CN1126731C - Process for preparing unsaturated quaternary ammonium salt - Google Patents
Process for preparing unsaturated quaternary ammonium salt Download PDFInfo
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- CN1126731C CN1126731C CN99112567A CN99112567A CN1126731C CN 1126731 C CN1126731 C CN 1126731C CN 99112567 A CN99112567 A CN 99112567A CN 99112567 A CN99112567 A CN 99112567A CN 1126731 C CN1126731 C CN 1126731C
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Abstract
The present invention discloses a method for preparing unsaturated quaternary ammonium salts. Unsaturated tertiary amine, halogenated hydrocarbon and water react in a column type reactor; the preparation method of the present invention can continuously prepare the unsaturated quaternary ammonium salts and can shorten the reaction time; accordingly, the hydrolysis of raw materials in the reaction process, and the generation of the side reaction, such as product polymerization, etc. are reduced, the product yield and the product quality are improved, and both the raw material conversion rate and the product yield reach more than 99.5%.
Description
The present invention relates to a kind of preparation method of unsaturated quaternary ammonium salt, particularly relate to a kind of method that in the presence of water, in tower reactor, prepares unsaturated quaternary ammonium salt with unsaturated tertiary amine and halohydrocarbon.
Unsaturated tertiary amine is a kind of important fine chemicals with extensive use, carries out building-up reactions by corresponding unsaturated tertiary amine and halohydrocarbon usually and makes.Building-up reactions can be carried out in reactor, can disposable adding reactor as the unsaturated tertiary amine of reaction raw materials and water, add halohydrocarbon (as Ri Tekaiping 3-206067) more continuously; Also unsaturated tertiary amine be can add in advance, halohydrocarbon and water (as special public clear 63-18936 of day) in reactor, added again respectively continuously.With the disposable adding reactor of reaction raw materials, unsaturated tertiary amine generates methacrylic acid or vinylformic acid especially for the easier generation hydrolysis of the unsaturated tertiary amine of oleic series in reaction process, and product yield is reduced.And add unsaturated tertiary amine in advance, in reactor, add halohydrocarbon and water more respectively continuously, though can reduce the hydrolysis of unsaturated tertiary amine to a certain extent, along with the prolongation in reaction times, polymerization can take place in reaction product, and quality product decline, yield are reduced.
Moreover the building-up reactions of above-mentioned unsaturated quaternary ammonium salt is a neutralization reaction, is accompanied by the carrying out of reaction, will produce a large amount of reaction heat, and the too high polymerization that will cause raw material or product of temperature of reaction.Therefore, reaction heat in time being shifted out reaction system, is significant problem to be solved in the preparation process.Use reactor to react, the heat transfer area of still is less, and for reaction heat is in time shifted out, the most normal employing is the way of the logical low-temperature cooling water of inner coil pipe, and this has just increased general facilities consumption, has limited the expansion of throughput.
Ri Tekaiping 7-206,790 disclose a kind of synthetic method of unsaturated quaternary ammonium salt, it is characterized in that building-up reactions carries out in the reactor of similar thin-film evaporator, pass through mechanical stirring, liquid material is assigned on the downtake, makes methyl chloride gas and unsaturated reactive tertiary amine.As everyone knows, gas-liquid speed of response is subjected to the influence of gas in fluid surface absorption and velocity of diffusion, compares with liquid-liquid phase reaction, and gas-liquid reaction speed is slower.Utilize the reactor of this similar thin-film evaporator, though can reduce the hydrolysis of raw material, product yield is low, and the structure of reactor complexity of this similar thin-film evaporator, production efficiency is low, and needs to stir auxiliary mass transfer, has limited this technology in industrial large-scale application.
Chinese patent application 99112245.3 is a kind of methods of synthesizing unsaturated quaternary ammonium salt in tubular reactor by Qilu Petroleum Chemistry Co. Inst.'s development.This method product yield height, the reaction times is short, feed stock conversion height, but in tubular reactor because gas, liquid two-phase can not uniform mixing, so this method that the solution-air inhomogeneous reaction is prepared unsaturated quaternary ammonium salt is not too suitable.
In order to overcome the weak point that exists in the prior art, the object of the present invention is to provide that a kind of technology is simple, the reaction times is short, product yield is high, quality is good, but reaction raw materials can also homogeneous phase charging of heterogeneous charging, and the continuous method for preparing unsaturated quaternary ammonium salt that reaction effect and quality product all are improved.
