture, and insoluble substances are removed by filtration after full stirring. Concentrating ethanol extractive solution by distillation to 70deg.C saturated state, i.e. stopping adding when solid begins to precipitateHeat at 1℃for 10min -1 Cooling to 25 ℃ at a speed, and precipitating betaine; filtering to remove betaine, slowly adding petroleum ether serving as a poor solvent of the betaine into the filtrate, wherein the petroleum ether is 5 times of the volume of ethanol, the dripping time of the poor solvent is 5-12 h, filtering after the betaine is separated, rectifying the filtrate, recycling, and drying the betaine by adopting a fluidized bed at a drying temperature of 160 ℃. Betaine content 97.70% and yield 98.34%.
Example III
Uniformly mixing a triethylamine solution and a sodium hydroxide solution at the temperature of between 5 ℃ below zero and 0 ℃, adding a chloroacetic acid solution, wherein the molar ratio of the chloroacetic acid solution to the sodium hydroxide solution is 1:1.04, the molar ratio of chloroacetic acid solution to triethylamine solution is 1:1.21, after reacting for 2 hours at 0-10 ℃, heating to 30-40 ℃ to continue reacting for 1 hour, and finally heating to 70 ℃ to react for 1 hour. When the solid content of the reaction liquid is between 81 and 82 percent, filtering and removing precipitated solid substances under the heat preservation condition, and continuing to distill until the solid content is between 91 and 92 percent; the filter cake is leached by methanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 2.5 times of that of the solid mixture, and insoluble matters are removed by filtration after full stirring. Concentrating methanol extractive solution by distillation to 70deg.C saturated state, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a rate, and separating out 2- (triethylammonium) acetate; filtering to remove precipitated solid, slowly adding diethyl ether serving as a poor solvent into the filtrate, wherein the diethyl ether is 5 times of the volume of methanol, the dropwise adding time of the poor solvent is 5-12 h, the 2- (triethylammonium) acetate is precipitated and then filtered, the filtrate can be recycled after rectification, and the betaine is dried by adopting a fluidized bed, and the drying temperature is 160 ℃.2- (triethylammonium) acetate content was 98.02% and yield was 96.27%.
Example IV
Uniformly mixing trimethylamine solution and sodium hydroxide solution at the temperature of-5 to 0 ℃, and then adding 2-chloropropionic acid solution, wherein the mole ratio of the added 2-chloropropionic acid solution to the sodium hydroxide solution is 1: the molar ratio of 1.04,2-chloropropionic acid solution to trimethylamine solution is 1:1.3, after reacting for 2 hours at 15-20 ℃, heating to 30-40 ℃ for continuous reaction for 1 hour, and finally heating to 70 ℃ for reactionAnd 1h. When the solid content of the reaction liquid is 80-81%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 91-92%; the filter cake is leached by methanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 3 times of that of the solid mixture, and insoluble matters are removed by filtration after full stirring. Concentrating methanol extractive solution by distillation to 70deg.C saturated state, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a rate, and separating out 2- (trimethylammonium) propionate; filtering to remove precipitated solid, slowly adding diethyl ether serving as a poor solvent into the filtrate, wherein the diethyl ether is 5 times of the volume of methanol, the dropwise adding time of the poor solvent is 5-12 h, the 2- (trimethylammonium) propionate is precipitated and then filtered, the filtrate can be recycled after rectification, and betaine is dried by adopting a fluidized bed, and the drying temperature is 160 ℃.2- (trimethylammonium) propionate content was 98.81% and yield 94.53%.
Comparative example one
Adding sodium hydroxide solution into chloroacetic acid solution, controlling the neutralization temperature not higher than 0 ℃, then adding trimethylamine solution, reacting for 2 hours at 0-10 ℃, heating to 30-40 ℃ for continuous reaction for 1 hour, and finally heating to 70 ℃ for reaction for 1 hour. When the solid content of the reaction liquid is 74-76%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 90-91%; the filter cake is leached by methanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 2.5 times of that of the solid mixture, and insoluble matters are removed by filtration after full stirring. Concentrating methanol extractive solution by distillation to 70deg.C saturated state, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a speed, and precipitating betaine; filtering to remove betaine, slowly adding diethyl ether which is a poor solvent of betaine into the filtrate, wherein the diethyl ether is 5 times of the volume of methanol, filtering after the betaine is separated out, rectifying the filtrate, and recycling, wherein the betaine is dried by adopting a fluidized bed, and the drying temperature is 160 ℃. Betaine content 98.60% and yield 87.01%.
