CN102702209B - Quaternary cationic quaternary ammnonium and preparation method thereof - Google Patents

Abstract

A tetracationic quaternary ammonium salt and its synthesis method are based on hexamethylenetetramine and organic halides as raw materials, and are synthesized in one step under the conditions of no solvent or corresponding solvent, corresponding catalyst and certain temperature, pressure, atmosphere protection and stirring out the target product. The invention has few synthesis steps, mild reaction conditions, simple operation and no pollution; the obtained target product has the characteristics of high surface activity, strong bactericidal power, wide grafting property, low toxicity, good stability and the like. It can be used in the fields of daily chemicals, food industry, textiles and materials.

Description

A kind of tetracation quaternary ammonium salt and preparation method thereof

technical field

The invention relates to a tetracation quaternary ammonium salt and a preparation method thereof, in particular to a tetracation quaternary ammonium salt with hexamethylenetetramine as a skeleton and a preparation method thereof.

technical background

Quaternary ammonium salt is one of the widely used fungicides, and the bactericidal performance of quaternary ammonium salt is closely related to its molecular structure. A large number of research results show that quaternary ammonium salt containing multiple positive nitrogen ions has strong adsorption and inhibition of microorganisms. Ability (Garacia-Rsao A., et. al. A study of structure-activity relationships of quaternary ammonium salts. Anales de Quimica, Serie C: Quimica Organica y Bioquimica, 1981, 77(1): 12-18). Therefore, polycationic quaternary ammonium salts have become one of the hot spots in the research and development of fungicides, and the non-polymeric polycationic quaternary ammonium salts containing the most positive nitrogen ions are tricationic quaternary ammonium salts.

At present, three cationic quaternary ammonium salts and preparation methods thereof mainly contain the following types:

Prior method one: take dodecane bromide, 3 chloro-1-propanol, methylamine, dodecyl dimethyl tertiary amine as raw material, prepare trication quaternary ammonium salt (Langmuir R by quaternization reaction . Zana, H. Levy, D. Papoutsi, G. Beinert. Micellization of two triquaternary ammonium surfactants in aqueous solution. Langmuir, 1995, 11:3694-3698). This preparation method needs to be carried out in four steps, and the reaction conditions of each step are relatively harsh, the conversion rate is low, and the total cost is high.

Prior Method 2: Using bromododecane and pentamethyldiethylenetriamine as raw materials, a series of monocationic quaternary ammonium salts, dicationic quaternary ammonium salts, and tricationic quaternary ammonium salts (Kunio Esumi , Kazuhiro Taguma, Yoshifumi Koide. Aqueous properties of multichain quaternary cationic surfactants. Langmuir, 1996, 12:4039-4041). This method can prepare different quaternary ammonium salts, but due to the dispersed positive and negative charges in its structure, its surface activity and bactericidal properties are not very good.

Prior method three: using octadecyl bromide, tetramethylethylenediamine, and 3-bromopropyltrimethylammonium bromide as raw materials, prepare octadecyl trication quaternary ammonium salt (Shaodian) by quaternization reaction Shen, Bozhi Tian, Chengzhou Yu, etc. Synthesis of highly ordered thermally stable cubic mesostructured zirconium oxphosphate templated by tri-headgroup quaternary ammonium surfactant. Chem. Mater, 2003, 15: 4046-4051). Although the method is novel, it needs to be carried out in two steps, the product purity is not high, and the conversion rate is low.

Prior method four: using citric acid, higher fatty tertiary amines and epoxyhaloalkanes as raw materials to prepare citrate tri-long-chain alkyl triquaternary ammonium salt cationic surfactant through one-pot reaction, publication number CN 1778459A.2006-05- 31). This method produces tricationic quaternary ammonium salt in one step, but its product has low purity and poor acid and alkali resistance, which limits its application.

Prior method five: using substituent polyoxyethylene ether, epoxy chloroalkane and pentamethyldiethylenetriamine as raw materials, a series of three polyoxyethylene ether chain trication quaternary ammonium salts were prepared (Xue Yongqiang, Zhang Junfeng, Tang Zhiping . Polyoxyethylene chain trication quaternary ammonium salt and its synthesis method. Chinese patent. CN 100415355C.2008-09-03). This method is carried out in two steps, and the prepared trication quaternary ammonium salt has good water solubility and surface activity, but its products are difficult to separate and the total yield is low.

