阅读说明：本技术 一种含功能基的可降解型Gemini季铵盐及其制备方法 (Degradable Gemini quaternary ammonium salt containing functional group and preparation method thereof ) 是由 孔洪涛 马秀侠 刘路 朱俊 刘哲 刘玲玲 于 2020-12-28 设计创作，主要内容包括：本发明提供一种含功能基的可降解型Gemini季铵盐,结构式为以下两种：其中R为C8-C16的长链烷基；X为Cl或Br；Y为本制备方法中合成的季铵盐,在酯化或酰胺缩合过程中反应条件温和,且无需通过将一个底物过量以提高产率,在纯化过程中只需洗涤浓缩即可制备高纯度产物。由于引入了易降解的酯键或酰胺键,使用之后排入自然水体容易降解,降解之后的物质不具有抗菌性能,不利于耐药菌的产生,是一种环保的新型季铵盐。(The present invention providesA degradable Gemini quaternary ammonium salt containing functional groups has the following two structural formulas: wherein R is C8-C16 long-chain alkyl; x is Cl or Br; y is)

1. A degradable Gemini quaternary ammonium salt containing functional groups is characterized in that the structural formula is as follows:

wherein R is C8-C16 long-chain alkyl;

x is Cl or Br;

y is

2. A method for preparing a degradable Gemini quaternary ammonium salt containing functional groups, which is characterized in that the method for preparing the compound of formula 1 in claim 1 comprises the following steps:

(1.1) Synthesis of fatty acyloxymethylene dimethyl Tertiary amine

Sequentially adding DCM, fatty alcohol, N-dimethylglycine, EDCI and DMAP into a single-mouth flask, stirring for 12 hours at room temperature, adding water for extraction for 2-3 times after the reaction is finished, and taking an organic phase for spin drying to obtain a fatty acyl oxygen methylene dimethyl tertiary amine product;

(1.2) Synthesis of Gemini Quaternary ammonium salt

And (3) sequentially adding acetonitrile, fatty acyl oxygen methylene dimethyl tertiary amine, a bridging group and an alkaline catalyst into a reactor with stirring reflux, stirring and refluxing for 12h at 60 ℃, performing spin drying after the reaction is finished, and washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules.

3. A method for preparing a degradable Gemini quaternary ammonium salt containing functional groups, which is characterized in that the method for preparing the compound shown in the formula 2 in claim 1 comprises the following steps:

(2.1) Synthesis of fatty amidopropyl dimethyl Tertiary amine

Adding DCM, fatty acid, EDCI and HOBT into a reactor with a stirrer and a flow dividing device, adding N-dimethyl-1, 3-propane diamine after stirring for 1h, continuing to react for 12h, adding water to extract for 2-3 times after the reaction is finished, taking organic phase, evaporating under reduced pressure, concentrating, and cooling to room temperature to obtain fatty amide propyl dimethyl tertiary amine;

(2.2) Synthesis of Gemini Quaternary ammonium salt

And (3) sequentially adding acetonitrile, fatty acid amide propyl dimethyl tertiary amine, a bridging group and a basic catalyst into a reactor with stirring reflux, stirring and refluxing for 12h at 60 ℃, performing spin drying after the reaction is finished, and washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules.

Technical Field

The invention belongs to the field of cationic quaternary ammonium salt surfactants, and particularly relates to a degradable Gemini quaternary ammonium salt containing functional groups and a preparation method thereof.

Background

Gemini type Gemini surfactant is also called dicationic detergent, biquaternary ammonium salt surfactant and dimeric surfactant, a linking group in a molecule connects two electropositive hydrophilic groups through a chemical bond, so that repulsion between the hydrophilic groups and a hydration layer thereof is weakened, adsorption of Gemini surfactant molecules on the surface of an aqueous solution and self-polymerization in the aqueous solution are promoted, and the Gemini surfactant has high surface adsorption capacity and aggregate forming capacity. Cationic gemini surfactants, due to their specific structure, exhibit many superior properties over traditional surfactants, such as: the surfactant has the advantages of good emulsifying property, low toxicity, lower critical micelle concentration, stronger bactericidal property, capability of more effectively reducing the surface tension of water, lower Krafft point than that of the common surfactant, good saponification dispersing capability, good synergistic effect when being mixed with other surfactants and the like, so the surfactant is called as a new-generation surfactant and is widely applied to the fields of preparing new materials and bactericides, inhibiting metal corrosion, dyeing and finishing fabrics, petroleum exploitation and the like.

Compared with the traditional single-chain and double-chain quaternary ammonium salts, the quaternary ammonium salt has 2 quaternary ammonium positive ions in 1 molecule and higher charge density, so that the effective adsorption of the quaternary ammonium salt on the surface of bacterial cells is enhanced, the permeability of cell walls is changed, the quaternary ammonium salt has stronger antibacterial and antifungal activities compared with the typical single-chain and double-chain quaternary ammonium salts, and the traditional alkyl gemini quaternary ammonium salt is limited in use due to poor biodegradability.

