阅读说明：本技术 一种腰果酚基季铵盐型阳离子表面活性剂及其应用 (Cardanol quaternary ammonium salt type cationic surfactant and application thereof ) 是由 王利民 刘娜 车飞 韩建伟 于 2020-11-27 设计创作，主要内容包括：本发明公开了一种腰果酚基季铵盐型阳离子表面活性剂,具有以下结构通式：其中,R_1、R_2、R_3各自独立的选自C1～C10烷基；X为氯或溴。本发明提供的腰果酚基季铵盐型阳离子表面活性剂,其基本原料腰果酚廉价易得、具有可再生性,且整个合成流程简单,不产生对环境有害的副产物；在酸性介质中具备优良的缓蚀性能,有望成为新型的环保型阳离子缓蚀剂。(The invention discloses a cardanol quaternary ammonium salt type cationic surfactant, which has the following structural general formula: wherein R is 1 、R 2 、R 3 Each independently selected from C1-C10 alkyl; x is chlorine or bromine. The cardanol quaternary ammonium salt cationic surfactant provided by the invention has the advantages that the cardanol as a basic raw material is cheap and easy to obtain, the regeneration is realized, the whole synthesis process is simple, and a byproduct harmful to the environment is not generatedAn agent; has excellent corrosion inhibition performance in an acid medium, and is expected to become a novel environment-friendly cationic corrosion inhibitor.)

1. The cardanol quaternary ammonium salt type cationic surfactant is characterized by having the following structural general formula:

wherein R is₁、R₂、R₃Each independently selected from C1-C10 alkyl; x is chlorine or bromine.

2. The cardanol-based quaternary ammonium salt-type cationic surfactant according to claim 1, having a structure shown below:

wherein R is₁、R₂、R₃Each independently selected from methyl, ethyl, - (CH)₂)₂CH₃、-CH(CH₃)₂、-(CH₂)₃CH₃、-(CH₂)₄CH₃、-(CH₂)₅CH₃、-(CH₂)₇CH₃、-(CH₂)₉CH₃。

3. The cardanol-based quaternary ammonium salt-type cationic surfactant according to claim 2, characterized in that the structure of the cardanol-based quaternary ammonium salt-type cationic surfactant is one of the following structures:

4. a method for producing the cardanol-based quaternary ammonium salt-type cationic surfactant according to any one of claims 1 to 3, comprising the steps of:

adding the compound 1a into a schlenk reaction tube, adding a solvent, adding an amine compound after the compound 1a is dissolved, wherein the molar ratio of the amine compound to the compound 1a is (1-1.5): 1, reacting for 1-48 h at the temperature of 75-85 ℃, grinding with n-hexane after the reaction is finished, and then taking out a precipitate to obtain the cardanol quaternary ammonium salt cationic surfactant.

5. The method for producing the cardanol quaternary ammonium salt-type cationic surfactant according to claim 4, wherein the amine-based compound is trimethylamine, N-dimethylethylamine, N-dimethylbutylamine, N-dimethylhexylamine, N-dimethyloctylamine, or N, N-dimethyldecylamine.

6. The method for producing the cardanol-based quaternary ammonium salt-type cationic surfactant according to claim 4, wherein the solvent is toluene.

7. The method for producing the cardanol-based quaternary ammonium salt-type cationic surfactant according to claim 4, wherein the method for producing the compound 1a comprises the steps of:

dissolving 1, 4-bis (bromomethyl) benzene in acetone, adding potassium carbonate, stirring, slowly adding cardanol, wherein the molar ratio of 1, 4-bis (bromomethyl) benzene to potassium carbonate to cardanol is (3-7): 8-12): 1, reacting at 50-60 ℃ for 1-48 h, pouring the reaction solution into a Bush funnel after the reaction is finished, filtering potassium carbonate solid to obtain an organic solution, recrystallizing for 3 times by using petroleum ether, and separating the obtained organic solution by column chromatography to obtain a compound 1 a.

8. Use of the cardanol-based quaternary ammonium salt-type cationic surfactant according to any one of claims 1 to 3 as a corrosion inhibitor.

