Novel cardanol cationic surfactant and preparation method thereof

Abstract

The invention discloses a novel cardanol cationic surfactant and a preparation method thereof, and relates to the technical field of surfactants. The invention discloses a novel cardanol cationic surfactant preparation method, which comprises: carrying out a reaction on cardanol and epoxy chloropropane to obtain cardanol chlorohydrin ether; the preparation method comprises the following steps: reacting cardanol chlorohydrin ether with diethanolisopropanolamine under the condition of adding a solvent to obtain the cardanol cationic surfactant. According to the preparation method, epoxy group-containing epoxy chloropropane and diethanolisopropanolamine are used as raw materials to prepare the cardanol cationic surface active agent; the prepared cardanol cationic surface active agent not only meets the wide requirements of the printing and dyeing textile industry and the pesticide adjuvant industry on the cationic surface active agent, but also has good industrial application potential and popularization value; and in addition, the composite material also has very high use value in oil fields and pesticide adjuvants, is easy to degrade and has small harm to human bodies.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and in particular to a novel cardanol cationic surfactant and a preparation method thereof. Background Art

[0002] Surfactants are composed of hydrophilic groups and hydrophobic groups and are amphiphilic. Their physical and chemical properties are affected by the structures of their hydrophobic and hydrophilic groups. Surfactant molecules can be arranged in a directional manner on the surface of aqueous solution to form an adsorption layer, which reduces the surface (interfacial) tension and makes the surfactant solution have good emulsification, foaming and wetting properties; they aggregate with each other inside the aqueous solution to form micelles, which have solubilization properties for water-insoluble compounds. According to the charge properties of the hydrophilic group, surfactants are divided into four categories: cationic, anionic, nonionic and amphoteric surfactants. Cationic surfactants represented by quaternary ammonium salts are widely used in antistatic agents, disinfectants, detergents, and leveling agents. They are a very promising class of surfactants. Research on them is increasing day by day. Cationic surfactants are widely used in the production of fabric softeners, foaming agents, bactericides, corrosion inhibitors, etc. In recent years, cardanol quaternary ammonium salt surfactants have attracted widespread attention due to their excellent performance, low environmental pollution, and economical and easy-to-obtain raw materials.

[0003] Cardanol cationic surfactant has many properties such as softening, antistatic, bactericidal, disinfecting, emulsifying, etc., and can be dissolved in alcohol and hot water. Cardanol has the following characteristics with its special chemical structure: 1. Contains hydroxyl group; 2. Contains benzene ring structure, has high temperature resistance; 3. C15 straight chain with unsaturated double bond in the meta position can provide the system with good toughness, excellent hydrophobicity, low permeability and self-drying property. It has good compatibility with cationic, nonionic surfactants or dyes, and should not be used with anionic surfactants, dyes or additives. It is mainly used as an excellent emulsifier for synthetic rubber, silicone oil, asphalt and chloroprene latex asphalt waterproof coatings; it is also the main component of hair conditioner; it can also be used as an antistatic agent for synthetic fibers, a softener for glass fibers, and a modifier for organic bentonite.

[0004] Shen Guopeng et al. prepared the active intermediate glycidyl trimethyl ammonium chloride (GTA) from epichlorohydrin and trimethylamine, and then reacted it with cardanol to obtain the cashew quaternary ammonium surfactant (3-cardanoloxy-2-hydroxy) propyl-N, N, N-trimethyl ammonium chloride; the product structure was characterized by IR and MS, and the optimal synthesis process was explored through single factor experiments: when the amount of GTA was 0.05 mol, the amount of solvent ethanol was 30 mL, the reaction temperature was 70 ° C, the reaction time was 6 h, n (cardanol): n (GTA) = 1.2: 1, under this condition, the yield can reach 76.69%. The critical micelle concentration (cmc) of the product was determined by surface tension method and conductivity method, which were 6.38×10 -3 and 6.36×10 -3 mol·L -1 ,γcmc=38.86mN·m -1 .

[0005] Patent application with patent publication number CN102824876A discloses a cardanol cationic surfactant and its preparation method. Its technical solution is implemented as follows: pentadecylphenol containing 0-3 unsaturated double bonds, ethylene oxide or epichlorohydrin are used as raw materials, the above substances are weighed in a molar ratio of 1:0.8-2, and then added to a reactor, heated and stirred with nitrogen, 0.8-2 mol of trimethylamine aqueous solution or triethylamine solution is added dropwise, 1-5 mol of alcohol solution is added, the temperature is raised to 60-80 ° C and refluxed, and the cationic surfactant is obtained after removing the solvent.