Along with the increasing awareness of environmental protection, biodegradable bactericides have gained increasing attention. Therefore, ester bonds or amido bonds are introduced into the Gemini quaternary ammonium salt, the hydrolysis performance of the Gemini quaternary ammonium salt is greatly improved, and electron-withdrawing groups are introduced into connecting groups to react with N⁺Influence of electric charge, N⁺The electropositivity is enhanced, so that the attractiveness of the antibacterial agent to negatively charged bacteria is enhanced, and the sterilization performance of the antibacterial agent is greatly improved.

Disclosure of Invention

The invention aims to provide a degradable Gemini quaternary ammonium salt with functional groups and a preparation method thereof, which are efficient, environment-friendly, simple and easy to prepare and can realize industrialization.

The specific technical scheme is as follows:

a degradable Gemini quaternary ammonium salt containing functional groups has the following two structural formulas:

wherein R is C8-C16 long-chain alkyl;

x is Cl or Br;

y is

The preparation method of the formula 1 comprises the following steps:

(1.1) Synthesis of fatty acyloxymethylene dimethyl Tertiary amine

Adding DCM, aliphatic alcohol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) into a single-neck flask in sequence, stirring at room temperature for 12h, adding water to extract for 2-3 times after the reaction is finished, taking an organic phase, and spin-drying to obtain the aliphatic acyloxymethylene dimethyl tertiary amine product.

(1.2) Synthesis of Gemini Quaternary ammonium salt

And (3) sequentially adding acetonitrile, fatty acyl oxygen methylene dimethyl tertiary amine (2eq), bridging group (1eq) and alkaline catalyst (0.1eq) into a reactor with stirring reflux, stirring and refluxing for 12h at 60 ℃, drying after the reaction is finished, and washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecule.

The synthetic route is as follows:

the preparation method of the formula 2 comprises the following steps:

(2.1) Synthesis of fatty amidopropyl dimethyl Tertiary amine

Adding DCM, fatty acid (1eq), EDCI (1.2eq) and HOBT (1.2eq) into a reactor with a stirrer and a flow dividing device, stirring for 1h, adding N-dimethyl-1, 3-propanediamine (1eq) to continue reacting for 12h, adding water to extract for 2-3 times after the reaction is finished, taking organic phase, evaporating under reduced pressure, concentrating, and cooling to room temperature to obtain the fatty amidopropyl dimethyl tertiary amine.

(2.2) Synthesis of Gemini Quaternary ammonium salt

And (3) sequentially adding acetonitrile, fatty acid amide propyl dimethyl tertiary amine (2eq), bridging group (1eq) and basic catalyst (0.1eq) into a reactor with stirring reflux, stirring and refluxing for 12h at 60 ℃, spin-drying after the reaction is finished, and washing for 2-3 times by using dichloromethane to obtain white powder, namely the quaternary ammonium salt molecule.

Compared with the prior art, the invention has the following advantages:

1. the quaternary ammonium salt synthesized in the preparation method has mild reaction conditions in the esterification or amide condensation process, does not need to increase the yield by adding excessive substrates, and can prepare a high-purity product by only washing and concentrating in the purification process.

2. The quaternary ammonium salt is introduced with easily degradable ester bonds or amido bonds, is easily degraded when being discharged into natural water after being used, has no antibacterial property after being degraded, is not beneficial to the generation of drug-resistant bacteria, and is a novel environment-friendly quaternary ammonium salt.

3. The quaternary ammonium salt provided by the invention has the advantages that as the functional group with electron withdrawing is introduced, the positive electricity of the quaternary ammonium salt molecule is enhanced, the attraction to microorganisms such as bacteria with negative electricity in the environment is stronger, and the minimum inhibitory concentration is lower. Can greatly reduce the usage amount of quaternary ammonium salt during sterilization.

Detailed Description

The specific technical scheme of the invention is described by combining the embodiment.

Example 1: the structure is as follows:

synthesis of N, N-dimethylglycine dodecyl ester: DCM, dodecanol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) are sequentially added into a single-neck flask, stirred at room temperature for 12 hours, added with water after the reaction is finished, extracted for 2-3 times, and taken out and dried by spinning, thus obtaining the oily N, N-dimethyl dodecyl glycine product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, N-dimethyl dodecyl glycine (2eq), 1, 3-dichloroacetone (1eq) and Na are added in sequence into a reactor with stirring reflux₂CO₃(0.1eq), stirring and refluxing for 12h at 60 ℃, spin-drying after the reaction is finished, washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules, performing biodegradation performance measurement on the structure according to the national standard GB/T15818-2006, and displaying the biodegradation on the seventh day by using a detection resultThe degree was 99.8%.

Example 2: the structure is as follows:

synthesis of N, N-dimethylglycine dodecyl ester: DCM, dodecanol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) are sequentially added into a single-neck flask, stirred at room temperature for 12 hours, added with water after the reaction is finished, extracted for 2-3 times, and taken out and dried by spinning, thus obtaining the oily N, N-dimethyl dodecyl glycine product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, N-dimethyl dodecyl glycine (2eq), 1, 3-dibromoacetone (1eq) and Na are added in sequence into a reactor with stirring reflux₂CO₃(0.1eq), stirring and refluxing for 12h at 60 ℃, performing spin-drying after the reaction is finished, washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules, and performing biodegradation performance measurement on the structure according to the national standard GB/T15818-2006, wherein the detection result shows that the biodegradation degree is 99.9% on the seventh day.

