CN106823984A - A kind of abietyl tertiary amine class surfactant and its preparation method and application - Google Patents

Abstract

The present invention relates to technical field of surfactant, more particularly to abietyl tertiary amine class surfactant and its preparation method and application.The abietyl tertiary amine class surfactant has Formulas I and the structure shown in formula II, and wherein n is CH for 15, R₃Or C₂H₅.The surfactant that the present invention is prepared has good surface-active and bacteriostatic activity, while having excellent water solubility and emulsifying capacity, can be used in antibacterial field of daily chemicals.

Description

A kind of rosin-based tertiary ammonium surfactant and its preparation method and application

technical field

The invention relates to the field of fine chemicals, in particular to a rosin-based tertiary ammonium surfactant and a preparation method and application thereof.

Background technique

At present, the requirements for surfactants are getting higher and higher, not only requiring surfactants to have unique properties, but also to have outstanding environmental protection. Due to the relative ease of synthesis and purification, quaternary ammonium cationic surfactants are one of the more researched ones.

Rosin is a rich and renewable natural resource with low price, and its synthetic surfactants generally have good ecological performance, which is in line with the theme of "green environmental protection". Its main component is resin acid, and rosin resin acid is an amphiphile molecule composed of a ternary phenanthrene skeleton structure with excellent lipophilicity and a carboxyl group with weak hydrophilicity. The ternary phenanthrene ring structure of rosin has good lipophilic properties. After the hydrophilic group is connected, it can be used as a good surface activity, and due to the strong hydrophobicity of the rosin, the compound obtained after the connection of the hydrophilic group has a good surface activity. The synthesis of high value-added surfactants from rosin has been extensively studied.

Rosin-based ester tertiary ammonium surfactant combines the softness, antistatic, emulsifying, disinfecting and bactericidal properties of tertiary ammonium surfactant with the good surface properties and high water solubility of tertiary ammonium surfactant, and has excellent emulsification and dispersion Sex, solubilization, thermal stability, etc., as well as good compatibility, easy biodegradability, low irritation, electrolyte resistance and antistatic properties, widely used in textiles, printing and dyeing, plastics, paper, leather and daily use Chemicals and other industrial fields. However, the types of rosin-based tertiary ammonium surfactants on the market are still limited, so it is necessary to do further research on rosin-based tertiary ammonium surfactants.

Contents of the invention

The first object of the present invention is to provide a kind of rosin base tertiary ammonium surfactant, be selected from a kind of in the compound with formula I, formula II structure:

Wherein, R is -CH ₃ or -C ₂ H ₅ , and n is an integer of 1-5; preferably, n is 1 or 2, and most preferably, n is 2.

The second object of the present invention is to provide a preparation method of rosin-based tertiary ammonium surfactant: CH ₂ OH(CH ₂ )nNR ₂ undergoes esterification reaction with modified rosin acid chloride in a solvent at room temperature to obtain rosin-based tertiary ammonium surfactant.

The solvent may be a conventional solvent in the art, such as an organic solvent such as benzene.

Wherein, the modified rosin acid chloride is prepared by reacting modified rosin with PCl ₃ using chloroform as a solvent. The modified rosin is obtained by modifying rosin through a modifier; the modifier is maleic acid or acrylic acid. The following reaction process shows that rosin generates corresponding modified rosin acid chlorides under the action of different modifiers:

In the preparation process of modified rosin by maleic acid, those skilled in the art can prepare according to the routine modification method in this field, and preferably adopt the following method to make in the present invention:

Grind rosin, heat and melt, when the material temperature reaches 150-165°C, add maleic acid, control the reaction temperature at 180-190°C, cool to room temperature after the reaction, separate water, dry, wash, and then dry to obtain relative Pure Malaya rosin.

In the preparation process of acrylic acid-modified rosin, those skilled in the art can prepare according to the conventional modification methods in this field. In the present invention, the following methods are preferably used:

Heat the rosin to 150-170°C, add acrylic acid to react, and wash after the reaction to obtain light yellow powdery acrylic acid-modified rosin.

