A method for preparing a sulfonated polyaromatic (thio)ether composite reverse osmosis membrane

Abstract

The application discloses a preparation method of a sulfonated polyaromatic (sulfur) ether composite reverse osmosis membrane, which comprises the following steps: dissolving water wheel phenol in a sodium hydroxide aqueous solution, adding polyethyleneimine, stirring to prepare a water wheel phenol / polyethyleneimine co-deposition alkaline solution, infiltrating a polysulfone ultrafiltration base membrane, and preparing a water wheel phenol / polyethyleneimine co-deposition microporous intermediate layer; adding sulfonated polyaromatic (sulfur) ether and tetrabutylammonium chloride into ethylene glycol monomethyl ether, stirring and dissolving, filtering, and preparing a coating solution; covering the coating solution on the water wheel phenol / polyethyleneimine co-deposition microporous intermediate layer, and drying to obtain the composite reverse osmosis membrane. In the application, the water wheel phenol / polyethyleneimine co-deposition microporous intermediate layer can provide physical support for the skin layer, the base membrane can be selected as a polyaromatic (sulfur) ether ultrafiltration microporous membrane with a larger pore size, and the membrane resistance of water passing through the skin layer can be reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of reverse osmosis, and more particularly relates to a preparation method of a sulfonated polyaromatic (sulfo) ether composite reverse osmosis membrane with a water wheel phenol / polyethyleneimine co-deposited microporous intermediate layer. BACKGROUND

[0002] At present, polyamide composite membranes prepared by interfacial crosslinking polymerization technology have become the mainstream of reverse osmosis (RO) membranes. However, polyamide is very sensitive to active chlorine, and active chlorine is a common disinfectant in aqueous solution. Based on the chlorination degradation mechanism of polyamide, many strategies have been proposed to improve the chlorine oxidation resistance of polyamide composite membranes, but only the chlorination degradation rate of polyamide can be delayed and the problem cannot be eliminated. Therefore, designing and developing new chlorine-resistant polymer membrane materials is the key to preparing new high-performance composite reverse osmosis membrane materials.

[0003] Sulfonated polyaromatic (sulfo) ether has good acid, alkali and chlorine resistance, and is a membrane material with excellent performance. US4818387 discloses a preparation method of a sulfonated polyaromatic (sulfo) ether composite membrane. The sulfonated polyaromatic (sulfo) ether composite membrane prepared by dip coating method is soaked in an aqueous solution with a chlorine content of 100 ppm for four weeks, and the performance of the composite membrane is basically unchanged, having very good chlorine resistance and oxidation resistance. However, the traditional sulfonated polyaromatic (sulfo) ether composite reverse osmosis membrane is limited by a small water flux, which may be caused by the "funnel effect" of the sulfonated polyaromatic (sulfo) ether composite reverse osmosis membrane: water molecules in the area directly above the membrane holes of the sulfonated polyaromatic (sulfo) ether composite reverse osmosis membrane can be effectively collected and passed through the membrane, while water molecules far from the area directly above the membrane holes need to be additionally transported horizontally in the sulfonated polyaromatic (sulfo) ether selective layer to the membrane holes to be collected and passed. This long-path water transport channel caused by the "funnel effect" far exceeds the thickness of the sulfonated polyaromatic (sulfo) ether active layer, increasing the hydraulic resistance and thus limiting the water flux of the sulfonated polyaromatic (sulfo) ether composite reverse osmosis membrane.

