Pyrrolidine compound polyoxyethylene ether composition and preparation method thereof

Abstract

The invention belongs to the technical field of polyoxyethylene ether production, and particularly relates to a pyrrolidine compound polyoxyethylene ether composition and a preparation method thereof.The reaction speed is further increased and N-hydroxyethyl pyrrolidine is prevented from being oxidized and discolored by adopting a negative-pressure feeding mode in a reactor, so that the yield of N-hydroxyethyl pyrrolidine is increased, and the production cost is reduced. The pyrrolidine polyoxyethylene ether composition is prepared by mixing pyrrolidine polyoxyethylene ether with different polymerization numbers, pyrrolidine polyoxyethylene ether sodium sulfate and pyrrolidine polyoxyethylene ether sodium carboxylate according to a certain mass ratio, and the proportion of pyrrolidine polyoxyethylene ether with different lengths can be adjusted in the composition. The balance of hydrophilicity and hydrophobicity is changed, so that excellent hydrophobic-hydrophilic, dispersion and wettability properties are realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyoxyethylene ether production, and specifically relates to a pyrrolidine compound polyoxyethylene ether composition and a preparation method thereof. Background Art

[0002] N-hydroxyethylpyrrolidine is an important organic synthesis intermediate, participating in various chemical reactions and playing an irreplaceable role in synthesizing compounds with specific functions and properties. Therefore, it is widely used in fields such as medicine, pesticides, dyes, and surfactants. Currently, there are few reports in the prior art on the preparation of pyrrolidine compound polyoxyethylene ethers from N-hydroxyethylpyrrolidine.

[0003] The Chinese invention patent with the publication number CN107141465B discloses a styrylphenol polyoxyethylene ether and a preparation method thereof, belonging to the technical field of carbocyclic compounds. It includes three steps: phenol alkylation reaction, ethylene oxide addition polymerization reaction, and polyether post-treatment. Phenol and an alkylation catalyst are heated to 80 - 100°C under nitrogen, styrene is added dropwise, and after heat preservation reaction until the refractive index of the product reaches 1.5985 - 1.6020; the temperature is raised to 100 - 110°C, vacuum dehydration is carried out, then the temperature is lowered and a polyaddition catalyst is added, heated to 80 - 120°C under nitrogen, ethylene oxide is added, and the reaction is completed at 80 - 120°C and 0.01 - 0.04 MPa; deionized water is added to raise the temperature to 60 - 70°C, phosphoric acid and an adsorbent are added, stirred, vacuum dehydrated, and filtered to obtain the finished product. This invention is applied to the preparation of non-ionic surfactants such as styrylphenol polyoxyethylene ether, and has the advantages of narrow distribution, light color, and low K + / Na + ion content. However, the prior art has the technical problem that the composition components of the polyoxyethylene ether are not further improved to achieve the improvement of the stability and wettability of the polyoxyethylene ether. Summary of the Invention

[0004] The purpose of the present invention is to provide a pyrrolidine compound polyoxyethylene ether composition and a preparation method thereof, which are used to solve the technical problem that the composition components of the polyoxyethylene ether in the prior art are not further improved to achieve the improvement of the stability and wettability of the polyoxyethylene ether.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions: A pyrrolidine compound polyoxyethylene ether composition is prepared from the following components by weight: 20 - 40 parts of pyrrolidine polyoxyethylene ether with a low polymerization number, 20 - 40 parts of pyrrolidine polyoxyethylene ether with a high polymerization number, 10 - 20 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 5 - 10 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

[0006] Preferably, the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a low polymerization number is 6 - 10; the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a high polymerization number is 16 - 19.