In the existing published literature, the tricationic quaternary ammonium salt molecule has a linear molecular structure, and the positive and negative charges are relatively dispersed, so that its surface activity and bactericidal performance are not good enough. Positive and negative charges are relatively concentrated, and tetracationic quaternary ammonium salts with three-dimensional molecular structure have not been reported yet, and polycationic quaternary ammonium salts with this structure have high surface activity, strong bactericidal power, and good stability. .

Contents of the invention

The technical problem to be solved in the present invention is to prepare a quaternary ammonium salt with concentrated polycations to improve the concentration and strength of positive and negative charges, so that it has excellent surface activity, efficient bactericidal ability and good stability , and provide a tetracation quaternary ammonium salt and a synthesis method thereof.

A kind of tetracation quaternary ammonium salt proposed by the present invention, its general structure formula is as follows:

Wherein: R is an alkyl group, benzyl group, organosilicon group or substituent polyether chain and other groups, and X is a halogen.

A kind of preparation method that the present invention is used for above-mentioned tetracation quaternary ammonium salt, its described method is carried out according to the following steps:

With hexamethylenetetramine and organic halides as raw materials, when the solvent is selected for reaction, the amount of organic halides is 4-6 times the amount of hexamethylenetetramine, and the amount of solvent is 1/2 of the volume of hexamethylenetetramine 3-8 times; when solvent-free reaction is selected, the amount of organic halide added is 6-8 times the volume of hexamethylenetetramine; under the conditions of mixed catalyst catalysis, nitrogen atmosphere protection and stirring conditions, the normal pressure reaction temperature is 60~ 120°C, under pressure, the reaction temperature is 60-160°C, react for 10-48 hours; after the reaction, cool the mixed solution to room temperature, and let it stand for 12-24 hours to fully crystallize the product; then filter to obtain a white solid Wash and dry with dichloromethane to obtain the described tetracation quaternary ammonium salt; the mother liquor after filtration can be recycled; the dichloromethane distilled from the washing liquid after washing can be recycled, and the residue after distillation is a small amount Solvents, unreacted reactants and catalysts can be recycled.

In the above technical scheme, its additional technical features are: the solvent is a mixture of one or more of methanol, ethanol, n-propanol, isopropanol, acetonitrile and tetrahydrofuran; the composition of the mixed catalyst And its content is: quaternary ammonium salt is 0-3% of the quality of hexamethylenetetramine, iodide is 1-3% of the quality of hexamethylenetetramine, water is 0-3% of the quality of hexamethylenetetramine 2%; The washing liquid of described washing is dichloromethane.

A kind of tetracationic quaternary ammonium salt and preparation method thereof provided by the present invention, compared with the prior art, has the following characteristics: the positive and negative charges of the tetracationic quaternary ammonium salt are relatively concentrated, and have very high surface activity and high , strong bactericidal performance and good stability; the synthetic method has the advantages of cheap and easy-to-obtain raw materials, few reaction steps, relatively mild reaction conditions, simple operation, high yield, high purity, recyclable mother liquor, and no environmental pollution Features.

Detailed ways

Specific embodiments of the present invention will be described below.

Implement a kind of tetracation quaternary ammonium salt of the present invention, its general structural formula is as follows:

Wherein: R is an alkyl group, benzyl group, organosilicon group or substituent polyether chain and other groups, and X is a halogen.

Implement a kind of preparation method that is used for above-mentioned tetracation quaternary ammonium salt of the present invention, take hexamethylenetetramine and organic halide as raw material, in solvent-free or corresponding solvent, corresponding catalyst and certain temperature, pressure, atmosphere protection and The tetracation quaternary ammonium salt is generated by quaternization reaction under stirring condition for a certain period of time; then the tetracation quaternary ammonium salt is obtained by cooling, standing still, crystallization, filtering, washing and drying. Its reaction formula is as follows:

In the preparation method of the above-mentioned four-cation quaternary ammonium salt, the organic halide such as selecting a carbon atom number as a haloalkane with 12-18 can produce a four-long-chain tetra-cation quaternary ammonium salt with high-efficiency bactericidal properties; Benzyl chloride or its derivatives with an alkyl chain of 12-18 atoms can produce a more efficient and low-toxic tetracationic quaternary ammonium fungicide; organic halides such as γ-chloropropyltrimethoxysilane and other halogens Silanes can be used to produce tetracationic organosilicon quaternary ammonium salt coupling agents with excellent performance; organic halides such as selected polyether halides can be used to produce tetracationic quaternary ammonium salt surfactants with good water solubility and surface activity; Organic halides, such as selecting quaternary ammonium salts containing halogenated groups, can produce quaternary ammonium salts with eight cations or even more cations. When selecting solvent reaction, the mol ratio of quaternizing agent and hexamethylenetetramine is 4-6; The addition amount is 6-8 times of the volume of added hexamethylenetetramine.

In the preparation method of the above-mentioned four-cation quaternary ammonium salt, the corresponding solvent is a strong polar organic solvent, considering the separation and recovery of the solvent after the reaction, preferably methanol, ethanol, n-propanol, isopropanol, acetonitrile or a mixture of one or more of tetrahydrofuran; the amount of solvent added is 3-8 times the volume of hexamethylenetetramine added.

In the preparation method of above-mentioned tetracation quaternary ammonium salt, used mixed catalyst is the mixture of quaternary ammonium salt, iodide and water; Dodecyl dimethyl benzyl ammonium chloride, dioctadecyl dimethyl ammonium bromide, octadecyl dimethyl hydroxyethyl ammonium nitrate and other common quaternary ammonium salt surfactants; of which iodide It is potassium iodide, sodium iodide or quaternary ammonium iodide. The dosages are: quaternary ammonium salt is 0-3% of the mass of hexamethylenetetramine, iodide is 1-3% of the mass of hexamethylenetetramine, and water is 0-3% of the mass of hexamethylenetetramine. 2%.

In the preparation method of the tetracationic quaternary ammonium salt, the reaction temperature is related to the pressure; the reaction temperature is 60-120°C under normal pressure; the reaction temperature is 60-160°C under pressure, preferably 120-160°C.

In the preparation method of the above-mentioned tetracationic quaternary ammonium salt, it is best to choose nitrogen atmosphere protection in the reaction process to reduce the oxidation of raw materials in the reaction process.

In the preparation method of the above-mentioned tetracationic quaternary ammonium salt, the reaction time is 10-48 hours.

In the preparation method of the above-mentioned four-cation quaternary ammonium salt, after the reaction is completed, the mixed solution is cooled to room temperature, and left to stand for 12 to 24 hours, so that the product is fully crystallized and precipitated; then filtered to obtain a white solid; washed with dichloromethane and dried. Obtain the tetracationic quaternary ammonium salt; the filtered mother liquor can be recycled; the dichloromethane distilled from the washing liquid after washing can be recycled, and the residue after the distillation is a small amount of solvent, unreacted reactant and catalyst Can be recycled.

The specific embodiment of the present invention will be further described in detail below through specific examples.

Example 1

Carry out the preparation method of a kind of tetracation quaternary ammonium salt of the present invention, take hexamethylenetetramine and organic halide as raw material and make tetracation quaternary ammonium salt through one-step reaction, compare with other preparation methods at present, Its characteristics mainly lie in its simple operation, high product yield and purity, and low cost; the positive and negative charges in the molecular structure of the prepared tetracationic quaternary ammonium salt are relatively concentrated and its strength is large, and it has high surface activity, high Strong bactericidal performance and good stability.

Concrete preparation method is as follows:

The selected raw materials are: hexamethylenetetramine, dodecane bromide, dichloromethane, tetrabutylammonium bromide and potassium iodide, and these raw materials are all commercially available industrially pure; wherein the choice of hexamethylenetetramine as raw material is Because it can provide four tertiary nitrogen atoms with a three-dimensional structure and relatively concentrated mutual positions, it has not been reported in other documents and patented technologies.

