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

Abstract

The present application 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 present application further accelerates the reaction speed and prevents the oxidative discoloration of N-hydroxyethyl pyrrolidine by adopting a feeding mode of negative pressure in the reactor, so that the yield of N-hydroxyethyl pyrrolidine is improved. The pyrrolidine compound polyoxyethylene ether composition is prepared by mixing pyrrolidine polyoxyethylene ethers with different polymerization numbers, pyrrolidine polyoxyethylene ether sodium sulfate and pyrrolidine polyoxyethylene ether carboxylate sodium according to a certain mass ratio. The composition can adjust the proportion of pyrrolidine polyoxyethylene ethers with different lengths, change the hydrophilicity and hydrophobicity balance, and make the composition have excellent hydrophobic-hydrophilic, dispersion and wetting properties.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyoxyethylene ether production, and particularly relates to a pyrrolidine compound polyoxyethylene ether composition and a preparation method thereof. BACKGROUND

[0002] N-hydroxyethyl pyrrolidine is an important organic synthesis intermediate, participates in various chemical reactions, and plays an irreplaceable role in the synthesis of compounds with specific functions and properties, and is therefore widely used in the fields of medicine, pesticide, dye and surfactant. At present, there are few reports on the preparation of pyrrolidine compound polyoxyethylene ether from N-hydroxyethyl pyrrolidine in the prior art.

[0003] A Chinese invention patent with publication number CN107141465B discloses a styryl phenol polyoxyethylene ether and a preparation method thereof, and belongs to the technical field of carbocyclic compounds. The preparation method comprises three steps of phenol alkylation reaction, ethylene oxide polymerization reaction and polyether post-treatment. The phenol and an alkylating catalyst are placed in nitrogen and heated to 80-100 DEG C, then styrene is added dropwise, and the product is kept at a constant temperature until the refractive index reaches 1.5985-1.6020. The temperature is raised to 100-110 DEG C, vacuum dehydration is carried out, then the temperature is lowered, a polymerization catalyst is added, the temperature is raised to 80-120 DEG C, ethylene oxide is added, and the reaction is completed at 80-120 DEG C and 0.01-0.04 MPa. Deionized water is added, the temperature is raised to 60-70 DEG C, phosphoric acid and an adsorbent are added, vacuum dehydration is carried out by stirring, and the finished product is obtained by filtration. The application is applied to the preparation of styryl phenol polyoxyethylene ether and other non-ionic surfactants, and has the advantages of narrow distribution, light color, low K + / Na + ion content and the like. However, the prior art has the technical problem that the composition of the polyoxyethylene ether is not further improved to improve the stability and wetting property of the polyoxyethylene ether. SUMMARY

[0004] The present application aims to provide a pyrrolidine compound polyoxyethylene ether composition and a preparation method thereof, and solve the technical problem in the prior art that the composition of the polyoxyethylene ether is not further improved to improve the stability and wetting property of the polyoxyethylene ether.

[0005] In order to achieve the above-mentioned purpose, the present application adopts the following technical solution:

[0006] A pyrrolidine compound polyoxyethylene ether composition is prepared from the following ingredients by weight:

[0007] 20-40 parts of low-polymerization-number pyrrolidine polyoxyethylene ether, 20-40 parts of high-polymerization-number pyrrolidine polyoxyethylene ether, 10-20 parts of pyrrolidine polyoxyethylene ether sodium sulfate and 5-10 parts of pyrrolidine polyoxyethylene ether sodium carboxylate.

[0008] Preferably, the low-polymer-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 6 to 10; the high-polymer-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 16 to 19.

[0009] A method for preparing a pyrrolidine compound polyoxyethylene ether composition includes the following steps:

[0010] S1. Add N-hydroxyethylpyrrolidine and catalyst to the reactor, purge the air in the reactor with nitrogen, raise the temperature to 40~50℃, add ethylene oxide dropwise over 1~2 hours, raise the temperature to 140~160℃ to react, and detect when the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid and filter to obtain low polymerization number pyrrolidine polyoxyethylene ether.