In order to achieve the above object, the technical solution used in the present invention is as follows:
The unsaturated tertiary amine aqueous solution and halohydrocarbon react in tower reactor, there is chuck the tower reactor outside, logical temperature is 40～80 ℃ a water in the chuck, preferable with effect in 45～70 ℃ of scopes, the purpose of water flowing provides initial reaction temperature in the chuck, and reaction heat shifted out reaction tower, control reaction temperature.
Reaction tower inside is filled with reaction raw materials and product is inert conventional distillation filler or built-in sieve plate, its objective is to impel reaction raw materials at the inner thorough mixing of reaction tower.The inner filler of filling of reaction tower all is inertia to reaction raw materials and product, and its material can be selected stainless steel, pottery, glass, inert plastic such as tetrafluoroethylene etc. for use; Packed height is generally 1～10 meter, and comparatively ideal is 6～8 meters; Or built-in sieve plate in the tower, the number of sieve plate is generally more suitable at 30～50.
In above-mentioned reactor, according to the difference of reaction raw materials, the needed reaction times of its complete reaction is also inequality.Reaction times generally was controlled in 3～20 minutes, was good with 5～10 minutes; If the reaction times is lower than 3 minutes, then reaction not exclusively; If the reaction times surpasses 20 minutes, the side reaction degree can increase; The size that the control in reaction times can be by adjusting packed height in the reaction tower or sieve plate number or filling kind or stuffing hole or the size in sieve plate hole or for example adjust packed height and filling kind simultaneously or fill out diameter or adjust the sieve plate number simultaneously or the hole diameter of sieve (perforated) plate is realized by above-mentioned corresponding both being used in combination; Increase packed height or increase stage number and can prolong the reaction times, on the contrary also anti-; Increase the size of filler or stuffing hole or the size in sieve plate hole the reaction times is shortened, on the contrary also anti-.
The tower interior reaction temperature can be controlled by the temperature of water in the tower external jacket, and temperature of reaction generally is controlled at 40～80 ℃, is good with 45～70 ℃; If temperature of reaction is lower than 40 ℃, side reaction easily takes place in long reaction time, and transformation efficiency is low, and quality product is descended; If temperature of reaction is higher than 80 ℃, then exothermic heat of reaction is fast, many, reacts wayward.
Be dissolved with an amount of stopper in the unsaturated tertiary amine of raw material.Raw material enters reaction tower dual mode: if reaction raw materials is a homogeneous, as liquid-liquid phase feeding, the aqueous solution and the liquid halogenated hydrocarbon with unsaturated tertiary amine enters tower reactor through static mixer mixing back from the cat head opening for feed so; If reaction raw materials is non-homogeneous, for example gas-liquid phase feeding is that the reaction raw materials halohydrocarbon is a gas, then gas halohydrocarbon opening for feed at the bottom of the tower enters tower reactor, and the aqueous solution that is dissolved with the unsaturated tertiary amine of an amount of stopper enters tower reactor from the cat head opening for feed.
The mol ratio of unsaturated tertiary amine of reaction raw materials and halohydrocarbon is 1: 0.9～1: 2.0, is good with 1: 1～1: 1.05; If not in this scope, after reaction finished, transformation efficiency was low, and unreacted raw material is many, and product is difficult with separating of unreacting material, causes quality product to descend; The consumption of water reaches 70%～80% for suitable so that reaction finishes the concentration of back product.
The structure of the unsaturated tertiary amine of above-mentioned raw materials is suc as formula shown in (I):
Formula (I)
R in the formula (I)
1Be H or CH
3, n is 2～4 natural number, described halohydrocarbon can be used formula (II) expression:
R
2X formula (II) wherein, R
2Be the alkyl of alkyl or band aromatic group, X is a halogen.
After reaction was finished, effluent discharge port at the bottom of the tower entered the liquid collecting jar, washs with solvent then, removes unreacted unsaturated tertiary amine and halohydrocarbon, promptly gets product.With the amount of the unsaturated tertiary amine that contains in the gas Chromatographic Determination cleaning solvent, calculate feed stock conversion; Measure content sour in the product with the acid base neutralization titration method, this reaction raw materials transformation efficiency is greater than 99.5% after measured.
