A method for continuously preparing polythiol chloride

Abstract

The present invention relates to the technical field of new material synthesis, and specifically to a method for continuously preparing polythiochloride, which comprises the following steps: step S1: mixing bis(dimethylaminoethyl)ether and water in a weight ratio of 1:1.1; step S2: continuously conveying the reaction raw material A obtained in step S1 and ethylene dichloride to a dynamic tubular reactor with a process setting temperature through pulses, controlling the feed amount to be respectively the process setting value, and discharging the material through a pressure reducing valve and analyzing the product by GC; step S3: continuously discharging the material through a pressure reducing valve and discharging the material through a pressure reducing valve, and the material is fed into a crude decolorization kettle, and then activated carbon is added for adsorption treatment, and the activated carbon is removed by positive pressure filtration, and the filtrate is decompressed and desolventized to remove part of the water. The present invention adopts bis(dimethylaminoethyl)ether aqueous solution and ethylene dichloride as raw materials, and respectively conveys them to a dynamic tubular reactor with a process setting temperature through pulses, and obtains a high-quality polythiochloride product after decolorization by activated carbon and desolventizing the filtrate.

Description

Technical Field

[0001] The invention relates to the technical field of new material synthesis, in particular to a method for continuously preparing polythiol chloride. Background Art

[0002] Polythiochloride, Chinese name: polydichloroethyl ether tetramethylethylenediamine, its CAS: [31075-24-8], English name: Polyquats-GreatAp126. This product is a cationic polymer fungicide algaecide, which can be used to prepare an excellent agent for controlling algae in swimming pools. It is the sixth generation of quaternary ammonium salt fungicide algaecide.

[0003] Its chemical structure is as follows:

[0004]

[0005] This product effectively inhibits all types of floating green algae, as well as black algae that adhere to the walls and bottom of swimming pools. Regular use in swimming pools effectively controls a range of problems caused by various bacteria and algae, including damage to the pool's appearance, turbidity, unpleasant odors, filter clogging, and gradually increasing chlorine demand. It can be used in both acidic and alkaline environments. Unlike conventional quaternary ammonium salts, this product will not produce foam even when added in high concentrations, and will not affect the use of sand, diatomaceous earth or other types of filters.

[0006] At present, there are four main synthetic routes for polythiol chloride:

[0007] 1. Applied Chemical Industry, Vol. 37, No. 2, February 2008, pp. 149-152 reported that Wang Ying et al. prepared a new type of polyquaternary ammonium salt by copolymerization reaction using N,N,N′,N′-tetramethylethylenediamine and dichloroethyl ether as raw materials, reacting at 70°C for 6 hours. The anaerobic bacteria were sterilized. When the dosage was 80 mg / L and the sterilization time was 9 hours, the sterilization rate reached 98%.

[0008] 2. Buckman Laboratory Chemicals discloses a method for preparing polythiochloride in U.S. Pat. No. 3,771,989 (A). In a 300-gallon stainless steel reactor equipped with a stirrer, 317 pounds of N,N,N',N'-tetramethylethylenediamine, 392 pounds of dichloroethyl ether and 381 pounds of water are added. The contents are stirred and hot water is introduced into the jacket. The temperature is maintained at 93-102° C. and the reaction time is up to 16 hours. At the end of this period, the resulting aqueous polymer solution is cooled and removed from the reactor.

[0009] 3. Patent CN103621502 (A) of Changzhou University - discloses a preparation method and application of an organic polymer heterotrophic fungicide, which uses tetramethylethylenediamine and dichloroethyl ether as main raw materials, hydrogen peroxide as initiator, heats to 70°C, and reacts for 8 hours to synthesize water-soluble PACZMT (polythiochloridum) in a "one-step" manner.

[0010] 4. Zhou Yi, Luan Anbo, Qiu Meijian - reported the synthesis and biocidal properties of a polyquaternary ammonium salt in Guangdong Chemical Industry. The specific operation is to add tetramethylethylenediamine and deionized water, mix well, wait for the temperature to rise to 98°C, slowly drip dichloroethyl ether, maintain the temperature unchanged, reflux reaction for 10-16 hours, and after the reaction is completed, cool to room temperature to obtain a viscous yellow liquid.

[0011] The reaction equation is as follows:

[0012] .