[0011] S2. Add N-hydroxyethylpyrrolidine and catalyst to the reactor, purge the air in the reactor with nitrogen, raise the temperature to 40~50℃, add ethylene oxide dropwise over 1~2 hours, raise the temperature to 140~160℃ to react, and detect when the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid and filter to obtain pyrrolidine polyoxyethylene ether with high polymerization number.

[0012] S3. Add the pyrrolidine polyoxyethylene ether obtained in step S1 to a sulfonation reactor, heat to 70-80℃, add sulfur trioxide and react for 5-10 seconds, add sodium hydroxide solution to neutralize to pH 8-9, heat to 80-90℃ for 1-2 hours to hydrolyze, and distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate.

[0013] S4. The pyrrolidine polyoxyethylene ether obtained in step S1 is diluted with ethanol, then sodium hydroxide and sodium chloroacetate are added, and the mixture is reacted at 50-60℃ for 3-4 hours. The temperature is then raised to 80-90℃ to remove the solvent, and sodium pyrrolidine polyoxyethylene ether carboxylate is obtained.

[0014] S5. Weigh the appropriate amounts of the pyrrolidine polyoxyethylene ether 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, mix them, and stir at 30~50℃ for 20~40 min to obtain the pyrrolidine compound polyoxyethylene ether composition.

[0015] Preferably, the chemical reactions involved in the pyrrolidine polyoxyethylene ether in S1 and S2 are as follows:

[0016]

[0017] Preferably, the molar ratio of N-hydroxyethylpyrrolidine to ethylene oxide in S1 is 1:5.2~8.2.

[0018] Preferably, the molar ratio of N-hydroxyethylpyrrolidine to ethylene oxide in S2 is 1:15.2~19.2.

[0019] Preferably, the catalysts in S1 and S2 are one or more combinations of sodium hydroxide, potassium hydroxide, potassium methoxide, and sodium methoxide, and the amount of catalyst added is 0.1 to 5% of the molar amount of N-hydroxyethylpyrrolidine.

[0020] Preferably, the chemical reaction involved in the preparation of sodium pyrrolidine polyoxyethylene ether sulfate in step S3 is as follows:

[0021]

[0022] Preferably, the mass ratio of pyrrolidine polyoxyethylene ether to sulfur trioxide in S3 is 3:1~1.2, and the concentration of sodium hydroxide solution is 10~20wt%.

[0023] Preferably, the chemical reaction involved in the preparation of sodium pyrrolidine polyoxyethylene ether carboxylate in step S4 is as follows:

[0024]

[0025] Preferably, the mass ratio of pyrrolidine polyoxyethylene ether to ethanol in S4 is 1:1~3.

[0026] 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.

[0027] Preferably, the method for preparing N-hydroxyethylpyrrolidine in S1 includes the following steps:

[0028] S11. Add the catalyst into the reactor, replace the air in the reactor with nitrogen, and then evacuate to -0.1~-0.04MPa using a vacuum system.

[0029] S12. Add tetrahydropyrrole to the reactor, heat the reactor to 40~50℃ using a heat exchanger, add ethylene oxide dropwise over 1~2 hours while maintaining the reactor temperature at 40~80℃ and the pressure at 0~0.4MPa. Increase the reactor temperature to 70~80℃ and continue reacting until the pressure in the reactor no longer decreases. Take a sample to analyze the residual ethylene oxide in the reactor material until it is less than 0.1%. Filter the material through a raw material pump and flow it out to the raw material metering tank to obtain a mixture containing N-hydroxyethylpyrrole.

[0030] S13. The mixture containing N-hydroxyethylpyrrolidine is purified to remove ethylene oxide, yielding N-hydroxyethylpyrrolidine.

[0031] Preferably, the reaction equation for the N-hydroxyethylpyrrolidine is as follows:

[0032]

[0033] The mass spectrometry analysis results were: m / z: 115.10 (100.0%), 116.10 (6.9%).

[0034] Preferably, the catalyst in S11 is one or more combinations of Lewis acid, alkali metal hydroxide, and alkali metal alkoxide.

