Multifunctional cardanol polyoxyethylene ether derivative as well as preparation method and application thereof

Abstract

The invention discloses a multifunctional cardanol polyoxyethylene ether derivative, which is obtained by synergistically modifying cardanol polyoxyethylene ether by biquinolinium and quaternary phosphonium salt, and is specifically prepared by the following steps: firstly, reacting quinoline with metal sodium to obtain a 4-(quinoline-4-yl) quinoline reaction product; then the reaction product is subjected to substitution reaction with brominated triphenyl phosphonium bromide and brominated carboxylic acid in sequence; and finally, the reaction product and cardanol polyoxyethylene ether are subjected to esterification reaction. The cardanol polyoxyethylene ether derivative disclosed by the invention not only has excellent surface activity, wettability and emulsibility, but also has excellent antibacterial ability and low permeability, so that the cardanol polyoxyethylene ether derivative meets the application of products such as personal care solutions, coatings, printing ink and textiles. The invention further discloses a preparation method and application of the multifunctional cardanol polyoxyethylene ether derivative.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and in particular to a multi-functional cardanol polyoxyethylene ether derivative and a preparation method and application thereof. Background Art

[0002] Cardanol polyoxyethylene ether, as a nonionic surfactant extracted from natural cashew nut shell oil, is valued in personal care products, cleaning agents and industrial applications due to its renewability and biodegradability, showing good emulsification and dispersibility. However, it has deficiencies in antibacterial and low permeability. For example, in the field of personal care, it has high requirements for the antibacterial ability of products to ensure hygiene and safety, prevent microbial growth and cross-infection. Cardanol polyoxyethylene ether is difficult to provide sufficient antibacterial protection due to the lack of effective antibacterial components, which limits its scope of application. At the same time, in applications where a protective layer needs to be formed, such as waterproof coatings, protective coatings and other fields, cardanol polyoxyethylene ether cannot effectively prevent the penetration of bacteria and other substances, affecting the protective performance and durability of the product. Therefore, the deficiencies of cardanol polyoxyethylene ether in antibacterial and low permeability, as well as the need to improve other properties such as wettability and emulsification, have prompted researchers to explore and develop new modification methods or derivatives to enhance their performance and broaden their application areas. Summary of the invention

[0003] In view of the above shortcomings of the prior art, one aspect of the present invention is to provide a multifunctional cardanol polyoxyethylene ether derivative to solve the limitations of traditional cardanol polyoxyethylene ether derivatives in terms of surface activity, wettability, emulsification, antibacterial properties and low permeability. The present invention achieves synergistic modification of cardanol polyoxyethylene ether by introducing biquinolinium and quaternary phosphonium salt, thereby overcoming the problem that a single modification method in the prior art is difficult to achieve multifunctionality at the same time.

[0004] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0005] A multifunctional cardanol polyoxyethylene ether derivative is obtained by synergistically modifying cardanol polyoxyethylene ether with biquinolinium and quaternary phosphonium salt, and its chemical structure is shown in the following formula:

[0006] Where R1 is C 15 H 31-m , m is 0, 2, 4, or 6, n is 2 to 25, R2 is an alkyl chain of 1 or 2 carbon atoms, R3 is an alkyl chain of 2 to 4 carbon atoms, and R4 is phenyl or substituted phenyl.

[0007] As a preferred technical solution, the cardanol polyoxyethylene ether derivative is first reacted with quinoline and metallic sodium to obtain a 4-(quinoline-4-yl)quinoline reaction product, and then the reaction product is successively subjected to a substitution reaction with bromotriphenylphosphonium bromide and a bromocarboxylic acid, and finally subjected to an esterification reaction with cardanol polyoxyethylene ether to obtain the product.

[0008] As a preferred technical solution, the bromotriphenylphosphonium bromide is at least one of (3-bromopropyl)triphenylphosphonium bromide, (3-bromobutyl)triphenylphosphonium bromide (1:1), (2-bromoethyl)triphenylphosphonium bromide, and (4-bromobutyl)triphenylphosphonium bromide.