[0004] To solve the "funnel effect", a higher permeable intermediate layer is introduced between the active layer and the substrate of the sulfonated poly (aromatic (sulfo) ether) composite reverse osmosis membrane. In order to achieve the minimum hydraulic resistance, the lateral path of water transport channel will be optimized in the intermediate layer area rather than in the lower permeability active layer area, which is also known as "flow guiding effect". Recent studies have shown that composite nanofiltration membranes with "flow guiding effect" often have higher water flux. Noria has a rich cavity structure, and its cavity diameter (~0.5nm) is larger than the diameter of water molecules (~0.28nm), which can be used as a water molecule transport channel, and is a potential excellent membrane structure regulating material. At present, studies have shown that a Noria / polyethyleneimine (PEI) co-deposited microporous layer as the intermediate layer of a polyamide nanofiltration membrane can achieve high water flux. However, there is no report on the preparation of a high-performance sulfonated poly (aromatic (sulfo) ether) composite reverse osmosis membrane on the surface of the Noria / PEI co-deposited microporous layer by coating method. SUMMARY

[0005] To solve the existing technical problems, the present application provides a preparation method of a sulfonated poly (aromatic (sulfo) ether) composite reverse osmosis membrane containing a Noria / polyethyleneimine co-deposited microporous intermediate layer. By introducing a Noria / polyethyleneimine co-deposited microporous intermediate layer between a poly (aromatic (sulfo) ether) ultrafiltration substrate and a sulfonated poly (aromatic (sulfo) ether) active layer, a sulfonated poly (aromatic (sulfo) ether) composite reverse osmosis membrane with suitable separation performance and excellent chlorine resistance is prepared. The introduction of the Noria / polyethyleneimine co-deposited microporous intermediate layer can provide physical support for the skin layer, so the substrate can select a poly (aromatic (sulfo) ether) ultrafiltration microporous membrane with a larger pore size, which is beneficial to reduce the membrane resistance after water passes through the skin layer. At the same time, the Noria / polyethyleneimine co-deposited microporous intermediate layer has small pore size and high porosity, which reduces the formation of the sulfonated poly (aromatic (sulfo) ether) active layer in the membrane pores. In addition, the surface of the Noria / polyethyleneimine co-deposited microporous intermediate layer is negatively charged, which is helpful for uniform coating and storage of the sulfonated poly (aromatic (sulfo) ether) solution, so that a complete sulfonated poly (aromatic (sulfo) ether) active layer can be formed at a lower concentration.

[0006] To achieve the above-mentioned purpose, the present application is realized by the following technical scheme:

[0007] A preparation method of a sulfonated poly (aromatic (sulfo) ether) composite reverse osmosis membrane, comprising the following steps:

[0008] Step (1): Dissolve Noria in a sodium hydroxide aqueous solution, add polyethyleneimine, stir to obtain a Noria / polyethyleneimine co-deposited alkaline solution, and immerse a poly (aromatic (sulfo) ether) ultrafiltration substrate to prepare a Noria / polyethyleneimine co-deposited microporous intermediate layer.

[0009] Preferably, the molar concentration of the aqueous sodium hydroxide solution is 0.2-0.5 mol / L; the concentration of water-soluble phenol in the water-soluble phenol / polyethyleneimine co-deposition alkaline solution is 5-15 g / L, and the concentration of polyethyleneimine is 15-45 g / L.

[0010] More preferably, the molar concentration of the aqueous sodium hydroxide solution is 0.25 mol / L; the concentration of water-soluble phenol in the water-soluble phenol / polyethyleneimine co-deposition alkaline solution is 10 g / L, and the concentration of polyethyleneimine is 30 g / L.

[0011] The polyaromatic (sulphur) ether ultrafiltration base membrane is one of a polysulfone ultrafiltration base membrane and a polyethersulfone ultrafiltration base membrane.

[0012] The infiltrated polyaromatic (sulphur) ether ultrafiltration base membrane is obtained by immersing a polyaromatic (sulphur) ether ultrafiltration base membrane in a water-soluble phenol / polyethyleneimine co-deposition alkaline solution for 10 seconds to 10 minutes.

[0013] The molar mass of the polyethyleneimine is 600-70,000 g / mol.

[0014] Step (2): The sulfonated polyaromatic (sulphur) ether is added to ethylene glycol monomethyl ether, stirred and dissolved, filtered, and a coating solution is prepared.

