Preparation method of gas-liquid separation membrane and its application in purge gas reactor

Abstract

The invention discloses a method for preparing a gas-liquid separation membrane and its application in a purge gas reactor; It belongs to the field of gas-liquid separation membrane technology; It includes the steps of: placing a resin matrix, a cross-linking agent, a chemical auxiliary agent and a solvent in a container, stirring and mixing uniformly, obtaining a resin composition, then coating the resin composition on a release film, peeling off, and obtaining a gas-liquid separation membrane; Wherein, the resin matrix is ​​at least one of polyethersulfone, polydimethylsiloxane, polyetherimide, polyvinylidene fluoride, polyacrylic resin, epoxy resin, and modified polyurethane resin; Modified polyurethane is prepared by 2-hydroxypropionate-modified polyurethane resin. The gas-liquid separation membrane prepared by the present invention has higher resistance to hydraulic pressure and air permeability and excellent water resistance, wear resistance and mechanical properties, and can be preferably applied to a purge gas reactor.

Description

Technical Field

[0001] The present invention belongs to the technical field of gas-liquid separation membranes, and in particular relates to a preparation method of a gas-liquid separation membrane and application of the membrane in a purge gas reactor. Background Art

[0002] Gas-liquid membrane separation is a novel membrane separation technology. Domestic research has explored the migration patterns of gaseous membranes. Gas-liquid separation membrane devices hold broad application prospects in environmental treatment of waste gas and wastewater, as well as in chemical separations. Currently, gas-liquid separation membranes are typically made of polytetrafluoroethylene (PTEF) microporous membranes, which are difficult and expensive to manufacture. Furthermore, the production of PTEF microporous membranes presents challenges in quantitatively controlling the stretching process, permeability, and pressure resistance. Furthermore, the manufacturing process is complex and costly. Silicone rubber (primarily composed of polydimethylsiloxane) is also a gas-liquid separation membrane material. Its excellent chemical properties, such as the helical structure of the Si-O chains, result in low inter-chain interactions, a large molar volume, and low surface tension. These properties facilitate mass transfer of gas components within the membrane, giving polydimethylsiloxane its strong permeability.

[0003] Existing technologies, such as publication number CN 106433100A, disclose a gas-liquid separation membrane, a gas-liquid separation membrane support material composite, and applications thereof; the raw material formula includes a resin base material, a cross-linking agent, a breathable additive, and a diluent; the gas-liquid separation membrane has high hydraulic pressure resistance and air permeability performance, and the prepared gas-liquid separation membrane support material composite is used in the field of resin infusion curing molding to manufacture composite material components, which can well ensure the quality of the cured finished product. Summary of the Invention

[0004] The purpose of the present invention is to provide a modified polyurethane with excellent heat resistance and high hardness, which is used as a component of a gas-liquid separation membrane to improve the hydraulic pressure resistance and air permeability, water resistance, wear resistance and mechanical properties of the gas-liquid separation membrane, and can be better used in a purge gas reactor.

[0005] The technical solutions adopted by the present invention to achieve the above-mentioned purpose are:

[0006] A gas-liquid separation membrane comprising an organic polymer resin;

[0007] The air permeability rate under the conditions of temperature of 23±2℃, liquid of isopropyl alcohol and pressure of 1atm is higher than 16×1000mL / Min·M 2 , hydraulic pressure resistance higher than 88.5kPa.

[0008] Preferably, in some embodiments of the present invention, a gas-liquid separation membrane comprises at least a resin matrix; the resin matrix is ​​at least one of polyethersulfone, polydimethylsiloxane, polyetherimide, polyvinylidene fluoride, polyacrylic resin, epoxy resin, and modified polyurethane resin;

[0009] The modified polyurethane resin is prepared from 2-hydroxypropionate-modified polyurethane resin. The modified polyurethane resin prepared by the present invention using 2-hydroxypropionate-modified polyurethane resin has excellent heat resistance and high hardness, and is superior to the heat resistance and mechanical properties of commercially available polyurethane resins.

[0010] Preferably, in some embodiments of the present invention, the gas-liquid separation membrane further comprises a cross-linking agent, a chemical additive, and a solvent. The present invention utilizes allyl 2-hydroxypropionate to modify a polyurethane resin to produce a modified polyurethane, which is used as a component of the gas-liquid separation membrane. This improves the membrane's resistance to hydraulic pressure and air permeability, thereby achieving a superior gas-liquid separation effect. Furthermore, the gas-liquid separation membrane exhibits excellent water resistance, wear resistance, and high mechanical properties.