[0007] A method for preparing a pyrrolidine compound polyoxyethylene ether composition, comprising the following steps: S1. Add N - hydroxyethylpyrrolidine and a catalyst into a reactor. After purging the air in the reactor with nitrogen, raise the temperature to 40 - 50°C, dropwise add ethylene oxide, complete the dropping within 1 - 2 h, raise the temperature to 140 - 160°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain a pyrrolidine polyoxyethylene ether with a low polymerization number; S2. Add N - hydroxyethylpyrrolidine and a catalyst into a reactor. After purging the air in the reactor with nitrogen, raise the temperature to 40 - 50°C, dropwise add ethylene oxide, complete the dropping within 1 - 2 h, raise the temperature to 140 - 160°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain a pyrrolidine polyoxyethylene ether with a high polymerization number; S3. Add the pyrrolidine polyoxyethylene ether obtained in step S1 into a sulfonation reactor, raise the temperature to 70 - 80°C, add sulfur trioxide for reaction for 5 - 10 s, add sodium hydroxide solution to neutralize to pH 8 - 9, raise the temperature to 80 - 90°C for hydrolysis for 1 - 2 h, distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate; S4. Dilute the pyrrolidine polyoxyethylene ether obtained in step S1 with ethanol, then add sodium hydroxide and sodium chloroacetate, react at 50 - 60°C for 3 - 4 h, raise the temperature to 80 - 90°C, remove the solvent to obtain sodium pyrrolidine polyoxyethylene ether carboxylate; S5. Weigh the corresponding amounts of the pyrrolidine polyoxyethylene ethers obtained in steps S1 and S2, the sodium pyrrolidine polyoxyethylene ether sulfate obtained in step S3, and the sodium pyrrolidine polyoxyethylene ether carboxylate obtained in step S4, then mix them and stir at 30 - 50°C for 20 - 40 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0008] Preferably, the chemical reactions involved in the pyrrolidine polyoxyethylene ether in S1 and S2 are as follows:

[0009] Preferably, the molar ratio of N - hydroxyethylpyrrolidine to ethylene oxide in S1 is 1:5.2 - 8.2.

[0010] Preferably, the molar ratio of N - hydroxyethylpyrrolidine to ethylene oxide in S2 is 1:15.2 - 19.2.

[0011] Preferably, the catalyst in S1 and S2 is one or more combinations of sodium hydroxide, potassium hydroxide, potassium methoxide, and sodium methoxide, and the addition amount of the catalyst is 0.1-5% of the molar amount of N-hydroxyethylpyrrolidine.

[0012] Preferably, the chemical reaction involved in the preparation of pyrrolidine polyoxyethylene ether sodium sulfate in S3 is as follows:

[0013] Preferably, the mass ratio of pyrrolidine polyoxyethylene ether to sulfur trioxide in S3 is 3:1-1.2, and the concentration of the sodium hydroxide solution is 10-20 wt%.

[0014] Preferably, the chemical reaction involved in the preparation of pyrrolidine polyoxyethylene ether carboxylate in S4 is as follows:

[0015] Preferably, the mass ratio of pyrrolidine polyoxyethylene ether to ethanol in S4 is 1:1-3.

[0016] Preferably, the molar ratio of pyrrolidine polyoxyethylene ether, sodium hydroxide, and sodium chloroacetate in S4 is 1:0.05-0.07:0.9-1.2.

[0017] Preferably, the preparation method of N-hydroxyethylpyrrolidine in S1 includes the following steps: S11: Put the catalyst into the reactor. After replacing the air in the reactor with nitrogen, evacuate to -0.1 to -0.04 MPa through the vacuum system; S12: Add pyrrolidine to the reactor. Heat the reactor to 40-50 °C with a heat exchanger, dropwise add ethylene oxide, finish dropping in 1-2 h and keep the temperature in the reactor at 40-80 °C and the pressure at 0-0.4 MPa. Raise the temperature of the reactor to 70-80 °C for reaction. When it is detected that the pressure in the reactor no longer decreases, take a sample to detect and analyze the residual amount of ethylene oxide in the material in the reactor to be less than 0.1%. Pressurize and filter through the feed pump and flow out to the feed metering tank to obtain a mixture containing N-hydroxyethylpyrrolidine; S13: Refine the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide to obtain N-hydroxyethylpyrrolidine.

[0018] Preferably, the reaction equation of N-hydroxyethylpyrrolidine is as follows:

[0019] The result of mass spectrometry analysis is: m / z: 115.10 (100.0%), 116.10 (6.9%).

[0020] Preferably, the catalyst in S11 is one or a combination of more of a Lewis acid, a hydroxide of an alkali metal, and an alcoholate of an alkali metal.

[0021] Preferably, the Lewis acid is one or a combination of more of boron trifluoride, boron trichloride, and aluminum chloride.

[0022] Preferably, the hydroxide of the alkali metal is one or two of sodium hydroxide and potassium hydroxide.

[0023] Preferably, the alcoholate of the alkali metal is one or two of potassium methoxide and sodium methoxide.

