阅读说明：本技术 一种季铵盐松香基Gemini表面活性剂及其制备方法 (Quaternary ammonium salt rosin-based Gemini surfactant and preparation method thereof ) 是由 侯琳熙 潘瑶琪 郭博庚 张永乐 李盼 于 2020-07-27 设计创作，主要内容包括：本发明公开了一种季铵盐松香基Gemini表面活性剂及其制备方法,该表面活性剂是一种带三环二萜结构的新型表面活性剂,其是将脱氢枞胺和环氧氯丙烷经开环反应得到中间体RGS,随后将中间体RGS分别和N,N-二甲基十二烷基胺(N,N-二甲基十四烷基胺、N,N-二甲基十六烷基胺、N,N-二甲基十八烷基胺)反应分别经反应、提纯制得。本发明制备的季铵盐松香基Gemini表面活性剂结构新颖,含有刚性环状结构对芳香类化合物有较好的乳化性能,同时具有较低的临界胶束浓度,并且具有良好的清洗性能,与其他表面活性剂复配时将会表现出良好的兼容性和协同作用。(The invention discloses a quaternary ammonium salt rosin-based Gemini surfactant and a preparation method thereof, wherein the surfactant is a novel surfactant with a tricyclic diterpene structure, and is prepared by carrying out ring-opening reaction on dehydroabietylamine and epoxy chloropropane to obtain an intermediate RGS, and then respectively reacting and purifying the intermediate RGS with N, N-dimethyldodecylamine (N, N-dimethyltetradecylamine, N-dimethylhexadecylamine and N, N-dimethyloctadecylamine) respectively. The quaternary ammonium salt rosin-based Gemini surfactant prepared by the invention is novel in structure, contains a rigid ring structure, has good emulsifying property on aromatic compounds, has low critical micelle concentration, has good cleaning performance, and can show good compatibility and synergistic effect when being compounded with other surfactants.)

1. A quaternary ammonium salt rosin-based Gemini surfactant is characterized in that: the structural formula is as follows:

wherein R = C₁₂H₂₅， C₁₄H₂₉，C₁₆H₃₃Or C₁₈H₃₇。

2. A method of preparing the quaternary ammonium rosin-based Gemini surfactant of claim 1, comprising: the method comprises the following steps:

(1) adding dehydroabietylamine with absolute ethyl alcohol as a solvent into a single-neck flask at 23-26 ℃, then slowly dropwise adding epoxy chloropropane, controlling the dropwise adding amount, completing dropwise adding for 1.5-2 h, stirring for 10-12 h, and after the reaction is finished, carrying out reduced pressure rotary evaporation to remove unreacted epoxy chloropropane and the solvent to obtain an intermediate RGS;

(2) mixing the intermediate RGS and N, N-dimethyl long-chain aliphatic amine according to a certain proportion, adding absolute ethyl alcohol as a solvent, heating and refluxing at 80 ℃ for 24 hours, and distilling under reduced pressure to remove the solvent; washing the obtained product with a mixed solvent of ethyl acetate/ethanol to remove unreacted N, N-dimethyl long-chain fatty amine; and recrystallizing, filtering and vacuum drying to obtain the quaternary ammonium salt rosin-based Gemini surfactant.

3. The method for preparing a quaternary ammonium rosin-based Gemini surfactant according to claim 2, wherein the quaternary ammonium rosin-based Gemini surfactant comprises the following steps: the mass ratio of dehydroabietylamine to epichlorohydrin used in step (1) was 1: 3.

4. The method for preparing a quaternary ammonium rosin-based Gemini surfactant according to claim 2, wherein the quaternary ammonium rosin-based Gemini surfactant comprises the following steps: the solvent added in the step (1) is 30-40 ml.

5. The method for preparing a quaternary ammonium rosin-based Gemini surfactant according to claim 2, wherein the quaternary ammonium rosin-based Gemini surfactant comprises the following steps: the N, N-dimethyl long-chain fatty amine in the step (2) is N, N-dimethyl dodecyl amine, N-dimethyl tetradecyl amine, N-dimethyl hexadecyl amine and N, N-dimethyl octadecyl amine respectively.

6. The method for preparing a quaternary ammonium rosin-based Gemini surfactant according to claim 2, wherein the quaternary ammonium rosin-based Gemini surfactant comprises the following steps: the mixed solvent in the step (2) is a mixed solvent of ethyl acetate/ethanol, wherein the volume ratio of ethyl acetate to ethanol is 10:1, 7:1, 6.5:1 and 6:1 respectively.

Technical Field

The invention belongs to the technical field of surfactant preparation, and particularly relates to a quaternary ammonium salt rosin-based Gemini surfactant and a preparation method thereof.