[0011] More preferably, in some embodiments of the present invention, the cross-linking agent is at least one of p-phenylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, and 1,4-cyclohexyl diisocyanate.

[0012] More preferably, in some embodiments of the present invention, the chemical auxiliary agent is at least one of calcium carbonate, diatomaceous earth, kaolin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and starch.

[0013] More preferably, in some embodiments of the present invention, the solvent is at least one of dichloromethane, tetrahydrofuran, acetone, ethyl acetate, and dimethylformamide.

[0014] More preferably, in some embodiments of the present invention, the preparation method of the modified polyurethane is as follows: polyester polyol is placed in a container, isophorone diisocyanate and a catalyst are added, the temperature is raised to 75-90°C and the reaction is carried out for 1-3 hours, then allyl 2-hydroxypropionate is added, and the mixture is cooled to obtain a polyurethane prepolymer, isophorone diisocyanate and ethyl acetate are added, the chain is extended at 30-45°C, and dibutylamine as a molecular weight regulator is added at the same time, and the reaction is carried out for 3-5 hours to obtain a modified polyurethane resin.

[0015] Preferably, in one embodiment of the present invention, the gas-liquid separation membrane has a gas permeability of higher than 18×1000 mL / Min·M under the conditions of a temperature of 23±2°C, a liquid of isopropyl alcohol, and a pressure of 1 atm. 2 , hydraulic pressure resistance higher than 92kPa.

[0016] The present invention also discloses a use of a gas-liquid separation membrane in a purge gas reactor. Since the gas-liquid separation membrane prepared by the present invention has high hydraulic pressure resistance and air permeability, it can be used in a purge gas reactor to achieve a better gas-liquid separation effect.

[0017] Another object of the present invention is to provide a method for preparing a gas-liquid separation membrane.

[0018] The technical solutions adopted by the present invention to achieve the above-mentioned purpose are:

[0019] A method for preparing a gas-liquid separation membrane comprises the following steps:

[0020] The resin matrix, cross-linking agent, chemical auxiliary agent and solvent are placed in a container, stirred and mixed evenly to obtain a resin composition, and then the resin composition is coated on a release film and peeled off to obtain a gas-liquid separation membrane.

[0021] Preferably, in some embodiments of the present invention, by weight, the resin matrix is ​​55-75 parts, the cross-linking agent is 3-8 parts, the chemical auxiliary agent is 5-12 parts, and the solvent is 4-9 parts.

[0022] The beneficial effects of the present invention compared to the prior art are as follows:

[0023] (1) A modified polyurethane resin is prepared by modifying polyurethane resin with allyl 2-hydroxypropionate, which has excellent heat resistance and high hardness, and is superior to the heat resistance and mechanical properties of commercially available polyurethane resins;

[0024] (2) A modified polyurethane resin is prepared by modifying polyurethane resin with 2-hydroxypropionate, and used as a component of a gas-liquid separation membrane, thereby improving the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane, thereby achieving a better gas-liquid separation effect; at the same time, the gas-liquid separation membrane has excellent water resistance, wear resistance and high mechanical properties.

[0025] Therefore, the present invention is a modified polyurethane resin with excellent heat resistance and high hardness. It is used as a component of the gas-liquid separation membrane to improve the hydraulic pressure resistance and air permeability, water resistance, wear resistance and mechanical properties of the gas-liquid separation membrane, and can be well applied to the purge gas reactor. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the infrared spectrum of the modified polyurethane in Example 1;

[0027] Figure 2 The hydraulic pressure resistance and air permeability of the gas-liquid separation membrane;

[0028] Figure 3 is the weight gain rate of the gas-liquid separation membrane;

[0029] Figure 4 is the wear rate of the gas-liquid separation membrane;

[0030] Figure 5 Tensile strength of gas-liquid separation membrane at 25℃ and 80℃ respectively. DETAILED DESCRIPTION

[0031] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those skilled in the art and are not intended to limit the present invention in any way.