[0006] The patent application with patent publication number CN104028163A discloses a method for synthesizing a quaternary ammonium salt surfactant of cardanol. Its technical scheme is implemented as follows: trimethylamine gas is introduced into the epichlorohydrin in the formula to react, and the reaction is immediately filtered and washed with acetone to obtain the vacuum-dried white crystal glycidyltrimethylammonium chloride, referred to as GTA; ethanol is used as a solvent, cardanol and GTA are added to a three-necked flask and heated, stirred for reaction, and the solvent ethanol is removed by rotary evaporation after the reaction is completed to obtain a crude product of the quaternary ammonium salt surfactant of cardanol; the crude product is washed with acetone several times to remove the unreacted raw materials, and then recrystallized with petroleum ether and placed in a vacuum drying oven to dry to obtain a light yellow solid, which is a pure product of the quaternary ammonium salt surfactant of cardanol.

[0007] The patent application with patent publication number CN112500299A discloses a cardanol-based quaternary ammonium salt type cationic surfactant and its application, having the following general structural formula: wherein R1, R2, and R3 are each independently selected from a C1-C10 alkyl group; and X is chlorine or bromine.

[0008] In summary, although researchers have developed a variety of cationic surfactants, these surfactants still have many defects, such as high raw material costs, reaction conditions that need to be improved, and high interfacial tension. Summary of the invention

[0009] The object of the present invention is to provide a novel cardanol cationic surfactant and a preparation method thereof, to solve the following technical problems: The existing cardanol cationic surfactants have the problems of high raw material cost, need to improve reaction conditions, high interfacial tension, etc.

[0010] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a novel cardanol cationic surfactant comprises the following steps: S1: reacting cardanol with epichlorohydrin to obtain cardanol chlorohydrin ether; S2: reacting cardanol chlorohydrin ether and diethanol monoisopropanolamine under the condition of adding a solvent to obtain a cardanol cationic surfactant.

[0011] As a further embodiment of the present invention: S1 reaction temperature is 60-90°C.

[0012] As a further solution of the present invention: the reaction time of S1 is 4-8h.

[0013] As a further embodiment of the present invention: the molar ratio of cardanol to epichlorohydrin in S1 is 1:1-4.

[0014] As a further embodiment of the present invention: the reaction temperature in S2 is 80-110°C.

[0015] As a further solution of the present invention: S2 reaction time is 5-20h.

[0016] As a further embodiment of the present invention: the molar ratio of cardanol chlorohydrin ether to diethanol monoisopropanolamine in S2 is 1:1-3.

[0017] As a further embodiment of the present invention: the solvent in S2 is any one of methanol, ethanol and isopropanol.

[0018] A novel cardanol cationic surfactant is prepared by any one of the above preparation methods.

[0019] Beneficial effects of the present invention: The present application uses epichlorohydrin, diethanol monoisopropanolamine and cardanol to synthesize a novel cardanol cationic surfactant; cardanol is used as the basis, and cardanol contains hydroxyl groups, benzene rings and C15 straight chains with unsaturated double bonds at the meta position, wherein cardanol contains hydroxyl groups and can react under mild conditions, greatly increasing the possibility of industrial production; cardanol contains benzene rings and has high temperature resistance; cardanol contains C15 straight chains with unsaturated double bonds at the meta position, which can provide the system with good toughness, excellent hydrophobicity, low permeability and self-drying properties; The present application uses epichlorohydrin, diethanol monoisopropanolamine and cardanol as raw materials, which not only reduces the cost of raw materials and mild reaction conditions, but also fully meets the extensive demand for cationic surfactants in the printing and dyeing textile industry and the pesticide adjuvant industry, and has good industrial application potential and promotion value. The new cardanol cationic surfactant prepared in the present application also has high use value in oil fields and pesticide adjuvants, is easily degradable, and has little harm to the human body. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The present invention will be further described below in conjunction with the accompanying drawings.

[0021] Figure 1 is the reaction formula for synthesizing cardanol chlorohydrin ether of the present invention; Figure 2 It is the reaction formula of synthesizing the cardanol cationic surfactant of the present invention. DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1 Please refer to Figure 1-2 , a method for preparing a cardanol cationic surfactant comprises the following steps: S1: Add 400g of cardanol to a 2000mL four-necked flask equipped with a stirrer, a condenser and a thermometer, stir and heat, heat to 60°C, and slowly drop 140g of epichlorohydrin. During the dropwise addition, the temperature is maintained at 65°C. The dropwise addition time is 1h. After the dropwise addition is completed, the temperature is raised to 90°C and the reaction is carried out for 6h to prepare cardanol chlorohydrin ether; S2: Add the cardanol chlorohydrin ether prepared in S1 and 400g of ethanol to a four-necked flask, heat to 60°C and stir, add 300g of diethanol monoisopropanolamine dropwise for 1h, raise the temperature to 100°C after the addition is completed, and react for 10h to obtain a cardanol cationic surfactant.

