A piperazine compound polyoxyethylene ether composition and a method for preparing the same

Abstract

The application discloses a kind of piperazine compound polyoxyethylene ether composition and preparation method thereof, it is related to polyoxyethylene ether material technical field.The piperazine compound polyoxyethylene ether composition includes the following weight parts of raw materials: piperazine compound polyoxyethylene ether 30-40 parts, antioxidant 1-1.5 parts, deionized water 35-45 parts.The application is generated intermediate 1 by 1,4-di (2-chloroethyl) piperazine and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octane amine reaction;Intermediate 1 and 8-chlorooctanoic acid reaction generate intermediate 2;Intermediate 2 and lauryl alcohol polyoxyethylene ether reaction generate piperazine compound polyoxyethylene ether.The piperazine compound polyoxyethylene ether composition prepared by the application has good surface tension and chemical corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of polyoxyethylene ether materials technology, specifically to a piperazine compound polyoxyethylene ether composition and its preparation method. Background Technology

[0002] Polyoxyethylene ether materials are widely used in coatings, adhesives, fine chemical auxiliaries, surface treatments, and functional coatings due to their excellent hydrophilicity, flexibility, and compatibility with various systems. In these applications, polyoxyethylene ethers are often used as wetting agents and surfactants to reduce surface tension and improve processing performance. However, traditional polyoxyethylene ethers are mostly nonionic structures with weak intermolecular forces, making them prone to interfacial desorption in complex operating environments. Furthermore, they exhibit limited stability under strong acid or alkali conditions, making them unsuitable for applications requiring high durability and environmental adaptability. To improve the interfacial properties of polyoxyethylene ether systems, existing technologies typically modify polyoxyethylene ethers by introducing amines, quaternary ammonium salts, or heterocyclic structures. Among these, piperazine compounds, containing two nitrogen atoms in their molecules, possess high reactivity and structural tunability, and are used to construct modified polyoxyethylene ether materials with specific functionalities. However, existing piperazine-modified polyoxyethylene ethers primarily focus on imparting certain hydrophilic or ionic properties to the materials. Their molecular structures lack hydrophobic units that effectively protect the piperazine backbone. Under acidic or alkaline chemically corrosive environments, the piperazine structure is prone to excessive protonation or chemical erosion, leading to decreased molecular structural stability. Therefore, developing a piperazine compound polyoxyethylene ether composition with a rational structural design, significant functional synergy, and suitability for various complex operating conditions is of great importance.

[0003] Chinese invention patent CN120173229A discloses a method for preparing a polyoxyethylene ether surfactant with a piperazine group. The method includes the following steps: Step 1: Adding piperazine to a container filled with deionized water, stirring to dissolve, adding ethylene oxide, heating and stirring to react, adding sodium hydroxide, continuing the reaction, and distilling under reduced pressure to obtain an intermediate; Step 2: Adding a composite stabilizer to deionized water, ultrasonically treating to obtain a composite stabilizer solution, adding it to the intermediate, stirring and mixing to obtain a mixed solution; Step 3: Adding a modified ionic liquid to the mixed solution, heating and stirring to react, cooling, filtering, extracting, and freeze-drying to obtain the polyoxyethylene ether surfactant with a piperazine group. The surfactant prepared by this method exhibits excellent stability, emulsifying properties, dispersibility, and interfacial activity, but its chemical corrosion resistance still needs improvement. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a piperazine compound polyoxyethylene ether composition and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A piperazine compound polyoxyethylene ether composition comprising the following raw materials in parts by weight: Piperazine compound polyoxyethylene ether 30-40 parts, antioxidant 1-1.5 parts, deionized water 35-45 parts; The piperazine compound polyoxyethylene ether is prepared by the following method: S1: 1,4-Di(2-chloroethyl)piperazine reacts with 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine to generate intermediate 1; the reaction equation is shown below:

[0006] S2: Intermediate 1 reacts with 8-chlorooctanoic acid to generate intermediate 2; the reaction equation is shown below:

[0007] S3: Intermediate 2 reacts with lauryl alcohol polyoxyethylene ether to generate piperazine compound polyoxyethylene ether. The reaction equation is shown below:

[0008] In step S1, the molar ratio of 1,4-bis(2-chloroethyl)piperazine to 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine is 1:(2.01-3.02).