[0032] According to the gas-liquid separation membrane of the present invention, the modified polyurethane in the resin matrix and the preparation method of the modified polyurethane, the addition amount of 2-hydroxypropionate is 4-10wt% of the polyester polyol; specifically preferably 4wt%, 6wt%, 8wt%, and 10wt%.

[0033] In the preparation method of the modified polyurethane of the present invention, the addition amount of isophorone diisocyanate is 15-25wt% of the polyester polyol; specifically preferably 15wt%, 18wt%, 20wt%, 23wt% and 25wt%.

[0034] In the preparation method of the modified polyurethane of the present invention, the added amount of the catalyst is 0.15-0.35wt% of the polyester polyol.

[0035] In the preparation method of the modified polyurethane of the present invention, the added amount of ethyl acetate is 3-6wt% of the polyurethane prepolymer.

[0036] In the preparation method of the modified polyurethane of the present invention, the addition amount of the molecular weight regulator dibutylamine is 2.5-7.5wt% of the polyurethane prepolymer, and specifically preferably 2.5wt%, 3.5wt%, 4.5wt%, 5.5wt%, 6.5wt% and 7.5wt%.

[0037] The method for preparing a gas-liquid separation membrane according to the present invention comprises the following steps:

[0038] 55-75 parts by weight of a resin matrix, 3-8 parts by weight of a cross-linking agent, 5-12 parts by weight of a chemical additive and 4-9 parts by weight of a solvent are placed in a stirrer, stirred at a stirring rate of 500-1000 r / min for 30-60 minutes, and then stirred at a stirring rate of 150-300 r / min for 1-2 hours to obtain a resin composition, and then the resin composition is coated on a release film with a thickness of 20-40 μm, and then dried at 120-180°C for 15-25 minutes, and the cured film is peeled off from the release film to obtain a gas-liquid separation membrane.

[0039] The present invention adds 1-3 parts by weight of pentaerythritol triacrylate to a resin composition for preparing a gas-liquid separation membrane. Pentaerythritol triacrylate interacts with a resin matrix, a crosslinking agent, and chemical additives in the resin composition to form a network structure through crosslinking, thereby obtaining a gas-liquid separation membrane. Due to the addition of a specific proportion of pentaerythritol triacrylate, the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane are further improved to achieve a better gas-liquid separation effect. At the same time, the gas-liquid separation membrane has better wear resistance, water resistance, and heat resistance.

[0040] The experimental methods in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are commercially available unless otherwise specified.

[0041] Example 1:

[0042] A method for preparing a modified polyurethane resin comprises the following steps: placing 85 parts by weight of poly(neopentyl adipate glycol) polyester polyol in a flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet and outlet device, adding 15 parts by weight of isophorone diisocyanate and 0.22 parts by weight of dibutyltin dilaurate, heating the mixture to 85°C for reaction for 2 hours, adding 6.8 parts by weight of allyl 2-hydroxypropionate, cooling the mixture to obtain a polyurethane prepolymer, adding 4.25 parts by weight of isophorone diisocyanate and 3.8 parts by weight of ethyl acetate, chain extension at 35°C, and simultaneously adding a molecular weight regulator, dibutylamine, reacting the mixture for 4 hours, and removing the solvent under vacuum to obtain the modified polyurethane resin.

[0043] Example 2:

[0044] A method for preparing a modified polyurethane resin is disclosed, which differs from Example 1 in that: 85 parts by weight of poly(neopentyl adipate glycol) polyester polyol are placed in a flask equipped with a stirrer, a condenser, a thermometer, and a gas inlet and outlet device; 17 parts by weight of isophorone diisocyanate and 0.26 parts by weight of dibutyltin dilaurate are added; the temperature is raised to 85° C. and reacted for 2 hours; 8.5 parts by weight of allyl 2-hydroxypropionate are then added and cooled to obtain a polyurethane prepolymer; 4.25 parts by weight of isophorone diisocyanate and 3.8 parts by weight of ethyl acetate are added and chain extension is carried out at 35° C.; 3 parts by weight of dibutylamine as a molecular weight regulator are simultaneously added and reacted for 4 hours; and the solvent is removed by vacuum to obtain a modified polyurethane resin.

