CN1314320C - A kind of preparation method of organosilicon quaternary ammonium salt bactericide - Google Patents

Abstract

The present invention discloses a preparation method of organic silicon quaternary ammonium salt germicide. The present invention has the steps that anhydrous sodium sulfate is dewatered; the anhydrous sodium sulfate is added in anhydrous alcohol to be stirred to prepare the anhydrous alcohol which is dewatered completely for standby; dimethyl octadecalamine are added in the anhydrous alcohol which is dewatered completely to be stirred until the dimethyl octadecalamine is dissolved, and then, gamma-chloropropyl triethoxysilane is dropped slowly to be stirred uniformly; the catalyst is added to have temperature reaction, after the 70 hour reaction, the Cl-content is measured once every five hours, and the complete degree of the reaction is calculated by taking the dimethyl octadecalamine as reference; the reaction is completed when reaching 98% and carries out continuously for 10 hours to obtain the organic silicon quaternary ammonium salt, the room temperature is lowered, and the pH of the organic silicon quaternary ammonium salt is adjusted to 7 by glacial acetic acid and is counted by weight percentage; the concentration of the organic silicon quaternary ammonium salt is adjusted to 40% by the anhydrous alcohol which is dewatered completely to obtain the organic silicon quaternary ammonium salt germicide. The method of the present invention has simple technology, low raw material price, easy raw material acquisition, high purity and high output, and the present invention is suitable for industrial production.

Description

A kind of preparation method of organosilicon quaternary ammonium salt bactericide

technical field

The invention relates to a preparation method of a bactericidal chemical, in particular to a preparation method of an organosilicon quaternary ammonium salt fungicide, and belongs to the field of fine chemicals.

Background technique

At present, there are many kinds of bactericidal chemicals being used in China, each with its own advantages and characteristics. Alkyl quaternary ammonium salts are a type of typical cationic surfactants, which have strong antibacterial and bactericidal effects, and are widely used in public places such as hospitals, swimming pools, sterilization of circulating cooling water It can be used as oilfield fungicide and water shutoff agent. However, alkyl quaternary ammonium salts have great disadvantages: low chemical activity, elution type when applied to textiles, and easy elution; relatively high toxicity, easy to gradually accumulate on the surface of human skin, and long-term use is prone to lesions. Moreover, the irritant of the alkyl quaternary ammonium salt is strong, and the scope of application is limited.

The antibacterial mechanism of the quaternary ammonium salt compound is as follows: the quaternary ammonium salt has a positive charge center [N ⁺ ], under the influence of the electric field, the metabolic function of the enzyme in the cell membrane is inactive, the respiratory function is destroyed, and the cell permeability is changed through osmotic diffusion. Sexuality, destruction of cell membrane and cell wall, inhibition of nucleic acid and protein synthesis enzymes, and ultimately lead to death of intracellular lysates.

Organosilicon quaternary ammonium fungicide is a compound obtained by modifying the alkyl group on the alkyl quaternary ammonium salt with siloxane. It is a cationic surfactant with a wide range of hydrophilic-lipophilic balance (HLB value), its chemical activity is greatly improved, and it can react with the active groups of the matrix, closely combine with them, and form a firm film with each other. Organosilicon quaternary ammonium salt fungicides have a wide range of antibacterial and bactericidal effects, and have good killing effects on Staphylococcus aureus, Escherichia coli, hepatitis B surface antigen, Salmonella typhi, Shigella and Neisseria gonorrhoeae. Organosilicon quaternary ammonium fungicides also have very high safety, and their semi-lethal dose is: LD ₅₀ >10g/Kg. It can be used for disinfection and sterilization of household and household items, as well as industrial fungicide.

In view of the good application prospects of organosilicon quaternary ammonium fungicides, it is of practical significance to realize large-scale production of organosilicon quaternary ammonium fungicides by adopting a preparation method with short synthetic route, simple synthesis process, low raw material cost and less environmental pollution .