Technical Field

The invention belongs to the technical field of surfactants, and particularly relates to a cardanol quaternary ammonium salt type cationic surfactant and a research on corrosion inhibition performance thereof.

Background

In recent years, quaternary ammonium salt cationic surfactants have undergone great development, and particularly have good application prospects in the aspect of being used as corrosion inhibitors. The corrosion inhibition mechanism of the quaternary ammonium salt surfactant is strong electronegative group N in molecules⁺Ions and empty orbitals of transition metal atoms form coordination bonds, so that the coordination bonds are adsorbed on the metal surface, the charge state and the interface property of the metal surface are changed, the energy of the metal surface tends to be stable, the activation energy required by corrosion reaction is greatly improved, and the corrosion speed is slowed down; on the other hand, a non-polar group in the corrosion inhibitor molecule forms a hydrophobic layer on the metal surface, so that charge and material transfer is hindered, and the corrosion rate is reduced. The cardanol is refined from natural cashew nut shell oil by an advanced technology, and is a green and environment-friendly chemical raw material. The molecule of the cardanol compound contains a benzene ring, a phenolic hydroxyl group and an unsaturated olefin long carbon chain, so that the cardanol compound has the characteristics of aliphatic and aromatic compounds. Owing to its excellent biodegradability, cardanol has replaced petroleum phenol in industry to prepare various surfactants. Cardanol is the most easily available biomass polymer raw material, and scholars modify phenolic hydroxyl groups, side chains and benzene rings of cardanol to obtain organic compounds with high value.

Anionic, nonionic, cationic, amphoteric surfactants have been prepared based on cardanol, and anionic and nonionic surfactants are more and cationic surfactants are less reported. The double bond and benzene ring structure in the cardanol-based cationic surfactant can improve the surface activity and corrosion inhibition performance of the cardanol-based cationic surfactant, and the cardanol-based cationic surfactant serving as a novel quaternary ammonium salt corrosion inhibitor has a certain development and application prospect.

Disclosure of Invention

The invention aims to provide a cardanol quaternary ammonium salt type cationic surfactant.

The second purpose of the invention is to provide a preparation method of the cardanol quaternary ammonium salt type cationic surfactant.

The third purpose of the invention is to provide the application of the cardanol quaternary ammonium salt type cationic surfactant as a corrosion inhibitor.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the first aspect of the invention provides a cardanol quaternary ammonium salt type cationic surfactant, which has the following structural general formula:

wherein R is₁、R₂、R₃Each independently selected from C1-C10 alkyl; x is chlorine or bromine.

More preferably, the cardanol quaternary ammonium salt cationic surfactant has the following structure:

wherein R is₁、R₂、R₃Each independently selected from methyl, ethyl, - (CH)₂)₂CH₃、-CH(CH₃)₂、-(CH₂)₃CH₃、-(CH₂)₄CH₃、-(CH₂)₅CH₃、-(CH₂)₇CH₃、-(CH₂)₉CH₃。

Most preferably, the cardanol quaternary ammonium salt type cationic surfactant has one of the following structures:

the second aspect of the present invention provides a preparation method of the cardanol-based quaternary ammonium salt type cationic surfactant, including the following steps:

adding the compound 1a into a schlenk reaction tube, adding a solvent, adding an amine compound after the compound 1a is dissolved, reacting for 1-48 h (the temperature is preferably 82 ℃ and the time is preferably 24h) under the condition that the molar ratio of the amine compound to the compound 1a is (1-1.5): 1 (preferably 1.2:1) and the temperature is 75-85 ℃, grinding by using n-hexane after the reaction is finished, and then taking out a precipitate to obtain the cardanol quaternary ammonium salt type cationic surfactant.

The amine compound is trimethylamine, N-dimethylethylamine, N-dimethylbutylamine, N-dimethylhexylamine, N-dimethyloctylamine, and N, N-dimethyldecylamine.

The solvent is toluene.

