WO2021244163A1

WO2021244163A1 - Method for preparing non-woven fabric substrate-supported polyethylene nanofiltration membrane

Info

Publication number: WO2021244163A1
Application number: PCT/CN2021/088075
Authority: WO
Inventors: 程跃; 王英杰; 邱长泉; 庄志; 虞少波
Original assignee: 上海恩捷新材料科技有限公司
Priority date: 2020-06-05
Filing date: 2021-04-19
Publication date: 2021-12-09
Also published as: CN111632498A

Abstract

Disclosed is a non-woven fabric substrate-supported polyethylene nanofiltration membrane, comprising a non-woven fabric substrate, a polyethylene microporous membrane, and a nanofiltration membrane skin layer. The polyethylene microporous membrane is supported on the non-woven fabric substrate so as to obtain a non-woven fabric-supported polyethylene microporous membrane. The non-woven fabric-supported polyethylene microporous membrane forms the nanofiltration membrane skin layer by means of interfacial polymerization of a polyamine aqueous-phase monomer and a polyacyl chloride oleic-phase monomer. Compared with a polyethylene microporous nanofiltration membrane without a non-woven fabric as a substrate for support, the present invention has a higher inorganic salt rejection rate, better and stable membrane filtration properties, and a longer service life. Compared with existing commercial polysulfone substrate nanofiltration membranes, the present invention can have higher flux and better overall performance while reaching the same rejection rate and service life.

Description

Preparation method of polyethylene nanofiltration membrane supported on non-woven fabric substrate

Technical field

The invention relates to the technical field of nanofiltration membranes, in particular to a method for preparing a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.

Background technique

After entering the 21st century, the problems of environmental destruction and resource shortage have become more prominent, among which the shortage of fresh water resources is very serious. Reusing fresh water from rivers and lakes, underground brackish water, sea water and even sewage and wastewater through membrane separation method can effectively alleviate water resources crisis and become an important part of sustainable development in the future. Functional nanofiltration membranes can effectively reduce water hardness, turbidity, color, bacteria, fungi and other microorganisms, and can obtain higher water production under low pressure. It has been widely used in foreign industrial manufacturing and household life.

In the existing commercial nanofiltration membranes, since the thickness of the finger-shaped pores & skin layer is high and the pore size is small after the polysulfone film is formed, the permeation resistance is relatively large, and the flux is at a low level; and the pores are formed by thermally induced phase separation & stretching The polyethylene microporous membrane has no dense skin, and the whole membrane is made of loose tendon-like fibers. The permeation resistance is small, and the flux is greatly improved compared with traditional polysulfone membranes. However, the feature of too thin polyethylene material also has its drawbacks, that is, its mechanical strength, especially its compression resistance.

Therefore, there is an urgent need in this field for a nanofiltration membrane with high mechanical strength, high flux, high rejection rate of inorganic salts, stable performance and good service life.

Summary of the invention

In view of this, the present invention expects to provide a method for preparing a polyethylene nanofiltration membrane supported on a non-woven fabric substrate to prepare a higher flux, higher rejection rate of inorganic salts, and use of Nanofiltration membrane with improved lifespan and more stable performance.

In order to achieve the above objective, the technical solution of the present invention is achieved as follows:

The present invention provides a method for preparing a polyethylene nanofiltration membrane supported on a non-woven fabric substrate. The method includes the following steps:

Dust the polyethylene microporous membrane, soak it with an organic solvent, and then rinse with deionized water;

Put the non-woven fabric under the polyethylene microporous membrane, flatten it, and fix it tightly around it to obtain the non-woven fabric supported polyethylene microporous membrane;

The non-woven fabric-supported polyethylene microporous membrane is immersed in a polyamine-containing aqueous solution; the composition of the polyamine aqueous solution includes: a polyfunctional amine monomer, an acid acceptor and a monomer diffusion promoter; The mass fraction of the multifunctional amine monomer in the water phase solution is 0.5 to 3.5%, the mass fraction of the acid acceptor in the water phase solution is 0.1 to 5%, and the monomer diffusion promoter is in the water phase solution. The mass fraction of is 0.01～1%; the immersion time is 5～150 seconds;

Take the membrane out of the water phase, remove the excess water phase solution, and then immerse it in the oil phase solution containing the polyacid chloride monomer. After a period of interfacial polymerization, take it out to obtain the nascent membrane; the mass fraction of the polyacid chloride monomer in the oil phase solvent is 0.01～1%, immersion time is 5～120 seconds;

The nascent membrane obtained in the above steps is heat-treated at 30-100° C. for 0.5-20 minutes, and then air-dried to obtain a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.

