阅读说明：本技术 一种提高碳纳米管水相杀菌能力的腰果酚基水相分散助剂及其合成方法 (Cardanol-based aqueous phase dispersing auxiliary agent for improving carbon nano tube aqueous phase sterilizing capability and synthesis method thereof ) 是由 罗玉娜 王一雷 马文婷 王鹏帅 于 2019-09-06 设计创作，主要内容包括：一种提高碳纳米管水相杀菌能力的腰果酚基水相分散助剂及其合成方法。解决碳纳米管在水溶液中稳定单根分散并提高碳纳米管水溶液抗菌性能的技术问题。该分散助剂化学名称为[2-(3-十五烯基苯氧基)-(C<Sub>2</Sub>H<Sub>4</Sub>)<Sub>m</Sub>基]-N-R<Sub>1</Sub>基-N,N-二甲基溴化铵,其结构式如下,其中m＝1-3；R<Sub>1</Sub>＝C<Sub>n</Sub>H<Sub>2n+1</Sub>,n＝1-8；X为卤素。制备方法为：从农副产品腰果壳油分离纯化得到的腰果酚滴加到弱碱性溶剂中反应得到卤代烷腰果醚,再在溶剂中与烷基胺或烷基吡啶反应得到粗产物,经过浓缩和重结晶得到目标产物。该分散助剂能够实现碳纳米管水溶液的单根稳定分散,并对大肠杆菌和金色葡萄球菌就有良好的杀灭作用,可接枝到壳聚糖、纤维素等高分子用于抗菌表面制备和水净化等领域。<Image he="353" wi="623" file="DDA0002193428820000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>或者<Image he="321" wi="700" file="DDA0002193428820000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A cardanol-based water-phase dispersing auxiliary agent for improving the water-phase bactericidal ability of carbon nanotubes and a synthesis method thereof. The technical problems of stabilizing single dispersion of the carbon nano tube in the aqueous solution and improving the antibacterial property of the aqueous solution of the carbon nano tube are solved. The chemical name of the dispersing assistant is [2- (3-pentadecenylphenoxy) - (C) 2 H 4 ) m Base of]‑N‑R 1 The group-N, N-dimethyl ammonium bromide has the following structural formula, wherein m is 1-3; r 1 ＝C n H 2n+1 N is 1-8; x is halogen. The preparation method comprises the following steps: the cardanol obtained by separating and purifying the agricultural and sideline product cashew nut shell oil is dripped into a weak alkaline solvent to react to obtain haloalkane cardanol ether, then the haloalkane cardanol ether reacts with alkylamine or alkylpyridine in the solvent to obtain a crude product, and the crude product is concentrated and recrystallized to obtain a target product. The dispersing auxiliary agent can realize the stable dispersion of single carbon nanotube aqueous solution, has good killing effect on escherichia coli and staphylococcus aureus, and can be grafted to high molecules such as chitosan, cellulose and the like to be used in the fields of antibacterial surface preparation, water purification and the like. Or)

1. A cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent for improving the aqueous phase bactericidal capacity of a carbon nanotube is characterized in that the chemical name of the aqueous phase dispersing auxiliary agent is [2- (3-pentadecenylphenoxy) - (C)₂H₄)_mBase of]-N-R₁The group-N, N-dimethyl ammonium bromide has a structural formula as follows:

or

Wherein m is 1-3, the type and chain length R of the quaternary ammonium nitrogen-linked alkane₁＝C_nH_2n+1N is 1-8, and X is bromine.

2. The synthesis method of the cardanol-based aqueous phase dispersing auxiliary agent for improving the bactericidal capacity of the carbon nanotube aqueous phase as claimed in claim 1, is characterized by comprising the following steps:

step one, dibromoalkane Br (CH)₂CH₂)_mBr, m-1-3 and potassium carbonate are dissolved in a solvent I, the mixture is stirred by magnetic force, cardanol is dripped at the temperature of 60-120 ℃, the molar equivalent of the cardanol is 0.1-0.5 of dibromoalkane, the cardanol continues to react for 6-24 hours after the dripping is finished, the obtained crude product is filtered to remove the potassium carbonate in the system, and the solvent is rotated and evaporated to obtain yellow transparent oily cardanol ether; wherein the solvent I is water or an organic solvent or a mixed solvent of water and the organic solvent;