Correspondingly, the above two modified rosin acid chlorides react with CH ₂ OH(CH ₂ )nNR ₂ to obtain the tertiary abietyl ammonium of formula I or formula II:

(1) CH ₂ OH(CH ₂ )nNR ₂ and modified rosin acid chloride Esterification takes place to obtain the compound of formula I

(2) CH ₂ OH(CH ₂ )nNR ₂ and modified rosin acid chloride Esterification takes place to obtain the compound of formula II

The third object of the present invention is to provide the application of any one of the above-mentioned rosin-based tertiary ammonium surfactants in antibacterial daily necessities.

The surfactant prepared by the invention has good surface activity and bacteriostasis activity as well as excellent water solubility and emulsification ability, and can be used in the field of bacteriostasis daily necessities.

Description of drawings

Fig. 1 is the IR spectrum of the compound of formula I-1.

Fig. 2 is the ¹³ C NMR spectrum of the compound of formula I-1.

Fig. 3 is the ¹ H NMR spectrum of the compound of formula I-1.

Fig. 4 is the IR spectrum of the compound of formula I-2.

Fig. 5 is the ¹³ C NMR spectrum of the compound of formula I-2.

Fig. 6 is the ¹ H NMR spectrum of the compound of formula I-2.

Fig. 7 is the IR spectrum of the compound of formula II-1.

Fig. 8 is the IR spectrum of the compound of formula II-2.

detailed description

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. The raw materials or reagents involved in the examples are all known products, and the operations involved are conventional technical operations in the art unless otherwise specified.

Among them, the maleic modified rosin involved in the embodiment is prepared as follows: 100g of rosin is pulverized, heated and melted, when the temperature of the material reaches 150-165°C, 46g of maleic acid is added, and the reaction temperature is controlled at 180-190°C. 8h, cooled to room temperature, separated water, dried, washed, and then dried to obtain relatively pure maleic rosin.

The acrylic acid-modified rosin involved in the examples is prepared as follows: take 100 g of rosin, heat it to about 160° C., add 25 mL of acrylic acid to react for 4 hours, and wash to obtain light yellow powdery acrylic acid-modified rosin.

The modified rosin acid chloride involved in the embodiment is prepared as follows: get 100g modified rosin, dissolve in 150ml chloroform, add PCl in the _four -necked bottle, the mol ratio of modified rosin and PCl is ₁ :(2- 3) Slowly add the chloroform solution of modified rosin dropwise, the reaction temperature is controlled at 55°C, continue to react for 3 hours after the dropwise addition is completed, transfer the reaction mixture into a round bottom flask, and obtain an orange-yellow viscous product modified rosin acid chloride after rotary evaporation .

The preparation of embodiment 1 formula Ⅰ-1 compound

Dissolve 0.01mol maleated rosin acid chloride in 15ml benzene solution, then slowly add it dropwise to 0.04mol N,N-dimethylethanolamine benzene solution, the mixture of modified rosin acid chloride and N,N-dimethylethanolamine The molar ratio was 1:4. After 5 minutes, 4 mL of triethylamine was added dropwise as an acid-binding agent. After reacting for 3 hours at room temperature, viscous compound I-1 was obtained by rotary evaporation.

Using the same method as in Example 1, replacing N,N-dimethylethanolamine with other alcohols with 1-5 carbon atoms (not 1), the compound of formula I in which n is 1-5 (not 1) can be obtained is the compound of 1).

The preparation of embodiment 2 formula Ⅰ-2 compound

Dissolve 0.01mol maleated rosin acid chloride in 15ml benzene solution and slowly add dropwise to 0.04mol N,N-diethylethanolamine benzene solution, the molar ratio is 1:4, after 5 minutes, drop triethylamine 4mL Acid-binding agent, after reacting at room temperature for 3 hours, viscous compound I-2 was obtained by rotary evaporation.

Using the same method as in Example 2, replacing N,N-diethylethanolamine with other alcohols with 1-5 carbon atoms (not 1), the n in the compound of formula I can be obtained (not 1) is the compound of 1).