In the 1970s, DOW Corning Company structured as follows:

The product of [(CH ₃ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- was put on the market, its brand name is: DC-5700, the product has passed strict performance test , which proves that its safety is very high, and its semi-lethal dose is: LD ₅₀ =12.27g/Kg, which has been certified by EPA. However, this product (DC-5700) uses methanol as a raw material and solvent, which is easy to cause poison to operators and limits its application.

Contents of the invention

Aiming at the deficiencies in the prior art, the problem to be solved in the present invention is to provide a preparation method of organosilicon quaternary ammonium salt bactericide, the method is simple and convenient in process, and the raw material is cheap and easy to obtain, and overcomes the weakness of DC-5700, effectively It meets the production needs of organic silicon quaternary ammonium fungicides and greatly expands the scope of application.

A kind of preparation method of organosilicon quaternary ammonium salt bactericide of the present invention, is made up of following steps:

A. Place anhydrous sodium sulfate in an environment with a temperature of 200±10°C, dry for 5 hours, and dehydrate;

B. the anhydrous sodium sulfate after dehydration joins in dehydrated alcohol in the amount of anhydrous sodium sulfate: dehydrated alcohol=5～10:100 with weight ratio, stirs 20～30 hours, prepares the dehydrated dehydrated alcohol completely ,spare;

C. At a stirring speed of 50-70 rpm, add dimethyl octadecyl tertiary amine to the above-mentioned completely dehydrated absolute ethanol until it dissolves, and then slowly add γ-chloropropyl triethoxy silane, and stir evenly, and the dropping time is controlled within 2 hours; wherein, the molar ratio of each component is dimethyl octadecyl tertiary amine C ₁₈ H ₃₇ N(CH ₃ ) ₂ : γ-chloropropyl triethyl Oxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ : absolute ethanol = 1.0: 1.1~1.3: 7.0~8.0;

D. In the solution described in step C, add the catalyst in a weight ratio of γ-chloropropyl triethoxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ =2～5:100, seal the reaction The kettle and the condenser are fed with water, heated to 80-84°C, and reacted for 80-100 hours in the state of ethanol reflux; wherein the catalyst is selected from potassium iodide, methyl iodide or ethyl iodide;

E. After reacting for 70 hours, measure the [Cl ^- ] content every 5 hours, and calculate the degree of completeness of the reaction based on dimethyloctadecanine tertiary amine. When the reaction reaches 98%, it is complete. Continue to react for 10 hours to obtain organic Silicon quaternary ammonium salt, its structural formula is: [(CH ₃ CH ₂ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- ;

F. Cool down to room temperature, adjust the pH of the above-mentioned organosilicon quaternary ammonium salt to 7 with glacial acetic acid, and adjust its concentration to 40% with the above-mentioned completely dehydrated absolute ethanol to obtain the sterilization of the organosilicon quaternary ammonium salt agent.

Wherein, the ratio of anhydrous sodium sulfate: absolute ethanol in step B is preferably 7-9:100, and the stirring time is preferably 23-25 hours.

Wherein, the molar ratio of the components described in step C is preferably tertiary dimethyl octadecylamine: γ-chloropropyl triethoxysilane: absolute ethanol = 1.0: 1.2: 7.5.

In the preparation method of the above-mentioned organic silicon quaternary ammonium salt bactericide, the catalyst described in step D is preferably potassium iodide.

In the preparation method of the above-mentioned organosilicon quaternary ammonium salt bactericide, in the reaction described in step E, the γ-chloropropyltriethoxysilane is excessive, and due to its strong volatility, it can be volatilized and removed under the condition of ethanol reflux. , so after the reaction is complete, the reaction should be continued for 10 hours to completely volatilize γ-chloropropyltriethoxysilane.