[0035] Preferably, the Lewis acid is one or a combination of boron trifluoride, boron trichloride, and aluminum chloride.

[0036] Preferably, the alkali metal hydroxide is one or both of sodium hydroxide and potassium hydroxide.

[0037] Preferably, the alkali metal alkoxide is one or both of potassium methoxide and sodium methoxide.

[0038] Preferably, the molar ratio of tetrahydropyrrole to ethylene oxide in S12 is 1:0.8~1.2, and the amount of catalyst added is 0.01~5% of the molar amount of tetrahydropyrrole.

[0039] Preferably, the refining process in S13 is carried out by vacuum distillation or rectification.

[0040] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0041] 2. The present invention prepares a pyrrolidine compound polyoxyethylene ether composition by mixing pyrrolidine polyoxyethylene ether, sodium pyrrolidine polyoxyethylene ether sulfate, and sodium pyrrolidine polyoxyethylene ether carboxylate with different numbers of ethylene oxide in a certain mass ratio. This composition can adjust the proportion of pyrrolidine polyoxyethylene ether with different lengths to change its hydrophilicity and hydrophobicity balance, so as to have excellent hydrophobic-hydrophilic, dispersion and wetting properties.

[0042] 3. In this invention, N-hydroxyethylpyrrolidine is first prepared, and then N-hydroxyethylpyrrolidine and ethylene oxide are used to synthesize pyrrolidine polyoxyethylene ethers with different numbers of ethylene oxides. The pyrrolidine polyoxyethylene ether is reacted with sulfur trioxide to prepare sodium pyrrolidine polyoxyethylene ether sulfate. A sulfate group is introduced at the end of the pyrrolidine polyoxyethylene ether, which makes the molecule have good resistance to calcium ions and can form easily soluble calcium salt compounds with calcium ions, thereby improving the hard water resistance of the pyrrolidine polyoxyethylene ether composition. The pyrrolidine polyoxyethylene ether is reacted with sodium chloroacetate to prepare sodium pyrrolidine polyoxyethylene ether carboxylate. A carboxylic acid group is introduced to enhance the hydrophilicity of the molecule end, thereby improving the wetting properties of the pyrrolidine polyoxyethylene ether composition.

[0043] 4. By adopting a negative pressure feeding method in the reactor and a suitable catalyst, this invention can further accelerate the reaction rate and prevent the oxidation and discoloration of N-hydroxyethylpyrrolidine. It also makes the reaction conditions relatively milder and the operation more controllable, thereby increasing the yield of N-hydroxyethylpyrrolidine. Attached Figure Description

[0044] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0045] Figure 1 A schematic diagram of the synthesis reaction system for N-hydroxyethylpyrrolidine of the present invention is shown;

[0046] Attached reference numerals: 1. Reactor; 2. Heat exchanger; 3. Raw material metering tank; 4. Raw material pump; 5. Circulation pump; 6. Circulation standby pump. Detailed Implementation

[0047] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] Example 1, see 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 circulating pump 5, and a circulating standby pump 6. The reactor 1 has raw material inlets on its top and side walls. The top of the reactor 1 is connected to the heat exchanger 2 via a pipe. The bottom outlet of the reactor 1 is connected in parallel to the circulating pump 5 and the circulating standby pump 6 via a pipe. The tops of the circulating pump 5 and the circulating standby pump 6 are connected to the bottom of the heat exchanger 2 via pipes. The bottoms of the circulating pump 5 and the circulating standby pump 6 are connected to the raw material metering tank 3 and the raw material pump 4 via pipes. The top of the raw material pump 4 is connected to the top of the raw material metering tank 3 via a pipe, and the bottom of the raw material pump 4 is connected to the bottom of the raw material metering tank 3 via a pipe.

[0049] Example 2, a pyrrolidine compound polyoxyethylene ether composition of this example, is prepared from the following components in parts by weight:

[0050] 20 parts low-polymerization-number pyrrolidine polyoxyethylene ether, 20 parts high-polymerization-number pyrrolidine polyoxyethylene ether, 10 parts sodium pyrrolidine polyoxyethylene ether sulfate, and 5 parts sodium pyrrolidine polyoxyethylene ether carboxylate.