First, in a 250ml four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel and a nitrogen protection device, add 1.40 grams of hexamethylenetetramine with a volume of about 13ml, 12.45 grams of bromododecane, 0.02 grams of four Butylammonium bromide, 0.02 g of potassium iodide, 0.02 g of water and 70 ml of methanol solvent were heated to the reflux temperature under electromagnetic stirring, and the stirring and reflux reaction was continued for 24 hours under the protection of nitrogen. The reaction time and temperature are general organic preparation conditions, and there are no special requirements. The equipment used in the above process is common preparation equipment, and no operation is required in the reaction step. After the reaction, the reacted mixture was cooled and allowed to stand, and the white solid product was fully crystallized and then filtered to obtain a white solid product. The filtrate here can be recycled, so there is no discharge of waste liquid and the pollution to the environment is also reduced. The purity of the product obtained in this way is higher than that of the distillation method, and it saves energy and does not require complicated operations. Then the white solid product obtained is washed 2-3 times with dichloromethane, and then oven-dried to obtain 11.55 grams of white solid, which is the tetracation quaternary ammonium salt containing four dodecyl chains in the target product, and the product purity is 99% More than %, the yield is 83.4%. Its chemical structural formula is as follows:

The yield of the quaternary ammonium salt obtained by this method is higher than other methods for preparing the quaternary ammonium salt, and the purity is high. The dichloromethane distilled from the washing liquid after washing can be recycled, and the residue after distillation is a small amount of solvent, unreacted reactant and catalyst, which can be recycled, thus reducing waste discharge and environmental pollution. It also saves costs. This preparation process only needs one-step reaction, which saves labor costs and raw material costs. With reference to the method of GB/T 5555-2003, the acid and alkali resistance of the target product were measured, and the results showed that its resistance, acid and alkali grades were all first grade. Under sterile conditions at 50°C, pour agar solution into 5 petri dishes respectively, and require them to contain 15ml of agar solution in an area of 9cm in diameter; then cool at room temperature and solidify; 105/ml Escherichia coli bacteria liquid was applied on the surface of the agar medium of the above-mentioned 5 petri dishes; 5 parts of 10 mg samples were respectively placed in 5 petri dishes; cultivated at 36-37°C for 48 hours; measured and Record the diameter of the bacteriostatic zone, and the result product is 31.30cm to the average bacteriostatic zone diameter of escherichia coli. Therefore, the tetracationic quaternary ammonium salt containing four dodecyl chains provided by the preparation process has strong stability and bactericidal properties.

The preparation process of Examples 2-8 is basically the same as that of Example 1, so the detailed preparation process will not be repeated in the following examples, and only the differences from Example 1 will be described.

Example 2

The selected raw materials are: benzyl chloride, hexamethylenetetramine, dichloromethane, ethanol and tetrabutylammonium iodide, and these raw materials are commercially available industrially pure.

In the preparation process, hexamethylenetetramine is 1.40 grams, benzyl chloride is 6.33 grams, tetrabutylammonium iodide is 0.02 grams, ethanol solvent is 70ml, the reaction temperature is the reflux temperature of ethanol, the reaction time is 30 hours, and other Same as the preparation process in Example 1. Finally, 6.58 grams of tetracation quaternary ammonium salts containing four benzyl chlorides were obtained, with a yield of 85.1%, which is slightly higher than that of the product prepared in Example 1. Its chemical structural formula is as follows:

The methanol solvent provided in this example has a relatively high polarity, which is beneficial to promote the reaction, increase the yield, and reduce energy consumption. The tetracationic quaternary ammonium salt containing four benzyl chlorides provided by this preparation process also has strong bactericidal properties and stability (the diameter of the antibacterial zone against Escherichia coli is 37.20 cm, and the acid and alkali resistance grades are all first grade).

Example 3

The selected raw materials are: 2-ethylbenzyl chloride, hexamethylenetetramine, isopropanol, dichloromethane, cetyltrimethylammonium bromide and sodium iodide, and these raw materials are commercially available industrial pure .