The organic silicon quaternary ammonium salt bactericide is prepared by the method of the present invention, the process is simple, the raw material is cheap and easy to obtain, the requirements for production equipment and environmental conditions are not high, and the output is large, it is very suitable for large-scale industrial production, and the organic silicon quaternary ammonium is realized. The development needs of the salt fungicide production industry. There are three ethoxy groups in the organic silicon quaternary ammonium salt compound prepared by the present invention, and ethanol can be used as a solvent, which is conducive to the selection of cheap and easy-to-obtain raw materials, and overcomes the poison caused by methanol as a solvent, and the reaction conditions are mild. The ethanol solution of the product is convenient for storage, transportation, packaging and use.

The preparation of the organic silicon quaternary ammonium salt bactericide of the present invention can be used as a portable bactericide for travel, a bactericide for bathtub water, a bactericide for underwear, a bactericide for guest room fabrics, a bactericide for indoor environment, and a bactericide for household fabrics.

Since organosilicon quaternary ammonium salts have many excellent qualities, it is of great significance to develop new and more products and apply them to other fields so that they can be fully utilized to increase the variety of fungicides and improve the safety of fungicides.

Detailed ways

The following examples are to further illustrate the present invention, but the present invention is not limited thereto.

Embodiment 1: A kind of preparation method of organosilicon quaternary ammonium salt fungicide

Consists of the following steps:

A. Anhydrous sodium sulfate is placed in an environment with a temperature of 200 ° C, dried for 5 hours, and dehydrated;

B. the anhydrous sodium sulfate after dehydration is joined in absolute ethanol with the weight ratio of anhydrous sodium sulfate: dehydrated alcohol=8: 100, stirs 24 hours, prepares the dehydrated dehydrated alcohol completely, for subsequent use;

C. At a stirring speed of 60 rpm, add dimethyl octadecyl tertiary amine to the above-mentioned completely dehydrated absolute ethanol until it dissolves, and then slowly add gamma-chloropropyl triethoxysilane dropwise, and stir evenly, and the dropping time is controlled within 2 hours; wherein, the molar ratio of each component is dimethyl octadecyl tertiary amine C ₁₈ H ₃₇ N(CH ₃ ) ₂ : γ-chloropropyl triethoxy Silane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ : absolute ethanol = 1.0: 1.2: 7.5;

D. In the solution described in step C, add catalyst potassium iodide in a weight ratio of catalyst: γ-chloropropyltriethoxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ =4.5:100, and seal the reaction vessel , the condenser works with water, the temperature is raised to 80-84 °C, and the reaction is carried out for 80-100 hours under the state of ethanol reflux;

E. After reacting for 70 hours, measure the [Cl ^- ] content every 5 hours, and calculate the degree of completeness of the reaction based on dimethyloctadecanine tertiary amine. When the reaction reaches 98%, it is complete. Continue to react for 10 hours to obtain organic Silicon quaternary ammonium salt, its structural formula is: [(CH ₃ CH ₂ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- ;

F. Cool down to room temperature, adjust the pH of the above-mentioned organosilicon quaternary ammonium salt to 7 with glacial acetic acid, and adjust its concentration to 40% with the above-mentioned completely dehydrated absolute ethanol to obtain the sterilization of the organosilicon quaternary ammonium salt agent.

In the preparation method of the above-mentioned organosilicon quaternary ammonium salt bactericide, in the reaction described in step E, γ-chloropropyltriethoxysilane is excessive, and because of its strong volatility, it can be volatilized and removed under the condition of ethanol reflux, so After the reaction is complete, the reaction should be continued for 10 hours to completely volatilize the γ-chloropropyltriethoxysilane.