Further, the multifunctional amine monomer is piperazine, homopiperazine, N-methylpiperazine, N-isopropylpiperazine, 1-amino-4-methylpiperazine, m-phenylenediamine, p-phenylenediamine, A combination of one or more of phenylenediamine, o-phenylenediamine, ethylenediamine, propylenediamine, and tris(2-diaminoethyl)amine.

Further, the acid acceptor is one or a combination of triethylamine, sodium acetate, N,N-diisopropylethylamine, pyridine, and potassium carbonate.

Further, the monomer diffusion promoter is tetrahydrofuran, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, ethoxylated nonylphenol, polyoxyalkylene ether, polyoxyethylene alkyl ether, octyl A combination of one or more of phenol ethoxylate, poloxamer, alkyl polyglucoside, cetyl alcohol or oleyl alcohol, polyoxyethylene (20) oleyl ether, and imidazolinone methanol.

Further, the polybasic acid chloride monomer is trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, biphenyl dicarboxylic acid chloride, naphthalene dicarboxylic acid chloride, cyclopropane tricarboxylic acid chloride, One of cyclopentane tricarboxylic acid chloride and cyclohexane tricarboxylic acid chloride.

Further, the oil phase solvent is one of n-hexane, cyclohexane, heptane, Isopar G, Isopar E, and Isopar L.

Further, the organic solvent includes methanol, ethanol, isopropanol, N-N dimethylformamide, N-N dimethylacetamide, and N-methylpyrrolidone.

Further, the mass fraction of the polybasic acid chloride monomer in the oil phase solvent is 0.05-0.5%.

Further, the non-woven fabric-supported polyethylene microporous membrane is immersed in the polyamine-containing aqueous solution for a time of 30-100 seconds.

Further, the immersion time in the oil phase solution containing the polybasic acid chloride monomer is 15-60 seconds.

Further, the heat treatment temperature of the nascent film is 50-80°C, and the heat treatment time is 3-10 minutes.

The beneficial effects of the present invention are as follows:

1) The present invention provides a polyethylene nanofiltration membrane supported on a non-woven fabric substrate. Compared with existing commercial nanofiltration membranes, its ultra-thin and loose membrane main structure can obtain better pure water permeability, and Higher flux, and maintain the same level of inorganic salt rejection;

2) The present invention provides a polyethylene nanofiltration membrane supported on a non-woven fabric substrate. Compared with the existing commercial nanofiltration membranes, the cost can be saved by more than 40%, the continuous industrial production capacity is strong, and the economic benefits of the product are very high. considerable;

3) The present invention provides a method for preparing a polyethylene nanofiltration membrane supported on a non-woven fabric substrate. After adding a non-woven fabric as a support, it overcomes the damage of the desalination layer and performance degradation caused by the thin thickness of the polyethylene microporous membrane. This prolongs the time that the membrane filtration performance remains stable, thereby effectively increasing the service life of the membrane.

Description of the drawings

Figure 1 is a schematic diagram of the preparation process of the non-woven fabric substrate supported polyethylene nanofiltration membrane provided by the present invention;

2 is a schematic diagram of the structure of a polyethylene nanofiltration membrane supported on a non-woven fabric substrate of the present invention;

Component label description

1 Nanofiltration membrane skin

2 Polyethylene microporous membrane

3 Non-woven fabric base

detailed description

The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not used to limit the present invention.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the end values of each range, between the end values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope should be considered as specifically disclosed herein.

The specific embodiment of the present invention provides a polyethylene nanofiltration membrane supported on a non-woven fabric substrate, comprising a non-woven fabric substrate 3, a polyethylene microporous membrane 2, a nanofiltration membrane skin layer 1; the polyethylene microporous membrane 2 supports After the non-woven fabric substrate 3, a non-woven fabric-supported polyethylene microporous membrane is obtained; the non-woven fabric-supported polyethylene microporous membrane is formed by interfacial polymerization of a polyamine aqueous monomer and a polyacid chloride oil phase monomer The nanofiltration membrane skin layer 1.