[0009] In step S2, the molar ratio of intermediate 1 to 8-chlorooctanoic acid is 1:(2.02-2.04).

[0010] In step S3, the molar ratio of intermediate 2 to lauryl alcohol polyoxyethylene ether is 1:(2.05-2.1).

[0011] The reaction temperature in step S1 is 50-60℃, and the reaction time is 6-8h.

[0012] The reaction temperature in step S2 is 65-75℃, and the reaction time is 8-10h.

[0013] The reaction temperature in step S3 is 25-30℃, and the reaction time is 17-18h.

[0014] The reaction solvent in step S1 is tetrahydrofuran; the reaction solvent in step S2 is anhydrous ethanol; and the reaction solvent in step S3 is tetrahydrofuran.

[0015] The antioxidant is 2,4-dimethyl-6-tert-butylphenol.

[0016] A method for preparing a piperazine compound polyoxyethylene ether composition includes the following steps: (1) Weigh out the following by weight: 30-40 parts of piperazine compound polyoxyethylene ether, 1-1.5 parts of antioxidant, and 35-45 parts of deionized water; (2) Mix piperazine compound polyoxyethylene ether, antioxidant and deionized water to obtain piperazine compound polyoxyethylene ether composition.

[0017] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The piperazine compound polyoxyethylene ether composition prepared by this invention has good surface tension and chemical corrosion resistance. Detailed Implementation

[0018] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0019] Example 1: Preparation of piperazine compound polyoxyethylene ether S1: Under nitrogen protection, 600 ml of tetrahydrofuran, 0.1 mol of 1,4-bis(2-chloroethyl)piperazine, and 0.201 mol of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine (CAS No. 30556-86-6) were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 50 °C and reacted for 8 h. After cooling to room temperature, the mixture was filtered, and distilled under reduced pressure at 40 °C for 1 h. 350 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, washed with cold n-hexane (3 × 50 ml), and dried under vacuum at 50 °C for 8 h to obtain intermediate 1. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 3.08 (s, 2H), 2.78 (qd, J= 12.4, 5.5 Hz, 4H), 2.62-2.55 (m, 8H), 2.50 (s, 8H), 2.43-2.30 (m, 4H); HRMS(m / z):865.1746[M+H] + ; S2: Under nitrogen protection, 750 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.202 mol of 8-chlorooctanoic acid were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 65 °C and reacted for 10 h. After cooling to room temperature, the mixture was filtered, and distilled under reduced pressure at 50 °C for 1 h. 450 ml of cold n-hexane was added and stirred to precipitate the mixture. The precipitate was filtered, and the filter cake was washed with cold n-hexane (3 × 50 ml). The mixture was then dried under vacuum at 50 °C for 8 h to obtain intermediate 2. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 11.47 (s, 2H),2.90-2.73 (m, 4H), 2.69 (s, 4H), 2.50 (d, J = 7.2 Hz, 8H), 2.48 (s, 8H), 2.29(m, 4H), 2.25 (t, J = 4.2 Hz, 4H), 1.55 (d, J = 14.3 Hz, 8H), 1.35-1.29 (m,12H); HRMS (m / z):1149.3734[M+H] + ; S3: Under nitrogen protection, 200 ml of tetrahydrofuran, 0.01 mol of intermediate 2, 0.021 mol of dicyclohexylcarbodiimide, and 0.004 mol of 4-dimethylaminopyridine were mixed and stirred for 15 min. Then, 0.0205 mol of lauryl polyoxyethylene ether (molecular weight 1199.56) was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of piperazine to polyoxyethylene ether was 10:1, and the product was distilled under reduced pressure at 30°C for 1 hour to obtain the piperazine compound polyoxyethylene ether. Its 1H NMR data are as follows: 1 H NMR (400MHz, Chloroform- d ) δ 4.20 (s, 4H), 3.63-3.52 (m, 184H), 2.91-2.73 (m, 4H), 2.69 (s, 4H), 2.50 (d, J = 7.2 Hz, 8H), 2.48 (s, 8H), 2.26 (d, J = 13.5 Hz,8H), 1.61-1.51 (m, 12H), 1.36-1.25 (m, 48H), 0.90 (t, J = 6.4 Hz, 6H); HRMS(m / z):3511.9582[M+H] + .

