CN1085660C

CN1085660C - Process for preparing monomer of sodium allylsulfonate

Info

Publication number: CN1085660C
Application number: CN99114744A
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: 2002-05-29
Anticipated expiration: 2019-03-26
Also published as: CN1243824A

Abstract

The present invention relates to a method for preparing sodium allylsulfonate monomers, which uses allyl chloride and sodium pyrosulfite as raw materials. A small quantity of OP emulsifying agent is firstly added in a sodium metabisulfite water solution with a certain concentration, then allyl chloride is added, and the sodium metabisulfite water solution with a certain concentration is controlled to have a proper pH value and temperature in a stirring device and a reflux device to react until the state without allyl chloride reflowing. Sodium allylsulfonate products with the purity of above 98 % can be obtained by separating and purifying reacting mixtures. The method has the advantages of less equipment investment, short reacting time, low energy consumption, easy product drying and low production cost. The monomers are mainly used as raw materials for producing chemical additives of the petroleum industry, additives of water treatment and additives of electroplating solutions.

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, and OP (polyoxyethylene octyl phenol ether) emulsifier is usedCarrying out an emulsification reaction in an oil-in-water type emulsification system; or a phase transfer agent is adopted, so that the reaction rate is greatly improved. The preparation method of the sodium allylsulfonate comprises the following steps: in the presence of OP emulsifier or phase transfer agent, adding allyl chloride into sodium metabisulfite aqueous solution, reacting until no allyl chloride flows back, concentrating the reaction mixture, filtering to remove salt, and drying the filtrate to obtain the product. 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, and the temperature is controlled between 40 ℃ and 70 ℃. And regulating the pH value of the reaction solution to be within the range of 8-11 by using a NaOH solution. The whole reaction time can be smoothly completed within 4-6 hours, and the mass ratio of the used raw materials of sodium metabisulfite and allyl chloride is 0.5-0.7: 1. After the reaction is finished, the reaction mixture contains a large amount of sodium chloride and a small amount of unreacted sodium sulfite besides the sodium allylsulfonate product. The liquid mixture has a product concentration of about 50%, and is concentrated and filtered 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 the solvent is dissolved and does not agglomerate, the solution preparation is easy to operate, thereby increasing the content of the product in the prepared liquid product mixture by about one time; in addition, sodium metabisulfite is much cheaper than sodium sulfite, which can reduce production cost. Emulsifying by using an OP emulsifier to form an oil-in-water type emulsifying system; or a phase transfer agent is used, 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 main chemical reaction equation of the preparation method of the sodium allylsulfonate monomer is as follows:

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 out, dissolved in 200 g ml of water and 30 g of allyl chloride was added dropwise with stirring under reflux. 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 under 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 out and dissolved in 110 mg of water, then 0.3 g of OP emulsifier was added and 50 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 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 indicate the presence of sulfur in the moleculeAn acid group. 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 917.3cm^-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 is solvent) is carried out¹HN-MR assay: delta_H＝5.00～6.00(2H，m，CH₂＝C)；4.39(H，S，C＝C-H)；3.24(2H，d，-CH₂-)。

The two analysis methods prove that the synthesized product has a structure of CH₂＝CHCH₂SO₃Na。

Claims

1. A preparation method of sodium allylsulfonate monomer is characterized by comprising the following steps: in the presence of OP emulsifier or phase transfer agent, adding allyl chloride into sodium metabisulfite aqueous solution, reacting until no allyl chloride flows back, concentrating the reaction mixture, filtering to remove salt, and drying the filtrate to obtain the product.

2. The method of claim 1, wherein: the reaction temperature is controlled to be between 40 and 70 ℃, and the pH is regulated to be within the range of 8 to 11.

3. The method of claim 1, wherein: the mass ratio of the sodium metabisulfite and the allyl chloride used as raw materials is 0.5-0.7: 1.