The preparation method of the compound 1a comprises the following steps:

dissolving 1, 4-bis (bromomethyl) benzene in acetone, adding potassium carbonate, stirring, slowly adding cardanol, wherein the molar ratio of 1, 4-bis (bromomethyl) benzene to potassium carbonate to cardanol is (3-7): 8-12): 1 (preferably 5:10:1), reacting at 50-60 ℃ for 1-48 h (preferably 56 ℃ for 12h), pouring the reaction solution into a Bush funnel after the reaction is finished, filtering potassium carbonate solid to obtain an organic solution, recrystallizing with petroleum ether for 3 times, and separating the obtained organic solution by column chromatography to obtain the compound 1 a.

The third aspect of the invention provides application of the cardanol quaternary ammonium salt type cationic surfactant as a corrosion inhibitor.

The cardanol quaternary ammonium salt cationic surfactant is a compound a, a compound b, a compound c, a compound d, a compound e and a compound f; in particular, the compound a, the compound b, the compound c and the compound d can be used as corrosion inhibitors.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the cardanol quaternary ammonium salt cationic surfactant provided by the invention is an organic compound with stable structure and mild property, and the structure comprises a benzene ring, a long carbon chain, a nitrogen positive ion and a benzene connecting group. The quaternary ammonium salt cationic surfactant synthesized by taking cardanol as a starting material has the characteristics of excellent surface activity, low toxicity, corrosion inhibition, static resistance and the like.

The cardanol quaternary ammonium salt type cationic surfactant provided by the invention is not reported, the preparation steps are simple, and the cardanol quaternary ammonium salt type cationic surfactant has great innovation in application research as a corrosion inhibitor.

The cardanol quaternary ammonium salt cationic surfactant provided by the invention has the advantages that the cardanol as a basic raw material is cheap and easy to obtain, the regeneration performance is realized, the whole synthesis process is simple, and a by-product harmful to the environment is not generated; has excellent corrosion inhibition performance in an acid medium, and is expected to become a novel environment-friendly cationic corrosion inhibitor.

Drawings

FIG. 1 is a schematic view showing the surface tension of cardanol-based quaternary ammonium salt-type cationic surfactant compounds a, b, c, d, e and f prepared in examples 1 to 6.

Fig. 2 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound a prepared in example 1.

Fig. 3 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound b prepared in example 2.

Fig. 4 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound c prepared in example 3.

Fig. 5 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound d prepared in example 4.

Fig. 6 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound e prepared in example 5.

Fig. 7 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound f prepared in example 6.

Fig. 8 is a schematic diagram of a polarization curve of the comparative article 1801.

Fig. 9 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound a prepared in example 1.

Fig. 10 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound b prepared in example 2.

Fig. 11 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound c prepared in example 3.

Fig. 12 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound d prepared in example 4.

Fig. 13 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound e prepared in example 5.

Fig. 14 is a Nyquist plot of cardanol-based quaternary ammonium salt-type cationic surfactant compound f prepared in example 6.

Fig. 15 is a schematic Nyquist plot for comparative example 1801.

FIG. 16 is a Bode diagram of blank.

Fig. 17 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound a prepared in example 1.

Fig. 18 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound b prepared in example 2.

Fig. 19 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound c prepared in example 3.

Fig. 20 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound d prepared in example 4.

Fig. 21 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound e prepared in example 5.

Fig. 22 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound f prepared in example 6.

Fig. 23 is a Bode schematic of the comparison 1801.

Fig. 24 is an equivalent circuit diagram obtained by fitting the Nyquist diagram.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the molecular weight of the polymer is the number average molecular weight.

Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.

The purity of cardanol in the following examples was 90%.

Example 1

Preparation of compound a:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

Adding the intermediate compound 1a (5mmol, 1equiv) into a schlenk reaction tube, adding 2mL of solvent toluene, adding trimethylamine (6mmol, 1.2equiv) after the intermediate compound is dissolved, reacting at 82 ℃ for 24 hours, grinding by using normal hexane after the reaction is finished, and taking out precipitate to obtain the target product compound a. Compound a.m.p. 138.5 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.63(d,J＝8.0Hz,1H),7.44(d,J＝8.0Hz,1H),7.11(t,J＝8.0Hz,0H),6.71(dd,J＝19.6,6.4Hz,2H),5.01(s,1H),4.97(s,7H),3.34(s,4H),2.61–2.41(m,1H),1.63–1.43(m,1H),1.18(s,8H),0.80(t,J＝6.8Hz,1H).¹³C NMR(101MHz,CDCl3)δ157.42,143.84,139.18,132.32,128.25,127.02,125.98,120.44,114.02,110.51,67.99,67.38,51.65,35.02,30.90,30.42,28.68,28.64,28.60,28.52,28.39,28.34,21.67,13.12.