During the synthetic unsaturated quaternary amine of conventional art, comprise reinforced and slaking, entire reaction course is wanted 2～6 hours altogether, and needs in the reaction process to stir and heat exchange always.Because the reaction times is longer, the percent hydrolysis of the unsaturated tertiary amine of raw material increases on the one hand, generates lipid acid, thereby causes product acid number height, influences its deep processing and utilization; Moreover product can be brought out polymerization reaction take place, influences quality product.Compare with conventional art, the present invention has simplified reaction process, and reaction raw materials enters reaction tower can heterogeneous charging or homogeneous phase charging, and the reaction times foreshortens to original 1/10～1/40, with the total power consumption of equal yield line product is original 1/2, has both reduced energy consumption, has reduced the percent hydrolysis of raw material and the percent polymerization of product again, thereby reduce production costs, improved production efficiency.
In order to describe technical characterstic of the present invention better, be described further below in conjunction with embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Reaction tower is outside common stainless steel tower with chuck, and specification is 25 * 2.5mm, highly is 2m.Interior dress φ 4 * 4mm stainless steel Dixon ring filler, 1.8 meters of packed heights.Bath temperature is 80 ℃ in the chuck.Dimethylaminoethyl acrylate methyl base amido ethyl ester, water and Benzyl Chloride add tubular static mixer simultaneously with the input speed of 5g/min, 2.6g/min and 4.1g/min respectively, enter reaction tower through mixing the back from the cat head opening for feed in static mixer.Reaction mass reacts in reaction tower after 3 minutes and enters the liquid collecting jar.Do not add by analysis that dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume is 0.1% in the reaction mixture of processing, promptly feed stock conversion is 99.9%.Will be after the reaction solution step-down in the liquid collecting jar with the solvent benzol washing, remove unreacted methyl chloride and dimethylaminoethyl acrylate methyl base amido ethyl ester after, promptly obtain product.
Embodiment 2
Reaction tower is outside common stainless steel tower with chuck, and specification is 25 * 2.5mm, highly is 2.7m.Interior dress φ 4 * 4mm stainless steel Dixon ring filler, packed height is 2.5 meters.Bath temperature keeps 70 ℃ in the chuck.Dimethylaminoethyl acrylate methyl base amido ethyl ester, water and Benzyl Chloride add tubular static mixer simultaneously with the input speed of 8.0g/min, 4.16g/min and 6.56g/min respectively, enter reaction tower in static mixer after Over emulsfication mixes.Reaction mass reacts in reaction tower after 4 minutes and enters the liquid collecting jar.Do not add by analysis that dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume is 0.1% in the reaction mixture of processing, promptly feed stock conversion is 99.9%.
Embodiment 3
Except that the reaction times is 5 minutes, all the other are all with embodiment 2.Feed stock conversion is 99.8% by analysis.
Embodiment 4
Built-in 40 sieve plates of reaction tower, 2.2 meters of tower heights, the solarization bore dia is 2.5mm, 5/square centimeter of perforates, the sieve plate spacing is 50mm, bath temperature keeps 80 ℃ in the chuck.The dimethylaminoethyl acrylate methyl base amido ethyl ester, water and the Benzyl Chloride that contain the MEHQ of 2000ppm add tubular static mixer simultaneously with the input speed of 8.0g/min, 4.14g/min and 6.56g/min respectively and enter reaction tower after Over emulsfication mix.Reaction mass reacts in reaction tower after 4 minutes and enters the liquid collecting jar.Do not add by analysis that dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume is 0.2% in the reaction mixture of processing, promptly feed stock conversion is 99.8%.With after the solvent benzol washing, product acid content is 0.13% with the reaction solution in the liquid collecting jar.
Embodiment 5
8 meters of reaction tower heights, packed height is 7 meters, and reaction tower is the common stainless steel tower, and the specification of tower and the size shape of filler are all with embodiment 1.Bath temperature keeps 70 ℃ in the chuck.Dimethylaminoethyl acrylate methyl base amido ethyl ester, water enter reaction tower after mixing through static mixer emulsification with the input speed of 8.0g/min, 6.56g/min respectively.Methyl chloride gas pressure remains 0.1Mpa in the reaction tower.Reaction mass reacts in reaction tower after 6 minutes and enters the liquid collecting jar.Do not add by analysis that dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume is 0.1% in the reaction mixture of processing, promptly feed stock conversion is 99.9%.