Comparative example two
Adding trimethylamine solution into chloroethylIn the acid solution, the neutralization temperature is controlled to be not higher than 0 ℃, then sodium hydroxide solution is added for reaction for 2 hours at the temperature of 0-10 ℃, the temperature is increased to 30-40 ℃ for continuous reaction for 1 hour, and finally the temperature is increased to 70 ℃ for reaction for 1 hour. When the solid content of the reaction liquid is 74-76%, filtering to remove precipitated solid substances under the heat preservation condition, and continuously distilling until the solid content is 90-91%; the filter cake is leached by methanol with the same volume, the leaching solution is used for dissolving and distilling the obtained solid mixture after supplementing new liquid, the solvent dosage is 2.5 times of that of the solid mixture, and insoluble matters are removed by filtration after full stirring. Concentrating methanol extractive solution by distillation to 70deg.C saturated state, stopping heating when solid starts to precipitate, and standing at 1deg.C for 10min -1 Cooling to 25 ℃ at a speed, and precipitating betaine; filtering to remove betaine, slowly adding diethyl ether which is a poor solvent of betaine into the filtrate, wherein the diethyl ether is 5 times of the volume of methanol, filtering after the betaine is separated out, rectifying the filtrate, and recycling, wherein the betaine is dried by adopting a fluidized bed, and the drying temperature is 160 ℃. Betaine content 98.72% and yield 89.55%.
Comparative example three
Water (1777 g), aqueous sodium hydroxide (50%, 203.7g,1.5 eq.) and aqueous trimethylamine (25%, 803 g,2.0 eq.) were mixed and stirred at 0deg.C. Ethyl (R) -4-chloro-3-hydroxybutyrate (content 91.7%,307.9 g) was added dropwise over 3 hours to the stirred reaction mixture. After a further one hour at 0 ℃, the reaction mixture was warmed to +20 ℃ to give L-carnitine in 85% yield.
The betaine content and the yield obtained by the above examples and comparative examples show that the different addition and mixing sequences of the tertiary amine, the alkaline compound and the chlorocarboxylic acid or the chlorocarboxylic acid ester have obvious influence on the yield of the product, the tertiary amine and the alkaline compound are mixed first, then the chlorocarboxylic acid or the chlorocarboxylic acid ester is added, the obtained betaine has the highest yield, the reaction temperature is controlled in a matched mode, the post-treatment process is optimized, and the like, so that the prepared betaine content, the quality and the like reach the optimal level.
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
While the present invention has been described with reference to the above-described embodiments, it is to be understood that the same is not limited to the above-described embodiments, but rather that the same is intended to be illustrative only, and that many modifications may be made by one of ordinary skill in the art without departing from the spirit of the invention and scope of the appended claims.
Claims (10)
1. The preparation method of betaine quaternary ammonium base is characterized by comprising the following steps: mixing tertiary amine and alkaline compound at below 25 deg.c, adding chlorocarboxylic acid or chlorocarboxylic ester, heating to 0-70 deg.c for reaction for 1-7 hr, concentrating the reaction liquid, desalting, re-crystallizing and drying to obtain the product.
2. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: the tertiary amine compound has the structural formula
In the middle of
R 1 、R 2 ＝—CH 3 or-CH 2 CH 3 ；
R 3 ＝—(CH 2 ) n CH 3 ，n＝0～17。
3. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: the alkaline compound is one of hydroxide, carbonate and bicarbonate of alkali metal, alkaline earth metal and ammonium.
4. A process for the preparation of betaine quaternary ammonium base according to claim 3, wherein: the alkaline compound is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, barium bicarbonate, ammonia water, ammonium carbonate and ammonium bicarbonate.
5. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: the structural formula of the chlorocarboxylic acid is
The structural formula of the chlorocarboxylic acid ester is
In the middle of
m=1 or 2;
R 4 ＝—CH 3 or-CH 2 CH 3 ；
R 5 ＝H、—CH 3 、—CH 2 CH 3 or-CH 2 C 6 H 5 。
6. A process for the preparation of betaine quaternary ammonium base according to any one of claims 1 to 5, characterized in that: the molar ratio of the chlorocarboxylic acid or the chlorocarboxylic acid ester to the monobasic basic compound is 1:1.04, the molar ratio of the chlorocarboxylic acid or the chlorocarboxylic acid ester to the dibasic basic compound is 1:0.52, the molar ratio of chlorocarboxylic acid or chlorocarboxylic acid ester to tertiary amine is 1:1.01 to 1.50.
7. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: concentrating the reaction solution, namely decompressing and distilling the reaction solution until the solid content is 74-82%, filtering under the condition of heat preservation to remove precipitated solids, and continuously distilling the filtrate until the solid content is 89-92%.
8. A process for the preparation of betaine quaternary ammonium base according to claim 1 or 7, characterized in that: the desalting process is to add organic solvent into the concentrated product, dissolve betaine completely and filter to eliminate insoluble matter.
9. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: the recrystallization process is that the filtrate after desalination is heated to 70 ℃, reduced pressure distillation is carried out until betaine starts to be separated out, then the temperature is slowly reduced to room temperature, the betaine is separated out, a poor solvent is slowly added into the filtrate after filtration, the betaine continues to be separated out, and a filter cake is filtered and collected.
10. A process for the preparation of betaine quaternary ammonium base according to claim 1, wherein: the drying is carried out by adopting a fluidized bed, and the drying temperature is 160 ℃.
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