example 2

Preparation of compound b:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

The intermediate compound 1a (5mmol, 1equiv) was added to a schlenk reaction tube, 2mL of toluene solvent was added, N was added after the intermediate compound was dissolved,n-dimethylethylamine (6mmol, 1.2equiv) reacts at 82 ℃ for 24 hours, after the reaction is finished, N-hexane is used for grinding, and then a precipitate is taken out to obtain a target product compound b. Compound b.m.p. 51.8 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.64(d,J＝8.1Hz,1H),7.42(d,J＝8.0Hz,1H),7.11(t,J＝8.0Hz,0H),6.73(d,J＝6.6Hz,1H),6.68(d,J＝8.1Hz,0H),5.01(s,1H),4.96(s,1H),3.64(q,J＝7.2Hz,1H),3.20(s,3H),2.55–2.40(m,1H),1.52(q,J＝7.1Hz,1H),1.38(t,J＝7.2Hz,2H),1.18(s,9H),0.80(t,J＝6.8Hz,1H).¹³C NMR(101MHz,CDCl₃)δ157.42,143.84,139.06,132.46,128.24,126.99,125.79,120.44,114.01,110.51,67.99,65.69,58.14,47.97,35.02,30.90,30.42,28.68,28.64,28.60,28.52,28.39,28.34,21.68,13.12,7.66.

example 3

Preparation of compound c:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

Adding the intermediate compound 1a (5mmol, 1equiv) into a schlenk reaction tube, adding 2mL of solvent toluene, adding N, N-dimethylbutylamine (6mmol, 1.2equiv) after the intermediate compound is dissolved, reacting at 82 ℃ for 24 hours, grinding by using N-hexane after the reaction is finished, and taking out a precipitate to obtain a target product compound c. Compound c.m.p. 106.6 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.64(d,J＝8.1Hz,1H),7.43(d,J＝8.0Hz,1H),7.12(t,J＝8.0Hz,1H),6.74(d,J＝6.1Hz,1H),6.69(d,J＝7.9Hz,0H),5.05(s,1H),4.97(s,1H),3.51(d,J＝16.9Hz,1H),3.24(s,3H),2.56–2.43(m,1H),1.73(p,J＝8.2Hz,1H),1.53(p,J＝7.4Hz,1H),1.33(q,J＝7.4Hz,1H),1.18(s,8H),0.90(t,J＝7.3Hz,1H),0.80(t,J＝6.8Hz,1H).¹³C NMR(101MHz,CDCl₃)δ157.43,143.83,139.03,132.47,128.24,126.97,125.86,120.44,114.01,110.51,68.01,65.97,62.49,48.61,35.02,30.90,30.42,28.67,28.64,28.60,28.52,28.38,28.34,23.73,21.67,18.67,13.12,12.75.

example 4

Preparation of compound d:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

Adding the intermediate compound 1a (5mmol, 1equiv) into a schlenk reaction tube, adding 2mL of solvent toluene, adding N, N-dimethylhexylamine (6mmol, 1.2equiv) after the intermediate compound is dissolved, reacting at 82 ℃ for 24 hours, grinding by using N-hexane after the reaction is finished, and taking out a precipitate to obtain a target product compound d. Compound d.m.p. 121.0 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.64(d,J＝8.1Hz,0H),7.43(d,J＝8.0Hz,0H),7.12(t,J＝8.0Hz,0H),6.74(d,J＝6.4Hz,0H),6.69(d,J＝9.8Hz,0H),5.07(s,0H),4.97(s,0H),3.47(d,J＝16.9Hz,0H),3.24(s,1H),2.56–2.43(m,0H),1.73(s,0H),1.53(p,J＝7.3Hz,0H),1.18(s,2H),0.80(dq,J＝7.0,3.2Hz,1H).¹³C NMR(101MHz,CDCl₃)δ157.44,143.83,139.05,132.46,128.24,126.98,125.86,120.45,114.03,110.51,68.02,65.97,62.63,48.58,35.02,30.90,30.41,30.31,28.67,28.64,28.60,28.52,28.38,28.34,24.94,21.85,21.67,21.39,13.12,12.88.