[0013] The disadvantage of the current production method is that tetramethylethylenediamine and dichloroethyl ether are used as raw materials to synthesize water-soluble high molecular weight polyquaternary ammonium salt under catalyst conditions. The introduction of catalysts will affect the quality of the product and lead to unqualified products. If the reaction temperature is 93-102°C and the reaction time is as long as 16 hours, the reaction conversion rate is low and the material appearance is soy sauce color, which does not meet the customer's product requirements.

[0014] In summary, finding a continuous preparation method for polythiochloridum with the advantages of "low raw material cost, high product purity and yield, and less three wastes" has become a technical problem that needs to be solved urgently. Summary of the invention

[0015] The object of the present invention is to provide a method for continuously preparing polythiol chloride to solve the problems raised in the above background technology.

[0016] To achieve the above object, the present invention provides the following technical solution: a method for continuously preparing polythiochloride, wherein the chemical formula of polythiochloride is as follows:

[0017] ;

[0018] And the preparation method includes the following steps:

[0019] Step S1: Preparation of reaction raw material A:

[0020] Mix bis(dimethylamino)ethyl ether and water in a weight ratio of 1:1.1;

[0021] Step S2: Continuous flow reaction operation:

[0022] The reaction raw material A obtained in step S1 and dichloroethane are continuously conveyed to a dynamic tubular reactor with a process set temperature by pulse, and the feed amount is controlled to be the process set value, the reaction pressure is 0.3-2.0MPa, the reaction temperature is 130-150°C, and the reaction time is 10-30 minutes. After the product is discharged by a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylaminoethyl)ether raw material in the amination product is less than 1%;

[0023] Step S3: Reaction treatment:

[0024] The material is discharged continuously through the pressure reducing valve and sent to the crude decolorization kettle. Then, activated carbon is added for adsorption treatment. The activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water. The solid content is tested. When it reaches 60-65%, the polythiochloride product is packaged.

[0025] Preferably, the flow rate ratio of the reaction raw material A to ethylene dichloride in step S2 is 1:0.6-6, preferably 1:1-3.

[0026] Preferably, the internal temperature of the dynamic tubular reactor in step S2 is 138-140°C.

[0027] Preferably, the reaction time in step S2 is 10-30 minutes.

[0028] Preferably, in step S2, the reaction pressure is adjusted to 1.0-2.0 MPa to obtain a polythiol chloride product with uniform quality and high purity.

[0029] Preferably, in step S3, after the activated carbon adsorption treatment, the activated carbon is removed by centrifugal filtration, so that the polythiochloride product can be better purified.

[0030] Preferably, in step S3, after the saturated solution is subjected to a reduced pressure desolventizing treatment, it is further concentrated to obtain a polythiochloridum product having a solid content of 70-75%.

[0031] Preferably, the product obtained in step S2 is treated in a crude product decolorization kettle and then decolorized by ultrafiltration to obtain a high-purity polythiol chloride product.

[0032] Preferably, in step S2, the reaction raw material A and ethylene dichloride are preheated in a pre-reactor and then reacted in a dynamic tubular reactor to improve the yield of polythiol chloride.

[0033] Preferably, in step S3, after the activated carbon is removed by positive pressure filtration, the concentrated liquid is treated with ozone oxidation to eliminate some impurities and improve the purity of the polythiochloridum product.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1. The present invention uses bis(dimethylaminoethyl) ether aqueous solution and ethylene dichloride as raw materials, which are respectively continuously transported to a dynamic tubular reactor with a process set temperature through pulses. After the reaction is completed, the filtrate is decolorized with activated carbon and desolventized to obtain a high-quality polythiochloride product.

[0036] 2. The present invention adopts a dynamic tubular continuous flow process to replace the traditional kettle process, which shortens the high temperature residence time of the reaction, greatly improves the appearance of the product, and the product quality indicators meet the industry standards, which is a significant innovative improvement on the existing technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0038] The present invention is further described below in conjunction with the accompanying drawings and specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form a new embodiment. It should be noted that the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0039] See also Figure 1 The present invention provides a technical solution: a method for continuously preparing polythiol chloride, the chemical formula of polythiol chloride is as follows:

[0040] ;

[0041] And the preparation method includes the following steps:

[0042] Step S1: Preparation of reaction raw material A:

[0043] Mix bis(dimethylamino)ethyl ether and water in a weight ratio of 1:1.1;

[0044] Step S2: Continuous flow reaction operation:

[0045] The reaction raw material A obtained in step S1 and dichloroethane are continuously conveyed to a dynamic tubular reactor with a process set temperature by pulse, and the feed amount is controlled to be the process set value, the reaction pressure is 0.3-2.0MPa, the reaction temperature is 130-150°C, and the reaction time is 10-30 minutes. After the product is discharged by a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylaminoethyl)ether raw material in the amination product is less than 1%;

[0046] Step S3: Reaction treatment:

[0047] The material is discharged continuously through the pressure reducing valve and sent to the crude decolorization kettle. Then, activated carbon is added for adsorption treatment. The activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water. The solid content is tested. When it reaches 60-65%, the polythiochloride product is packaged.