Background

The Gemini surfactant is composed of two hydrophobic chains and two hydrophilic head groups, and the two hydrophobic chains and the two hydrophilic head groups are connected through a flexible or rigid group spacer, so that Gemini surfactant molecules have hydrophilicity and lipophilicity, have better emulsibility compared with the traditional surfactant Gemini surfactant, and can be applied as a cleaning agent. Printed circuit boards, which are important electronic components, are considered to be low-technology products, but are now being developed into high-technology products, and almost all electronic products can find the printed circuit boards, but many pollutants are introduced in the electronic manufacturing process, for example, rosin soldering flux with high activity is required to be used in the process of assembly and connection welding of assembled circuit boards, and the rosin soldering flux remains on the assembled circuit boards, so that the circuit boards and components are corroded, the surface insulation resistance of the assembled circuit boards is reduced, and particularly under the conditions of high temperature and high humidity, serious corrosion and electric leakage occur, and the reliability of the whole machine is affected. The development direction of the industrial cleaning agent in the future is a water-based cleaning agent, and the surfactant is the soul of the water-based cleaning agent. Therefore, designing and synthesizing the surfactant with simple and high efficiency and application value is the main working direction of the next step in the field. For example, Chinese patent (CN 110787720A) discloses a fluorine-containing gemini surfactant and a preparation method thereof, and mainly relates to the technical field of preparation of novel fluorine-containing materials. The method comprises the steps of preparing a mixture of a 4-6 perfluoroalkene R_f-A-CH=CH₂With N, N' -dimethylalkyldiamine CH₃NHRNHCH₃The reaction is carried out to generate fluorine-containing di-tertiary amine, and then the fluorine-containing di-tertiary amine is subjected to oxidation reaction with hydrogen peroxide, quaternization reaction with sodium chloroacetate (sodium chloroalkyl sulfonate) and halogen-containing alkane, and the product is obtained after blending. But do notThe emulsification performance of the Gemini surfactant on rosin is not good. Chinese patent (CN 110961030A) discloses a morpholine head group cationic gemini surfactant and preparation and application thereof. But due to the structural factor, the fire-fighting agent is more applied to the fields of oil field adoption and fire fighting. Therefore, the development of the rosin-based Gemini surfactant which is efficient, environment-friendly and easy to prepare is of far great significance in the field of cleaning of rosin substances.

Disclosure of Invention

The invention aims to provide a quaternary ammonium salt rosin-based Gemini surfactant and a preparation method thereof, aiming at the defects of the type of the existing Gemini surfactant. The quaternary ammonium salt rosin-based Gemini surfactant has good emulsifying property on aromatic compounds, has lower critical micelle concentration and good cleaning property, shows good compatibility and synergistic effect when being compounded with other surfactants, and is a novel efficient surfactant.

In order to achieve the purpose, the invention adopts the following technical scheme:

a quaternary ammonium salt rosin-based Gemini surfactant takes ammonium ions as hydrophilic groups, takes long-chain alkane and rosin groups as hydrophobic groups, and has the following specific structural formula:

(ii) a Wherein R = C₁₂H₂₅, C₁₄H₂₉, C₁₆H₃₃Or C₁₈H₃₇。

The preparation method of the Gemini surfactant comprises the following steps:

(1) adding dehydroabietylamine which takes absolute ethyl alcohol as a solvent into a single-neck flask at a certain temperature, then slowly dropwise adding epoxy chloropropane, controlling the dropwise adding amount, completing dropwise adding for 1.5-2 h, stirring for 10-12 h, and after the reaction is finished, carrying out reduced pressure rotary evaporation to remove unreacted epoxy chloropropane and the solvent to obtain an intermediate RGS, wherein the structural formula of the intermediate RGS is as follows:

；

(2) mixing the intermediate RGS and N, N-dimethyl long-chain aliphatic amine according to a certain proportion, adding absolute ethyl alcohol as a solvent, heating and refluxing at 80 ℃ for 24 hours, and distilling under reduced pressure to remove the solvent. The obtained product is washed by a mixed solvent of ethyl acetate/ethanol to remove unreacted N, N-dimethyl long-chain aliphatic amine. The products are four quaternary ammonium salt rosin Gemini surface active agents RGS-12, RGS-14, RGS-16 and RGS-18 after recrystallization, filtration and vacuum drying. The mass ratio of dehydroabietylamine to epichlorohydrin used in the step (1) was 1: 3.

The mixed solvent described in the above step (2) is a mixture of intermediate RGS and N, N-dimethyldodecylamine (N, N-dimethyltetradecylamine, N-dimethylhexadecylamine, N-dimethyloctadecylamine), wherein the mass ratio of the intermediate RGS to the N, N-dimethyldodecylamine (N, N-dimethyltetradecylamine, N-dimethylhexadecylamine, N-dimethyloctadecylamine) is 1: 3.

compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the quaternary ammonium salt rosin-based Gemini surfactant prepared by the invention is a surfactant with a novel structure, and has low critical micelle concentration, good foaming capability and foam stability.

(2) The quaternary ammonium salt rosin-based Gemini surfactant prepared by the invention has the advantages that the hydrophobic tail chain is an alkane chain with different lengths and a large rigid ring, and has a quaternary ammonium salt structure, N on the quaternary ammonium salt has an activating effect on cleaning rosin, so that the cleaning condition can be reduced (a small amount of surfactant is used for achieving a good cleaning effect), the cleaning rate can be improved, and the cleaning cost can be reduced.

(3) The quaternary ammonium salt rosin-based Gemini surfactant prepared by the invention is simple in preparation process and easy for industrial production.

Drawings

FIG. 1 is an infrared spectrum of a quaternary ammonium salt rosin-based Gemini surfactant;

FIG. 2 is a contact angle diagram of a quaternary ammonium salt rosin-based Gemini surfactant;

FIG. 3 is a diagram showing the effect of quaternary ammonium salt rosin-based Gemini surfactant in cleaning a circuit board.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.