example 5

Preparation of compound e:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

Adding the intermediate compound 1a (5mmol, 1equiv) into a schlenk reaction tube, adding 2mL of solvent toluene, adding N, N-dimethyl octylamine (6mmol, 1.2equiv) after the intermediate compound is dissolved, reacting at 82 ℃ for 24 hours, grinding by using N-hexane after the reaction is finished, and taking out a precipitate to obtain a target product compound e. Compound e.m.p. 90.4 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.64(d,J＝7.9Hz,0H),7.43(d,J＝7.8Hz,0H),7.12(t,J＝8.0Hz,0H),6.74(d,J＝6.1Hz,0H),6.69(d,J＝8.4Hz,0H),5.08(s,0H),4.97(s,0H),3.47(d,J＝16.5Hz,0H),3.24(s,1H),2.50(t,J＝7.7Hz,1H),1.73(s,1H),1.55–1.44(m,1H),1.18(s,4H),0.93–0.70(m,1H).¹³C NMR(101MHz,CDCl₃)δ157.43,143.84,139.06,132.46,128.24,126.99,125.83,120.45,114.01,110.49,68.01,65.94,62.59,48.56,35.02,30.90,30.60,30.42,28.67,28.64,28.60,28.52,28.38,28.34,28.19,28.02,25.28,21.90,21.68,21.56,13.12,13.05.

example 6

Preparation of compound f:

1, 4-bis (bromomethyl) benzene (15mmol, 5equiv) was placed in a 100mL round-bottom flask, 30mL of acetone was added, and the mixture was completely dissolved in acetone, and potassium carbonate (30mmol, 10equiv) was added and stirred for 30 minutes. Cardanol (3mmol, 1equiv) was then added slowly and reacted at 56 ℃ for 12 hours. After the reaction is finished, pouring the reaction solution into a Bush funnel, filtering potassium carbonate solid to obtain an organic solution, then recrystallizing for 3 times by using petroleum ether, recovering the filtered solid compound, preparing a dry sample from the obtained organic solution, and carrying out column chromatography separation, wherein the mobile phase is petroleum ether/dichloromethane which is 4:1, so as to obtain a compound intermediate 1 a.

Adding the intermediate compound 1a (5mmol, 1equiv) into a schlenk reaction tube, adding 2mL of solvent toluene, adding N, N-dimethyldecylamine (6mmol, 1.2equiv) after the intermediate compound is dissolved, reacting at 82 ℃ for 24 hours, grinding with N-hexane after the reaction is finished, and taking out a precipitate to obtain a target product compound f. Compound f.M.p. 45.5 ℃ white solid,¹H NMR(400MHz,Chloroform-d)δ7.63(d,J＝8.1Hz,1H),7.43(d,J＝8.0Hz,1H),7.12(t,J＝8.1Hz,0H),6.77–6.72(m,4H),6.69(d,J＝9.7Hz,0H),5.07(s,15H),4.97(s,1H),3.54–3.39(m,1H),3.24(s,3H),2.55–2.44(m,1H),1.72(s,1H),1.58–1.46(m,1H),1.18(s,12H),0.80(t,J＝6.8Hz,2H).¹³C NMR(101MHz,CDCl₃)δ157.44,143.83,139.06,132.46,128.24,126.99,125.83,120.45,114.02,110.51,68.01,65.98,62.59,48.61,35.03,30.90,30.82,30.42,28.68,28.64,28.60,28.53,28.38,28.35,28.25,28.23,25.29,21.92,21.68,21.64,13.11.

example 7

The cardanol-based quaternary ammonium salt-type cationic surfactants prepared in examples 1 to 6 were measured at 18(± 3) ° c by using a full-automatic tensiometer model JK99B of the morning digital technology equipment ltd. On the basis of 20mL of deionized water solution, 0.001mol/L of the cardanol quaternary ammonium salt type cationic surfactant aqueous solution prepared in examples 1 to 6 was sequentially added according to a gradient concentration gradient increasing manner, the concentration of the cardanol quaternary ammonium salt type cationic surfactant aqueous solution was calculated, and then the surface tension after each dropwise addition was measured. Before each measurement, the platinum sheet was thoroughly cleaned and dried, and each experiment was repeated several times until good reproducibility was obtained (as shown in fig. 1, fig. 1 is a schematic view of the surface tension of cardanol quaternary ammonium salt type cationic surfactant compounds a, b, c, d, e, f prepared in examples 1 to 6).