[0009] As a preferred technical solution, the bromocarboxylic acid is at least one of bromoacetic acid, 2-bromopropionic acid, and 3-bromopropionic acid.

[0010] Another aspect of the present invention is to provide a method for preparing the multi-functional cardanol polyoxyethylene ether derivative as described above, the preparation method comprising the following steps:

[0011] S1: heating quinoline and metallic sodium to reflux in a reaction vessel, and separating to obtain 4-(quinolin-4-yl)quinoline after the reaction is completed;

[0012] S2: dissolving the 4-(quinolin-4-yl)quinoline obtained in step S1 in an organic solvent, first adding bromotriphenylphosphonium bromide to carry out a mono-substitution reaction, and then adding bromocarboxylic acid to carry out a di-substitution reaction to obtain a biquinolinium intermediate compound containing a carboxylic acid group;

[0013] S3: dissolving cardanol polyoxyethylene ether in an organic solvent, and then adding the biquinolinium intermediate compound obtained in step S2 to carry out esterification reaction, and finally obtaining a multi-functional cardanol polyoxyethylene ether derivative.

[0014] As a preferred technical solution, in step S1, the reaction temperature of the heating reflux reaction is 100-150°C, and the reaction time is 12-36h; ice cubes are added after the reaction is completed, and then separation operations such as standing, vacuum rotary evaporation and recrystallization are carried out in sequence.

[0015] As a preferred technical solution, in step S2, the bromotriphenylphosphonium bromide and bromocarboxylic acid are added in a molar ratio of 4-(quinolin-4-yl)quinoline to bromotriphenylphosphonium bromide and bromocarboxylic acid of 1:1:1 to 1.1.

[0016] As a preferred technical solution, in step S3, the reaction temperature of the esterification reaction is 130-165° C., and an appropriate amount of sulfuric acid solution is added.

[0017] Another aspect of the present invention is to provide an application of the multi-functional cardanol polyoxyethylene ether derivative as described above, wherein the cardanol polyoxyethylene ether derivative is applied to personal care liquids, coatings, inks, textiles and other products.

[0018] The cardanol polyoxyethylene ether derivative of the present invention combines the characteristics of the alkane long chain and polyether functional group of cardanol polyoxyethylene ether, as well as the synergistic effect of biquinolinium and quaternary phosphonium salt introduced by chemical modification, so that it has excellent surface activity, wettability, emulsification, antibacterial, low permeability and other properties. Specifically, the alkane long chain of cardanol polyoxyethylene ether itself provides hydrophobic properties, while the polyether functional group imparts hydrophilicity. This built-in amphiphilic property is the basis of the surface activity of the derivative. On this basis, the function of the derivative has been significantly expanded through the synergistic modification with biquinolinium and quaternary phosphonium salt. The introduction of biquinolinium not only enhances the surface activity of the derivative, but also increases the intermolecular steric hindrance due to its larger molecular structure and polycyclic system, thereby improving the low permeability of the derivative, which is of great significance for application scenarios that need to prevent material penetration, such as sensitive skin protection in personal care products and waterproof coatings in the coating and ink industry. At the same time, the addition of quaternary phosphonium salts further enhances the antibacterial properties of the derivatives. The antibacterial activity of quaternary phosphonium salt antibacterial agents is two orders of magnitude higher than that of quaternary ammonium salt polymers of the same structure. It has the advantages of broad spectrum, high efficiency, and low toxicity, which is crucial for preventing product deterioration and improving hygiene and safety standards in personal care products. Quaternary phosphonium salts, due to their cationic properties, can effectively destroy bacterial cell membranes, inhibit microbial growth, and provide a strong antibacterial barrier. In addition, the introduction of biquinolinium and quaternary phosphonium salts also provides additional hydrophilicity to the derivatives, which, combined with their inherent hydrophobicity, makes the derivatives perform well in wettability and emulsification, can improve the contact between the product and the skin or substrate, improve the stability and uniformity of emulsions and creams, and improve the dispersibility of pigments and fillers in coatings and inks.