Comparative Examples 1
Add the dimethylaminoethyl acrylate methyl base amido ethyl ester 157g of the MEHQ that contains 2000ppm in the 500ml flask, flask places 40 ℃ of water-baths.80g water and 126.5g Benzyl Chloride added flask respectively in 60 minutes, reaction is under agitation carried out.After reaction raw materials adds, bath temperature is brought up to 50 ℃, continued slaking reaction 1 hour.Dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume is 0.6% in the reaction end post analysis reaction mixture, and promptly feed stock conversion is 99.4%.After the benzene washing, product acid content is 0.24%
Comparative Examples 2
Add the dimethylaminoethyl acrylate methyl base amido ethyl ester 157g and the 80g water of the MEHQ that contains 2000ppm in the 500ml flask, flask places 40 ℃ of water-baths.126.5g Benzyl Chloride added flask in 60 minutes, other operation is 0.6% with dimethylaminoethyl acrylate methyl base amido ethyl ester residual volume in the Comparative Examples 1. reaction end post analysis reaction mixtures, and promptly feed stock conversion is 99.4%.After the benzene washing, product acid content is 0.43%.
Claims (10)
1. the preparation method of a unsaturated quaternary ammonium salt, comprise halohydrocarbon shown in the unsaturated tertiary amine shown in the formula (I), the formula (II) and water are added in the reactor, under 40～80 ℃, react, the mol ratio of unsaturated tertiary amine and halohydrocarbon is 1: 0.9～1: 2.0, it is characterized in that reacting in tower reactor carrying out;
R in formula (I) formula (I)
1Be H or CH
3, n is 2～4 natural number;
R
2X formula (II)
R in the formula (II)
2Be the alkyl of alkyl or band aromatic group, X is a halogen.
2, the method for claim 1 is characterized in that being equipped with in the tower reactor reaction raw materials and product is the inert filler.
3, the method for claim 1 is characterized in that built-in sieve plate in the tower reactor.
4, method as claimed in claim 2 is characterized in that loading in the tower reactor material and highly is 1～10 meter.
5, method as claimed in claim 4 is characterized in that loading the height of expecting in the tower reactor is 6～8 meters.
6, method as claimed in claim 3, the number that it is characterized in that built-in sieve plate in the tower reactor is 30～50.
7,, it is characterized in that the reaction times is 3～20 minutes as the described method of one of claim 1～6.
8, method as claimed in claim 7 is characterized in that the reaction times is 5～10 minutes.
9, the method for claim 1 is characterized in that temperature of reaction is 45～70 ℃.
10, the method for claim 1, the mol ratio that it is characterized in that described unsaturated tertiary amine and halohydrocarbon is 1: 1～1: 1.05.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112567A CN1126731C (en) | 1999-11-17 | 1999-11-17 | Process for preparing unsaturated quaternary ammonium salt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112567A CN1126731C (en) | 1999-11-17 | 1999-11-17 | Process for preparing unsaturated quaternary ammonium salt |
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| CN1296942A CN1296942A (en) | 2001-05-30 |
| CN1126731C true CN1126731C (en) | 2003-11-05 |
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| CN99112567A Expired - Fee Related CN1126731C (en) | 1999-11-17 | 1999-11-17 | Process for preparing unsaturated quaternary ammonium salt |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7973195B2 (en) * | 2009-07-22 | 2011-07-05 | Kemira Oyj | Process for unsaturated quaternary ammonium salt |
| US8247597B2 (en) * | 2010-01-21 | 2012-08-21 | Nalco Company | Continuous production of DMAEA quaternary salts |
| CN102219703B (en) * | 2010-04-16 | 2014-04-23 | 中国科学院理化技术研究所 | Benzyl-contained cationic polymerizable surface activated monomer and preparation method and ionic copolymer |
| CN104744275A (en) * | 2015-03-23 | 2015-07-01 | 浙江友联化学工业有限公司 | Preparation method of quaternary ammonium cationic monomer aqueous solution |
| CN115253995B (en) * | 2022-09-30 | 2023-04-07 | 江苏富淼科技股份有限公司 | Tower-type quaternary ammonium salt production device and quaternary ammonium salt production method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174188A (en) * | 1996-07-08 | 1998-02-25 | 埃勒夫阿托化学有限公司 | Stabilized aqueous solutions of unsaturated quaternary ammonium salts |
| CN1176961A (en) * | 1996-07-08 | 1998-03-25 | 埃勒夫阿托化学有限公司 | Process for manufacture of aqueous solutions of unsaturated quaternary ammonium salts |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174188A (en) * | 1996-07-08 | 1998-02-25 | 埃勒夫阿托化学有限公司 | Stabilized aqueous solutions of unsaturated quaternary ammonium salts |
| CN1176961A (en) * | 1996-07-08 | 1998-03-25 | 埃勒夫阿托化学有限公司 | Process for manufacture of aqueous solutions of unsaturated quaternary ammonium salts |
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