CN1243824A

CN1243824A - Process for preparing monomer of sodium allylsulfonate

Info

Publication number: CN1243824A
Application number: CN 99114744
Authority: CN
Inventors: 梁发书; 李建波
Original assignee: Southwest Petroleum University
Current assignee: Southwest Petroleum University
Priority date: 1999-03-26
Filing date: 1999-03-26
Publication date: 2000-02-09
Anticipated expiration: 2019-03-26
Also published as: CN1085660C

Abstract

本发明涉及一种以烯丙基氯和焦亚硫酸钠为原料,制备烯丙基磺酸钠单体的方法。先在一定浓度的焦亚硫酸钠水溶液中,加入水许OP乳化剂,再滴加烯丙基氯,在有搅拌和回流装置中控制适当pH值和温度,反应至无烯丙基氯回流时为止。反应混和物经分离、提纯可得纯度为98%以上的烯丙基磺酸钠产品。本方法设备投资少、反应时间短、能耗低、产品易干燥、生产成本低。本单体主要用于石油工业化学添加剂、水处理添加剂、电镀液添加剂的生产原料。The invention relates to a method for preparing allyl sodium sulfonate monomer by using allyl chloride and sodium pyrosulfite as raw materials. Firstly, add a little OP emulsifier in a certain concentration of sodium metabisulfite aqueous solution, then add allyl chloride dropwise, control the appropriate pH value and temperature in a stirring and reflux device, and react until there is no allyl chloride reflux. The reaction mixture is separated and purified to obtain sodium allyl sulfonate with a purity of over 98%. The method has the advantages of less equipment investment, short reaction time, low energy consumption, easy drying of products and low production cost. This monomer is mainly used as a raw material for the production of chemical additives in the petroleum industry, water treatment additives, and electroplating solution additives.

Description

Preparation method of sodium allylsulfonate monomer

The invention relates to a method for preparing an allyl sodium sulfonate monomer by using allyl chloride and sodium metabisulfite as main raw materials, belonging to a preparation method of an alkene monomer.

In chemical production, the sulfonation of aromatic hydrocarbon is easier to introduce sulfonic acid groups on aromatic rings, but the introduction of sulfonic acid groups in non-aromatic hydrocarbons and high molecular compounds without aromatic rings is more difficult. Due to the introduction of sulfonic acid groups, many properties of the compound are obviously changed, such as greatly increased water solubility, enhanced thermal stability and increased electrolyte resistance, so that the compound has wider application. Chemical additives are commonly used in the petroleum industry and are required to be highly water soluble, not decomposed at high temperatures and have little effect on formation water salinity. Practice proves that a proper amount of sulfonic acid groups are introduced into some additive molecules, so that the requirements of the petroleum engineering technology can be met. In addition, a proper amount of sulfonic acid groups are often required to be introduced into the molecules of the water treatment additive and the electroplating solution additive so as to meet certain performance requirements. The sulfonic group can be conveniently introduced into the macromolecular compound by copolymerizing the sodium allylsulfonate monomer and other monomers such as acrylic acid, acrylamide, acrylonitrile and the like.

At present, from the relevant data at home and abroad, the method for preparing sodium allylsulfonate discloses a method for directly synthesizing sodium allylchloride and sodium sulfite in journal of 5 th period of natural industry in 93 years (the author is the inventor of the patent). This method has been found to have serious drawbacks when it is industrially produced, and thus, the industrial applicability thereof is lost. The main performance is as follows: (1) the raw material allyl chloride and the solvent water are not mutually soluble, and the reaction system is an inhomogeneous system, so that the reaction must be vigorously stirred during the reaction. Even in this case, the reaction time is long, the energy consumption is high, and the raw material loss is large, because the reaction time is 20 hours or more when the reaction is completed. (2) The solubility of the sodium sulfite as the raw material in water is low, the sodium sulfite is easy to agglomerate, and if the operation is wrong, the sodium sulfite is easy to form large blocks, thereby bringing great difficulty to production operation. When the product is prepared, a large amount of water is added to dissolve the product, and finally the product is low in content and high in moisture content. In order to dry the product, the liquid product needs to be concentrated for a long time to obtain a solid product, and the liquid product is usually self-polymerized due to high temperature in the concentration process, so that the product quality is affected, and the cost is increased.

The invention aims to overcome the defects of the prior art and provides a novel method for preparing sodium allylsulfonate. So as to accelerate the reaction speed, shorten the reaction time and achieve the purpose of reducing the product cost and realizing industrial production.

The invention is mainly characterized in that: sodium pyrosulfite and allyl chloride are used as raw materials, OP (polyoxyethylene octyl phenol ether) emulsifier (or phase transfer agent) is adopted for emulsification (or phase transfer), and reaction is carried out in an oil-in-water type emulsification system, so that the reaction speed is greatly improved. The preparation method of the sodium allylsulfonate comprises the following steps: in the aqueous solution of sodium pyrosulfite with a certain concentration, a little OP emulsifier is firstly added, and allyl chloride is added according to a certain proportion and a certain dropping speed. The reaction is carried out in a reaction kettle with a stirring and refluxing device, a constant-temperature heater is arranged in the reaction kettle, the temperature is controlled to be 40-70 ℃, the PH of a reaction solution is regulated and controlled to be within the range of 8-11 by using a NaOH solution, and no allyl chloride is refluxed and reactsWhen the reaction is completed, the reaction is terminated. The whole reaction time can be smoothly finished within 4-6 hours, and the used raw materials are in the following proportion (molar ratio): sodium metabisulfite and allyl chloride are 0.5-0.7: 1. After the reaction is finished, the product is a liquid product, and the concentration of the product is about 50%. Besides the sodium allylsulfonate, a large amount of sodium chloride and sodium sulfite which is not completely reacted are contained in the reaction mixture. Concentrating the liquid mixture, filtering to remove salt (NaCl, Na)₂SO₃) And drying the filtrate to obtain the sodium allylsulfonate product with the purity of more than 98 percent.