[0051] The low-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 9; the high-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 16.

[0052] The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to this embodiment includes the following steps:

[0053] S1. Add 1150g of N-hydroxyethylpyrrolidine and 5g of sodium hydroxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 40°C and add 3610g of ethylene oxide dropwise over 1 hour. Then heat the reactor to 140°C and continue the reaction until the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid, and filter to obtain low-polymerization-number pyrrolidine polyoxyethylene ether.

[0054] S2. Add 1150g of N-hydroxyethylpyrrolidine and 20g of sodium hydroxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 40°C and add 6690g of ethylene oxide dropwise over 1 hour. Then heat the reactor to 140°C and continue the reaction 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.

[0055] S3. Take 300g of the pyrrolidine polyoxyethylene ether obtained in step S1 and add it to the sulfonation reactor. Heat the reactor to 70°C, add 100g of sulfur trioxide and react for 10s. Add 10wt% sodium hydroxide solution to neutralize to pH 8, heat the reactor to 80°C and hydrolyze for 2h. Distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate.

[0056] S4. Take 190g of the pyrrolidine polyoxyethylene ether obtained in step S1, add 200g of ethanol to dilute it, then add 1g of sodium hydroxide and 60g of sodium chloroacetate, react at 50℃ for 3h, raise the temperature to 80℃, remove the solvent, and obtain sodium pyrrolidine polyoxyethylene ether carboxylate.

[0057] S5. Weigh the appropriate amounts of the pyrrolidine polyoxyethylene ether 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, mix them, and stir at 50°C for 20 minutes to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0058] The preparation method of N-hydroxyethylpyrrolidine in this embodiment includes the following steps:

[0059] S11. Add 3.3g of sodium hydroxide into reactor 1, replace the air in the reactor with nitrogen, and then evacuate to -0.098MPa using a vacuum system.

[0060] S12. Add 1020g of tetrahydropyrrole to the reactor. Heat exchanger 2 heats the reactor to 40°C. Add 630g of ethylene oxide dropwise over 1 hour while maintaining the reactor temperature at 40°C and the pressure at 0.3MPa. Heat the reactor to 70°C and continue reacting until the pressure in the reactor no longer decreases. Take a sample to analyze the residual ethylene oxide content in the reactor until it is less than 0.1%. Filter the sample through a raw material pump and flow it out to the raw material metering tank to obtain a mixture containing N-hydroxyethylpyrrole.

[0061] S13. Distill the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide. The distillation pressure is -0.09 MPa. Collect the fraction at 75°C to obtain N-hydroxyethylpyrrolidine.

[0062] Example 3, see Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition of this embodiment is prepared from the following components in parts by weight:

[0063] 25 parts of low-polymerization-number pyrrolidine polyoxyethylene ether, 25 parts of high-polymerization-number pyrrolidine polyoxyethylene ether, 15 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 5 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

[0064] The low-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 7; the high-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 17.

[0065] The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to this embodiment includes the following steps:

[0066] S1. Add 1150g of N-hydroxyethylpyrrolidine and 5g of potassium hydroxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 45°C and add 2720g of ethylene oxide dropwise over 1 hour. Then heat the reactor to 145°C and continue the reaction until the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid, and filter to obtain low-polymerization-number pyrrolidine polyoxyethylene ether.

[0067] S2. Add 1150g of N-hydroxyethylpyrrolidine and 5g of potassium hydroxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 45°C and add 7130g of ethylene oxide dropwise over 1 hour. Then heat the reactor to 145°C and continue the reaction 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.

[0068] S3. Take 300g of the pyrrolidine polyoxyethylene ether obtained in step S1 and add it to the sulfonation reactor. Heat the reactor to 75°C, add 110g of sulfur trioxide and react for 7s. Add 10wt% sodium hydroxide solution to neutralize to pH 8.5. Heat the reactor to 90°C and hydrolyze for 1h. Distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate.

