Cardanol-based Gemini cationic surfactant and preparation method thereof
By preparing cashew phenol-based Gemini cationic surfactant, the problems of complex preparation and poor performance of existing cashew phenol-based Gemini surfactant are solved, high surfactivity and degradability are achieved, and the application of biomass resources in the field of surfactant is promoted.
Patent Information
- Application Number
- CN202510468764.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-08-01
AI Technical Summary
The existing cashew phenol-based Gemini surfactants are complex in preparation, harsh process conditions, poor performance, and petroleum-based surfactants are non-renewable and have poor biocompatibility, which limits their application in the food and biomedical fields.
A two-step method was used to prepare a cardanol-based Gemini cationic surfactant. Using biomass cashew phenol as raw material, it condensed with 3-dimethylaminopropylamine and formaldehyde through electrophilic substitution reaction under weak acid catalytic conditions to construct an unsaturated long-carbon chain hydrophobic tertiary amine intermediate, and then reacted with dibromoalkyl monomers to form a symmetric bisN,N-dimethyl quaternary ammonium head group and bisunsaturated hydrophobic alkyl chain Gemini molecular structure.
The prepared surfactants are naturally degradable, have improved hydrophobicity, significantly enhanced surfactivity, low critical micelle concentration and low surface tension, which improves crude oil recovery and promotes green and efficient development in the utilization of biomass resources.
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Figure CN120398783A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of surfactants and their preparation methods, and particularly relates to a cardanol-based Gemini cationic surfactant. The present invention also relates to a preparation method of the above surfactant. Background Art
[0002] Gemini surfactants are formed by connecting two or more traditional surfactant molecules through a linker at the hydrophilic group or near the hydrophilic group, forming a unique structure. This structure endows them with higher surface activity, lower critical micelle concentration, and better water solubility than traditional surfactants. At the same time, cationic Gemini surfactants have stronger adsorption ability and affinity when interacting with negatively charged biomass materials (such as certain biological macromolecules, cell membranes, etc.), and show broad application prospects in the fields of biomass separation, purification, enzyme simulation, gene transfection, etc. Currently, the main raw materials used for synthesizing Gemini surfactants are derived from petroleum, but petroleum-based surfactants are non-renewable, non-degradable, and lack biocompatibility, which limits their application in the fields of food, biomedicine, etc.
[0003] Cardanol is an extract of waste cashew nutshells. It contains a large amount of active single-component phenols and a small amount of diphenols, and is a rich, cheap, and renewable resource. Its structure not only contains highly reactive phenolic hydroxyl groups that can undergo esterification, addition, etherification, etc. reactions, but also the long alkyl chain has good flexibility and hydrophobicity, making it an ideal material for synthesizing surfactants.
[0004] Most of the existing preparations of cardanol-based Gemini surfactants are mainly anionic and non-ionic. The preparation process is complex, the process conditions are harsh, and the original alkyl chain hydrophobicity of cardanol is limited, resulting in poor surfactant performance. Summary of the Invention
[0005] The purpose of the present invention is to provide a cardanol-based Gemini cationic surfactant, which has the characteristics of natural degradability and high surface activity.
[0006] Another purpose of the present invention is to provide a preparation method of a cardanol-based Gemini cationic surfactant, which uses biomass cardanol as the main raw material, and the process is simple and environmentally friendly.
[0007] The technical solution adopted by the present invention is as follows: A preparation method of a cardanol-based Gemini cationic surfactant is specifically implemented according to the following steps: Step 1: adding cardanol, 3-dimethylaminopropylamine and formaldehyde to ethanol, and then reacting under stirring and high temperature conditions. After the reaction is completed, the product is post-treated to obtain a tertiary amine intermediate CP-T containing an unsaturated long carbon chain hydrophobic group; Step 2: dissolving the intermediate CP-T obtained in step 1 and 1,4-dibromobutane in acetonitrile, reacting under stirring and high temperature conditions, and after the reaction is completed, post-treating the product to obtain a cardanol-based Gemini cationic surfactant CPS-G.
[0008] The present invention is also characterized in that: During the reaction of step 1, the stirring speed is 200 r / min, the reaction temperature is 90-110° C., and the reaction time is 12 h.
[0009] In step 1, the post-treatment process of the reaction product is specifically as follows: washing the product with deionized water and then drying it at 60°C.
[0010] In step 1, the molar ratio of cardanol, 3-dimethylaminopropylamine, formaldehyde and ethanol is (0.8~1):1:2:4.