[0024] Preferably, in S12, the molar ratio of pyrrolidine to ethylene oxide is 1:0.8 - 1.2, and the addition amount of the catalyst is 0.01% - 5% of the molar amount of pyrrolidine.

[0025] Preferably, in S13, the refining process is carried out by vacuum distillation or rectification for refining.

[0026] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows: 2. By mixing pyrrolidino polyoxyethylene ethers with different numbers of ethylene oxide, sodium pyrrolidino polyoxyethylene ether sulfates, and sodium pyrrolidino polyoxyethylene ether carboxylates in a certain mass ratio, the present invention prepares a pyrrolidine compound polyoxyethylene ether composition. This composition can adjust the proportion of pyrrolidino polyoxyethylene ethers with different lengths, change the balance of its hydrophilicity and hydrophobicity, and enable it to have excellent hydrophobic-hydrophilic, dispersing, and wetting properties.

[0027] 3. After first preparing N-hydroxyethylpyrrolidine, the present invention then synthesizes pyrrolidino polyoxyethylene ethers with different numbers of ethylene oxide from N-hydroxyethylpyrrolidine and ethylene oxide, reacts pyrrolidino polyoxyethylene ether with sulfur trioxide to prepare sodium pyrrolidino polyoxyethylene ether sulfate, introduces a sulfate group at the end of the pyrrolidino polyoxyethylene ether, enabling its molecule to have good tolerance to calcium ions and be able to form an easily soluble calcium salt compound with calcium ions, thus improving the hard water resistance of the pyrrolidine compound polyoxyethylene ether composition; reacts pyrrolidino polyoxyethylene ether with sodium chloroacetate to prepare sodium pyrrolidino polyoxyethylene ether carboxylate, introducing a carboxylic acid group, enhancing the hydrophilic property at the end of its molecule, and improving the wetting property of the pyrrolidine compound polyoxyethylene ether composition.

[0028] 4. By adopting the feeding method with negative pressure in the reactor and a suitable catalyst, the present invention can further accelerate the reaction rate and prevent the oxidation and discoloration of N-hydroxyethylpyrrolidine, and also makes the reaction conditions relatively milder and the operation more controllable, thereby increasing the yield of N-hydroxyethylpyrrolidine. Description of the Drawings

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0030] Figure 1 Shows a schematic diagram of the synthesis reaction system of N - hydroxyethylpyrrolidine of the present invention; Reference numerals: 1, reactor; 2, heat exchanger; 3, raw material metering tank; 4, raw material pump; 5, circulation pump; 6, circulation standby pump. Specific embodiments

[0031] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0032] Example 1, refer to Figure 1 As shown, this embodiment provides a synthesis reaction system for N - hydroxyethylpyrrolidine, including a reactor 1, a heat exchanger 2, a raw material metering tank 3, a raw material pump 4, a circulation pump 5 and a circulation standby pump 6. Raw material inlets are provided on both the top and side walls of the reactor 1. The top of the reactor 1 is connected to the heat exchanger 2 through a pipeline. The bottom discharge port of the reactor 1 is connected in parallel with the circulation pump 5 and the circulation standby pump 6 through pipelines. The tops of the circulation pump 5 and the circulation standby pump 6 are both connected to the bottom of the heat exchanger 2 through pipelines. The bottoms of the circulation pump 5 and the circulation standby pump 6 are connected to the raw material metering tank 3 and the raw material pump 4 through pipelines. The top of the raw material pump 4 is connected to the top of the raw material metering tank 3 through a pipeline, and the bottom of the raw material pump 4 is connected to the bottom of the raw material metering tank 3 through a pipeline.

[0033] Example 2, a pyrrolidine compound polyoxyethylene ether composition in this embodiment is prepared from the following components in parts by weight: 20 parts of pyrrolidine polyoxyethylene ether with a low polymerization number, 20 parts of pyrrolidine polyoxyethylene ether with a high polymerization number, 10 parts of pyrrolidine polyoxyethylene ether sodium sulfate, and 5 parts of pyrrolidine polyoxyethylene ether carboxylate.

[0034] The polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a low polymerization number is 9; the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a high polymerization number is 16.