[0020] Example 2 Preparation of piperazine compound polyoxyethylene ether S1: Under nitrogen protection, 600 ml of tetrahydrofuran, 0.1 mol of 1,4-bis(2-chloroethyl)piperazine, and 0.2015 mol of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 55 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered, and the mixture was distilled under reduced pressure at 40 °C for 1 h. 350 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold n-hexane (3 × 50 ml). The mixture was then dried under vacuum at 50 °C for 8 h to obtain intermediate 1. S2: Under nitrogen protection, 750 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.203 mol of 8-chlorooctanoic acid were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 70 °C and reacted for 9 h. After cooling to room temperature, the mixture was filtered, and the mixture was distilled under reduced pressure at 50 °C for 1 h. 450 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold n-hexane (3 × 50 ml). The mixture was then dried under vacuum at 50 °C for 8 h to obtain intermediate 2. S3: Under nitrogen protection, 200 ml of tetrahydrofuran, 0.01 mol of intermediate 2, 0.021 mol of dicyclohexylcarbodiimide, and 0.004 mol of 4-dimethylaminopyridine were mixed and stirred for 15 min. Then, 0.0208 mol of lauryl polyoxyethylene ether (molecular weight 1199.56) was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 =10:1), distilled under reduced pressure at 30℃ for 1 h to obtain piperazine compound polyoxyethylene ether.

[0021] Example 3 Preparation of piperazine compound polyoxyethylene ether S1: Under nitrogen protection, 600 ml of tetrahydrofuran, 0.1 mol of 1,4-bis(2-chloroethyl)piperazine, and 0.202 mol of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 60 °C and reacted for 6 h. After cooling to room temperature, the mixture was filtered, and the mixture was distilled under reduced pressure at 40 °C for 1 h. 350 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold n-hexane (3 × 50 ml). The mixture was dried under vacuum at 50 °C for 8 h to obtain intermediate 1. S2: Under nitrogen protection, 750 ml of anhydrous ethanol, 0.1 mol of intermediate 1, and 0.204 mol of 8-chlorooctanoic acid were stirred and mixed. 0.205 mol of triethylamine was added, and the mixture was heated to 75 °C and reacted for 8 h. After cooling to room temperature, the mixture was filtered, and the mixture was distilled under reduced pressure at 50 °C for 1 h. 450 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with cold n-hexane (3 × 50 ml). The mixture was then dried under vacuum at 50 °C for 8 h to obtain intermediate 2. S3: Under nitrogen protection, 200 ml of tetrahydrofuran, 0.01 mol of intermediate 2, 0.021 mol of dicyclohexylcarbodiimide, and 0.004 mol of 4-dimethylaminopyridine were mixed and stirred for 15 min. Then, 0.021 mol of lauryl polyoxyethylene ether (molecular weight 1199.56) was added, and the mixture was reacted at 30 °C for 17 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 =10:1), distilled under reduced pressure at 30℃ for 1 h to obtain piperazine compound polyoxyethylene ether.