Preferably, the material of the non-woven fabric substrate 3 is one or a combination of polyethylene terephthalate, polyethylene, polypropylene, polyamide, and polyurethane.

Preferably, the non-woven fabric substrate 3 has a thickness of 70-110 μm, and a mass per unit area of 10-150 g/m ² .

Specifically, the non-woven fabric substrate 3 has a thickness of 90-100 μm, and a mass per unit area of 50-100 g/m ² .

Preferably, the thickness of the polyethylene microporous membrane 2 is between 5-25 μm, and the average pore diameter is between 0.01-0.2 μm.

Specifically, the thickness of the polyethylene microporous membrane 2 is between 9-20 μm, and the average pore diameter is between 0.02-0.06 μm.

Preferably, the non-woven fabric substrate supports polyethylene nanofiltration membrane at 0.48MPa, the pure water flux is 60-90L/m ² h, the monovalent salt rejection rate is more than 35%, and the divalent salt rejection rate is 98%. above.

The present invention also provides a method for preparing the polyethylene nanofiltration membrane supported on the non-woven fabric substrate. The method includes the following steps:

Remove dust from the polyethylene microporous membrane 2, soak it with an organic solvent, and then rinse with deionized water;

Place the non-woven fabric under the polyethylene microporous membrane 2, flatten it, and press and fix it around to obtain a non-woven fabric-supported polyethylene microporous membrane;

Preferably, the multifunctional amine monomer is piperazine, homopiperazine, N-methylpiperazine, N-isopropylpiperazine, 1-amino-4-methylpiperazine, m-phenylenediamine, p-phenylenediamine, A combination of one or more of phenylenediamine, o-phenylenediamine, ethylenediamine, propylenediamine, and tris(2-diaminoethyl)amine.

Preferably, the acid acceptor is one or a combination of triethylamine, sodium acetate, N,N-diisopropylethylamine, pyridine, and potassium carbonate.

Preferably, the monomer diffusion promoter is tetrahydrofuran, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, ethoxylated nonyl phenol, polyoxyalkylene ether, polyoxyethylene alkyl ether, octane A combination of one or more of phenol ethoxylate, poloxamer, alkyl polyglucoside, cetyl alcohol or oleyl alcohol, polyoxyethylene (20) oleyl ether, and imidazolinone methanol.

Preferably, the polybasic acid chloride monomer is trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, biphenyl dicarboxylic acid chloride, naphthalene dicarboxylic acid chloride, cyclopropane tricarboxylic acid chloride, One of cyclopentane tricarboxylic acid chloride and cyclohexane tricarboxylic acid chloride.

Preferably, the oil phase solvent is one of n-hexane, cyclohexane, heptane, Isopar G, Isopar E, and Isopar L.

Preferably, the organic solvent includes methanol, ethanol, isopropanol, N-N dimethylformamide, N-N dimethylacetamide, and N-methylpyrrolidone.

Preferably, the mass fraction of the polybasic acid chloride monomer in the oil phase solvent is 0.05-0.5%.

Preferably, the non-woven fabric-supported polyethylene microporous membrane is immersed in the polyamine-containing aqueous solution for a time of 30-100 seconds.

Preferably, the immersion time in the oil phase solution containing the polybasic acid chloride monomer is 15-60 seconds.

Preferably, the heat treatment temperature of the nascent film is 50-80°C, and the heat treatment time is 3-10 minutes.

Hereinafter, the present invention will be described in detail through examples.

In the following examples and comparative examples, the performance parameters are determined according to the following methods:

(1) Thickness: Measured according to the GB/T6672-2001 Plastic Film and Sheet Thickness Measurement Method with German Marr Film Thickness Gauge C1216, the same sample is tested 5 times, and the average value is taken as the thickness.

(2) Average pore size and porosity: The average pore size of the polyethylene separation membrane is obtained by testing with an automatic water pressure meter of model AAQ-3K-A-1 produced by Porous Materials Inc. (PMI) And porosity. The water pressure of the automatic water pressure meter is controlled at 100-1500 psi, the water surface tension is 72 dyn/cm, and the contact angle between water and the polyethylene separation membrane is 115 degrees.