Embodiment 2: A kind of preparation method of organosilicon quaternary ammonium salt fungicide

Consists of the following steps:

A. Anhydrous sodium sulfate is placed in an environment with a temperature of 210°C, dried for 5 hours, and dehydrated;

B. the anhydrous sodium sulfate after dehydration is joined in absolute ethanol with the weight ratio of anhydrous sodium sulfate: dehydrated alcohol=10:100, stirs 30 hours, prepares dehydrated dehydrated alcohol completely, for subsequent use;

C. At a stirring speed of 50-70 rpm, add dimethyl octadecyl tertiary amine to the above-mentioned completely dehydrated absolute ethanol until it dissolves, and then slowly add γ-chloropropyl triethoxy silane, and stir evenly, and the dropping time is controlled within 2 hours; wherein, the molar ratio of each component is dimethyl octadecyl tertiary amine C ₁₈ H ₃₇ N(CH ₃ ) ₂ : γ-chloropropyl triethyl Oxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ : absolute ethanol = 1.0: 1.3: 8.0;

D. Add catalyst ethyl iodide to the solution described in step C in a weight ratio of catalyst: γ-chloropropyltriethoxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ =3.5:100, seal Reactor and condenser work with water, heat up to 80-84°C, and react for 80-100 hours in the state of ethanol reflux;

E. After reacting for 70 hours, measure the [Cl ^- ] content every 5 hours, and calculate the degree of completeness of the reaction based on dimethyloctadecanine tertiary amine. When the reaction reaches 98%, it is complete. Continue to react for 10 hours to obtain organic Silicon quaternary ammonium salt, its structural formula is: [(CH ₃ CH ₂ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- ;

F. Cool down to room temperature, adjust the pH of the above-mentioned organosilicon quaternary ammonium salt to 7 with glacial acetic acid, and adjust its concentration to 40% with the above-mentioned completely dehydrated absolute ethanol to obtain the sterilization of the organosilicon quaternary ammonium salt agent.

In the preparation method of the above-mentioned organosilicon quaternary ammonium salt bactericide, in the reaction described in step E, the γ-chloropropyltriethoxysilane is excessive, and due to its strong volatility, it can be volatilized and removed under the condition of ethanol reflux. , so after the reaction is complete, the reaction should be continued for 10 hours to completely volatilize γ-chloropropyltriethoxysilane.

Embodiment 3: A kind of preparation method of organosilicon quaternary ammonium salt fungicide

Consists of the following steps:

A. Place anhydrous sodium sulfate in an environment with a temperature of 190°C, dry for 5 hours, and dehydrate;

B. the anhydrous sodium sulfate after dehydration is joined in absolute ethanol with the weight ratio of anhydrous sodium sulfate: dehydrated alcohol=5: 100, stirs 20 hours, prepares dehydrated dehydrated alcohol completely, for subsequent use;

C. At a stirring speed of 50-70 rpm, add dimethyl octadecyl tertiary amine to the above-mentioned completely dehydrated absolute ethanol until it dissolves, and then slowly add γ-chloropropyl triethoxy silane, and stir evenly, and the dropping time is controlled within 2 hours; wherein, the molar ratio of each component is dimethyl octadecyl tertiary amine C ₁₈ H ₃₇ N(CH ₃ ) ₂ : γ-chloropropyl triethyl Oxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ : absolute ethanol = 1.0: 1.1: 7.0;

D. In the solution described in step C, add catalyst methyl iodide in a weight ratio of catalyst: γ-chloropropyltriethoxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ =2.5:100, seal the reaction The kettle and the condenser are fed with water, the temperature is raised to 80-84°C, and the reaction is carried out for 80-100 hours under the condition of ethanol reflux;

E. After reacting for 70 hours, measure the [Cl ^- ] content every 5 hours, and calculate the degree of completeness of the reaction based on dimethyloctadecanine tertiary amine. When the reaction reaches 98%, it is complete. Continue to react for 10 hours to obtain organic Silicon quaternary ammonium salt, its structural formula is: [(CH ₃ CH ₂ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- ;

F. Cool down to room temperature, adjust the pH of the above-mentioned organosilicon quaternary ammonium salt to 7 with glacial acetic acid, and adjust its concentration to 40% with the above-mentioned completely dehydrated absolute ethanol to obtain the sterilization of the organosilicon quaternary ammonium salt agent.