[0069] S4. Take 190g of the pyrrolidine polyoxyethylene ether obtained in step S1, dilute it with 300g of ethanol, then add 1g of sodium hydroxide and 55g of sodium chloroacetate, react at 55℃ for 3h, raise the temperature to 80℃, remove the solvent, and obtain sodium pyrrolidine polyoxyethylene ether carboxylate.

[0070] S5. Weigh the appropriate amounts of the pyrrolidine polyoxyethylene ether 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, mix them, and stir at 35°C for 25 minutes to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0071] The preparation method of N-hydroxyethylpyrrolidine in this embodiment includes the following steps:

[0072] S11. Add 3.3g of potassium hydroxide into reactor 1, replace the air in the reactor with nitrogen, and then evacuate to -0.098MPa using a vacuum system.

[0073] S12. Add 1020g of tetrahydropyrrole to the reactor. Heat exchanger 2 heats the reactor to 50°C. Add 630g of ethylene oxide dropwise over 1.5 hours while maintaining the reactor temperature at 75°C and the pressure at 0.2MPa. Heat the reactor to 70°C and continue reacting until the pressure in the reactor no longer decreases. Take a sample to analyze the residual ethylene oxide in the reactor material until it is less than 0.1%. Filter the material through a raw material pump and flow it out to the raw material metering tank to obtain a mixture containing N-hydroxyethylpyrrole.

[0074] S13. Distill the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide. The distillation pressure is -0.09 MPa. Collect the fraction at 78°C to obtain N-hydroxyethylpyrrolidine.

[0075] Example 4, see Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition of this embodiment is prepared from the following components in parts by weight:

[0076] 30 parts of low-polymerization-number pyrrolidine polyoxyethylene ether, 30 parts of high-polymerization-number pyrrolidine polyoxyethylene ether, 20 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 5 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

[0077] The low-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 8; the high-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 18.

[0078] The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to this embodiment includes the following steps:

[0079] S1. Add 1150g of N-hydroxyethylpyrrolidine and 10g of sodium methoxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 50°C and add 3080g of ethylene oxide dropwise over 1.5 hours. Then heat the reactor to 160°C and continue the reaction until the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid, and filter to obtain low-polymerization-number pyrrolidine polyoxyethylene ether.

[0080] S2. Add 1150g of N-hydroxyethylpyrrolidine and 10g of sodium methoxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 50°C and add 7480g of ethylene oxide dropwise over 2 hours. Then heat the reactor to 160°C and continue the reaction 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.

[0081] S3. Take 300g of the pyrrolidine polyoxyethylene ether obtained in step S1 and add it to the sulfonation reactor. Heat the reactor to 70°C, add sulfur trioxide and react for 5s. Add 15wt% sodium hydroxide solution to neutralize to pH 8.5. Heat the reactor to 90°C and hydrolyze for 1h. Distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate.

[0082] S4. Take 190g of the pyrrolidine polyoxyethylene ether obtained in step S1, dilute it with 400g of ethanol, then add 1.4g of sodium hydroxide and 65g of sodium chloroacetate, react at 55℃ for 3h, raise the temperature to 85℃, remove the solvent, and obtain sodium pyrrolidine polyoxyethylene ether carboxylate.

[0083] S5. Weigh the appropriate amounts of the pyrrolidine polyoxyethylene ether 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, mix them, and stir at 30°C for 20 minutes to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0084] The preparation method of N-hydroxyethylpyrrolidine in this embodiment includes the following steps:

[0085] S11. Add 4.6g of boron trichloride into reactor 1, replace the air in the reactor with nitrogen, and then evacuate to -0.05MPa using a vacuum system.

[0086] S12. Add 1020g of tetrahydropyrrole to the reactor. Heat exchanger 2 heats the reactor to 50°C. Add 630g of ethylene oxide dropwise over 2 hours while maintaining the reactor temperature at 70°C and the pressure at 0.4MPa. Heat the reactor to 80°C and continue reacting until the pressure in the reactor no longer decreases. Take a sample to analyze the residual ethylene oxide content in the reactor until it is less than 0.1%. Filter the sample through a raw material pump and flow it out to the raw material metering tank to obtain a mixture containing N-hydroxyethylpyrrole.