[0045] Example 3:

[0046] A method for preparing a gas-liquid separation membrane comprises the following steps:

[0047] 60 parts by weight of the modified polyurethane in Example 1, 5 parts by weight of trimethyl hexamethylene diisocyanate, 8 parts by weight of hydroxyethyl cellulose and 8 parts by weight of acetone were placed in a stirrer and stirred at a stirring rate of 800 r / min for 45 minutes, and then stirred at a stirring rate of 250 r / min for 1 hour to obtain a resin composition. The resin composition was then coated on a release film with a thickness of 40 μm, and then dried at 160°C for 15 minutes. The cured film was peeled off from the release film to obtain a gas-liquid separation membrane.

[0048] Example 4:

[0049] A method for preparing a gas-liquid separation membrane, which is different from Example 3 in that the modified polyurethane in Example 1 is replaced by the modified polyurethane in Example 2.

[0050] Example 5:

[0051] A method for preparing a gas-liquid separation membrane, which is different from Example 3: 60 parts by weight of the modified polyurethane in Example 1, 5 parts by weight of diphenylmethane diisocyanate, 8 parts by weight of diatomaceous earth and 8 parts by weight of ethyl acetate are placed in a mixer, stirred at a stirring rate of 800 r / min for 45 minutes, and then stirred at a stirring rate of 250 r / min for 1 hour to obtain a resin composition, and then the resin composition is coated on a release film with a thickness of 40 μm, and then dried at 160°C for 15 minutes, and the cured film is peeled off from the release film to obtain a gas-liquid separation membrane.

[0052] Example 6:

[0053] A method for preparing a gas-liquid separation membrane, which is different from Example 3 in that: 60 parts by weight of the modified polyurethane in Example 1, 5 parts by weight of trimethyl hexamethylene diisocyanate, 8 parts by weight of hydroxyethyl cellulose, 1.5 parts by weight of pentaerythritol triacrylate and 8 parts by weight of acetone are placed in a mixer, stirred at a stirring rate of 800 r / min for 45 minutes, and then stirred at a stirring rate of 250 r / min for 1 hour to obtain a resin composition, and then the resin composition is coated on a release film with a thickness of 40 μm, and then dried at 160°C for 15 minutes, and the cured film is peeled off from the release film to obtain a gas-liquid separation membrane.

[0054] Example 7:

[0055] A method for preparing a gas-liquid separation membrane, which is different from Example 6 in that: the amount of pentaerythritol triacrylate added is 1 part by weight.

[0056] Example 8:

[0057] A method for preparing a gas-liquid separation membrane, which is different from Example 6 in that: the amount of pentaerythritol triacrylate added is 3 parts by weight.

[0058] Example 9:

[0059] A method for preparing a gas-liquid separation membrane, which is different from Example 6 in that: the amount of pentaerythritol triacrylate added is 0.5 parts by weight.

[0060] Example 10:

[0061] A method for preparing a gas-liquid separation membrane, which is different from Example 6 in that: the amount of pentaerythritol triacrylate added is 3.5 parts by weight.

[0062] Example 11:

[0063] A method for preparing a gas-liquid separation membrane is different from that of Example 6 in that the modified polyurethane in Example 1 is replaced by a polyurethane resin (CAS No. 9009-54-5).

[0064] Comparative Example 1:

[0065] A method for preparing a gas-liquid separation membrane is different from that of Example 3 in that the modified polyurethane in Example 1 is replaced by a polyurethane resin (CAS No. 9009-54-5).

[0066] Performance test characterization:

[0067] 1. Infrared spectroscopy

[0068] The infrared structure of the modified polyurethane was determined using an infrared spectrometer FTIR-100 with a scanning range of 500-4000 cm -1 .

[0069] Figure 1 is the infrared spectrum of the modified polyurethane in Example 1; Figure 1 It can be seen that at 1710cm -1 The characteristic absorption peaks appearing around 1670 cm are the stretching vibrations of C=O in allyl 2-hydroxypropionate; -1 The characteristic absorption peaks appearing around 1625cm are the stretching vibrations of C=C in allyl 2-hydroxypropionate; -1 The characteristic absorption peaks appearing around 1550cm are the stretching vibrations of C=O in the amide bond; -1 The characteristic absorption peaks appearing on the left and right are the bending vibration absorption peaks of NH in the amide bond; therefore, modified polyurethane was successfully prepared by using 2-hydroxypropionate to modify the polyurethane resin.