[0011] During the reaction of step 2, the stirring speed is 200 r / min, the reaction temperature is 100° C., and the reaction time is 24 h.
[0012] In step 2, the post-treatment process of the reaction product is specifically as follows: the reaction product is distilled under reduced pressure, washed with ethyl acetate 1 to 3 times, and vacuum dried to constant weight.
[0013] In step 2, the molar ratio of the intermediate CP-T, 1,4-dibromobutane and acetonitrile is (1-1.2):0.5:6.
[0014] Another technical solution adopted by the present invention is: Cardanol-based Gemini cationic surfactant, which is prepared by the above method, has the following structural formula:
[0015] The beneficial effects of the present invention are: The method of the present invention is based on renewable natural phenolic compounds and prepares a double hydrophilic head group-double hydrophobic chain Gemini surfactant through a two-step method. Cardanol is used as a bio-based raw material. First, a tertiary amine intermediate CP-T containing an unsaturated long carbon chain hydrophobic group is prepared by condensing with 3-dimethylaminopropylamine and formaldehyde through an electrophilic substitution reaction under weakly acidic catalytic conditions; then, a dibromoalkyl monomer is used as a cross-linking agent to construct a Gemini molecular structure with a symmetrical double N,N-dimethyl quaternary ammonium cationic head group and a double unsaturated hydrophobic alkyl chain through a quaternization reaction. The reaction conditions are mild, no catalyst is required, and separation and purification are easy.
[0016] The surfactant of the present invention has the environmental protection characteristics of being naturally degradable. In addition, the hydrophobic chain of the surfactant contains a benzoxazine structure, which increases its hydrophobicity and improves its surface activity, including a low critical micelle concentration of 0.58 mmol / L and a minimum surface tension of 32.4 mN / m (25 °C). The surface activity index is significantly better than that of traditional single-chain cationic surfactants. In tertiary oil recovery, it can increase the oil recovery rate by 12%, and has a super synergistic effect when compounded with anionic surfactants. In addition, the method of the present invention uses biomass cardanol to prepare surfactants, which enriches the application of biomass resources in the surfactant field to a certain extent and promotes the green and efficient development of this field. Description of the Drawings
[0017] Figure 1 It is the surface tension of the surfactant prepared in Example 1 of the present invention at different concentrations. Detailed Description of the Invention
[0018] The present invention will be described in detail below with reference to the drawings and specific embodiments.
[0019] The structural formula of the cardanol-based Gemini cationic surfactant of the present invention is as follows:
[0020] The preparation method of the cardanol-based Gemini cationic surfactant of the present invention is specifically implemented according to the following steps: Step 1, prepare the intermediate CP-T: Add cardanol, 3-dimethylaminopropylamine and formaldehyde to ethanol and stir evenly, then transfer the mixture to a three-necked flask with a condensing device, heat it to 90 - 110 °C at a rotation speed of 200 r / min and react for 12 h. After the reaction is completed, wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T containing an unsaturated long carbon chain hydrophobic group.
[0021] Among them, the molar ratio of cardanol, 3-dimethylaminopropylamine, formaldehyde and ethanol is: (0.8 - 1):1:2:4.
[0022] Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve the intermediate CP-T obtained in Step 1 and 1,4-dibromobutane in acetonitrile, then place the mixture in a three-necked flask equipped with a condensation device, stir the mixture at a rotation speed of 200 r / min and a temperature of 100 °C for 24 h, then distill the reaction product under reduced pressure, wash it with ethyl acetate 1 - 3 times, and dry it in vacuo to constant weight to obtain the cardanol-based Gemini cationic surfactant CPS-G, which has a symmetric double N,N-dimethyl quaternary ammonium cationic head group and a double unsaturated hydrophobic alkyl chain.
[0023] Among them, the molar ratio of the intermediate CP-T, 1,4-dibromobutane and acetonitrile is (1 - 1.2):0.5:6.
[0024] Example 1 Step 1, prepare the intermediate CP-T: Add 12.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 90 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve 21.4 g of the intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at a rotation speed of 200 r / min and a temperature of 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0025] Figure 1 The surface tension of the surfactant CPS-G prepared in this example at different concentrations is shown. It can be seen that because the hydrophobic chain of the prepared surfactant CPS-G contains a benzoxazine structure, the steric hindrance and volume of the hydrophobic chain are increased, the interfacial adsorption efficiency is improved, the surfactant forms micelles at a lower concentration, showing a low CMC value (0.58 mM) and surface tension (32.17 mN / m). Applying the surfactant in this example to crude oil recovery, the crude oil recovery rate is increased by more than 8%.