The surface tension data of cardanol quaternary ammonium salt cationic surfactant compounds a, b, c, d, e and f prepared in examples 1 to 6 are shown in table 1:

TABLE 1 surface tension of Cardanol quaternaries cationic surfactant

Wherein CMC is the critical micelle concentration; gamma ray_CMCIs the surface tension value at the solution concentration of CMC; c₂₀The concentration of the surfactant is reduced by 20mN/m when the surface tension of the solution is reduced; pC20 is a C20 negative log function; Γ max is the maximum surface excess, i.e., the difference between the amount of solute species contained by the solvent in a surface layer per unit area and the amount of solute species contained by the same amount of solvent in solution; a. the_minThe minimum area occupied by the adsorbed molecules when the gas-liquid interface is saturated.

As can be seen from FIG. 1, the trend of the surface tension of the solutions of compounds a, b, c, d, e and f with concentration is: the first decrease, after reaching the Critical Micelle Concentration (CMC), tends to be equilibrium, having the properties of typical surfactants. As shown in Table 1, the lowest critical micelle concentration CMC value of the cardanol quaternary ammonium salt cationic surfactant compounds a, b, c, d, e and f prepared in examples 1 to 6 can reach 0.00492mmol/L, and the lowest surface tension Gamma is_CMCThe value can reach 7.3571 mN/m. The cardanol quaternary ammonium salt cationic surfactant compounds a, b, c, d, e and f prepared in examples 1 to 6 have good surface activity, can reduce the surface tension of a solution with a small amount of the compounds, and have remarkable application value.

Example 8

The experimental electrochemical evaluation was carried out using a Switzerland Wantong Autolab electrochemical workstation, which belongs to a three-electrode system and consists of a reference electrode, an auxiliary electrode and a working electrode, wherein a Saturated Calomel Electrode (SCE) is the reference electrode, a platinum electrode is the auxiliary electrode, stainless steel 304 is the working electrode, and the periphery of the working electrode is coated and sealed by epoxy resin to ensure that the exposed area of the working electrode in a solution is 1cm². Before testing, the glass is polished to a mirror surface by 1400-mesh sand paper, degreased by acetone, washed by ethanol, washed by distilled water and wiped to be dry. The experiment was carried out at 25. + -. 1 ℃ with the test solution being 1% HCl solution and the electrochemical polarization curves being measured under 100mL of 1% hydrochloric acid solution and 100mL of 1% hydrochloric acid solution without the addition of quaternary ammonium salt in amounts of 50mg/L, 100mg/L and 150mg/L, respectively. And inserting electrodes according to the position sequence, connecting corresponding leads, and opening test software to perform polarization curve test. The potential scanning range of the polarization curve test is-0.15V-0.15V (compared with open circuit voltage), the scanning rate is 2.44mV/s, the polarization curves of the cathode and the anode can be obtained after the test is finished, electrochemical parameters such as anode tafel slope (ba), cathode tafel (bc), corrosion current density (icorr), corrosion voltage (Ecorr), inhibition efficiency (IE%) and the like can be obtained through data fitting calculation, and the electrochemical action mechanism of the corrosion inhibitor can be known through the change trend of the electrochemical parameters. The control is imidazoline derivative 1801 (commercial cationic corrosion inhibitor).