The preparation of embodiment 3 formula Ⅱ-1 compound

Dissolve 0.05mol of acrylic acid-modified rosin chloride in 75ml of benzene solution and slowly add it dropwise to 0.15mol of N,N-dimethylethanolamine-benzene solution, the molar ratio is 1:3, after 5 minutes, add dropwise 5mL of triethylamine to bind Acid agent, reacted at room temperature for 3 hours, and then evaporated to obtain viscous compound Ⅱ-1.

Using the same method as in Example 3, replacing N,N-dimethylethanolamine with other alcohols with 1-5 carbon atoms (not 1), the n in the compound of formula II can be obtained. is the compound of 1).

The preparation of embodiment 4 formula II-2 compound

Dissolve 0.05mol of acrylic acid-modified rosin chloride in 75ml of benzene solution and slowly add it dropwise to 0.15mol of N,N-diethylethanolamine-benzene solution at a molar ratio of 1:3. After 5 minutes, add dropwise 5mL of triethylamine to bind Acid agent, reacted at room temperature for 3 hours, and then evaporated to obtain viscous compound Ⅱ-2.

Using the same method as in Example 4, replacing N,N-diethylethanolamine with other alcohols with 1-5 carbon atoms (not 1), the compound of formula II in which n is 1-5 (not 1) can be obtained is the compound of 1).

Structure Characterization

Compound of formula Ⅰ-1

The IR spectrum is shown in Figure 1. Compared with rosin, 1722cm ^-1 and 1772cm ^-1 are the C=O stretching vibration peaks of the ester, 1078cm ^-1 is the CO stretching vibration peak, and the C=C stretching vibration in the rosin acid skeleton The peaks appear at 1466cm ^-1 , 1384cm ^-1 and 1155cm ^-1 , 1028cm ^-1 is the CN stretching vibration peak, and 782cm ^-1 , 806cm ^-1 and 834cm ^-1 are the CN bending vibration peaks, indicating the success of compound Ⅰ-a Synthesis, the ¹³ C spectrum is shown in Figure 2, the analysis is shown in Table 1, and the ¹ H spectrum is shown in Figure 3.

Table 1: ¹³ C spectrum results of the compound of formula I-1

Compound of formula Ⅰ-2

The IR spectrum is shown in Figure 3. Compared with the compound of formula Ⅰ-2, it is changed from 782cm ^-1 , 806cm ^-1 and 834cm ^-1 to 716cm ^-1 , 757cm ^-1 and 813cm ^-1 , which are CN bending vibration peaks. This illustrates the successful synthesis of compound I-b. The ¹³ C spectrum is shown in Figure 4, the analysis is shown in Table 1, and the ¹ H spectrum is shown in Figure 5.

Table 2: ¹³ C spectrum results of the compound of formula I-2

Compound of formula Ⅱ-1

The IR spectrum is shown in Figure 7. Compared with rosin, 1722cm ^-1 is the C=O stretching vibration peak of the ester, 1078cm ^-1 is the CO stretching vibration peak, and the C=C stretching vibration peak in the rosin acid skeleton is at ^{1461cm- 1.} 1380cm ^-1 and 1175cm ^-1 appear, 1043cm ^-1 is the CN stretching vibration peak, and 767cm ^-1 , 828cm ^-1 and 885cm ^-1 are the CN bending vibration peak, indicating the successful synthesis of compound Ⅱ-1.

Compound of formula Ⅱ-2

The IR spectrum is shown in Figure 7. Compared with formula II-a, the changes from 767cm ^-1 , 828cm ^-1 and 885cm ^-1 to 762cm ^-1 , 798cm ^-1 and 818cm ^-1 are CN bending vibration peaks, indicating that The successful synthesis of compound Ⅱ-2.

Emulsifying Performance (EP) Test

Add the formula I-1 that the embodiment 1-4 of 40ml mass fraction 0.1% prepares in 100ml measuring cylinder, I-2, II-1, the aqueous solution of II-2 compound and 40ml benzene, shake up and down 5 times, static Set it aside for 1 min, then oscillate 5 times, repeat this 5 times, then record the time for separating 10mL of water, repeat the test 3 times, and calculate the average value.