[0035] A preparation method of a pyrrolidine compound polyoxyethylene ether composition in this embodiment includes the following steps: S1. Add 1150 g of N - hydroxyethylpyrrolidine and 5 g of sodium hydroxide into the reactor. After purging the air in the reactor with nitrogen, heat up to 40°C, and then dropwise add 3610 g of ethylene oxide within 1 h. After dropping, heat up to 140°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a low polymerization degree; S2. Add 1150 g of N - hydroxyethylpyrrolidine and 20 g of sodium hydroxide into the reactor. After purging the air in the reactor with nitrogen, heat up to 40°C, and then dropwise add 6690 g of ethylene oxide within 1 h. After dropping, heat up to 140°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a high polymerization degree; S3. Measure 300 g of the pyrrolidine polyoxyethylene ether prepared in step S1 and add it into the sulfonation reactor. Heat up to 70°C, add 100 g of sulfur trioxide for reaction for 10 s, add 10 wt% sodium hydroxide solution to neutralize to pH 8, heat up to 80°C for hydrolysis for 2 h, distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate; S4. Measure 190 g of the pyrrolidine polyoxyethylene ether prepared in step S1, dilute it with 200 g of ethanol, then add 1 g of sodium hydroxide and 60 g of sodium chloroacetate, react at 50°C for 3 h, heat up to 80°C, and remove the solvent to obtain sodium pyrrolidine polyoxyethylene ether carboxylate; S5. Weigh the corresponding amounts of the pyrrolidine polyoxyethylene ethers prepared in steps S1 and S2, the sodium pyrrolidine polyoxyethylene ether sulfate prepared in step S3, and the sodium pyrrolidine polyoxyethylene ether carboxylate prepared in step S4, then mix them, and stir at 50°C for 20 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0036] The preparation method of N - hydroxyethylpyrrolidine in this example includes the following steps: S11. Put 3.3 g of sodium hydroxide into reactor 1. After purging the air in the reactor with nitrogen, evacuate to - 0.098 MPa through the vacuum system; S12. Add 1020 g of pyrrolidine into the reactor. Heat the reactor to 40°C with heat exchanger 2, and dropwise add 630 g of ethylene oxide within 1 h while keeping the temperature in the reactor at 40°C and the pressure at 0.3 MPa. Then heat the reactor to 70°C for reaction. When it is detected that the pressure in the reactor no longer decreases, sample and analyze the residual amount of ethylene oxide in the reactor material until it is less than 0.1%. Then pressurize and filter through the feed pump and flow out to the feed metering tank to obtain a mixture containing N - hydroxyethylpyrrolidine; S13. Rectify the mixture containing N - hydroxyethylpyrrolidine to remove ethylene oxide. The rectification pressure is - 0.09 MPa, and collect the fraction at 75°C to obtain N - hydroxyethylpyrrolidine.

[0037] Example 3, refer to Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition of this example is prepared from the following components by weight: 25 parts of pyrrolidine polyoxyethylene ether with a low polymerization number, 25 parts of pyrrolidine polyoxyethylene ether with a high polymerization number, 15 parts of pyrrolidine polyoxyethylene ether sodium sulfate, and 5 parts of pyrrolidine polyoxyethylene ether carboxylate sodium.

[0038] The polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a low polymerization number is 7; the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a high polymerization number is 17.

