JPH03502451A - Quaternary chlorination method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Quaternary chlorination method This invention relates to the production of an aqueous solution of an unsaturated quaternary ammonium salt corresponding to the following formula (1). It concerns the method: H,C=CH-C(0)-A-R,-N” (R, )(R,)(R), X-where, A is an oxygen atom or an NH group, R5 is a linear or branched alkyl group having 1 to 6 carbon atoms, R1, R2 and R are an alkyl group or an aryl group, and may be the same or different. , and X is CL Br, , I SC1 (s-Cow and CH, -5 Selected from O4.

European patent application EP-A-250325 discloses that at least one polymerization inhibitor In the presence of the agent, the following formula (■): 11, c=C(R3)-C(0)-A-R, - At least one (meth)acrylic monomer of N(R1)(R2) and the formula (■) : From at least one quaternizing agent (quaternary chlorinating agent) of RX, the following formula (I): )12C=C(R3) -C(0)-A-R,-N"(R,)(R2 ) (R), X - (where, A is an oxygen atom or an NH group, R5 is a hydrogen atom or a methyl group, R4 is a straight or branched alkyl group having 2 to 4 carbon atoms, R, and R2 are an alkyl group or an aryl group, and may be the same or different from each other. often, R is an alkyl or aryl group, and X is C1,0rSr, (:)Is -COs, CL-S mouth) A method is described for producing an aqueous solution of an unsaturated quaternary ammonium salt corresponding to . This method is characterized by: (a) The quaternizing agent is continuously introduced into the reactor. 5 to 20% by weight of (methyl)amine is introduced and the amount necessary for the reaction of the quaternizing agent (III). Kryl monomers are reacted in a closed reactor, (c) then water and the remaining quaternized agent (III) to achieve the desired concentration of quaternary ammonium salt (1) in water; (c) The temperature in stages (a) and (b) is maintained between 30 and 60°C, ( d) introduced into the reactor during stages (a) and (a), especially near the end of the reaction. The ratio of the total volume of gas coming out of the reactor to the oxygen capacity being produced is 100/1. Maintain an oxygen gas flow in the reaction medium such that:

By using this method, unsaturated quaternary ammonia which is stable for more than one year at ambient temperature can be obtained. It is possible to produce aqueous solutions of um salts. However, there are impurities in this aqueous solution. , especially hydrolysis products such as CH*=CH-〇(0)-^H(IV) and acrylic contains monomer (II). The content of these impurities is determined when A is an oxygen atom. This is particularly high when Moreover, this method requires a considerably long reaction time. Therefore, it is clearly economically disadvantageous.

The problem to be solved by the present invention is to reduce the production of impurities while at the same time reducing the quaternization reaction. We present a method for producing water-soluble unsaturated quaternary ammonium salts that can be produced in a short time. It is about providing.

A subject of the invention is the following formula (■) in the presence of at least one polymerization inhibitor: 11, c=cH-C(0)-A-R, -N(R,)(R,) (R, R, in the formula R2, R5, Ai6 and x have the meanings given above) at least one acrylic monomer of the formula RX; and at least one quaternizing agent of the formula RX. , the following formula (I): H,C=CH-C(0)-A-R,-N"(R,)(R 2) Method for producing an aqueous solution of unsaturated quaternary ammonium salt corresponding to (R) and X- The law is (1) In the first step (a), the amount necessary for the reaction of at least one quaternizing agent is 0-30% by weight, preferably 5-25% by weight of at least one acrylic monomer (II>) or unsaturated quaternary ammonium containing 50 to 85% by weight of the above salt. reacting 5 to 50% by weight, preferably 5 to 20% by weight of the aqueous solution of the um salt, (2) v. In the second step (c), add water and quaternizing agent (III), (3) Step (a) above: The reaction of step) is carried out in the presence of oxygen from 10°C to 90°C, preferably from 40°C to 80°C. (4) At the end of the reaction, the pressure is gradually lowered to atmospheric pressure and at the same time is the total gas exiting the reactor relative to the volumetric flow rate of oxygen introduced into the reactor. In a method in which the volumetric flow rate of the gas is 100 or less, preferably 50 or less, The method is characterized in that the reaction is carried out under an absolute pressure of 3 to 10 bar.

To ensure the presence of oxygen during the above reaction, (1) the reaction medium must be air or pure maintained under pressure of an oxygen-containing gas such as oxygen, or (2) total volumetric flow rate of oxygen coming out of the reactor relative to the volumetric flow rate of oxygen introduced into the reactor; The oxygen content is adjusted so that the ratio of the total volumetric flow rate of the gas is 100 or less, preferably 50 or less. Scavenge with gas.