[0019] Beneficial effects of the present invention:

[0020] The multifunctional cardanol polyoxyethylene ether derivative of the present invention, by innovatively combining the characteristics of the alkane long chain and polyether functional group of cardanol polyoxyethylene ether, and introducing biquinolinium and quaternary phosphonium salt for synergistic modification, not only significantly enhances the surface activity and wettability of the derivative, improves its application performance in personal care products and coating ink industry, and effectively improves the antibacterial ability of the derivative, especially the introduction of quaternary phosphonium salt makes the antibacterial activity of the derivative higher than the quaternary ammonium salt polymer of the same structure by two orders of magnitude, with the advantages of broad spectrum, high efficiency, low toxicity, etc., which is very important for preventing product deterioration and improving health and safety standards in personal care products. In addition, the introduction of biquinolinium increases the intermolecular steric hindrance, thereby improving the low permeability of the derivative, which is of great significance for application scenarios that need to prevent material penetration, such as sensitive skin protection and waterproof coatings. Therefore, the derivative of the present invention can meet the needs of high-performance surfactants, wetting agents, emulsifiers and antibacterial agents, especially in those application fields with high requirements for environmental protection and safety. DETAILED DESCRIPTION

[0021] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0022] The synthesis process of the multi-functional cardanol polyoxyethylene ether derivative of the present invention is divided into three steps:

[0023] The first step is to synthesize 4-(quinolin-4-yl)quinoline, and obtain the desired target product under the catalytic action of metallic sodium; the reaction equation is as follows:

[0024] The second step is to synthesize a biquinolinium intermediate compound containing a carboxylic acid group, and the 4-(quinolin-4-yl)quinoline synthesized in the first step is subjected to a substitution reaction with bromotriphenylphosphonium bromide and bromocarboxylic acid to obtain the corresponding biquinolinium intermediate compound. The reaction equation is as follows:

[0025] The third step is to synthesize the multifunctional cardanol polyoxyethylene ether derivatives, and the biquinolinium intermediate compound containing a carboxylic acid group synthesized in the second step is subjected to an esterification reaction with cardanol polyoxyethylene ether to obtain the corresponding cardanol polyoxyethylene ether derivatives. The reaction equation is as follows:

[0026] Where R1 is C 15 H 31-m, m is 0, 2, 4, or 6, n is 2 to 25, R2 is an alkyl chain of 1 or 2 carbon atoms, R3 is an alkyl chain of 2 to 4 carbon atoms, and R4 is phenyl or substituted phenyl.

[0027] The preparation process of the multi-functional cardanol polyoxyethylene ether derivative is described in detail below through specific examples.

[0028] Example 1

[0029] The preparation method of the multi-functional cardanol polyoxyethylene ether derivative of this embodiment comprises the following steps:

[0030] S1: 0.25 mol of quinoline and 0.05 mol of sodium metal are heated to reflux reaction in a reaction vessel, and the reaction temperature is controlled to be 120°C and the reaction time is 24 hours; after the reaction is completed and cooled, ice cubes are added to complete the reaction of excess sodium metal; then standing oil-water separation, vacuum rotary evaporation and recrystallization are successively performed to further remove other unreacted substances, and after the above separation operation, a light yellow product, i.e., 4-(quinolin-4-yl)quinoline, is obtained.

[0031] S2: Dissolve 0.1 mol of 4-(quinolin-4-yl)quinoline obtained in step S1 in 200 ml of acetonitrile, an organic solvent, first add 0.1 mol of (3-bromopropyl)triphenylphosphonium bromide, raise the temperature to 95°C for a monosubstitution reflux reaction, react for 12 hours, then add 0.11 mol of bromoacetic acid, and carry out a disubstitution reaction under the protection of a nitrogen atmosphere. After reacting for 12 hours, a biquinolinium intermediate compound containing a carboxylic acid group is obtained.

[0032] S3: 0.05 mol of cardanol polyoxyethylene ether is dissolved in 150 ml of organic solvent toluene, and then 0.07 mol of the biquinolinium intermediate compound obtained in step S2 is added to carry out esterification reaction. During the esterification reaction, 18 ml of sulfuric acid solution with a mass concentration of 30% is added, and the reaction temperature is controlled to 150°C. After reacting for 8 hours, the multi-functional cardanol polyoxyethylene ether derivative is finally obtained.