step two, adding cardanol ether and R in a reactor₁Dimethylamine or R₁Radical pyridine, R₁＝C_nH_2n+1Dissolving n-1-8 in a solvent II according to a molar ratio of 1 (1.2-4.2), magnetically stirring, and refluxing at 80-120 ℃ for 6-24 hours to obtain a white cardanol quaternary ammonium salt precipitate; wherein the solvent II is petroleum ether, n-pentane, dichloromethane, trichloromethane, diethyl ether, ethyl acetate, ethanol, acetone,One or two of isopropanol, acetonitrile and dioxane are mixed to form a solvent;

step three, recrystallizing the white cardanol quaternary ammonium salt precipitate obtained in the step two by using a solvent III to obtain a purified cardanol-based carbon nano tube water phase dispersing auxiliary agent; wherein the solvent III is one or two of petroleum ether, tetrahydrofuran, dioxane, acetic acid, diethyl ether, ethyl acetate, acetone, ethanol, isopropanol, acetonitrile, pyridine, N-dimethylformamide and N-methylpyrrolidone.

3. The method for synthesizing the cardanol-based aqueous phase dispersing auxiliary agent for improving the bactericidal ability of the carbon nanotube aqueous phase according to claim 2, wherein the organic solvent in the first solvent is one or a combination of two of methanol, ethanol, isopropanol, butanol, ethyl acetate, acetone, dioxane, toluene, dichloromethane, chloroform, carbon tetrachloride, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

4. The method for synthesizing the cardanol-based aqueous dispersion auxiliary agent for improving the bactericidal ability of the carbon nanotube aqueous phase as claimed in claim 2, wherein the quaternary ammonium salt is formed by R₁Radical pyridine or R₁Dimethylamine, R_1＝C_nH_2n+1And n is 1-8.

Technical Field

The invention relates to a cardanol-based aqueous phase dispersing auxiliary agent for improving the aqueous phase sterilizing capability of a carbon nano tube and a synthesis method thereof.

Background

The application of the carbon nano tube in the antibacterial field can greatly improve the antibacterial performance of the traditional material, and particularly has the inherent advantage for drug-resistant super bacteria. Because the larger specific surface area of the carbon nanotube and the sharp carbon nanotube port facilitate penetration of the bacterial cell wall; the unique electrical properties can induce the generation of photo-generated singlet oxygen, resulting in the inactivation of bacterial functional polypeptides, proteins or polysaccharides. However, the extremely strong pi-pi interactions and hydrophobic sidewalls between carbon nanotubes make it difficult to stabilize the carbon nanotubes and to disperse the individual carbon nanotubes in water. The dispersion state of the carbon nanotubes in the aqueous solution directly influences that the diameter and the specific surface area of the carbon nanotubes in the aqueous phase deviate from the intrinsic values, and the surfaces of microbial cells are negatively charged, and phospholipid contained in cell membranes and some membrane protein hydrolyzes are also negatively charged. The quaternary ammonium salt assistant dispersant has positive charge, and the mutual attraction of opposite charges can improve the adsorption capacity of the carbon nano tube on the surface of bacteria, so that the sterilization capacity of the carbon nano tube can be further improved.

Chinese patent publication No. CN102805103A discloses a method for synthesizing a carbon nanotube-based disinfecting material. Is applied to killing escherichia coli in water. However, the method needs to use alkali to pretreat the carbon tube, then use concentrated sulfuric acid and concentrated nitric acid to cut and refine, and then use 1 wt% of one of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate or new basic polyoxyethylene ether to disperse. The pretreatment process is complex, the damage to the carbon tube structure is serious, the concentration of the dispersing auxiliary agent is high, and the killing capability to escherichia coli is weak.

Disclosure of Invention

The invention aims to solve the problem that the antibacterial capability of a carbon nano tube is reduced due to an anionic or nonionic aqueous phase dispersing aid, and provides a cardanol-based aqueous phase dispersing aid for improving the aqueous phase sterilizing capability of the carbon nano tube and a synthesis method thereof.

Technical scheme of the invention

A cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent for improving the carbon nanotube aqueous phase sterilization capability is disclosed, and the chemical name of the aqueous phase dispersing auxiliary agent is [2- (3-pentadecenylphenoxy) - (CH)₂CH₂)_mBase of]-N-R₁The group-N, N-dimethyl ammonium bromide has a structural formula as follows:

or

Wherein m is 1-3, the type and chain length R of the quaternary ammonium nitrogen-linked alkane₁＝C_nH_2n+1N is 1-8, and X is bromine.