(3) Pure water flux and rejection rate:

Pure water flux: measured by a nanofiltration testing machine (homemade).

Retention rate: Measured with a conductivity meter (HQ30d, Hach, USA).

Flux and rejection rate: The pure water flux is an important parameter to characterize the water permeability of the separation membrane. Under 0.48MPa pressure, deionized water is used as the feed liquid to pre-press the membrane for 1 hour to stabilize the effluent; then perform the pure water flux test, The effective membrane area of the test device is 32 cm ² . The calculation formula is as follows:

Among them, Q is the volume of permeated pure water (L), Δt is the permeation time (h), and A is the effective area of the permeable membrane (cm ² ).

Retention performance: Retention rate (R) two indicators. After the pre-compression of the membrane is completed, use 2000 mg/L MgSO ₄ and 500 mg/L NaCl test solution, and test at room temperature 25°C. Calculated as follows:

C _P and C _F are the concentration of the permeate and the feed solution (mg/L). Generally, the conductivity and the salt concentration are considered to be linearly related. Therefore, the conductivity can be used instead of the concentration to calculate the salt cutoff rate R.

Example 1

The polyethylene microporous membrane 2 (thickness 9 μm, average pore diameter 0.046 μm) was infiltrated with a 50% mass fraction of isopropanol solution, and then washed with deionized water. Then it was placed on the polyethylene terephthalate non-woven fabric substrate 3 (thickness 90 μm, mass per unit area 76 g/m ² ), and flattened and fixed.

The non-woven fabric supported polyethylene microporous membrane is immersed in the polyamine aqueous solution, where the polyfunctional amine monomer is piperazine (mass concentration 3%), and the acid acceptor is triethylamine (mass concentration 0.5%). The bulk diffusion promoter is sodium lauryl sulfate (mass concentration 0.1%), and the immersion time is 30 seconds; the film is taken out of the water phase, the excess liquid is removed, and then immersed in the polyacid chloride oil phase solution, where the polyacid chloride monomer is benzene Triformyl chloride (mass concentration 0.1%), the solvent used is n-hexane, and it is taken out after being immersed for 30 seconds; heat-treated at 80° C. for 5 minutes to obtain a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.

Example 2

The polyethylene microporous membrane 2 was replaced with a thickness of 5 μm, an average pore diameter of 0.051 μm, and a polyethylene terephthalate non-woven fabric substrate 3 with a thickness of 70 μm was used for support. The other conditions were the same as those in Example 1. The woven fabric substrate supports polyethylene nanofiltration membrane.

Example 3

A polyethylene terephthalate non-woven fabric substrate 3 with a thickness of 100 μm is used for loading, and other conditions are the same as in Example 1, to obtain a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.

Example 4

The polyethylene microporous membrane 2 was replaced with a thickness of 20 μm and an average pore diameter of 0.041 μm, and other conditions were the same as in Example 1, to obtain a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.

Example 5

Replace the polyethylene terephthalate non-woven fabric substrate 3 with a polypropylene non-woven fabric substrate 3 (thickness 90 μm, mass per unit area 81 g/m ² ), and other conditions are the same as in Example 1, to obtain a non-woven fabric substrate Support polyethylene nanofiltration membrane.

Example 6

In Example 1, the mass concentration of the water-phase polyamine monomer piperazine was adjusted to 2%, the mass concentration of triethylamine was 1%, the monomer diffusion promoter was 5% isopropanol by mass, and the heat treatment temperature was adjusted to 60. ℃, other conditions are unchanged, and a polyethylene nanofiltration membrane supported on a non-woven fabric substrate is obtained.

Example 7

Replace the polyethylene microporous membrane 2 in Example 1 with a thicker 25μm microporous membrane with an average pore diameter of 0.036μm, and use a polyethylene terephthalate ^{with a thickness of 110μm and a mass per unit area of 93g/m 2} The non-woven fabric substrate 3 is loaded, and other conditions remain unchanged. A polyethylene nanofiltration membrane supported on a non-woven fabric substrate is obtained.