Sodium metabisulfite is used instead of sodium sulfite because sodium metabisulfite has a solubility two times greater than sodium sulfite and its hydrolysis is carried out gradually, so that the amount of water used in the preparation of the aqueous sodium metabisulfite solution can be reduced by about half. Because it is not easy to be dissolved and agglomerated, the content of the prepared liquid product is increased by about one time, and in addition, the sodium metabisulfite is much cheaper than sodium sulfite, so that the production cost can be reduced. The OP emulsifier (or phase transfer agent) is adopted for emulsification (or phase transfer) to form an oil-in-water type emulsification system, so that the reaction time can be shortened. The whole production process is easy to operate, the product quality can be improved, and the industrial production of the sodium allylsulfonate becomes possible.

The preparation method of the sodium allylsulfonate monomer comprises the following main chemical reaction equation:

1.

2.

3.

the sodium allylsulfonate product of the invention has wide application, and is mainly used as a raw material in the production and preparation of chemical additives, water treatment additives, electroplating liquid additives and the like in the petroleum industry.

Compared with the prior art, the preparation method of the product has the following advantages:

(1) the sodium metabisulfite is used to replace sodium sulfite, the whole production process is easy to operate, the equipment investment is low, the product is easy to dry, and the production cost is low.

(2) The emulsifier (or phase transfer agent) is adopted, the reaction time is greatly shortened, the energy consumption is reduced, and the industrial production of the catalyst becomes possible.

Two examples are given to illustrate the preparation of sodium allylsulfonate and to compare the effect of emulsifiers on the reaction rate.

Example 1 sodium metabisulfite 60.0 g was weighed, dissolved in 200 ml of water, and 30 g of allyl chloride was added dropwise under stirring and refluxing. After the addition, the temperature was raised to 60 ℃ and maintained at a constant temperature. The pH was adjusted to 10 with sodium hydroxide. When the reaction was carried out to reflux without allyl chloride, the end point of the reaction was reached, which took about 24 hours. Cooling the liquid product to room temperature, filtering to remove salt, concentrating the filtrate, and drying to obtain white powder product.

Example 2 sodium metabisulfite 60.0 g was weighed, dissolved in 110 ml of water, followed by the addition of 0.3 g of OP emulsifier and the dropwise addition of 50 g of allyl chloride under stirring and reflux. After the addition, the temperature was raised to 60 ℃ and maintained at a constant temperature. The pH was adjustedto 10 with sodium hydroxide. When the reaction was carried out to reflux without allyl chloride, the end point of the reaction was reached, which took about 5 hours. And cooling the liquid product to room temperature, filtering to remove insoluble substances and salt, concentrating the filtrate, and drying to obtain the sodium allylsulfonate product.

Characterization of the product synthesized above: the infrared spectrum of the product was determined on a Bruker-120 FI-IR spectrometer by KBr pellet: at 1043.4cm^-1And 1158cm^-1All have strong absorption peaks, which indicates that the molecules have sulfonic acid groups. At 1642.6cm^-1The stretching vibration peak of C-C bond appears at 3087.3cm^-1A symmetric stretching vibration peak of C-H appears at 1844cm^-1、995.4cm^-1And 947.3cm^-1Is ═ CH₂Is provided with an out-of-plane rocking bending shock absorbing peak.

With FX-90Q nuclear magnetic resonance apparatus (internal standards TMS, D)₂O as solvent) was determined by' HN-MR: δ H is 5.00 to 6.00(2H, m, CH)₂＝C)；4.39(H.S.C＝C-H)；3.42(2H，d，-CH₂-)。

Warp of the aboveTwo analysis methods prove that the synthesized product has the structure as follows: CH (CH)₂＝CHCH₂SO₃Na。

Claims

1. a preparation method of sodium allyl sulfonate monomer is characterized in that: use sodium pyrosulfite and allyl chloride as raw material, adopt OP emulsifier to carry out emulsification, first in the sodium pyrosulfite aqueous solution of certain concentration, add a little OP emulsifier (polyoxyethylene octyl phenol ether), add allyl chloride at a certain drop rate, and react in a stirring and reflux device until there is no allyl chloride reflux, and the reaction mixture is filtered to remove salt. The filtrate is concentrated and dried to obtain the product.

2. The preparation method according to claim 1, characterized in that: the reaction temperature is controlled between 40-70° C., and the pH is regulated within the range of 8-11.

3. The preparation method according to claim 1, characterized in that: the ratio of raw materials used (molar ratio) is, sodium metabisulfite: allyl chloride=0.5～0.7:1.