[0024] Example 2 Please refer to Figure 1-2 , a method for preparing a cardanol cationic surfactant comprises the following steps: S1: Add 380g of cardanol to a 2000mL four-necked flask equipped with a stirrer, a condenser and a thermometer, stir and heat, heat to 55°C, and slowly drop 180g of epichlorohydrin. During the dropwise addition, the temperature is maintained at 75°C. The dropwise addition time is 2h. After the dropwise addition is completed, the temperature is raised to 95°C and the reaction is carried out for 8h to prepare cardanol chlorohydrin ether; S2: Add the cardanol chlorohydrin ether prepared in S1 and 600g of methanol into a four-necked flask, heat to 65°C and stir, add 500g of diethanol monoisopropanolamine dropwise, the addition time is 1.5h, the temperature rises to 90°C after the addition is completed, the reaction time is 10h, and the cardanol cationic surfactant is obtained.

[0025] Example 3 Please refer to Figure 1-2 , a method for preparing a cardanol cationic surfactant comprises the following steps: S1: Add 350g of cardanol to a 2000mL four-necked flask equipped with a stirrer, a condenser and a thermometer, stir and heat, heat to 45°C, and slowly drop 180g of epichlorohydrin. During the dropwise addition, the temperature is maintained at 55°C. The dropwise addition time is 1h. After the dropwise addition is completed, the temperature is raised to 85°C and the reaction is carried out for 7h to prepare cardanol chlorohydrin ether; S2: Add the cardanol chlorohydrin ether prepared in S1 and 700g of isopropanol into a four-necked flask, heat to 65°C and stir, add 350g of diethanol monoisopropanolamine dropwise, the addition time is 2h, the temperature rises to 105°C after the addition is completed, the reaction time is 15h, and the cardanol cationic surfactant is obtained.

[0026] Performance Testing (1) Emulsifying performance: The water separation method was used to measure the emulsifying performance. At room temperature, the cardanol cationic surfactant prepared in Examples 1-3 was prepared into 1 g / L, 2 g / L, 3 g / L, 4 g / L, and 5 g / L aqueous solutions of the cardanol cationic surfactant. 30 mL was transferred to a stoppered measuring cylinder, and 10 mL of liquid paraffin was added. The stopper was tightly closed and the solution was kept in a constant temperature water bath at 30°C or 55°C for half an hour. The solution was taken out and shaken up and down violently for 60 times. The solution was observed at rest and the time required to separate 10 mL of water was recorded as the emulsifying performance of the solution to liquid paraffin. The test results are shown in Table 1. Table 1: Example 1-3 Cardanol cationic surfactant emulsification performance test table

[0027] It can be seen from Table 1 that the cardanol cationic surfactant has a good emulsifying ability for liquid paraffin. With the increase of product concentration, the product emulsifying ability first increases and then decreases. With the increase of temperature, the product emulsifying ability decreases. When the temperature is 30°C and the product concentration is 3g / L, the emulsifying ability of the cardanol cationic surfactant for liquid paraffin reaches the maximum value.

[0028] (2) Wetting performance: The cardanol cationic surfactant prepared in Examples 1-3 was prepared into a 2 g / L aqueous solution of the cardanol cationic surfactant, which was added dropwise onto a clean polyester film to form droplets. After the droplets were stable for 1 min, the contact angle of the droplets on the polyester film was measured using a contact angle meter. The contact angle was used to characterize the wetting performance of the cardanol cationic surfactant solution on the polyester film surface. The test results are shown in Table 2. Table 2: Wetting performance test table of cardanol cationic surfactant in Examples 1-3

[0029] As shown in Table 2, the contact angle of the cardanol cationic surfactant solution prepared in the present application on the polyester film is less than 75°, indicating that the cardanol quaternary ammonium salt surfactant has a certain wettability on the polyester film. The active contact angle of the cardanol cationic surface is greater than that of the sodium dodecylbenzene sulfonate solution. Since the larger hydrophilic group of the quaternary ammonium salt surfactant leads to a larger surface tension, the contact angle is larger than that of sodium dodecylbenzene sulfonate.

[0030] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a novel cardanol cationic surfactant, characterized in that: The steps include: S1: reacting cardanol with epichlorohydrin to obtain cardanol chlorohydrin ether; S2: reacting cardanol chlorohydrin ether and diethanol monoisopropanolamine under the condition of adding a solvent to obtain a cardanol cationic surfactant.

2. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: S1 reaction temperature is 60-90℃.

3. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: The reaction time of S1 is 4-8h.

4. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: The molar ratio of cardanol to epichlorohydrin in S1 is 1:1-4.

5. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: The reaction temperature in S2 is 80-110°C.

6. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: S2 reaction time is 5-20h.

7. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: The molar ratio of cardanol chlorohydrin ether to diethanol monoisopropanolamine in S2 is 1:1-3.

8. The method for preparing a novel cardanol cationic surfactant according to claim 1, characterized in that: The solvent in S2 is any one of methanol, ethanol and isopropanol.

9. A novel cardanol cationic surfactant, characterized in that: Prepared by the preparation method described in any one of claims 1 to 8.

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