[0039] A preparation method of a pyrrolidine compound polyoxyethylene ether composition of this example includes the following steps: S1. Add 1150 g of N-hydroxyethylpyrrolidine and 5 g of potassium hydroxide into a reactor. After purging the air in the reactor with nitrogen, heat up to 45°C, dropwise add 2720 g of ethylene oxide, finish dropping in 1 h, heat up to 145°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a low polymerization number; S2. Add 1150 g of N-hydroxyethylpyrrolidine and 5 g of potassium hydroxide into a reactor. After purging the air in the reactor with nitrogen, heat up to 45°C, dropwise add 7130 g of ethylene oxide, finish dropping in 1 h, heat up to 145°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a high polymerization number; S3. Measure 300 g of the pyrrolidine polyoxyethylene ether prepared in step S1 and add it into a sulfonation reactor. Heat up to 75°C, add 110 g of sulfur trioxide and react for 7 s, add 10 wt% sodium hydroxide solution to neutralize to pH 8.5, heat up to 90°C and hydrolyze for 1 h, distill to remove impurities to obtain pyrrolidine polyoxyethylene ether sodium sulfate; S4. Measure 190 g of the pyrrolidine polyoxyethylene ether prepared in step S1, add 300 g of ethanol for dilution, then add 1 g of sodium hydroxide and 55 g of sodium chloroacetate, react at 55°C for 3 h, heat up to 80°C, and remove the solvent to obtain pyrrolidine polyoxyethylene ether carboxylate sodium; S5. Weigh the corresponding amounts of the pyrrolidine polyoxyethylene ether prepared in step S1 and step S2, the pyrrolidine polyoxyethylene ether sodium sulfate prepared in step S3, and the pyrrolidine polyoxyethylene ether carboxylate sodium prepared in step S4, then mix them and stir at 35°C for 25 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0040] A preparation method of N-hydroxyethylpyrrolidine of this example includes the following steps: S11. Put 3.3 g of potassium hydroxide into the reactor 1. After replacing the air in the reactor with nitrogen, evacuate it to -0.098 MPa through the vacuum system. S12. Add 1020 g of pyrrolidine to the reactor. Heat the reactor to 50 °C with the heat exchanger 2, and dropwise add 630 g of ethylene oxide. Finish dropping in 1.5 h and keep the temperature in the reactor at 75 °C and the pressure at 0.2 MPa. Raise the temperature of the reactor to 70 °C for reaction. Detect until the pressure in the reactor no longer decreases. Take a sample to detect and analyze the residual amount of ethylene oxide in the reactor material until it is less than 0.1%. Pressurize and filter through the feed pump and flow out to the feed metering tank to obtain a mixture containing N - hydroxyethylpyrrolidine. S13. Rectify the mixture containing N - hydroxyethylpyrrolidine to remove ethylene oxide. The rectification pressure is -0.09 MPa, and collect the fraction at 78 °C to obtain N - hydroxyethylpyrrolidine.

[0041] Example 4, refer to Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition of this example is prepared from the following components by weight: 30 parts of pyrrolidine polyoxyethylene ether with a low polymerization number, 30 parts of pyrrolidine polyoxyethylene ether with a high polymerization number, 20 parts of pyrrolidine polyoxyethylene ether sodium sulfate, and 5 parts of pyrrolidine polyoxyethylene ether carboxylate.

[0042] The polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a low polymerization number is 8; the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a high polymerization number is 18.

[0043] A preparation method of a pyrrolidine compound polyoxyethylene ether composition of this example includes the following steps: S1. Put 1150 g of N - hydroxyethylpyrrolidine and 10 g of sodium methoxide into the reactor. After replacing the air in the reactor with nitrogen, raise the temperature to 50 °C, and dropwise add 3080 g of ethylene oxide. Finish dropping in 1.5 h, raise the temperature to 160 °C for reaction. Detect until the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a low polymerization number. S2. Put 1150 g of N - hydroxyethylpyrrolidine and 10 g of sodium methoxide into the reactor. After replacing the air in the reactor with nitrogen, raise the temperature to 50 °C, and dropwise add 7480 g of ethylene oxide. Finish dropping in 2 h, raise the temperature to 160 °C for reaction. Detect until the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a high polymerization number. S3. Measure 300 g of the pyrrolidine polyoxyethylene ether prepared in step S1, add it to a sulfonation reactor, heat up to 70 °C, add sulfur trioxide and react for 5 s, add a 15 wt% sodium hydroxide solution to neutralize to pH 8.5, heat up to 90 °C and hydrolyze for 1 h, then distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate; S4. Measure 190 g of the pyrrolidine polyoxyethylene ether prepared in step S1, dilute it with 400 g of ethanol, then add 1.4 g of sodium hydroxide and 65 g of sodium chloroacetate, react at 55 °C for 3 h, heat up to 85 °C, and remove the solvent to obtain sodium pyrrolidine polyoxyethylene ether carboxylate; S5. Weigh the corresponding amounts of the pyrrolidine polyoxyethylene ethers prepared in steps S1 and S2, the sodium pyrrolidine polyoxyethylene ether sulfate prepared in step S3, and the sodium pyrrolidine polyoxyethylene ether carboxylate prepared in step S4, then mix them and stir at 30 °C for 20 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0044] The preparation method of N - hydroxyethylpyrrolidine in this example includes the following steps: S11. Put 4.6 g of boron trichloride into reactor 1. After replacing the air in the reactor with nitrogen, evacuate to - 0.05 MPa through a vacuum system; S12. Add 1020 g of pyrrolidine to the reactor. Heat the reactor to 50 °C with heat exchanger 2, dropwise add 630 g of ethylene oxide, finish dropping in 2 h and keep the temperature in the reactor at 70 °C and the pressure at 0.4 MPa. Heat the reactor to 80 °C for reaction. When it is detected that the pressure in the reactor no longer decreases, take a sample to detect and analyze the residual amount of ethylene oxide in the reactor material to be less than 0.1%, then pressurize and filter through a feed pump and flow out to a raw material metering tank to obtain a mixture containing N - hydroxyethylpyrrolidine; S13. Rectify the mixture containing N - hydroxyethylpyrrolidine to remove ethylene oxide. The rectification pressure is - 0.09 MPa, and collect the fraction at 80 °C to obtain N - hydroxyethylpyrrolidine.