[0033] Example 2

[0034] The preparation method of the multi-functional cardanol polyoxyethylene ether derivative of this embodiment comprises the following steps:

[0035] S1: 0.2 mol of quinoline and 0.04 mol of metallic sodium are heated to reflux reaction in a reaction vessel, and the reaction temperature is controlled to be 120°C and the reaction time is 24 hours; after the reaction is completed and cooled, ice cubes are added to complete the reaction of excess metallic sodium; then standing for oil-water separation, vacuum rotary evaporation and recrystallization are successively performed to further remove other unreacted substances, and after the above separation operation, a light yellow product, i.e., 4-(quinolin-4-yl)quinoline, is obtained.

[0036] S2: Dissolve 0.1 mol of 4-(quinolin-4-yl)quinoline obtained in step S1 in 200 ml of acetonitrile, an organic solvent, first add 0.1 mol of (2-bromoethyl)triphenylphosphonium bromide, raise the temperature to 95°C for a monosubstitution reflux reaction, react for 12 hours, then add 0.11 mol of 2-bromopropionic acid, and carry out a disubstitution reaction under the protection of a nitrogen atmosphere. After reacting for 12 hours, a biquinolinium intermediate compound containing a carboxylic acid group is obtained.

[0037] S3: 0.05 mol of cardanol polyoxyethylene ether is dissolved in 150 ml of organic solvent toluene, and then 0.07 mol of the biquinolinium intermediate compound obtained in step S2 is added to carry out esterification reaction. During the esterification reaction, 18 ml of sulfuric acid solution with a mass concentration of 30% is added, and the reaction temperature is controlled to 150°C. After reacting for 8 hours, the multi-functional cardanol polyoxyethylene ether derivative is finally obtained.

[0038] Example 3

[0039] The preparation method of the multi-functional cardanol polyoxyethylene ether derivative of this embodiment comprises the following steps:

[0040] S1: 0.2 mol of quinoline and 0.04 mol of metallic sodium are heated to reflux reaction in a reaction vessel, and the reaction temperature is controlled to be 120°C and the reaction time is 24 hours; after the reaction is completed and cooled, ice cubes are added to complete the reaction of excess metallic sodium; then standing for oil-water separation, vacuum rotary evaporation and recrystallization are successively performed to further remove other unreacted substances, and after the above separation operation, a light yellow product, i.e., 4-(quinolin-4-yl)quinoline, is obtained.

[0041] S2: Dissolve 0.1 mol of 4-(quinolin-4-yl)quinoline obtained in step S1 in 200 ml of acetonitrile, an organic solvent, first add 0.1 mol of (4-bromobutyl)triphenylphosphonium bromide, heat to 95°C for a monosubstitution reflux reaction, react for 12 h, then add 0.11 mol of 3-bromopropionic acid, and carry out a disubstitution reaction under nitrogen atmosphere protection. After reacting for 12 h, a biquinolinium intermediate compound containing a carboxylic acid group is obtained.

[0042] S3: 0.05 mol of cardanol polyoxyethylene ether is dissolved in 150 ml of organic solvent toluene, and then 0.07 mol of the biquinolinium intermediate compound obtained in step S2 is added to carry out esterification reaction. During the esterification reaction, 18 ml of sulfuric acid solution with a mass concentration of 30% is added, and the reaction temperature is controlled to 150°C. After reacting for 8 hours, the multi-functional cardanol polyoxyethylene ether derivative is finally obtained.

[0043] Example 4

[0044] The raw material composition and preparation steps of the multifunctional cardanol polyoxyethylene ether derivative and the preparation method thereof of this embodiment are basically the same as those of Example 1, except that, in the preparation method of this embodiment, (3-bromobutyl)triphenylphosphonium bromide (1:1) is used instead of (3-bromopropyl)triphenylphosphonium bromide.