[0070] 2. Modified polyurethane performance determination

[0071] The modified polyurethane prepared in Example 1 and Example 2 and a commercially available polyurethane resin emulsion (CAS No. 9009-54-5) were poured onto a polytetrafluoroethylene plate and dried at room temperature. The dried film was then placed in a vacuum oven and dried at 50°C to constant weight, and then sealed for later use.

[0072] (1) Heat resistance test

[0073] The test was performed using a thermogravimetric analyzer (Pyris-1) under a nitrogen atmosphere at a test temperature of 25-800° C., a heating rate of 20° C. / min, and a sample weight of 15 mg.

[0074] Table 1 Initial decomposition temperature of modified polyurethane

[0075] Sample Initial decomposition temperature polyurethane 262 Example 1 293 Example 2 297

[0076] As can be seen from Table 1, the initial decomposition temperature of the modified polyurethanes in Examples 1 and 2 is higher than 290° C., which is higher than the initial decomposition temperature of commercially available polyurethanes. This indicates that the modified polyurethane resin prepared by modifying the polyurethane resin with allyl 2-hydroxypropionate has excellent heat resistance.

[0077] (2) Hardness measurement

[0078] Shore A hardness was tested according to GB / T531-2008. The prepared film was cut into pieces measuring 25mm x 10mm, with a thickness of 8mm. Using an LX-A Shore hardness tester, the film was quickly pressed onto the presser foot, keeping the presser foot parallel to the film surface and the indenter perpendicular to the film surface. Test temperatures were set at 25°C, 80°C, and 100°C, with three parallel tests performed and the average value calculated.

[0079] Table 2 Hardness of modified polyurethane

[0080]

[0081] As can be seen from Table 2, at 25°C, the hardness of the modified polyurethanes in Examples 1 and 2 is higher than 68 Shore A, which is higher than the hardness of commercially available polyurethanes. This indicates that the use of 2-hydroxypropionate-modified polyurethane resin to prepare a modified polyurethane resin improves the hardness of the modified polyurethane, giving it excellent mechanical properties. With increasing temperature, the hardness of the modified polyurethane and the commercially available polyurethane decreases to a certain extent. When the temperature is raised to 100°C, the hardness reduction rate of the modified polyurethanes in Examples 1 and 2 is less than 19%, which is much lower than that of the commercially available polyurethane. This once again verifies that the use of 2-hydroxypropionate-modified polyurethane resin to prepare a modified polyurethane with excellent heat resistance can be used.

[0082] 3. Gas-liquid separation membrane performance measurement

[0083] (1) Hydraulic pressure resistance and air permeability measurement

[0084] Using carbon monoxide as the fluid medium, install the gas-liquid separation membrane for testing. Open the compressed air pressure regulating valve, adjust the pressure gauge, and read the air flow reading on the flow meter, which is the air permeability of the gas-liquid separation membrane. The test temperature is 23±2℃; the liquid in the hydraulic resistance test is isopropyl alcohol; the test gas is carbon monoxide; and the test pressure is 1atm.

[0085] Figure 2 is the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane; Figure 2 It can be seen that the gas-liquid separation membranes in Examples 3-5 have a hydraulic pressure resistance higher than 88.5 kPa and a gas permeability higher than 16×1000 mL / Min·M 2 ; Comparing Example 3, Example 4 with Comparative Example 1, and Example 6 with Example 11, the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane in Example 3 and Example 4 are higher than those in Comparative Example 1, and the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane in Example 6 are higher than those in Example 11, indicating that the modified polyurethane resin prepared by using 2-hydroxypropionate-modified polyurethane resin and using it as a component of the gas-liquid separation membrane improves the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane, thereby achieving better gas-liquid separation effect.

[0086] Depend on Figure 2 It can also be seen that the gas-liquid separation membranes in Examples 6-8 have a hydraulic pressure resistance higher than 92 kPa and a gas permeability higher than 18×1000 mL / Min·M 2 Comparing Example 3 with Examples 6-8, the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane in Example 6-8 are both higher than those in Example 3. This indicates that the addition of pentaerythritol triacrylate to the resin composition for preparing the gas-liquid separation membrane may interact with the resin matrix, crosslinking agent, and chemical additives in the resin composition, possibly forming a cross-linked network structure, thereby obtaining a gas-liquid separation membrane, which improves the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane. Comparing Examples 6-10, the hydraulic pressure resistance and air permeability of the gas-liquid separation membrane in Example 6-8 are higher than those in Examples 9-10, indicating that the addition of 1-3 parts by weight of pentaerythritol triacrylate to the resin composition can produce a gas-liquid separation membrane with higher hydraulic pressure resistance and air permeability.