Example 3: the structure is as follows:

synthesis of N, N-dimethyldecyl glycinate: DCM, 1-decanol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) are sequentially added into a single-neck flask, stirred at room temperature for 12 hours, added with water to extract for 2-3 times after the reaction is finished, and an organic phase is taken out to be dried in a spinning mode to obtain an oily N, N-dimethyl decyl glycinate product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, N-dimethyl decyl glycinate (2eq), 1, 3-dichloroacetone (1eq) and Na are added in sequence into a reactor with stirring reflux₂CO₃(0.1eq), stirring and refluxing for 12h at 60 ℃, spin-drying after the reaction is finished, washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules, and performing raw production on the structure according to the national standard GB/T15818-2006The biodegradability test shows that the biodegradability of the seventh day is 99.9%.

Example 4: the structure is as follows:

synthesis of octylamidopropyldimethylamine: adding DCM, octanoic acid (1eq), EDCI (1.2eq) and HOBT (1.2eq) into a reactor with a stirrer and a flow dividing device, stirring for 1h, adding N-dimethyl-1, 3-propanediamine (1eq) to continue reacting for 12h, adding water to extract for 2-3 times after the reaction is finished, taking the organic phase, evaporating under reduced pressure, concentrating, and cooling to room temperature to obtain a light yellow transparent liquid octylamidopropyl dimethylamine product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, octylamidopropyldimethylamine (2eq), 1, 4-dichloro-2, 5-dinitrobenzene (1eq), and K are added in sequence into a reactor with stirring reflux₂CO₃(0.1eq), stirring and refluxing for 12h at 60 ℃, performing spin-drying after the reaction is finished, washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules, and performing biodegradation performance measurement on the structure according to the national standard GB/T15818-2006, wherein the detection result shows that the biodegradation degree is 99.3% on the seventh day.

Example 5: the structure is as follows:

synthesis of N, N-dimethylglycine dodecyl ester: DCM, dodecanol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) are sequentially added into a single-neck flask, stirred at room temperature for 12 hours, added with water after the reaction is finished, extracted for 2-3 times, and taken out and dried by spinning, thus obtaining the oily N, N-dimethyl dodecyl glycine product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, N-dimethyl dodecyl glycine (2eq), 1, 4-dichloro-2, 5-dinitrobenzene (1eq), and K are added in sequence into a reactor with stirring reflux₂CO₃(0.1eq)，60℃Stirring and refluxing for 12h, performing spin-drying after the reaction is finished, washing for 2-3 times by using dichloromethane to obtain white powder of the quaternary ammonium salt molecules, and performing biodegradation performance measurement on the structure according to the national standard GB/T15818-2006, wherein the detection result shows that the biodegradation degree is 99.7% on the seventh day.

Example 6: the structure is as follows:

synthesis of octylamidopropyldimethylamine: adding DCM, octanoic acid (1eq), EDCI (1.2eq) and HOBT (1.2eq) into a reactor with a stirrer and a flow dividing device, stirring for 1h, adding N-dimethyl-1, 3-propanediamine (1eq) into the reactor, continuing to react for 12h, adding water into the reactor after the reaction is finished, extracting for 2-3 times, taking the organic phase, evaporating and concentrating under reduced pressure, and cooling to room temperature to obtain a light yellow transparent liquid octylamidopropyl dimethylamine product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, octylamidopropyldimethylamine (2eq) and malonyl chloride (1eq) are sequentially added into a reactor with stirring reflux, stirring reflux is carried out for 12h at 60 ℃, after the reaction is finished, spinning drying is carried out, dichloromethane is used for washing for 2-3 times, white powder of the quaternary ammonium salt molecule is obtained, the biodegradation performance of the structure is measured according to the national standard GB/T15818-2006, and the detection result shows that the biodegradation degree in the seventh day is 99.6%.

Example 7: the structure is as follows:

synthesis of N, N-dimethyldecyl glycinate: DCM, 1-decanol (1eq), N-dimethyl glycine (1eq), EDCI (1.2eq) and DMAP (0.15eq) are sequentially added into a single-neck flask, stirred at room temperature for 12 hours, added with water to extract for 2-3 times after the reaction is finished, and an organic phase is taken out to be dried in a spinning mode to obtain an oily N, N-dimethyl decyl glycinate product.

Synthesis of Gemini quaternary ammonium salt: acetonitrile, N-dimethyl decyl glycinate (2eq) and malonyl chloride (1eq) are sequentially added into a reactor with stirring reflux, stirring reflux is carried out for 12h at 60 ℃, after the reaction is finished, spinning drying is carried out, dichloromethane is used for washing for 2-3 times to obtain white powder quaternary ammonium salt molecules, the structure is subjected to biodegradation performance measurement according to the national standard GB/T15818-2006, and the detection result shows that the biodegradation degree is 99.8% on the seventh day.