The results are shown in table 2:

TABLE 2 polarization curve-related parameters of Cardanol quaternaries-type cationic compounds

As is clear from FIGS. 2 to 8, FIG. 2 is a schematic view showing the polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound a prepared in example 1, fig. 3 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound b prepared in example 2, fig. 4 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound c prepared in example 3, fig. 5 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound d prepared in example 4, fig. 6 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound e prepared in example 5, fig. 7 is a schematic view of a polarization curve of cardanol-based quaternary ammonium salt-type cationic surfactant compound f prepared in example 6, and fig. 8 is a schematic view of a polarization curve of comparative example 1801. In addition to the compounds e and f, the 1% HCl solutions of other quaternary ammonium salt compounds a, b, c, d, and 1801 are added, and the polarization curves are shifted down to different degrees, which indicates that the addition of the cardanol quaternary ammonium salt cationic surfactants prepared in examples 1 to 6 reduces the corrosion current density on the sample surface and the corrosion rate, and indicates that the cardanol quaternary ammonium salt cationic surfactant compounds a, b, c, and d prepared in examples 1 to 6 have a certain inhibition effect on corrosion of 304 carbon steel in 1% HCl. Meanwhile, the shapes of the cathode polarization curves of the cardanol quaternary ammonium salt cationic surfactants prepared in the embodiments 1 to 6 under different concentrations are not obviously changed and are basically parallel to the cathode polarization curve of 304 carbon steel blank HCl, which shows that the addition of the cardanol quaternary ammonium salt cationic surfactants prepared in the embodiments 1 to 6 does not affect the cathode reaction mechanism, the shapes of the anode polarization curves of the cardanol quaternary ammonium salt cationic surfactants are greatly changed, and the passivation tendency is generated.

As can be seen from table 2, the corrosion voltage variation range with the addition of the cardanol quaternary ammonium salt cationic surfactants prepared in examples 1 to 6 is-0.41534V to-0.34688V, and the corrosion voltage is considered to be not much changed within the error tolerance range (± 80mV) compared to-4.0656V of the blank solution, so the cardanol quaternary ammonium salt cationic surfactants prepared in examples 1 to 6 are mixed corrosion inhibitors that simultaneously inhibit the cathode and anode reactions. Wherein, the corrosion inhibition rate of the compounds b and c can reach 70 percent, which is higher than that of the imidazoline derivatives 1801 sold in the market.

Example 9

Experimental use of Switzerland Wantong Autolab electrochemical workstationPerforming electrochemical evaluation, belonging to a three-electrode system, comprising a reference electrode, an auxiliary electrode and a working electrode, wherein a Saturated Calomel Electrode (SCE) is the reference electrode, a platinum electrode is the auxiliary electrode, stainless steel 304 is the working electrode, and the periphery of the reference electrode is coated with epoxy resin to ensure that the exposed area of the reference electrode in the solution is 1cm². Before testing, the glass is polished to a mirror surface by 1400-mesh sand paper, degreased by acetone, washed by ethanol, washed by distilled water and wiped to be dry. The experiment was performed at 25. + -. 1 ℃ with the test solution being 1% HCl solution, and the alternating current impedance (EIS) was measured under the conditions of 100mL of 1% hydrochloric acid solution in which the cardanol quaternary ammonium salt type cationic surfactant prepared in examples 1 to 6 was added at 50mg/L, 100mg/L and 150mg/L, and 100mL of 1% hydrochloric acid solution in which no quaternary ammonium salt was added, respectively. According to the alternating current impedance test, the alternating current amplitude is 10mV, the test frequency is 100KHz-0.01Hz, Nyquist and Bode graphs can be obtained through the test, and the influence of the cardanol quaternary ammonium salt cationic surfactant prepared in the examples 1-6 as a corrosion inhibitor on a system can be known through comparison. The control is imidazoline derivative 1801 (commercial cationic corrosion inhibitor).