[0087] S13. Distill the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide. The distillation pressure is -0.09 MPa. Collect the fraction at 80°C to obtain N-hydroxyethylpyrrolidine.

[0088] Example 5, see Figure 1 As shown, a pyrrolidine compound polyoxyethylene ether composition of this embodiment is prepared from the following components in parts by weight:

[0089] 40 parts of low-polymerization-number pyrrolidine polyoxyethylene ether, 40 parts of high-polymerization-number pyrrolidine polyoxyethylene ether, 20 parts of sodium pyrrolidine polyoxyethylene ether sulfate, and 10 parts of sodium pyrrolidine polyoxyethylene ether carboxylate.

[0090] The low-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 9; the high-polymerization-number pyrrolidine polyoxyethylene ether has a polyoxyethylene number of 19.

[0091] The preparation method of a pyrrolidine compound polyoxyethylene ether composition according to this embodiment includes the following steps:

[0092] S1. Add 1150g of N-hydroxyethylpyrrolidine and 5g of potassium methoxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 50°C and add 3520g of ethylene oxide dropwise over 1 hour. Then heat the reactor to 150°C and continue the reaction until the pressure in the reactor no longer decreases. Distill to remove impurities, neutralize with acetic acid, and filter to obtain low-polymerization-number pyrrolidine polyoxyethylene ether.

[0093] S2. Add 1150g of N-hydroxyethylpyrrolidine and 5g of potassium methoxide to the reactor. After purging the reactor with nitrogen to replace the air, heat the reactor to 50°C and add 7920g of ethylene oxide dropwise over 2 hours. Then heat the reactor to 150°C and continue the reaction 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.

[0094] S3. Take 300g of the pyrrolidine polyoxyethylene ether obtained in step S1 and add it to the sulfonation reactor. Heat the reactor to 80°C, add 120g of sulfur trioxide and react for 10s. Add 20wt% sodium hydroxide solution to neutralize to pH 9, heat the reactor to 90°C and hydrolyze for 2h. Distill to remove impurities to obtain sodium pyrrolidine polyoxyethylene ether sulfate.

[0095] S4. Take 190g of the pyrrolidine polyoxyethylene ether obtained in step S1, dilute it with 500g of ethanol, then add 1.4g of sodium hydroxide and 70g of sodium chloroacetate, react at 60℃ for 3h, raise the temperature to 90℃, remove the solvent, and obtain sodium pyrrolidine polyoxyethylene ether carboxylate.

[0096] S5. Weigh the appropriate amounts of the pyrrolidine polyoxyethylene ether 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, mix them, and stir at 35°C for 30 minutes to obtain a pyrrolidine compound polyoxyethylene ether composition.

[0097] The preparation method of N-hydroxyethylpyrrolidine in this embodiment includes the following steps:

[0098] S11. Add 5g of aluminum chloride to reactor 1, replace the air in the reactor with nitrogen, and then evacuate to -0.07MPa using a vacuum system.

[0099] S12. Add 1020g of tetrahydropyrrole to the reactor. Heat exchanger 2 heats the reactor to 50°C. Add 630g of ethylene oxide dropwise over 2 hours while maintaining the reactor temperature at 80°C and the pressure at 0.4MPa. Heat the reactor to 70°C and continue reacting until the pressure in the reactor no longer decreases. Take a sample to analyze the residual ethylene oxide in the reactor material until it is less than 0.1%. Filter the material through a raw material pump and flow it out to the raw material metering tank to obtain a mixture containing N-hydroxyethylpyrrole.

[0100] S13. Distill the mixture containing N-hydroxyethylpyrrolidine to remove ethylene oxide. The distillation pressure is -0.09 MPa. Collect the fraction at 79°C to obtain N-hydroxyethylpyrrolidine.

[0101] Comparative Example 1 differs from Example 1 in that the two different pyrrolidine polyoxyethylene ethers are replaced with pyrrolidine polyoxyethylene ethers with a polyoxyethylene number of 25.

[0102] Comparative Example 2 differs from Example 1 in that N-hydroxyethylpyrrolidine is replaced with dodecyl alcohol.