[0087] (2) Water resistance test

[0088] Cut the gas-liquid separation membrane into a 5cm×10cm rectangle, weigh it and record it as M0, immerse it in 25℃ deionized water for 24h, and then weigh it again and record it as M1. Calculate its weight gain rate using the following formula:

[0089] Weight gain rate (%) = (M1-M0) / M0

[0090] Figure 3 is the weight gain rate of the gas-liquid separation membrane; Figure 3It can be seen that the weight gain rate of the gas-liquid separation membranes in Examples 3-5 is less than 9%. Comparing Examples 3 and 4 with Comparative Example 1, and Example 6 with Example 11, the weight gain rate of the gas-liquid separation membranes in Examples 3 and 4 is lower than that in Comparative Example 1, and the weight gain rate of the gas-liquid separation membrane in Example 6 is lower than that in Example 11. This indicates that the modified polyurethane resin prepared by using 2-allyl hydroxypropionate to modify the polyurethane resin improves the water resistance of the gas-liquid separation membrane. The weight gain rate of the gas-liquid separation membranes in Examples 6-8 is less than 7%. Comparing Examples 3 with Examples 6-10, the weight gain rate of the gas-liquid separation membranes in Examples 6-8 is lower than that in Examples 3 and Examples 9-10. This indicates that the addition of 1-3 parts by weight of pentaerythritol triacrylate to the resin composition for preparing the gas-liquid separation membrane may interact with the resin matrix, crosslinking agent, and chemical additives in the resin composition to form a crosslinked network structure, thereby obtaining the gas-liquid separation membrane, which further improves the water resistance of the gas-liquid separation membrane.

[0091] (3) Wear resistance test

[0092] The gas-liquid separation membrane was made into a size of 50 mm × 50 mm. A C-10 rubber grinding wheel was used for abrasion with a load of 500 g and a rotation speed of 1500 for each sample. The wear rate of the sample was calculated. The wear rate (S) was calculated as follows:

[0093] S=(m1-m2) / m1×100%

[0094] Where: m1 and m2 are the mass of the gas-liquid separation membrane before and after the test, g.

[0095] Figure 4 is the wear rate of the gas-liquid separation membrane; Figure 4 It can be seen that the wear rate of the gas-liquid separation membranes in Examples 3-5 is less than 0.35%. Comparing Examples 3 and 4 with Comparative Example 1, and Example 6 with Example 11, the wear rate of the gas-liquid separation membranes in Examples 3 and 4 is lower than that in Comparative Example 1, and the wear rate of the gas-liquid separation membrane in Example 6 is lower than that in Example 11. This indicates that the modified polyurethane resin prepared by modifying the polyurethane resin with 2-allyl hydroxypropionate and using it as a component of the gas-liquid separation membrane improves the wear resistance of the gas-liquid separation membrane. The wear rate of the gas-liquid separation membranes in Examples 6-8 is less than 0.15%. Comparing Examples 3 with Examples 6-10, the wear rate of the gas-liquid separation membranes in Examples 6-8 is lower than that in Examples 3 and Examples 9-10. This indicates that the addition of 1-3 parts by weight of pentaerythritol triacrylate to the resin composition for preparing the gas-liquid separation membrane interacts with the resin matrix, crosslinking agent, and chemical additives in the resin composition to produce the gas-liquid separation membrane, further improving the wear resistance of the gas-liquid separation membrane.

[0096] (4) Mechanical properties measurement

[0097] The gas-liquid separation membrane was cut into a size of 25 mm × 5 mm and subjected to tensile testing using a high and low temperature servo-controlled tensile testing machine (AI-700-S). The tensile rate was 500 mm / min and the test temperatures were 25°C and 80°C, respectively. Each sample was tested three times in parallel and the average value was taken.

