JP2022173002A - Novel benzalkonium chloride functional silane coupling agent - Google Patents

Abstract

To provide a novel alkoxy group-containing silicon compound having antibacterial properties and a method for synthesizing the same.SOLUTION: A novel benzalkonium chloride functional silane coupling agent is a product from the reaction between a trialkoxysilane having a chloromethylphenyl group bound to a trialkoxysilyl group with an alkylene group and a long-chain alkyl amine.EFFECT: The novel benzalkonium chloride functional silane coupling agent has antibacterial and antiviral properties.SELECTED DRAWING: None

Description

Detailed description of the invention

An object of the present invention is to provide a novel benzalkonium chloride-functional silane coupling agent.

A silane compound having both an organic functional group and an alkoxysilyl group, called a silane coupling agent, has been used for a long time as a material for imparting the function of an organic functional group to the surface of a substrate as a surface treatment agent for substrates. On the other hand, benzalkonium chloride is widely used as a disinfectant, but no silane coupling agent having benzalkonium chloride as an organic functional group has been developed so far.

prior art

Silane coupling agents with antimicrobial functional groups include silane coupling agents as long-chain alkylammonium-functional alkoxysilane compounds, well known as octadecyldimethyl(8-trimethoxysilylpropyl)ammonium chloride in methanol. It was provided by THE DOW CHEMICAL COMPANY (former DOW CORNING CORPORATION) under the name of DC5700 antimicrobial treatment agent, and has been utilized as a treatment method for imparting antibacterial properties to fibers called BIOSIL processing. In recent years, an ethanol solution of octadecyldimethyl(8-triethoxysilylpropyl)ammonium chloride has been industrialized as having an effect as an antiviral agent (Patent Document 1).

JP 2011-98976

In the present invention, material development was investigated with the object of synthesizing a novel silane coupling agent having benzalkonium chloride, which is widely used as a sterilizing agent, as an organic functional group.

As a result of intensive research to achieve the above object, the present inventors have found a chloromethylphenyl group in which a trialkoxysilyl group and a chloromethylphenyl group are bonded via an alkylene group having 2 carbon atoms by a hydrosilylation reaction of chloromethylstyrene and trialkoxysilane. The inventors have found that a methylphenyl-functional trialkoxysilane can be produced, and have also found that a benzalkonium chloride-functional alkoxysilane compound can be synthesized by reaction with a long-chain alkyldimethylamine, thereby completing the present invention. The chloromethylphenyl-functional trialkoxysilane obtained by the hydrosilylation reaction of chloromethylstyrene and trialkoxysilane was isolated and purified by distillation, and gas chromatography showed that silicon was α-adduct and β-adduct with respect to the vinyl group. ¹ H-NMR and FT-IR confirmed that it was a chloromethylphenyl-functional trialkoxysilane (Figs. 1, 2, 3). .

The novel benzalkonium chloride-functional silane coupling agent of the present invention has a structure in which benzalkonium chloride, which has a high bactericidal disinfectant function, and alkoxysilane, which has adhesiveness to various substrates, are chemically bonded. Therefore, it is expected that the base material surface will have a high sterilization and disinfection effect for a long period of time.

1 is a gas chromatograph chart of a chloromethylphenyl-functional trialkoxysilane synthesized in Examples. 1 is an NMR spectrum chart of a chloromethylphenyl-functional trialkoxysilane synthesized in Examples. 1 is an FT-IR spectrum chart of a chloromethylphenyl-functional trialkoxysilane synthesized in Examples.

The present invention will be described in detail below.

（式中、Ｒ^３は炭素数１～６のアルキル基を示し、Ｒ^４は炭素数２～６のアルキレン基を示す。）で表されるクロロメチルフェニル官能性トリアルコキシシランとアミン化合物を反応させて得られる下記一般式（１）；

（式中、Ｒ^１は炭素数１０～１８のアルキル基を示し、Ｒ^２、Ｒ^３は炭素数１～６のアルキル基を示し、Ｒ^４は炭素数２～６のアルキレン基を示す。）で表される新規の塩化ベンザルコニウム官能性シランカップリング剤である。The benzalkonium chloride functional silane coupling agents described herein have the following general formula (a);

(wherein R ³ represents an alkyl group having 1 to 6 carbon atoms, and R ⁴ represents an alkylene group having 2 to 6 carbon atoms). The following general formula (1) obtained by

(In the formula, R ¹ represents an alkyl group having 10 to 18 carbon atoms, R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms, and R ⁴ represents an alkylene group having 2 to 6 carbon atoms.) is a novel benzalkonium chloride-functional silane coupling agent represented by

The chloromethylphenyl-functional trialkoxysilanes of formula (a) can be obtained by platinum-catalyzed hydrosilylation of chloromethylstyrene and trialkoxysilanes. The chloromethyl group and vinyl group attached to the benzene ring of chloromethylstyrene have positional isomers such as ortho, meta, and para isomers. As the reaction progresses, a chloromethylphenyl-functional trialkoxysilane is obtained. Chloromethylstyrene is more preferably meta-form or para-form, and may be a mixture of meta-form and para-form.

Examples of alkyl groups having 10 to 18 carbon atoms for R ¹ in formula (1) include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl groups.

The alkyl group having 1 to 6 carbon atoms for R ² in formula (1) is exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. Among them, a methyl group is preferred.