[0045] Example 5, refer to Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition in this example is prepared from the following components by weight: 40 parts of pyrrolidine polyoxyethylene ether with a low polymerization degree, 40 parts of pyrrolidine polyoxyethylene ether with a high polymerization degree, 20 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 10 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

[0046] The number of polyoxyethylene units of the pyrrolidine polyoxyethylene ether with a low polymerization degree is 9; the number of polyoxyethylene units of the pyrrolidine polyoxyethylene ether with a high polymerization degree is 19.

[0047] The preparation method of a pyrrolidine compound polyoxyethylene ether composition in this example includes the following steps: S1. Add 1150 g of N - hydroxyethylpyrrolidine and 5 g of potassium methoxide into the reactor. After purging the air in the reactor with nitrogen, heat up to 50°C, and dropwise add 3520 g of ethylene oxide within 1 h. After dropping, heat up to 150°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a low polymerization degree. S2. Add 1150 g of N - hydroxyethylpyrrolidine and 5 g of potassium methoxide into the reactor. After purging the air in the reactor with nitrogen, heat up to 50°C, and dropwise add 7920 g of ethylene oxide within 2 h. After dropping, heat up to 150°C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a high polymerization degree. S3. Measure 300 g of the pyrrolidine polyoxyethylene ether prepared in step S1 and add it into the sulfonation reactor. Heat up to 80°C, add 120 g of sulfur trioxide for reaction for 10 s, add 20 wt% sodium hydroxide solution to neutralize to pH 9, heat up to 90°C for hydrolysis for 2 h, distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate. S4. Measure 190 g of the pyrrolidine polyoxyethylene ether prepared in step S1, dilute it with 500 g of ethanol, then add 1.4 g of sodium hydroxide and 70 g of sodium chloroacetate, react at 60°C for 3 h, heat up to 90°C, and remove the solvent to obtain sodium pyrrolidine polyoxyethylene ether carboxylate. S5. Weigh the corresponding amounts of the pyrrolidine polyoxyethylene ethers prepared in steps S1 and S2, the sodium pyrrolidine polyoxyethylene ether sulfate prepared in step S3, and the sodium pyrrolidine polyoxyethylene ether carboxylate prepared in step S4, then mix them and stir at 35°C for 30 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0048] The preparation method of N - hydroxyethylpyrrolidine in this example includes the following steps: S11. Put 5 g of aluminum chloride into reactor 1. After purging the air in the reactor with nitrogen, evacuate to - 0.07 MPa through the vacuum system. S12. Add 1020 g of pyrrolidine into the reactor. Heat the reactor to 50°C with heat exchanger 2, dropwise add 630 g of ethylene oxide within 2 h while keeping the temperature in the reactor at 80°C and the pressure at 0.4 MPa. Then heat up the reactor to 70°C for reaction. When it is detected that the pressure in the reactor no longer decreases, sample and analyze the residual amount of ethylene oxide in the reactor material until it is less than 0.1%. Pressurize and filter through the feed pump and flow out to the raw material metering tank to obtain a mixture containing N - hydroxyethylpyrrolidine. S13. Rectify the mixture containing N - hydroxyethylpyrrolidine to remove ethylene oxide. The rectification pressure is - 0.09 MPa, and collect the fraction at 79°C to obtain N - hydroxyethylpyrrolidine.

[0049] Comparative Example 1. The difference between this comparative example and Example 1 is that two different pyrrolidine polyoxyethylene ethers are replaced by pyrrolidine polyoxyethylene ether with a polyoxyethylene number of 25.