[0022] Example 4 Preparation of piperazine compound polyoxyethylene ether composition (1) Weigh the following by weight: 30g of piperazine compound polyoxyethylene ether (prepared in Example 1), 1g of antioxidant (2,4-dimethyl-6-tert-butylphenol), and 35g of deionized water; (2) Mix piperazine compound polyoxyethylene ether, antioxidant and deionized water, and stir at 250 rpm for 30 min to obtain piperazine compound polyoxyethylene ether composition.

[0023] Example 5 Preparation of piperazine compound polyoxyethylene ether composition (1) Weigh the following by weight: 35g of piperazine compound polyoxyethylene ether (prepared in Example 2), 1.2g of antioxidant (2,4-dimethyl-6-tert-butylphenol), and 40g of deionized water; (2) Mix piperazine compound polyoxyethylene ether, antioxidant and deionized water, and stir at 250 rpm for 30 min to obtain piperazine compound polyoxyethylene ether composition.

[0024] Example 6 Preparation of piperazine compound polyoxyethylene ether composition (1) Weigh the following by weight: 40g of piperazine compound polyoxyethylene ether (prepared in Example 3), 1.5g of antioxidant (2,4-dimethyl-6-tert-butylphenol), and 45g of deionized water; (2) Mix piperazine compound polyoxyethylene ether, antioxidant and deionized water, and stir at 250 rpm for 30 min to obtain piperazine compound polyoxyethylene ether composition.

[0025] Comparative Example 1 The raw material composition and preparation method of the piperazine compound polyoxyethylene ether composition are basically the same as those in Example 5, except that the piperazine compound polyoxyethylene ether is replaced with an equal weight of piperazine compound polyoxyethylene ether prepared by the following method: The preparation method of piperazine compound polyoxyethylene ether is basically the same as that in Example 2, except that 1,4-bis(2-chloroethyl)piperazine in step S1 is replaced with 0.2 mol of (9Cl)-1-(2-chloroethyl)-4-propylpiperazine (CAS No. 342403-10-5); the amount of 8-chlorooctanoic acid in step S2 is replaced with 0.103 mol; and the amount of lauryl alcohol polyoxyethylene ether in step S3 is replaced with 0.0108 mol.

[0026] Comparative Example 2 The raw material composition and preparation method of the piperazine compound polyoxyethylene ether composition are basically the same as those in Example 5, except that the piperazine compound polyoxyethylene ether is replaced with an equal weight of piperazine compound polyoxyethylene ether prepared by the following method: The preparation method of piperazine compound polyoxyethylene ether is basically the same as that in Example 2, except that 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine in step S1 is replaced with an equimolar amount of 1H,1H-perfluoropentaneamine.

[0027] Comparative Example 3 The raw material composition and preparation method of the piperazine compound polyoxyethylene ether composition are basically the same as those in Example 5, except that the piperazine compound polyoxyethylene ether is replaced with an equal weight of piperazine compound polyoxyethylene ether prepared by the following method: The preparation method of piperazine compound polyoxyethylene ether is basically the same as that in Example 2, except that 8-chlorooctanoic acid in step S2 is replaced with an equimolar amount of 3-chloropropionic acid.

[0028] The piperazine compound polyoxyethylene ether compositions prepared in Examples 4-6 and Comparative Examples 1-3 were tested, and the test results are shown in Table 1.

[0029] Surface tension test: The surface tension of the piperazine compound polyoxyethylene ether compositions prepared in Examples 4-6 and Comparative Examples 1-3 was tested using a surface tension meter.

[0030] Acid and alkali stability test: The piperazine compound polyoxyethylene ether compositions prepared in Examples 4-6 and Comparative Examples 1-3 were diluted to a concentration of 0.1 mol / L and divided into two portions of 2 ml each. One portion was added with 0.5 ml of 5 wt% sodium hydroxide solution and the other portion was added with 0.5 ml of 3 wt% hydrochloric acid solution. After standing for 24 hours, the surface tension was tested again.