At the end of the reaction, when the reaction medium is at atmospheric pressure, an oxygen-containing gas such as air is Volatile quaternizing agent (III) dissolved in the reaction medium in large quantities Remove traces of.

Preferably, the reaction time does not exceed about 10 hours.

In step (b) above, the saturated or nearly saturated unsaturated quaternary ammonium salt (1) is Adjust the amount of water and the amount of quaternizing agent (II) to maintain it in the aqueous reaction medium. do. This is generally done by selecting a water/quaternary agent molar ratio of about 1.5 to 3. be exposed.

This ratio increases as the reaction temperature decreases and the amount of quaternizing agent introduced in step (a) increases. The higher the number, the higher the value.

If the quaternizing agent (n) is a volatile compound under the reaction conditions, the The quaternizing agent is introduced in such a way that its disappearance is minimized. By doing so, The loss is maintained below 10% of the stoichiometric amount, for example 3%. The gas coming out of the reactor is , a process to almost completely remove traces of the quaternizing agent (1) contained in the gas. lead to the physical equipment. Preferably, the quaternizing agent is added to the gas exiting the reactor into the dielectric 2 reactor. There, the acrylic monomer and the quaternizing agent are reacted.

The method of the present invention uses easily hydrolyzed acrylic monomers, such as dimethylaminoethyl Acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl Suitable for quaternization such as acrylamide.

Quaternizing agents suitable for the process of the invention include halogenated hydrocarbons, such as methyl chloride, odor Methyl chloride, ethyl chloride, ethyl bromide, ethyl iodide, benzyl chloride, dimethyl chloride ruphate, dimethyl carbonate.

Polymerization inhibitors suitable for the present invention include butyl-4-hydro for 3,5-ditases. xy-toluene, hydroquinone methyl ether, phenothiazine, hydroxy-toluene non-catechol, catechol and tert-butylcatechol. acrylic single Using 1100 pp to 500 ppra of polymerization inhibitor for polymer (II) is desirable.

The method of the present invention has an extremely low amount of impurities, for example, acrylic monomer (II>0.6). Less than % by weight, CH2=C[I-C(0)-AI　, (rV) (A has the above meaning ) is less than 0.4% by weight and the concentration of salt (1) in water is about 50-8 An aqueous solution of unsaturated quaternary ammonium salt (1) which is 5% by weight can be prepared. Ru.

Furthermore, the aqueous solution of unsaturated quaternary ammonium salt obtained by the method of the present invention is It can be stored stably for more than a year at low temperatures.

The invention may be better understood by means of the examples given below by way of illustration. In addition , percentage is weight %.

Using 700 ppm hydroquinone methyl ether in a jacketed reactor. Add 515 g of dimethylaminoethyl acrylate stabilized by stirring. .

While maintaining the following conditions during the reaction period, air was continuously introduced into the reactor at a rate of 0.2N1/h. Voiced by: (1) Temperature 47℃ (2) Atmospheric pressure (3) The flow rate from the ventro is 0.7N+ or less (i.e., the amount of water introduced into the reactor (The volume ratio of the effluent from the vent to the oxygen produced should be less than 17.5) In the first stage, 18 g of methyl chloride was added into the reactor at a rate of 30 g per hour (i.e. 11% of the total amount of CH and CI required. In the second step, methane chloride water and water were continuously blown into the reactor at a water/CH3Cl weight ratio of 0.95. Get into it.

When the reaction approaches the end, gradually reduce the flow rate of methyl chloride to 10 g/h, and The flow rate from the reactor is kept below INI/h (therefore, the amount of oxygen entering the reactor is (The ratio of the outflow amount from the ventro to that from the vent hole is less than 25).

The operation is stopped after 15 hours of reaction.

In this operation, 174 g of water and 196 g of methyl chloride are used to produce 865 g of acrylate. Liloyloxyethyltrimethylammonium chloride is an 80% aqueous solution. will be collected.

Next, air was introduced into the product at a flow rate of 7 NI/h for 30 minutes under heating, and then at room temperature. Blow in for 30 minutes.

The properties of the final product are as follows: Water 20.4% acrylic acid 0.69% dimethylaminoethyl acrylate 1. 3% methyl chloride 15ppm storage stability 　　　　　　　　Over 1 year Example 2 700 ppm of 71-hydroquinone methyl ether in a jacketed reactor. 357.5 g of dimethylethylaminoethyl acrylate stabilized using Add while stirring.