[0045] Comparative Example 1

[0046] The raw material composition and preparation steps of the multi-functional cardanol polyoxyethylene ether derivative and the preparation method thereof in this comparative example are basically the same as those in Example 1, except that in the preparation method of this comparative example, (3-bromopropyl)triphenylphosphonium bromide is not added in step S2 for substitution reaction, but bromoacetic acid is used for substitution reaction.

[0047] Comparative Example 2

[0048] This comparative example is commercially available cardanol polyoxyethylene ether.

[0049] Application Examples

[0050] The cardanol polyoxyethylene ether derivatives prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were used as additives in coating products for performance testing, and the performance results are shown in Table 1. The formula of the coating product refers to the raw material composition and weight fractions of Example 1 in patent document CN201710213806.2. Table 1

[0051] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention, and these changes and improvements fall within the scope of the present invention claimed.

Claims

1. A multifunctional cardanol polyoxyethylene ether derivative, characterized in that: The cardanol polyoxyethylene ether derivative is obtained by modifying cardanol polyoxyethylene ether in coordination with biquinolinium and quaternary phosphonium salt, and its chemical structure is shown in the following formula: Where R1 is C 15 H 31-m , m is 0, 2, 4, or 6, n is 2 to 25, R2 is an alkyl chain of 1 or 2 carbon atoms, R3 is an alkyl chain of 2 to 4 carbon atoms, and R4 is phenyl or substituted phenyl.

2. The multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: The cardanol polyoxyethylene ether derivative is firstly reacted with quinoline and metallic sodium to obtain a 4-(quinoline-4-yl)quinoline reaction product, and then the reaction product is successively subjected to a substitution reaction with bromotriphenylphosphonium bromide and a bromocarboxylic acid, and finally subjected to an esterification reaction with cardanol polyoxyethylene ether to obtain the derivative.

3. The multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: The bromotriphenylphosphonium bromide is at least one of (3-bromopropyl)triphenylphosphonium bromide, (3-bromobutyl)triphenylphosphonium bromide (1:1), (2-bromoethyl)triphenylphosphonium bromide, and (4-bromobutyl)triphenylphosphonium bromide.

4. The multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: The bromocarboxylic acid is at least one of bromoacetic acid, 2-bromopropionic acid and 3-bromopropionic acid.

5. A method for preparing the multifunctional cardanol polyoxyethylene ether derivative according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: S1: heating quinoline and metallic sodium to reflux in a reaction vessel, and separating to obtain 4-(quinolin-4-yl)quinoline after the reaction is completed; S2: dissolving the 4-(quinolin-4-yl)quinoline obtained in step S1 in an organic solvent, first adding bromotriphenylphosphonium bromide to carry out a mono-substitution reaction, and then adding bromocarboxylic acid to carry out a di-substitution reaction to obtain a biquinolinium intermediate compound containing a carboxylic acid group; S3: dissolving cardanol polyoxyethylene ether in an organic solvent, and then adding the biquinolinium intermediate compound obtained in step S2 to carry out esterification reaction, and finally obtaining a multi-functional cardanol polyoxyethylene ether derivative.

6. The method for preparing the multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: In step S1, the reaction temperature of the heating reflux reaction is 100-150° C., and the reaction time is 12-36 hours. After the reaction is completed, ice cubes are added, and then separation operations such as standing, vacuum rotary evaporation and recrystallization are successively performed.

7. The method for preparing the multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: In step S2, the amount of the bromotriphenylphosphonium bromide and the bromocarboxylic acid added is 1:1:1 to 1.1 molar ratio of 4-(quinolin-4-yl)quinoline to bromotriphenylphosphonium bromide and bromocarboxylic acid.

8. The method for preparing the multifunctional cardanol polyoxyethylene ether derivative according to claim 1, characterized in that: In step S3, the reaction temperature of the esterification reaction is 130-165° C., and an appropriate amount of sulfuric acid solution is added.

9. An application of the multifunctional cardanol polyoxyethylene ether derivative according to any one of claims 1 to 4, characterized in that: The cardanol polyoxyethylene ether derivative is used in personal care liquids, coatings, inks, textiles and other products.

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