As shown in the figure, fig. 9 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound a prepared in example 1, fig. 10 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound b prepared in example 2, fig. 11 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound c prepared in example 3, fig. 12 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound d prepared in example 4, fig. 13 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound e prepared in example 5, fig. 14 is a schematic diagram of the Nyquist curve of cardanol-based quaternary ammonium salt type cationic surfactant compound f prepared in example 6, and fig. 15 is a schematic diagram of the Nyquist curve of cardanol contrast compound 1801. It can be seen from the Nyquist curves of fig. 9 to 15 that the impedance spectrum of the 304 carbon steel in the hydrochloric acid solution is an irregular semicircle, and the diameter of the semicircle reflects the corrosion inhibition effect. And the capacitive arc radii measured by adding the cardanol quaternary ammonium salt cationic surfactant prepared in examples 1-6 as a corrosion inhibitor are all larger than those of a blank control group which is not added, which shows that a system added with the corrosion inhibitor plays a role in inhibiting corrosion to metal materials, the radius of a half arc can have an extreme value along with the increase of the concentration of the cardanol quaternary ammonium salt cationic surfactant prepared in examples 1-6 as the corrosion inhibitor, and the figure shows that the compound c and the compound d have the largest capacitive arc radii when the concentration is 50mg/L, namely the electrochemical corrosion resistance is the largest and the corrosion rate is the smallest under the concentration, so that the corrosion inhibition rate reaches the maximum value, the compound a and the compound b have the largest capacitive arc radii when the concentration is 150mg/L, the corresponding corrosion inhibition rate is the highest, and the capacitive arc radii of the compounds e and f do not greatly differ from the blank group, which shows that the compound has almost no corrosion inhibition effect, this is consistent with the conclusions drawn from the electrochemical polarization curves.

Alternating current impedance (EIS) tests obtain a bode diagram and a Nyquist diagram, wherein the bode diagram and the Nyquist diagram are two expressions of two impedances, the bode diagram reflects the relation between a real part of the impedance and an imaginary part of the impedance, and the Nyquist diagram reflects the relation between the impedance and the logarithm of frequency and the relation between the impedance and a phase angle. Where the bode plot and the nyquist plot are to be in agreement, the bode plot of fig. 16-23 has two peaks corresponding to the nyquist plots of fig. 9-15 with two capacitive reactance arcs. The bode plot is a verification complement to the nyquist plot. FIG. 16 is a Bode diagram of blank. Fig. 17 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound a prepared in example 1. Fig. 18 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound b prepared in example 2. Fig. 19 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound c prepared in example 3. Fig. 20 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound d prepared in example 4. Fig. 21 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound e prepared in example 5. Fig. 22 is a Bode schematic of cardanol-based quaternary ammonium salt-type cationic surfactant compound f prepared in example 6. Fig. 23 is a Bode schematic of the comparison 1801.

TABLE 3 impedance spectrogram-related parameters of Cardanol quaternary ammonium salt-type cationic compound

The Nyquist curve can be fitted by Nova software carried by Autolab, and an equivalent circuit diagram matched with the alternating current impedance experiment can be obtained at the same time, as shown in fig. 24, fig. 24 is the equivalent circuit diagram obtained by fitting the Nyquist diagram. Relevant parameters of the alternating current impedance spectrum test experiment fitted by Nova software are shown in table 3, wherein Rs, Rct, Cdl, Rp and IE in an equivalent circuit respectively represent the resistance of a solution, the resistance of charge transfer, the capacitance of a diffusion double-layer interface, polarization resistance and corrosion inhibition rate, wherein Rct ═ Rp-Rs, IE can be calculated by the following formula:

wherein Rct is the resistance of charge transfer with the corrosion inhibitor added, and Rct' is the resistance of charge transfer without the corrosion inhibitor added.

As can be seen from the data in table 3, compared with the blank group, the film capacitance charge transfer resistance of the cardanol quaternary ammonium salt cationic surfactant prepared in examples 1 to 6 added as the corrosion inhibitor is increased, which indicates that the resistance of the corrosion reaction is enhanced by adding the compound corrosion inhibitor, and is represented by the increase of the charge transfer resistance. The corrosion inhibition rate of the 304 carbon steel sample in the hydrochloric acid solution added with the cardanol quaternary ammonium salt type cationic surfactant with different concentrations can be calculated by using a formula. The data show that the compounds e and f have almost no corrosion inhibition effect, when the concentration of the compounds c and d is 50mg/L, the coverage is the largest, the corrosion inhibition efficiency is the highest, and is 70% and 67%, and the corrosion inhibition rate is higher than that of the commercially available imidazoline derivatives 1801, which is consistent with the conclusion obtained by an electrochemical polarization curve.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.