[0098] Figure 5 The tensile strength of gas-liquid separation membrane at 25℃ and 80℃ respectively; Figure 5 It can be seen that at 25°C, the tensile strength of the gas-liquid separation membranes in Examples 3-5 is higher than 47.5 MPa, and at 80°C, the tensile strength is not less than 41.5 MPa, that is, the tensile strength retention rate at 80°C is higher than 86%; comparing Example 3, Example 4 with Comparative Example 1, and Example 6 with Example 11, at 25°C and 80°C, the tensile strength and tensile strength retention rate of the gas-liquid separation membranes in Examples 3 and 4 are higher than those in Comparative Example 1, and the tensile strength and tensile strength retention rate of the gas-liquid separation membrane in Example 6 are higher than those in Example 11, indicating that the modified polyurethane resin prepared by modifying the polyurethane resin with 2-hydroxypropionate and using it as a component of the gas-liquid separation membrane improves the mechanical properties of the gas-liquid separation membrane and can still maintain good mechanical properties under heating conditions, that is, it has excellent heat resistance.

[0099] Depend on Figure 5 It can also be seen that at 25°C, the tensile strength of the gas-liquid separation membrane in Examples 6-8 is higher than 53 MPa, and at 80°C, the tensile strength is higher than 49 MPa, that is, the tensile strength retention rate at 80°C is higher than 91.5%; comparing Example 3 with Example 6-10, at 25°C and 80°C, the tensile strength and tensile strength retention rate of the gas-liquid separation membrane in Examples 6-8 are higher than those in Example 3, Example 9, and Example 10; this indicates that 1-3 parts by weight of pentaerythritol triacrylate is added to the resin composition for preparing the gas-liquid separation membrane, and it interacts with the resin matrix, crosslinking agent and chemical additives in the resin composition to obtain a gas-liquid separation membrane, which further improves the mechanical properties of the gas-liquid separation membrane and can still maintain good mechanical properties under heating conditions.

[0100] The conventional operations in the operating steps of the present invention are well known to those skilled in the art and will not be described in detail here.

[0101] The embodiments described above provide a detailed description of the technical solutions of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements or similar substitutions made within the scope of the principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A gas-liquid separation membrane comprising an organic polymer resin; wherein the gas-liquid separation membrane has a gas permeability greater than 18×1000 mL / min·m at a temperature of 23±2°C, a liquid of isopropyl alcohol, and a pressure of 1 atm. 2 , hydraulic pressure resistance higher than 92kPa; The gas-liquid separation membrane comprises at least a resin matrix and pentaerythritol triacrylate, wherein the resin matrix interacts with a cross-linking agent, a chemical auxiliary agent, and pentaerythritol triacrylate to form the gas-liquid separation membrane; the resin matrix is ​​a modified polyurethane resin, and the modified polyurethane resin is prepared from a polyurethane resin modified with 2-hydroxypropionate allyl; The preparation method of the modified polyurethane comprises the following steps: placing polyester polyol in a container, adding isophorone diisocyanate and a catalyst, heating to 75-90° C. and reacting for 1-3 hours, then adding allyl 2-hydroxypropionate, cooling to obtain a polyurethane prepolymer, adding isophorone diisocyanate and ethyl acetate, chain extension at 30-45° C., and simultaneously adding a molecular weight regulator, dibutylamine, and reacting for 3-5 hours to obtain a modified polyurethane resin.

2. A gas-liquid separation membrane according to claim 1, characterized in that: The gas-liquid separation membrane further comprises a cross-linking agent, a chemical auxiliary agent, and a solvent.

3. A gas-liquid separation membrane according to claim 2, characterized in that: The cross-linking agent is at least one of p-phenylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, and 1,4-cyclohexyl diisocyanate.

4. A gas-liquid separation membrane according to claim 2, characterized in that: The chemical auxiliary agent is at least one of calcium carbonate, diatomaceous earth, kaolin, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and starch.

5. Use of the gas-liquid separation membrane according to claim 1 in a purge gas reactor.

6. A method for preparing a gas-liquid separation membrane according to claim 1, comprising the steps of: placing a resin matrix, a cross-linking agent, a chemical additive, pentaerythritol triacrylate, and a solvent in a container, stirring and mixing them uniformly to obtain a resin composition, coating the resin composition on a release film, and peeling the film off to obtain a gas-liquid separation membrane.

7. The method for preparing a gas-liquid separation membrane according to claim 6, characterized in that: By weight, the resin matrix accounts for 55-75 parts, the cross-linking agent accounts for 3-8 parts, the chemical auxiliary agent accounts for 5-12 parts, and the solvent accounts for 4-9 parts.

Images