[0050] Comparative Example 2. The difference between this comparative example and Example 1 is that N-hydroxyethyl pyrrolidine is replaced by dodecanol.

[0051] Comparative Example 3. The difference between this comparative example and Example 1 is that the amount of sodium pyrrolidine polyoxyethylene ether carboxylate is replaced by 30 parts.

[0052] Performance Test Surface Tension The pyrrolidine compound polyoxyethylene ether composition prepared in each example and comparative example was added to deionized water to prepare an aqueous solution with a concentration of 1 g / L, and the static surface tension was measured with a surface tensiometer.

[0053] Wetting Performance According to the method specified in GB / T 11983-2008 "Determination of Wetting Power of Surfactants - Immersion Method", the wetting time of the samples in each example and comparative example for wetting cotton textiles was tested.

[0054] Emulsification Performance The pyrrolidine compound polyoxyethylene ether composition prepared in each example and comparative example was added to deionized water to prepare an aqueous solution with a concentration of 1 g / L. The aqueous solution and kerosene were added to a homogenizer and emulsified at a shear rate of 5000 r / min for 5 min. Immediately after emulsification, the liquid was poured into a stoppered graduated cylinder. When 10 mL of water was separated from the emulsion, the time was recorded, which is the emulsification time.

[0055] Electrolyte Resistance Performance The pyrrolidine compound polyoxyethylene ether composition prepared in each example and comparative example was added to deionized water to prepare an aqueous solution with a concentration of 10 g / L. 5 mL of the aqueous solution was taken and placed in an environment at 40 °C. Calcium chloride solid was added every 12 h, shaken well, and it was observed whether the solution became turbid or showed oil floating after 12 h, and the mass of calcium chloride solid added was recorded.

[0056] The test results are shown in Table 1 below: Table 1

[0057] As can be seen from the data in Table 1, the static surface tension of the pyrrolidine compound polyoxyethylene ether compositions prepared in Examples 2 to 5 is between 27.8 and 28.5 mN / m, and the wetting time is between 24 and 27 s. In Comparative Example 2, N-hydroxyethylpyrrolidine was replaced with dodecanol, and the lipophilic end is a straight-chain alkyl group, and its lipophilic ability is weaker than that of pyrrolidine. Therefore, its static surface tension is only 24.9 mN / m, and the wetting time is 34 s, indicating that the pyrrolidine compound polyoxyethylene ether composition prepared by the present invention has excellent hydrophobic-hydrophilic properties and wetting properties; the emulsification time of the pyrrolidine compound polyoxyethylene ether compositions prepared in Examples 2 to 5 is between 132 and 135 min, indicating that the pyrrolidine compound polyoxyethylene ether composition prepared by the present invention has excellent emulsification properties; when the aqueous solution of the pyrrolidine compound polyoxyethylene ether composition prepared in Examples 2 to 5 shows turbidity or oil floating phenomenon, the mass of calcium chloride solid added is between 8.2 and 8.4 g, indicating that the pyrrolidine compound polyoxyethylene ether composition prepared by the present invention has excellent hard water resistance.

[0058] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and should be covered within the protection scope of the present invention.

[0059] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the present invention to only the specific embodiments. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A pyrrolidine compound polyoxyethylene ether composition, characterized in that, It is prepared from the following components in parts by weight: 20 to 40 parts of pyrrolidine polyoxyethylene ether with a low polymerization degree, 20 to 40 parts of pyrrolidine polyoxyethylene ether with a high polymerization degree, 10 to 20 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 5 to 10 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

2. The pyrrolidine compound polyoxyethylene ether composition according to claim 1, wherein The polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a low polymerization degree is 6 to 10; the polyoxyethylene number of the pyrrolidine polyoxyethylene ether with a high polymerization degree is 16 to 19.