Comparative example 1

The polyethylene microporous membrane 2 (thickness 9 microns, average pore diameter 0.0 46 μm) was infiltrated with a 50% isopropanol solution, and then washed with deionized water; no non-woven fabric was added for loading.

The interfacial polymerization process was carried out, and the steps and reagents were the same as in Example 1, and a polyethylene microporous nanofiltration membrane was obtained.

Comparative example 2

The non-woven fabric substrate 3 in Example 4 was removed, and then the nanofiltration membrane was prepared. The steps and conditions were the same as those in Example 4 to obtain a polyethylene microporous nanofiltration membrane.

Comparative example 3

The substrate in Example 1 was replaced with a commercial polysulfone ultrafiltration membrane (the thickness of the non-woven fabric was 90 μm, and the thickness of the polysulfone membrane skin layer was 40 μm), and other conditions were unchanged to prepare a polysulfone substrate nanofiltration membrane.

Examples 1-7 and Comparative Examples 1-3 were tested for pure water flux and inorganic salt rejection rate. The test results are as follows:

Table 1 Example and comparative example pure water flux, inorganic salt rejection test results

It can be seen from Table 1:

In Comparative Example 1, because there is no non-woven fabric as the substrate to provide support, the thickness of the polyethylene microporous membrane is too thin, and the water-phase monomer is not uniformly distributed, resulting in many defects in the prepared nanofiltration membrane, and high flux during performance testing. The interception is low; after 18 hours of scouring, the polyethylene support is partially destroyed, and the MgSO4 interception rate drops to 90%. After 100 hours, the interception loss rate reaches 15.2%, and the membrane life is poor;

In Comparative Example 2, after replacing it with a thicker polyethylene base film, the interception can be maintained above 90% after 100 hours, and the interception loss is alleviated, but still 6.3%;

Comparative Example 3 uses a commercial ultrafiltration membrane as the substrate, which can obtain high retention, good long-term stability, and retention loss rate as low as 0.8%, but the disadvantage is that the flux is low, only 45L/m ² .h;

Example 1 With the support of non-woven fabric, the rejection rate after being made into a nanofiltration membrane is relatively high. After 100h test, there is still a rejection rate of more than 98%, and the rejection rate is as low as 1.1%. The performance of the membrane can still be maintained after being compressed. stability;

Example 2 replaced the ultra-thin polyethylene microporous membrane with a thinner non-woven fabric support, and obtained a ^{high flux of 85L/m 2} .h. At the same time, the salt interception performance is good, but because the bottom membrane and the support are too Thin, insufficient mechanical strength, high interception loss after long-term operation, interception loss rate is about 2.1%;

Example 3 is supported by a thicker non-woven fabric base, which can effectively alleviate the problem of poor impact strength, the interception loss rate is effectively reduced to 1.4%, and the flux is 77L/m ² .h, which is still maintained at a relatively high level;

In Example 4, the polyethylene microporous membrane 2 was selected to thicken, and it was found that although the flux was slightly lower at this time, the interception was more stable, and the interception loss rate was only 0.9%, which was close to the performance of a commercial membrane;

In Example 5, after replacing the polypropylene material non-woven fabric 3, the hydrophobicity is stronger than that of the polyester material, so the pure water penetration resistance is higher, the flux is reduced, the interception performance is worse than that of the example 2, and the interception loss rate rises to 1.7%;

Example 6 After adjusting the formula and process parameters, the flux increased significantly, and the corresponding interception was reduced to 98.2%, the performance remained good after 100h test, and the interception loss rate was about 1.0%;

Example 7 is replaced with a thicker non-woven fabric 3. At this time, the flux is reduced to 63L/m ² .h, and the interception level is higher, reaching 99.4%. At the same time, the interception loss rate is only 0.8%, which is comparable to that of commercial ultrafiltration membranes. The prepared nanofiltration membranes are of comparable level, but the flux is significantly higher than that of commercial membranes;

It can be seen from this that the non-woven fabric substrate provided by the present invention supports polyethylene nanofiltration membrane, and compared with the polyethylene microporous nanofiltration membrane without non-woven fabric as the support 3, it has a higher rejection of inorganic salts. The membrane filtration performance is better and stable, and the service life is longer; compared with the existing commercial polysulfone-based nanofiltration membrane, the invention can achieve the same level of rejection and service life, and the present invention has higher flux , The overall performance is better.