Examples of the alkyl group having 1 to 6 carbon atoms for R ³ in formula (1) include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, with methyl group and ethyl group being preferred. .

The alkylene group having 2 to 6 carbon atoms for R ⁴ in formula (1) is exemplified by methylmethylene, ethylene, propylene, methylethylene, butylene, pentylene and hexylene. group, the ethylene group is preferred.

The benzalkonium chloride functional silane coupling agent of formula (1) is a viscous liquid or solid at room temperature and can be handled as a diluted solution in methanol or ethanol. When the alkoxy group of the alkoxysilyl group is a methoxy group, it is preferably diluted with methanol, and when the alkoxy group of the alkoxysilyl group is an ethoxy group, it is preferably handled by dilution with ethanol. A dilution rate of 5% to 80% solids content can be used, but it is preferable to use a dilution rate of about 30% to 60% solids content.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.

The alcohol solution of the benzalkonium chloride-functional silane coupling agent thus obtained can be applied, sprayed, or immersed onto various substrates to obtain the benzalkonium chloride-functional silyl groups based on the properties of the alkoxysilyl groups. It chemically bonds with moisture and hydroxyl groups on the surface of the base material, and a base material having benzalkonium chloride functional groups on the surface for a long period of time can be obtained. For this surface treatment, a dilute solution diluted with alcohol may be used, or an aqueous solution of several percent may be used for the surface treatment.

In a nitrogen atmosphere, 123 g of chloromethylstyrene of a mixture of meta-isomer and para-isomer (approximately 45:55) was charged into a 500 mL flask, and a platinum catalyst was added so that the amount of platinum was 5 ppm of the total amount. While stirring with a magnetic stirrer, the mixture was heated to 120° C. and 120 g of triethoxysilane was slowly added dropwise. An exothermic reaction occurred, and when the reaction solution was checked with a gas chromatograph after dropping, it was confirmed that a mixture of α-adduct and β-adduct was synthesized in which the vinyl group of chloromethylstyrene was hydrosilylated with triethoxysilane. was confirmed. A fraction having a boiling point of 110° C. to 120° C./60 Pa was collected by distillation under reduced pressure to obtain 170 g of a liquid. Gas chromatography (Fig. 1), NMR spectrum (Fig. 2), and FT-IR spectrum indicate that it is a mixture of triethoxysilylethylbenzyl chloride and methyl-triethoxysilylmethylbenzyl chloride, which is an isomer mixture of meta and para isomers. was confirmed (refractive index 1.4811).

85 g of the mixture of benzyl chloride having a triethoxysilyl group as a substituent obtained in Example 1 was added to a solution prepared by dissolving 57 g of dimethyldodecylamine in 214 g of ethanol and heating to 60° C. under a nitrogen atmosphere while stirring with a magnetic stirrer. Dripped. An exothermic reaction occurred, and the dropping rate was adjusted so that the temperature of the reaction solution was around 70°C. After completion of the dropwise addition, ethanol was refluxed for 30 minutes and cooled to obtain 350 g of an ethanol solution of a yellow transparent liquid having a solid content of 40%. When the concentration of free chloride ions was measured, it was confirmed that an ammonium salt was formed at 2.7%.

85 g of the mixture of benzyl chloride having a triethoxysilyl group as a substituent obtained in Example 1 was added to a solution of 65 g of dimethyltetradecylamine dissolved in 226 g of ethanol. was dripped. An exothermic reaction occurred, and the dropping rate was adjusted so that the temperature of the reaction solution was around 70°C. After completion of the dropwise addition, ethanol was refluxed for 30 minutes and cooled to obtain 375 g of an ethanol solution of a yellow transparent liquid having a solid content of 40%. When the concentration of free chloride ions was measured, it was confirmed that an ammonium salt was formed at 2.5%.

In a nitrogen atmosphere, 85 g of the mixture of benzyl chloride having a triethoxysilyl group as a substituent obtained in Example 1 was added to a solution of 80 g of dimethyloctadecylamine dissolved in 248 g of ethanol and heated to 60° C. while stirring with a magnetic stirrer. Dripped. An exothermic reaction occurred, and the dropping rate was adjusted so that the temperature of the reaction solution was around 70°C. After completion of the dropwise addition, ethanol was refluxed for 30 minutes and cooled to obtain 414 g of a yellow transparent liquid ethanol solution having a solid content of 40%. When the concentration of free chloride ions was measured, it was confirmed that an ammonium salt was formed at 2.3%.

The novel benzalkonium chloride-functional alkoxysilane compounds of the present invention are expected to be usable as materials having antibacterial and antiviral effects.

Claims (4)

the following general formula (1);

(In the formula, R ¹ represents an alkyl group having 10 to 18 carbon atoms, R ² and R ³ represent alkyl groups having 1 to 6 carbon atoms, and R ⁴ represents an alkylene group having 2 to 6 carbon atoms.) A novel benzalkonium chloride-functional silane coupling agent represented by A benzalkonium chloride-functional silane coupling agent, wherein the benzalkonium chloride-functional silane coupling agent represented by the above general formula (1) is trimethoxysilane. A benzalkonium chloride-functional silane coupling agent, wherein the benzalkonium chloride-functional silane coupling agent represented by the above general formula (1) is triethoxysilane. A benzalkonium chloride-functional silane coupling agent, wherein R4 of the benzalkonium chloride-functional silane coupling agent represented by the general formula (1) is an alkylene group having 2 carbon atoms.

Images