The invention also provides a preparation method of the cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent, and the reaction process is represented as follows:

the method comprises the following steps:

step one, dibromoalkane Br (CH)₂CH₂)_mBr (m-1-3) and potassium carbonate are dissolved in a solvent I, the mixture is stirred by magnetic force, cardanol is dropwise added at the temperature of 60-120 ℃, the molar equivalent is 0.1-0.5 of dibromoalkane, the reaction is continued for 6-24 hours after the dropwise addition is finished, the obtained crude product is filtered to remove potassium carbonate in a system, and the solvent is rotationally evaporated to obtain yellow transparent oily cardanol ether;

step two, adding cardanol ether and R in a reactor₁Dimethylamine or R₁Radical pyridine (R)₁＝C_nH_2n+1N is 1-8) is dissolved in a solvent II according to the molar ratio of 1 (1.2-4.2), and is stirred by magnetic force and refluxed for 6-24 hours at the temperature of 80-120 ℃ to obtain white precipitate;

step three, recrystallizing the white precipitate obtained in the step two by using a solvent III to obtain a purified cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent;

in the first step, the solvent I is water or an organic solvent, or a mixed solvent of water and an organic solvent. The organic solvent is one or the combination of two of methanol, ethanol, isopropanol, butanol, ethyl acetate, acetone, dioxane, toluene, dichloromethane, chloroform, carbon tetrachloride, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide; the structure formula of the dibromoalkane is Br (CH)₂CH₂)_mBr，m＝1-3；

In step two, the quaternary ammonium salt is reacted with R₁Radical pyridine or R₁Dimethylamine (R)₁＝C_nH_2n+1N-1-8); the solvent II is a solvent formed by mixing one or two of petroleum ether, n-pentane, dichloromethane, trichloromethane, diethyl ether, ethyl acetate, ethanol, acetone, isopropanol, acetonitrile and dioxane;

in the third step, the chromatographic column filler is one of silica gel, alumina, cross-linked dextran, cross-linked agarose and cross-linked polyacrylamide; the solvent III is one or two of petroleum ether, tetrahydrofuran, dioxane, acetic acid, diethyl ether, ethyl acetate, acetone, ethanol, isopropanol, acetonitrile, pyridine, N-dimethylformamide or N-methylpyrrolidone.

The invention has the advantages and beneficial effects that:

1. the invention develops a method for preparing a cashew nut shell extract by using agricultural and sideline products: cardanol is used as a raw material to synthesize the cardanol-based carbon nano tube aqueous phase dispersing auxiliary agent for improving the aqueous phase sterilizing capability of the carbon nano tube.

2. The cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent for improving the aqueous phase bactericidal capacity of the carbon nanotube, which is synthesized by the invention, has the characteristics of simple preparation method and process, easily controlled reaction conditions and easily separated and purified products.

3. The synthesized cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent for improving the carbon nanotube aqueous phase sterilizing capability has excellent single carbon nanotube dispersing capability, the carbon nanotube aqueous phase dispersing concentration is 2-10mg/L, and a dispersion liquid can be stably stored for 90 days at room temperature. The minimum antimicrobial concentration is greatly reduced compared to dodecane basic sodium sulfonate dispersed carbon nanotubes. The minimum bactericidal concentration for Staphylococcus aureus is 0.02-0.24. mu.g/mL, and the bactericidal concentration for Escherichia coli can be 0.65-6.02. mu.g/mL.

The cardanol-based carbon nanotube aqueous phase dispersing auxiliary agent capable of improving the aqueous phase sterilization capability of the carbon nanotube can be used in the fields of water sterilization, functional coatings, drilling auxiliary agents and the like.

Drawings

FIG. 1 is an electron microscope photograph of Escherichia coli, Staphylococcus aureus, and carbon nanotube/cardanol-based carbon nanotube aqueous dispersion aid aqueous solution after action.

Fig. 2 shows ultraviolet-visible-near infrared absorption spectra before and after the carbon nanotube/cardanol-based carbon nanotube aqueous phase dispersion auxiliary aqueous solution is left to stand for 90 days.

Fig. 3 is an atomic force microscope test of the diameter of the carbon nanotube in the carbon nanotube/cardanol-based carbon nanotube aqueous phase dispersing aid aqueous solution, wherein a is a cardanol-based dispersed carbon nanotube atomic force microscope test chart, and B is a carbon nanotube diameter curve chart.

Detailed Description