[0048] The flow rate ratio of the reaction raw material A to dichloroethane in step S2 is 1:0.6-6, preferably 1:1-3.

[0049] The internal temperature of the dynamic tubular reactor in step S2 is 138-140°C.

[0050] The reaction time in step S2 is 10-30 minutes.

[0051] In step S2, the reaction pressure is adjusted to 1.0-2.0 MPa to obtain a polythiol chloride product with uniform quality and high purity.

[0052] In step S3, after the activated carbon adsorption treatment, the activated carbon is removed by centrifugal filtration, so that the polythiol chloride product can obtain a better purification effect.

[0053] In step S3, the saturated solution is subjected to a reduced pressure desolventizing treatment and then further concentrated to obtain a polythiochloridum product having a solid content of 70-75%.

[0054] The product obtained in step S2 is treated in a crude product decolorization kettle and then decolorized by ultrafiltration to obtain a high-purity polythiol chloride product.

[0055] In step S2, the reaction raw materials A and ethylene dichloride are preheated in a pre-reactor and then enter into a dynamic tubular reactor for reaction to improve the yield of polythiochloridone.

[0056] In step S3, after the activated carbon is removed by positive pressure filtration, the concentrated liquid is treated by ozone oxidation to eliminate some impurities and improve the purity of the polythiochloridum product.

[0057] Example 1 Internal temperature selection of dynamic conduit:

[0058] On the basis of other conditions remaining unchanged, different process temperatures are adopted to obtain the data listed in Table 1 below:

[0059] Table 1

[0060]

[0061] Example 2 Flow rate selection of reaction system:

[0062] On the basis of other conditions remaining unchanged, the flow rate ratio of the reaction raw material A and dichloroethane was adjusted to obtain the data listed in Table 2 below: The flow rate ratio of the reaction raw material A and dichloroethane in the step S2 is 1:(0.6-6), preferably 1:(1-3).

[0063] Table 2

[0064]

[0065] Embodiment 3:

[0066] Step S1: 50 g of bis(dimethylaminoethyl)ether and 55 g of water were mixed in a weight ratio of 1:1.1.

[0067] Step S2: The reaction raw materials obtained in step S1 and 30 g of ethylene dichloride are continuously conveyed to a dynamic tubular reactor at 140° C. by pulses, and the feed rate is controlled to be 60 ml / min, the reaction pressure is 1.5 MPa, and the reaction time is 15 minutes. After the product is discharged by the pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylamino)ethyl ether raw material in the amination product is less than 1%.

[0068] Step S3: The material is continuously discharged through the pressure reducing valve under reduced pressure, and the discharged material is sent to the crude product decolorization kettle, and then 30 grams of activated carbon is added for adsorption treatment, and the activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water, and the solid content is detected. When the solid content reaches 65%, the polythiochloride product is packaged.

[0069] Embodiment 4:

[0070] Step S1: 100 g of bis(dimethylamino)ethyl ether and 110 g of water were mixed in a weight ratio of 1:1.1.

[0071] Step S2: The reaction raw materials obtained in step S1 and 60 g of ethylene dichloride are continuously conveyed to a dynamic tubular reactor at 138° C. by pulses, and the feed rate is controlled to be 80 ml / min, the reaction pressure is 1.2 MPa, and the reaction time is 20 minutes. After the product is discharged by the pressure reducing valve under reduced pressure, the GC analysis shows that the content of the bis(dimethylamino)ethyl ether raw material in the amination product is less than 1%.

[0072] Step S3: The material is continuously discharged through the pressure reducing valve under reduced pressure, and the discharged material is sent to the crude product decolorization kettle, and then 40 grams of activated carbon is added for adsorption treatment, and the activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water, and the solid content is detected. When the solid content reaches 70%, the polythiochloride product is packaged.

[0073] Embodiment 5:

[0074] Step S1: 80 g of bis(dimethylamino)ethyl ether and 88 g of water were mixed in a weight ratio of 1:1.1.