In the preparation method of the above-mentioned organosilicon quaternary ammonium salt bactericide, in the reaction described in step E, the γ-chloropropyltriethoxysilane is excessive, and due to its strong volatility, it can be volatilized and removed under the condition of ethanol reflux. , so after the reaction is complete, the reaction should be continued for 10 hours to completely volatilize γ-chloropropyltriethoxysilane.

Claims (5)

1. a preparation method of organosilicon quaternary ammonium salt bactericide, is made up of following steps: A. Place anhydrous sodium sulfate in an environment with a temperature of 200±10°C, dry for 5 hours, and dehydrate; B. the anhydrous sodium sulfate after dehydration joins in dehydrated alcohol in the amount of anhydrous sodium sulfate: dehydrated alcohol=5～10:100 with weight ratio, stirs 20～30 hours, prepares the dehydrated dehydrated alcohol completely ,spare; C. At a stirring speed of 50-70 rpm, add dimethyl octadecyl tertiary amine to the above-mentioned completely dehydrated absolute ethanol until it dissolves, and then slowly add γ-chloropropyl triethoxy silane, and stir evenly, and the dropping time is controlled within 2 hours; wherein, the molar ratio of each component is dimethyl octadecyl tertiary amine C ₁₈ H ₃₇ N(CH ₃ ) ₂ : γ-chloropropyl triethyl Oxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ : absolute ethanol = 1.0: 1.1~1.3: 7.0~8.0; D. In the solution described in step C, add the catalyst in a weight ratio of γ-chloropropyl triethoxysilane ClC ₃ H ₆ Si(OC ₂ H ₅ ) ₃ =2～5:100, seal the reaction The kettle and the condenser are fed with water, heated to 80°C, and reacted for 80 to 100 hours in the state of ethanol reflux; wherein the catalyst is selected from potassium iodide, methyl iodide or ethyl iodide; E. After reacting for 70 hours, measure the [Cl ^- ] content every 5 hours, and calculate the degree of completeness of the reaction based on dimethyloctadecanine tertiary amine. When the reaction reaches 98%, it is complete. Continue to react for 10 hours to obtain organic Silicon quaternary ammonium salt, its structural formula is: [(CH ₃ CH ₂ O) ₃ Si(CH ₂ ) ₃ N(CH ₃ ) ₂ (C ₁₈ H ₃₇ )] ⁺ Cl ^- ; F. Cool down to room temperature, adjust the pH of the above-mentioned organosilicon quaternary ammonium salt to 7 with glacial acetic acid, and adjust its concentration to 40% with the above-mentioned completely dehydrated absolute ethanol to obtain the sterilization of the organosilicon quaternary ammonium salt agent. 2. the preparation method of organosilicon quaternary ammonium salt bactericide as claimed in claim 1 is characterized in that, anhydrous sodium sulfate described in step B: dehydrated alcohol=7～9: 100, and described stirring time is 23 ~25 hours. 3. the preparation method of organosilicon quaternary ammonium salt fungicide as claimed in claim 1 is characterized in that, each component mol ratio described in step C is dimethyl octadecyl tertiary amine: gamma-chloropropyl triethyl Oxysilane: absolute ethanol = 1.0: 1.2: 7.5. 4. the preparation method of organosilicon quaternary ammonium salt bactericide as claimed in claim 1 is characterized in that, the catalyzer described in step D is selected potassium iodide. 5. the preparation method of organosilicon quaternary ammonium salt fungicide as claimed in claim 1 is characterized in that, in the described reaction of step E, gamma-chloropropyltriethoxysilane is excessive, after reaction is complete, should continue reaction After 10 hours, the γ-chloropropyltriethoxysilane was completely volatilized.