The results are I-1, I-2, II-1, II-2 (63s, 79s, 340s, 352s).

Compared with commercially available surfactant sodium dodecylbenzenesulfonate (SDBS) and cetyltrimethylammonium bromide (CTAB), the emulsifying properties of SDBS and CTAB are respectively 12s and 73s, and I- 1, I-2, II-1, II-2 four tertiary amine surfactants have better emulsifying properties than SDBS, and I-2, II-1, II-2 have better emulsifying properties than CTAB.

Bacteriostatic performance test

The antibacterial activity was tested by the filter paper method.

Dilute the activated bacterial solution with sterile broth to a concentration equivalent to 0.5 McFarland turbidimetric tube, ie 107Cfu/mL. Add 1mL of bacterial solution to a sterile plate with a diameter of 9cm, then pour into the M-H agar medium that has been melted and cooled to 55°C, and rotate to mix. After solidification, use a 6 mm sterilized copper tube to make 4 holes on the M-H agar, take out the medium in the copper tube with sterile tweezers, and add the compound Ⅰ-1 of Example 1 and the compound Ⅱ- 2. Gentamicin and rosin are each 0.05mL, cultured at 37°C for 12h. Take out the plate and measure the diameter of the inhibition zone.

Observation: No zone of inhibition, represented by "-";

The diameter of the antibacterial zone is <10mm, and "+" means mild antibacterial;

The diameter of the antibacterial zone is between 10 and 15mm, and "++" means moderate antibacterial;

The diameter of the inhibition zone is >15mm, and "+++" indicates a high degree of inhibition.

Table 1 Bacteriostatic activity

From the results in Table 1, it can be seen that the antibacterial degree of compound I-1 of Example 1 and compound II-2 of Example 4 is equivalent to that of gentamicin, and has significant antibacterial effect.

Compound I-1 of Example 2 and Compound II-2 of Example 3 were tested according to the above method, and their antibacterial effects were equivalent to those of Examples 1 and 4.

Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (9)

1. A rosin-based tertiary ammonium surfactant, characterized in that it has one of formula I and formula II structural compounds: Wherein, R is -CH ₃ or -C ₂ H ₅ , and n is an integer of 1-5. 2 . The rosin-based tertiary ammonium surfactant according to claim 1 , wherein the R is —CH ₃ or —C ₂ H ₅ , and n is 1 or 2. 3. A method for preparing a rosin-based tertiary ammonium surfactant, characterized in that CH ₂ OH(CH ₂ )nNR ₂ and modified rosin acid chloride undergo an esterification reaction in a solvent at room temperature to obtain the product. 4. preparation method according to claim ₃ , is characterized in that, described modified rosin acid chloride is to be solvent with chloroform, is prepared by reaction of modified rosin and PCl; The modified rosin is obtained by modifying rosin with maleic acid or acrylic acid. 5. preparation method according to claim 4, is characterized in that, described modified rosin obtains through maleic acid modification by rosin, is specifically: Grind the rosin, heat and melt, when the material temperature reaches 150-165°C, add maleic acid, control the reaction temperature at 180-190°C, cool to room temperature after the reaction, separate the water, dry, wash, and then dry to obtain the product. 6. preparation method according to claim 4, is characterized in that, described modified rosin obtains by acrylic acid modification of rosin, specifically: Take rosin and heat it to 150-170°C, add acrylic acid to react, and wash after the reaction. 7. preparation method according to claim 5, is characterized in that, CH ₂ OH(CH ₂ )nNR ₂ and Maleic Acid Modified Rosinyl Chloride Esterification reaction occurs, that is, Compound of formula I. 8. preparation method according to claim 6, is characterized in that, CH ₂ OH(CH ₂ )nNR ₂ and Acrylic Modified Rosinyl Chloride Esterification takes place to obtain the compound of formula II 9. the application of the rosin-based tertiary ammonium surfactant described in claim 1 or 2 in antibacterial daily necessities.