[0075] Step S2: The reaction raw materials obtained in step S1 and 36 g of ethylene dichloride are continuously conveyed to a dynamic tubular reactor at 145° C. by pulses, and the feed rate is controlled to be 40 ml / min, the reaction pressure is 0.3 MPa, and the reaction time is 10 minutes. After the product is discharged by the pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylamino)ethyl ether raw material in the amination product is less than 1%.

[0076] Step S3: The material is continuously discharged through the pressure reducing valve under reduced pressure, and the discharged material is sent to the crude product decolorization kettle, and then 20 grams of activated carbon is added for adsorption treatment, and the activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water, and the solid content is detected. When the solid content reaches 60%, the polythiochloride product is packaged.

[0077] Embodiment 6:

[0078] Step S1: 120 g of bis(dimethylamino)ethyl ether and 132 g of water were mixed in a weight ratio of 1:1.1.

[0079] Step S2: The reaction raw materials obtained in step S1 and 72 g of ethylene dichloride are continuously conveyed to a dynamic tubular reactor at 140° C. by pulses, and the feed rate is controlled to be 100 ml / min, the reaction pressure is 1.8 MPa, and the reaction time is 25 minutes. After the product is discharged by the pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylaminoethyl)ether raw material in the amination product is less than 1%.

[0080] Step S3: The material is continuously discharged through the pressure reducing valve under reduced pressure, and the discharged material is sent to the crude product decolorization kettle, and then 50 grams of activated carbon is added for adsorption treatment, and the activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water, and the solid content is detected. When the solid content reaches 75%, the polythiochloride product is packaged.

[0081] The above-mentioned embodiments are only preferred embodiments of the present invention, and cannot be used to limit the scope of protection of the present invention. Various changes made by ordinary technicians in this field based on the above-mentioned concepts without creative work all fall within the scope of protection of the present invention.

Claims

1. A method for continuously preparing polythiol chloride, characterized in that: The chemical structure of polythiochloride is as follows: ； And the preparation method includes the following steps: Step S1: Preparation of reaction raw material A: Mix bis(dimethylamino)ethyl ether and water in a weight ratio of 1:1.1; Step S2: Continuous flow reaction operation: The reaction raw material A obtained in step S1 and dichloroethane are continuously conveyed to a dynamic tubular reactor with a process set temperature by pulse, and the feed amount is controlled to be the process set value, the reaction pressure is 0.3-2.0MPa, the reaction temperature is 130-150°C, and the reaction time is 10-30 minutes. After the product is discharged by a pressure reducing valve under reduced pressure, the product is analyzed by GC, and the content of the bis(dimethylaminoethyl)ether raw material in the amination product is less than 1%; Step S3: Reaction treatment: The material is discharged continuously through the pressure reducing valve and sent to the crude decolorization kettle. Then, activated carbon is added for adsorption treatment. The activated carbon is removed by positive pressure filtration. The filtrate is decompressed and desolventized to remove part of the water. The solid content is tested. When it reaches 60-65%, the polythiochloride product is packaged.

2. A method for continuously preparing polythiol chloride according to claim 1, characterized in that: The flow rate ratio of the reaction raw material A to the ethylene dichloride in step S2 is 1: 0.6-6.

3. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: The internal temperature of the dynamic tubular reactor in step S2 is 138-140°C.

4. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: In step S2, the reaction pressure is adjusted to 1.0-2.0 MPa to obtain a polythiol chloride product with uniform quality and high purity.

5. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: In step S3, after the activated carbon adsorption treatment, the activated carbon is removed by centrifugal filtration, so that the polythiol chloride product can obtain a better purification effect.

6. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: In step S3, the saturated solution is subjected to a reduced pressure desolventizing treatment and then further concentrated to obtain a polythiochloridum product having a solid content of 70-75%.

7. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: The product obtained in step S2 is treated in a crude product decolorization kettle and then decolorized by ultrafiltration to obtain a high-purity polythiol chloride product.

8. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: In step S2, the reaction raw materials A and ethylene dichloride are preheated in a pre-reactor and then enter into a dynamic tubular reactor for reaction to improve the yield of polythiochloridone.

9. The method for continuously preparing polythiol chloride according to claim 1, characterized in that: In step S3, after the activated carbon is removed by positive pressure filtration, the concentrated liquid is treated by ozone oxidation to eliminate some impurities and improve the purity of the polythiochloridum product.

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