The above content related to common knowledge will not be described in detail, and those skilled in the art can understand.

The above are only some specific embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the present invention. Within the scope of protection. The technical scope of the present invention is not limited to the content of the description, and its technical scope must be determined according to the scope of the claims.

Claims

A method for preparing a polyethylene nanofiltration membrane supported on a non-woven fabric substrate is characterized in that the method includes the following steps:

Dust the polyethylene microporous membrane, soak it with an organic solvent, and then rinse with deionized water;

Place the non-woven fabric under the polyethylene microporous membrane, flatten it, and fix it tightly around it to obtain the non-woven fabric supported polyethylene microporous membrane;

Immerse the aforementioned non-woven fabric-supported polyethylene microporous membrane in an aqueous solution containing polyamines;

Take the membrane out of the water phase, remove the excess water phase solution, and then immerse it in the oil phase solution containing the polyacid chloride monomer, and take it out after the interfacial polymerization reaction to obtain the primary membrane;

The nascent membrane obtained in the above steps is heat-treated and then air-dried to obtain a polyethylene nanofiltration membrane supported on a non-woven fabric substrate.
The preparation method according to claim 1, wherein the aqueous solution containing polyamine comprises a polyfunctional amine monomer, an acid acceptor and a monomer diffusion promoter; the polyfunctional amine monomer is in the water phase The mass fraction in the solution is 0.5 to 3.5%, the mass fraction of the acid acceptor in the aqueous phase solution is 0.1 to 5%, and the mass fraction of the monomer diffusion promoter in the aqueous phase solution is 0.01 to 1% .
The preparation method according to claim 1, characterized in that: the non-woven fabric-supported polyethylene microporous membrane is immersed in the polyamine-containing aqueous solution for 5 to 150 seconds; and the polyacid chloride-containing monomer In the oil phase solution of the body, the mass fraction of the polybasic acid chloride monomer in the oil phase solvent is 0.01-1%, and the immersion time is 5 to 120 seconds; the heat treatment conditions are 30 to 100° C., 0.5 to 20 minutes.
The preparation method according to claim 2, wherein the polyfunctional amine monomer is piperazine, homopiperazine, N-methylpiperazine, N-isopropylpiperazine, 1-amino-4- A combination of one or more of methylpiperazine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, ethylenediamine, propylenediamine, and tris(2-diaminoethyl)amine.
The preparation method according to claim 2, wherein the acid acceptor is one or more of triethylamine, sodium acetate, N,N-diisopropylethylamine, pyridine, and potassium carbonate combination.
The preparation method according to claim 2, characterized in that: the monomer diffusion promoter is tetrahydrofuran, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, ethoxylated nonylphenol, polyoxyethylene Alkyl ether, polyoxyethylene alkyl ether, octylphenol ethoxylate, poloxamer, alkyl polyglucoside, cetyl alcohol or oleyl alcohol, polyoxyethylene (20) oleyl ether, imidazolinone methanol A combination of one or more.
The preparation method according to claim 1, wherein the polybasic acid chloride monomer is trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, biphenyl dicarboxylic acid chloride, One of naphthalene dicarboxylic acid chloride, cyclopropane tricarboxylic acid chloride, cyclopentane tricarboxylic acid chloride, and cyclohexane tricarboxylic acid chloride.
The preparation method according to claim 1, wherein the oil phase solvent is one of n-hexane, cyclohexane, heptane, isoparaffin G, isoparaffin E, and isoparaffin L.
The preparation method according to claim 1, wherein the organic solvent comprises methanol, ethanol, isopropanol, N-N dimethylformamide, N-N dimethylacetamide, and N-methylpyrrolidone.
The preparation method according to claim 3, characterized in that: the non-woven fabric-supported polyethylene microporous membrane is immersed in the polyamine-containing aqueous solution for 30-100 seconds; the polyacid chloride monomer The mass fraction in the oil phase solvent is 0.05 to 0.5%, and the immersion time is 15 to 60 seconds; the heat treatment temperature of the primary film is 50 to 80° C., and the heat treatment time is 3 to 10 minutes.