3. A method for preparing a pyrrolidine compound polyoxyethylene ether composition, characterized in that, It includes the following steps: S1. Add N-hydroxyethylpyrrolidine and a catalyst into a reactor. After purging the air in the reactor with nitrogen, heat up to 40 to 50 °C, and dropwise add ethylene oxide, which is added dropwise within 1 to 2 h. Then heat up to 140 to 160 °C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a low polymerization degree; S2. Add N-hydroxyethylpyrrolidine and a catalyst into a reactor. After purging the air in the reactor with nitrogen, heat up to 40 to 50 °C, and dropwise add ethylene oxide, which is added dropwise within 1 to 2 h. Then heat up to 140 to 160 °C for reaction. When it is detected that the pressure in the reactor no longer decreases, distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with a high polymerization degree; S3. Add the pyrrolidine polyoxyethylene ether prepared in step S1 into a sulfonation reactor, heat up to 70 to 80 °C, add sulfur trioxide and react for 5 to 10 s, add sodium hydroxide solution to neutralize to pH 8 to 9, heat up to 80 to 90 °C and hydrolyze for 1 to 2 h, distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate; S4. Dilute the pyrrolidine polyoxyethylene ether prepared in step S1 with ethanol, then add sodium hydroxide and sodium chloroacetate, react at 50 to 60 °C for 3 to 4 h, heat up to 80 to 90 °C, and remove the solvent to obtain sodium pyrrolidine polyoxyethylene ether carboxylate; S5. Weigh the corresponding parts of the pyrrolidine polyoxyethylene ether prepared in step S1 and step S2, the sodium pyrrolidine polyoxyethylene ether sulfate prepared in step S3, and the sodium pyrrolidine polyoxyethylene ether carboxylate prepared in step S4, and then mix them, stir at 30 to 50 °C for 20 to 40 min to obtain a pyrrolidine compound polyoxyethylene ether composition.

4. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 3, characterized in that, In S1, the molar ratio of N-hydroxyethylpyrrolidine to ethylene oxide is 1:5.2 to 8.2; in S2, the molar ratio of N-hydroxyethylpyrrolidine to ethylene oxide is 1:15.2 to 19.

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5. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 3, characterized in that, In S1 and S2, the catalyst is one or a combination of sodium hydroxide, potassium hydroxide, potassium methoxide, and sodium methoxide, and the addition amount of the catalyst is 0.1 to 5% of the molar amount of N-hydroxyethylpyrrolidine.

6. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 3, characterized in that, In S3, the mass ratio of pyrrolidine polyoxyethylene ether to sulfur trioxide is 3:1 to 1.2, and the concentration of the sodium hydroxide solution is 10 to 20 wt%.

7. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 3, characterized in that, In S4, the mass ratio of pyrrolidine polyoxyethylene ether to ethanol is 1:1 to 3, and the molar ratio of pyrrolidine polyoxyethylene ether, sodium hydroxide, and sodium chloroacetate is 1:0.05 to 0.07:0.9 to 1.

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8. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 3, characterized in that, The preparation method of N-hydroxyethylpyrrolidine in S1 includes the following steps: S11. Charge a catalyst into the reactor. After replacing the air in the reactor with nitrogen, evacuate the reactor to -0.1 to -0.04 MPa through a vacuum system. S12. Add pyrrolidine to the reactor. Heat the reactor to 40 to 50 °C with a heat exchanger, and add ethylene oxide dropwise. Finish dropping within 1 to 2 h while maintaining the temperature in the reactor at 40 to 80 °C and the pressure at 0 to 0.4 MPa. Raise the temperature of the reactor to 70 to 80 °C for reaction. When it is detected that the pressure in the reactor no longer decreases, take a sample for detection and analysis of the residual amount of ethylene oxide in the materials in the reactor until it is less than 0.1%. Pressurize and filter through a feed pump and flow out to a feed metering tank to obtain a mixture containing N-hydroxyethylpyrrolidine. S13. Refine the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide to obtain N-hydroxyethylpyrrolidine.

9. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 8, characterized in that, In the S11, the catalyst is one or more combinations of a Lewis acid, a hydroxide of an alkali metal, and an alcoholate of an alkali metal. The Lewis acid is one or more combinations of boron trifluoride, boron trichloride, and aluminum chloride.

10. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 9, characterized in that, The hydroxide of the alkali metal is one or both of sodium hydroxide and potassium hydroxide, and the alcoholate of the alkali metal is one or both of potassium methoxide and sodium methoxide.

11. A method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 8, characterized in that, In the S12, the molar ratio of pyrrolidine to ethylene oxide is 1:0.8 to 1.2, and the addition amount of the catalyst is 0.01 to 5% of the molar amount of pyrrolidine.

12. The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to claim 8, characterized in that, In the S13, the refining process is carried out by vacuum distillation or rectification for refining.

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