During the preparation process, 1.40 grams of hexamethylenetetramine, 7.73 grams of 2-ethylbenzyl chloride, 0.02 grams of cetyltrimethylammonium bromide, 0.02 grams of sodium iodide, and 70 ml of isopropanol solvent , the reaction temperature is the reflux temperature of isopropanol, the reaction time is 26 hours, and the others are the same as the preparation process in Example 1. Finally, 6.89 grams of four cation quaternary ammonium salts containing four 2-ethylbenzyl chlorides were obtained, with a yield of 84.7%. Its chemical structural formula is as follows:

The isopropanol solvent provided in this example has a higher boiling point, which is beneficial to promote the reaction, increase the yield, and reduce energy consumption. The tetracationic quaternary ammonium salt containing four 2-ethylbenzyl chlorides provided by this preparation process also has strong bactericidal properties and stability (the diameter of the inhibition zone to Escherichia coli is 38.65cm, and the acid and alkali resistance grades are both level one).

Example 4

The selected raw materials are: γ-chloropropyltrimethoxysilane, hexamethylenetetramine, n-propanol, dichloromethane, dodecyldimethylbenzyl ammonium chloride and potassium iodide, all of which are commercially available Industrial pure.

In the preparation process, hexamethylenetetramine was 1.40 grams, γ-chloropropyltrimethoxysilane was 10.00 grams, dodecyldimethylbenzyl ammonium chloride was 0.02 grams, potassium iodide was 0.02 grams, and water was 0.01 grams. Gram, n-propanol solvent is 70ml, and temperature of reaction is the reflux temperature of n-propanol, and the reaction times is 35 hours, and other are with the preparation process among the embodiment 1. Finally, 9.51 grams of four cation quaternary ammonium salts containing four benzyl chlorides were obtained, with a yield of 83.7%. Its chemical structural formula is as follows:

The n-propanol solvent provided in this example has a higher boiling point, which is beneficial to promote the reaction, increase the yield, and reduce energy consumption. The tetracationic quaternary ammonium salt containing four organosilicon groups provided by this preparation process also has strong bactericidal properties (the diameter of the bacteriostatic zone against E. Silicone functional groups can be widely used in other fields.

Example 5

The selected raw materials are: propylene oxide lauryl polyoxyethylene ether (EO=5), hexamethylenetetramine, acetonitrile, dilute hydrochloric acid, dichloromethane, dioctadecyldimethylammonium bromide and Potassium iodide, these raw materials are commercially available industrial pure.

In the preparation process, 1.40 grams of hexamethylenetetramine, 11.75 grams of propylene oxide lauryl polyoxyethylene ether (EO=5), 5 ml of dilute hydrochloric acid, and dioctadecyldimethylammonium bromide It is 0.02 gram, potassium iodide is 0.02 gram, water is 0.02 gram, acetonitrile solvent is 70ml, and reaction temperature is the reflux temperature of acetonitrile, and the reaction times is 40 hours, and other are with the preparation process among the embodiment 1. Finally, 8.92 grams of tetracationic quaternary ammonium salts containing four substituent polyoxyethylene ether chains were obtained, with a yield of 82.6%. Its chemical structural formula is as follows:

The acetonitrile solvent provided in this example has a relatively high polarity, which is beneficial to promote the reaction, increase the yield, and reduce energy consumption. The tetracation quaternary ammonium salt containing four substituent polyoxyethylene ether chains provided by this preparation process has excellent surface activity (the surface tension of an aqueous solution with a concentration of 1×10 ^-4 g/ml is reduced to 4.50×10 ^-3 N /m).

Example 6

The selected raw materials are: γ-chloropropyltrimethoxysilane, hexamethylenetetramine, tetrahydrofuran, dichloromethane, octadecyldimethylhydroxyethylammonium nitrate and potassium iodide, and these raw materials are commercially available industrial pure.

In the preparation process, 1.40 grams of hexamethylenetetramine, 10.00 grams of γ-chloropropyltrimethoxysilane, 0.02 grams of octadecyldimethylhydroxyethylammonium nitrate, 0.02 grams of potassium iodide, and 0.02 grams of tetrahydrofuran solvent 70ml, the reaction temperature under pressurized conditions was 160°C, and the reaction time was 10 hours. Others were the same as the preparation process in Example 1. Finally, 9.97 grams of tetracationic organosilicon quaternary ammonium salts were obtained, with a yield of 87.7%. The structure of the tetracationic organosilicon quaternary ammonium salt provided by this preparation process is the same as that of the tetracationic organosilicon quaternary ammonium salt in Example 4.