[0031] Table 1 Performance Test Data

[0032] As can be seen from Table 1, the piperazine compound polyoxyethylene ether compositions prepared in Examples 4-6 of this application have good surface tension and chemical corrosion resistance.

[0033] The piperazine compound polyoxyethylene ether compositions prepared in Examples 5-7 of this application possess both excellent surface tension regulation and chemical corrosion resistance primarily due to the synergistic effect of multiple functional structures within the designed piperazine compound polyoxyethylene ether molecules. Specifically, the introduced perfluorocarbon chain exhibits extremely low surface energy and high hydrophobic and oleophobic properties, preferentially oriented at gas-liquid and solid-liquid interfaces, significantly reducing interfacial free energy and thus effectively lowering surface tension. The long-chain alkyl structure, acting as a flexible hydrophobic group, forms a synergistic hydrophobic effect with the perfluorocarbon chain, further enhancing the molecule's stable adsorption capacity at the interface. The polyoxyethylene ether segments in the molecule impart good hydrophilicity and spatial compliance, ensuring good dispersion of the molecule in the aqueous phase and forming a dense and continuous adsorption layer at the interface, inhibiting interfacial rearrangement and desorption. Furthermore, the high-strength CF bonds in the perfluorocarbon chain provide excellent chemical inertness, working together with the rigid framework of the piperazine ring to construct an anti-corrosion barrier, effectively resisting attacks on the molecular backbone from acidic and alkaline environments. The synergistic effect of multiple structural units in the piperazine compound polyoxyethylene ether molecule enables the piperazine compound polyoxyethylene ether composition to exhibit good surface tension and chemical corrosion resistance.

[0034] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A piperazine compound polyoxyethylene ether composition, characterized in that, The ingredients include the following parts by weight: Piperazine compound polyoxyethylene ether 30-40 parts, antioxidant 1-1.5 parts, deionized water 35-45 parts; The piperazine compound polyoxyethylene ether is prepared by the following method: S1: 1,4-Di(2-chloroethyl)piperazine reacts with 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine to generate intermediate 1; S2: Intermediate 1 reacts with 8-chlorooctanoic acid to generate intermediate 2; S3: Intermediate 2 reacts with lauryl alcohol polyoxyethylene ether to generate piperazine compound polyoxyethylene ether.

2. The piperazine compound polyoxyethylene ether composition according to claim 1, characterized in that, In step S1, the molar ratio of 1,4-bis(2-chloroethyl)piperazine to 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octaneamine is 1:(2.01-3.02).

3. The piperazine compound polyoxyethylene ether composition according to claim 1, characterized in that, In step S2, the molar ratio of intermediate 1 to 8-chlorooctanoic acid is 1:(2.02-2.04).

4. The piperazine compound polyoxyethylene ether composition according to claim 1, characterized in that, In step S3, the molar ratio of intermediate 2 to lauryl alcohol polyoxyethylene ether is 1:(2.05-2.1).

5. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction temperature in step S1 is 50-60℃, and the reaction time is 6-8h.

6. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction temperature in step S2 is 65-75℃, and the reaction time is 8-10h.

7. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction temperature in step S3 is 25-30℃, and the reaction time is 17-18h.

8. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction solvent in step S1 is tetrahydrofuran; the reaction solvent in step S2 is anhydrous ethanol; and the reaction solvent in step S3 is tetrahydrofuran.

9. The piperazine compound polyoxyethylene ether composition according to claim 1, characterized in that, The antioxidant is 2,4-dimethyl-6-tert-butylphenol.

10. A method for preparing a piperazine compound polyoxyethylene ether composition according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 30-40 parts of piperazine compound polyoxyethylene ether, 1-1.5 parts of antioxidant, and 35-45 parts of deionized water; (2) Mix piperazine compound polyoxyethylene ether, antioxidant and deionized water to obtain piperazine compound polyoxyethylene ether composition.

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