[0026] Example 2 Step 1, prepare the intermediate CP-T: Add 13.6 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 90 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve 23.6 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile. Stir the mixture at 200 r / min and 100 °C for 24 h. Post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0027] Example 3 Step 1, preparation of intermediate CP-T: Add 15.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine, and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 90 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, preparation of cardanol-based Gemini cationic surfactant CPS-G: Dissolve 25.7 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile. Stir the mixture at 200 r / min and 100 °C for 24 h. Post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0028] Example 4 Step 1, preparation of intermediate CP-T: Add 12.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine, and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 110 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, preparation of cardanol-based Gemini cationic surfactant CPS-G: Dissolve 21.4 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile. Stir the mixture at 200 r / min and 100 °C for 24 h. Post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0029] Example 5 Step 1, preparation of intermediate CP-T: Add 13.6 g of cardanol, 5.1 g of 3-dimethylaminopropylamine, and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 100 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, preparation of cardanol-based Gemini cationic surfactant CPS-G: Dissolve 23.6 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at 200 r / min and 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0030] Example 6 Step 1, prepare intermediate CP-T: Add 15.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 110 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve 25.7 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at 200 r / min and 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0031] Example 7 Step 1, prepare intermediate CP-T: Add 12.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 100 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve 21.4 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at 200 r / min and 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0032] Example 8 Step 1, prepare intermediate CP-T: Add 13.6 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 110 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, prepare the cardanol-based Gemini cationic surfactant CPS-G: Dissolve 23.6 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at a rotation speed of 200 r / min and a temperature of 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0033] Example 9 Step 1, preparation of intermediate CP-T: Add 15.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 100 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, preparation of cardanol-based Gemini cationic surfactant CPS-G: Dissolve 25.7 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at a rotation speed of 200 r / min and a temperature of 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
[0034] Example 10 Step 1, preparation of intermediate CP-T: Add 12.1 g of cardanol, 5.1 g of 3-dimethylaminopropylamine and 3.0 g of formaldehyde to 9.2 g of ethanol, stir evenly, and react at 105 °C for 12 h. Wash the product with deionized water and dry it at 60 °C to obtain the tertiary amine intermediate CP-T; Step 2, preparation of cardanol-based Gemini cationic surfactant CPS-G: Dissolve 21.4 g of intermediate CP-T and 5.4 g of 1,4-dibromobutane in 12.3 g of acetonitrile, stir the mixture at a rotation speed of 200 r / min and a temperature of 100 °C for 24 h, and post-treat the reaction product to obtain the cardanol-based Gemini cationic surfactant CPS-G.
Claims
1. Preparation method of cardanol-based Gemini cationic surfactant, characterized in that, The implementation is specifically carried out according to the following steps: Step 1: Add cardanol, 3-dimethylaminopropylamine and formaldehyde into ethanol, and then react under stirring and high-temperature conditions. After the reaction is completed, post-treat the product to obtain a tertiary amine intermediate CP-T containing unsaturated long carbon chain hydrophobic groups; Step 2: Dissolve the intermediate CP-T obtained in Step 1 and 1,4-dibromobutane in acetonitrile, and react under stirring and high-temperature conditions. After the reaction is completed, post-treat the product to obtain a cardanol-based Gemini cationic surfactant CPS-G.
2. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, characterized in that, During the reaction process of Step 1, the stirring speed is 200 r / min, the reaction temperature is 90 - 110 °C, and the reaction time is 12 h.
3. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, characterized in that, In Step 1, the post-treatment process of the reaction product is specifically: wash the product with deionized water, and then dry it at 60 °C.
4. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, wherein, In Step 1, the molar ratio of cardanol, 3-dimethylaminopropylamine, formaldehyde and ethanol is (0.8 - 1):1:2:
4.
5. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, characterized in that, During the reaction process of Step 2, the stirring speed is 200 r / min, the reaction temperature is 100 °C, and the reaction time is 24 h.
6. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, characterized in that In Step 2, the post-treatment process of the reaction product is specifically: distill the reaction product under reduced pressure, wash it with ethyl acetate 1 - 3 times, and vacuum dry it to a constant weight.
7. The preparation method of the cardanol-based Gemini cationic surfactant according to claim 1, characterized in that, In Step 2, the molar ratio of intermediate CP-T, 1,4-dibromobutane and acetonitrile is (1 - 1.2):0.5:
6.
8. A cardanol-based Gemini cationic surfactant, characterized in that it is prepared by the method according to any one of claims 1 - 7, and its structural formula is as follows: 。