During the reaction period, air was continuously blown into the reactor at a flow rate of 0.15N1/h. Adjust the valve attached to the throttle to maintain an absolute pressure of 4 knots. temperature of operation Adjust the temperature to 50°C throughout the entire process.

During the synthesis, the flow rate from the ventro should be kept below 0.8 NI/h (i.e., blowing into the reactor). Keep the ratio of the volume of gas flowing out from the vent to the oxygen injected to 30 or less. Two.

In the first stage, 15 g of methyl chloride (i.e., the CH3C required for the reaction) is added to the reactor. 1) for 30 minutes.

In the second step, the remaining methyl chloride and water are mixed at a water/CH, CI weight ratio of 0.95. and infuse continuously over 3 hours.

Increase the flow rate of air fed into the reactor to INI/h and The outflow rate should be less than 10 NI/h (therefore, the amount of oxygen from the ventro The system pressure is gradually reduced to atmospheric pressure over an hour by controlling the ratio to the outflow capacity to 50 or less. get closer to

This operation uses 121 g of water and 139 g of methyl chloride to produce 601 g Acrylooxyethyltrimethylammonium chloride is an 80% aqueous solution. and collected.

This product was blown with air at a flow rate of 10 NI/h for 30 minutes under heating and then at room temperature. Infuse for 30 minutes.

The properties of the final product are as follows: Water 20.1% acrylic acid 0.30% dimethylaminoethyl acrylate 0.40% methyl chloride 10ppm storage stability International search report for more than 1 year

Claims (1)

[Claims] 1. Formula (I) below: H2C=CH-C(0)-A-R3-N+(R1)(R2)(R),X-(here in, A is an oxygen atom or an NH group, R3 is a straight or branched alkyl group having 1 to 6 carbon atoms; R1, R2 and R are an alkyl group or an aryl group, and may be the same or different. and X is C1, Br, I, CH3-C03 and CH3-S04. (selected from) An aqueous solution of an unsaturated quaternary ammonium salt represented by at least one polymerization inhibitor in the presence of the following formula (II): H2C=CH-C(0)-A-R3-N(R1 )(R2) (Here, R, R1, R2, R3, A and X in the formula have the above meanings. have) at least one acrylic monomer of formula (III): RX (1) In the first step (a), at least and at least 0 to 30% by weight of the amount necessary for the reaction of one quaternizing agent (III). React one acrylic monomer (II) or contain 50-85% by weight of the above salts. reacting 5 to 50% by weight of an aqueous solution of an unsaturated quaternary ammonium salt, (2) In the second step (b), the concentration of unsaturated quaternary ammonium salt in water is Add water and quaternizing agent (III) until the desired value is reached, (3) The reactions in steps (a) and (b) above are carried out at 10°C to 90°C in the presence of oxygen. Performed at a temperature between (4) At the end of the reaction, the pressure is gradually lowered to atmospheric pressure and at the same time the pressure is introduced into the reactor. The ratio of the total volumetric flow rate of gas exiting the reactor to the volumetric flow rate of oxygen introduced is 10 In the method of making it 0 or less, A method characterized in that the reaction is carried out under an absolute pressure of about 3 to 10 bar. 2. In the first step (a), 5 to 25% by weight of the amount required for the reaction of the quaternizing agent (III) % of at least one acrylic monomer is reacted. The method described in paragraph 1. 3. In the first step (a), at least one acrylic monomer is converted into an unsaturated quaternary ammonium 5 to 20% by weight of an aqueous solution of the nium salt (I). A method according to scope 1 or 2. 4. At the end of the reaction, the volumetric flow rate of oxygen introduced into the reactor leaving the reactor Claims 1 to 3 are characterized in that the ratio of the total volumetric flow rate of the gas is 50 or less. The method according to any one of Item 3. 5. Claims 1 to 4, characterized in that the reaction time does not exceed 10 hours. The method described in any one of the above. 6. Claims characterized in that the temperature is maintained between 40 and 80° C. during the reaction. The method according to any one of items 1 to 5. 7. In the second step (b), the saturation of the unsaturated quaternary ammonium salt (I) in the reaction medium water and the quaternizing agent (III) to maintain an aqueous or near saturated aqueous solution. According to any one of claims 1 to 6, the flow rate is adjusted. the method of. 8. characterized in that the molar ratio of water/quaternizing agent in the second step (b) is between 1.5 and 3; The method according to claim 7.