[0103] Comparative Example 3 differs from Example 1 in that the amount of sodium pyrrolidine polyoxyethylene ether carboxylate is replaced with 30 parts.

[0104] Performance testing

[0105] Surface tension

[0106] The pyrrolidine compound polyoxyethylene ether compositions prepared in each example and comparative example were added to deionized water to prepare a 1 g / L aqueous solution, and the static surface tension was measured using a surface tension meter.

[0107] Wetting properties

[0108] The wetting time of the cotton fabrics in each example and comparative example was tested according to the method specified in GB / T 11983-2008 "Determination of Wetting Power of Surfactants - Submersion Method".

[0109] Emulsifying properties

[0110] The pyrrolidine compound polyoxyethylene ether compositions prepared in each example and comparative example were added to deionized water to prepare a 1 g / L aqueous solution. 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 separated from the emulsion, the time was recorded, which is the emulsification time.

[0111] Electrolyte resistance

[0112] The pyrrolidine compound polyoxyethylene ether compositions prepared in each example and comparative example were added to deionized water to prepare a 10 g / L aqueous solution. 5 mL of each aqueous solution was placed in an environment of 40°C. Calcium chloride solid was added every 12 h, and the solution was shaken and mixed. After 12 h, it was observed whether the solution became turbid or oily. The mass of calcium chloride solid added was recorded.

[0113] The test results are shown in Table 1 below:

[0114] Table 1

[0115]

[0116] As shown in Table 1, the static surface tension of the pyrrolidine compound polyoxyethylene ether compositions prepared in Examples 2-5 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 an alkyl straight chain, which has weaker lipophilic ability than pyrrolidine. Therefore, its static surface tension is only 24.9 mN / m, and the wetting time is 34 s. This indicates that the pyrrolidine compound polyoxyethylene ether compositions prepared in this invention have excellent hydrophobic-hydrophilic properties. The emulsification time of the pyrrolidine compound polyoxyethylene ether compositions prepared in Examples 2-5 was between 132 and 135 min, indicating that the pyrrolidine compound polyoxyethylene ether compositions prepared in this invention have excellent emulsification properties. When the aqueous solution of the pyrrolidine compound polyoxyethylene ether compositions prepared in Examples 2-5 showed turbidity or oil floating, the mass of added calcium chloride solid was between 8.2 and 8.4 g, indicating that the pyrrolidine compound polyoxyethylene ether compositions prepared in this invention have excellent hard water resistance.

[0117] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0118] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A pyrrolidine compound polyoxyethylene ether composition characterized by, Prepared from the following ingredients by weight: 20~40 parts of low polymerization number pyrrolidine polyoxyethylene ether, 20~40 parts of high polymerization number pyrrolidine polyoxyethylene ether, 10~20 parts of pyrrolidine polyoxyethylene ether sodium sulfate and 5~10 parts of pyrrolidine polyoxyethylene ether carboxylic acid sodium; The pyrrolidine polyoxyethylene ether is prepared after preparing N-hydroxyethyl pyrrolidine, and then synthesizing N-hydroxyethyl pyrrolidine and ethylene oxide; The polyoxyethylene number of the low polymerization number pyrrolidine polyoxyethylene ether is 6~10; and the polyoxyethylene number of the high polymerization number pyrrolidine polyoxyethylene ether is 16~19.