Example 7

The selected raw materials are: benzyl chloride (both as a solvent and as a quaternization reagent), dichloromethane, hexamethylenetetramine and potassium iodide, all of which are commercially available and industrially pure.

In the preparation process, hexamethylenetetramine was 1.40 g, benzyl chloride was 20.50 g, potassium iodide was 0.02 g, the reaction temperature was 85° C., and the reaction time was 25 hours. Others were the same as the preparation process in Example 1. Finally obtain 7.50 grams of four cationic quaternary ammonium salts containing four benzyl chlorides, yield 88.5%, the yield is slightly higher than the product yield prepared in Example 1; the solvent-free reaction preparation method provided in the present embodiment has It is beneficial to promote the reaction, increase the yield and reduce energy consumption. The structure of the tetracationic organosilicon quaternary ammonium salt provided by this preparation process is the same as that of the tetracationic organosilicon quaternary ammonium salt in Example 1.

Example 8

The selected raw materials are: 3-bromopropyltrimethylammonium bromide, hexamethylenetetramine, methanol-ethanol mixed solvent (methanol-ethanol volume ratio is 3:7), dichloromethane, tetrabutylammonium bromide and potassium iodide, these raw materials are all commercially available commercially pure.

In the preparation process, hexamethylenetetramine was 1.40 grams, 3-bromopropyltrimethylammonium bromide was 13.70 grams, tetrabutylammonium bromide was 0.02 grams, potassium iodide was 0.02 grams, and methanol-ethanol mixed solvent was 70ml , the reaction temperature is the reflux temperature of the mixed solvent, the reaction time is 25 hours, and the others are the same as the preparation process in Example 1. Finally, 12.60 grams of octacation quaternary ammonium salts were obtained, with a yield of 89.4%. Its chemical structural formula is as follows:

The mixed solvent provided in this example has a relatively high polarity, which is beneficial to promote the reaction, increase the yield, and reduce energy consumption. The octacation quaternary ammonium salt provided by this preparation process also has strong bactericidal properties and stability (the diameter of the antibacterial zone against Escherichia coli is 39.70 cm, and the acid and alkali resistance grades are all first grade).

Claims (3)

1. four cation quaternary ammonium salts, its general structure is as follows:

Wherein: R is benzyl, organosilicon radical or substituting group polyether chain group;

Described organosilicon radical is :-CH ₂cH ₂cH ₂si (OCH ₃) ₃; Described substituting group polyether chain group is-CH ₂cH (OH) CH ₂(C ₂h ₄o) ₅oC ₁₂h ₂₅, X is Cl simultaneously ^-.

2. a preparation method for four cation quaternary ammonium salts according to claim 1, described in it, method is as follows:

With vulkacit H and Organohalogen compounds for raw material, react having under solvent or condition of no solvent, when selecting there is solvent reaction, Organohalogen compounds consumption be the 4-6 of vulkacit H amount of substance doubly, solvent load be the 3-8 of vulkacit H volume doubly; When selecting solvent-free reaction, Organohalogen compounds add-on is 6-8 times of vulkacit H volume; Under mixed catalyst catalysis, nitrogen atmosphere protection and agitation condition, react 10 ~ 48 hours, reaction is divided into synthesis under normal pressure or compressive reaction, during synthesis under normal pressure, temperature of reaction is 60 ~ 120 DEG C, during compressive reaction, temperature of reaction is 60 ~ 160 DEG C, after completion of the reaction, through cooling standing, crystallization, filtration, washing and drying, four cation quaternary ammonium salts are obtained;

Composition and the content thereof of described mixed catalyst are: the quaternary ammonium salt of the 0-3% of vulkacit H quality, the iodide of the 1-3% of vulkacit H quality, the water of the 0-2% of vulkacit H quality; Described iodide are potassiumiodide, sodium iodide or quaternary ammonium iodide salt

Described Organohalogen compounds are Benzyl Chloride or γ-r-chloropropyl trimethoxyl silane;

Described solvent is the mixing of one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile and tetrahydrofuran (THF).

3. preparation method as claimed in claim 2, the washings washed described in it is methylene dichloride.