2. A method for producing a pyrrolidine compound polyoxyethylene ether composition, characterized by comprising: Comprising the following steps: S1, adding N-hydroxyethyl pyrrolidine and a catalyst into a reactor, replacing the air in the reactor with nitrogen, heating to 40~50℃, adding ethylene oxide dropwise, dropwise for 1~2h, heating to 140~160℃ for reaction, detecting that the pressure in the reactor no longer decreases, distilling impurities, neutralizing with acetic acid and filtering to obtain low polymerization number pyrrolidine polyoxyethylene ether; S2, adding N-hydroxyethyl pyrrolidine and a catalyst into a reactor, replacing the air in the reactor with nitrogen, heating to 40~50℃, adding ethylene oxide dropwise, dropwise for 1~2h, heating to 140~160℃ for reaction, detecting that the pressure in the reactor no longer decreases, distilling impurities, neutralizing with acetic acid and filtering to obtain high polymerization number pyrrolidine polyoxyethylene ether; S3, adding the pyrrolidine polyoxyethylene ether prepared in step S1 into a sulfonation reactor, heating to 70~80℃, adding sulfur trioxide for 5~10s, neutralizing with sodium hydroxide solution to pH 8~9, heating to 80~90℃ for hydrolysis for 1~2h, distilling impurities to obtain pyrrolidine polyoxyethylene ether sodium sulfate; S4, adding the pyrrolidine polyoxyethylene ether prepared in step S1 into ethanol for dilution, then adding sodium hydroxide and sodium chloroacetate, reacting at 50~60℃ for 3~4h, heating to 80~90℃ to remove the solvent to obtain pyrrolidine polyoxyethylene ether carboxylic acid sodium; S5, mixing the pyrrolidine polyoxyethylene ethers prepared in steps S1 and S2, the pyrrolidine polyoxyethylene ether sodium sulfate prepared in step S3 and the pyrrolidine polyoxyethylene ether carboxylic acid sodium prepared in step S4 in corresponding proportions, stirring at 30~50℃ for 20~40min to obtain a pyrrolidine compound polyoxyethylene ether composition; The molar ratio of N-hydroxyethyl pyrrolidine to ethylene oxide in S1 is 1:5.2~8.2; and the molar ratio of N-hydroxyethyl pyrrolidine to ethylene oxide in S2 is 1:15.2~19.

2.

3. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 2, characterized in that, The catalysts in S1 and S2 are 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-hydroxyethyl pyrrolidine.

4. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 2, characterized in that, The mass ratio of pyrrolidine polyoxyethylene ether to sulfur trioxide in S3 is 3:1~1.2, and the concentration of sodium hydroxide solution is 10~20wt%.

5. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 2, characterized in that, The mass ratio of pyrrolidine polyoxyethylene ether to ethanol in S4 is 1:1~3, and the molar ratio of pyrrolidine polyoxyethylene ether, sodium hydroxide and sodium chloroacetate is 1:0.05~0.07:0.9~1.

2.

6. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 2, characterized in that, The preparation method of the N-hydroxyethyl pyrrolidine in S1 comprises the following steps: S11, a catalyst is put into a reactor, and after nitrogen is used to replace the air in the reactor, a vacuum system is used to draw a vacuum to-0.1~ -0.04 MPa; S12, tetrahydropyrrole is added into the reactor, a heat exchanger is used to heat the reactor to 40~50℃, ethylene oxide is added dropwise, the dropping is completed in 1~2h, and the temperature in the reactor is kept at 40~80℃, the pressure is kept at 0~0.4 MPa, the reactor is heated to 70~80℃ for reaction, and when it is detected that the pressure in the reactor no longer decreases, sampling is performed to detect and analyze the residual amount of ethylene oxide in the material in the reactor to be less than 0.1%, a raw material pump is used to pressurize and filter to flow out to a raw material metering tank to obtain a mixture containing N-hydroxyethyl pyrrolidine; S13, the mixture containing N-hydroxyethyl pyrrolidine is refined to remove ethylene oxide to obtain N-hydroxyethyl pyrrolidine.

7. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 6, characterized in that, The catalyst in S11 is one or more combinations of a Lewis acid, an alkali metal hydroxide and an alkali metal alcoholate, the Lewis acid is one or more combinations of boron trifluoride, boron trichloride and aluminum chloride.

8. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 7, characterized in that, The alkali metal hydroxide is one or both of sodium hydroxide and potassium hydroxide, and the alkali metal alcoholate is one or both of potassium methoxide and sodium methoxide.

9. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 6, characterized in that, In S12, the molar ratio of tetrahydropyrrole 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 tetrahydropyrrole.

10. The method for preparing a pyrrolidine compound polyoxyethylene ether composition according to claim 6, characterized in that, In S13, the refining process is performed by using vacuum distillation or rectification.

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