[0015] Preferably, the coating solution further comprises tetrabutylammonium chloride, and the sulfonated polyaromatic (sulphur) ether and tetrabutylammonium chloride are added to ethylene glycol monomethyl ether, stirred and dissolved, filtered, and a coating solution is prepared.

[0016] Preferably, the mass fraction of each component in the coating solution is: 0.1-1.0% of the sulfonated polyaromatic (sulphur) ether, 0-1.0% of tetrabutylammonium chloride, and the balance is ethylene glycol monomethyl ether.

[0017] The sulfonation degree of the sulfonated polyaromatic (sulphur) ether is 15-50%.

[0018] Step (3): The coating solution is coated on the water-soluble phenol / polyethyleneimine co-deposition microporous intermediate layer, dried at a temperature of 50-100°C for 3-6 minutes, and a sulfonated polyaromatic (sulphur) ether composite reverse osmosis membrane containing a water-soluble phenol / polyethyleneimine co-deposition microporous intermediate layer is prepared.

[0019] The sulfonated polyaromatic (sulphur) ether includes sulfonated polyaromatic (sulphur) ether sulfone, sulfonated polyaromatic (sulphur) ether ketone, sulfonated polyaromatic (sulphur) ether nitrile, or sulfonated polyaromatic (sulphur) ether phosphine oxide.

[0020] The sulfonated polyaromatic (sulphur) ether includes:

[0021]

[0022] m, p, q are in the range of 0-1, and m + p + q = 1;

[0023] X = O, S, N;

[0024] Ar 1 : monocyclic, bicyclic, fused or heterocyclic aromatic ring system containing 1-2 sulfonic acid or its salt groups;

[0025] Ar 2 : monocyclic, bicyclic, fused or heterocyclic aromatic ring system not containing sulfonic acid or its salt groups;

[0026] Ar 3 : another monocyclic, bicyclic, fused, spiro or heterocyclic aromatic ring system not containing sulfonic acid or its salt groups, different from Ar 2

[0027] Ar 4 : monocyclic, bicyclic, fused, spiro or heterocyclic bis(thio)phenol system containing para or meta position;

[0028] M = H, alkali metal of the first group, amine NR 1 R 2 R 3 (R 1 , R 2 , R 3 = H, C1-C6 alkyl or aryl)

[0029] R = mono or di-substituted aromatic substituent; non-cyclic aliphatic linear or branched substituent having general formula C n H 2n ; cyclic aliphatic substituent having general formula C n H 2n-2 , wherein n is an integer of 1-12, and typical structure is as follows:

[0030]

[0031] R 4 = aliphatic or aromatic substituent.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] 1. By introducing water wheel phenol / polyethylene imine co-deposition microporous intermediate layer between the ultrafiltration bottom membrane and the sulfonated polyaromatic (thio) ether active layer, and preparing the sulfonated polyaromatic (thio) ether composite reverse osmosis membrane by coating method on the surface of the microporous intermediate layer, the sulfonated polyaromatic (thio) ether composite reverse osmosis membrane has suitable separation performance and excellent chlorine resistance;

[0034] ​2. The introduction of the water-soluble resorcinol / formaldehyde co-deposited microporous interlayer provides physical support for the skin layer, thus the base membrane can be selected as a polyaromatic (sulphur) ether ultrafiltration microporous membrane with a larger pore size, which is beneficial to reduce the membrane resistance of water passing through the skin layer;

[0035] 3. The water-soluble resorcinol / formaldehyde co-deposited microporous interlayer has a small pore size and high porosity, which reduces the formation of the sulfonated polyaromatic (sulphur) ether active layer in the membrane pores;

[0036] 4. The surface of the water-soluble resorcinol / formaldehyde co-deposited microporous interlayer is negatively charged, which is helpful for the uniform coating and storage of the sulfonated polyaromatic (sulphur) ether solution, so that a complete sulfonated polyaromatic (sulphur) ether active layer can be formed at a lower concentration. DETAILED DESCRIPTION

[0037] The present application will be further described with reference to the following specific examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various modifications and changes can be made to the present application by those skilled in the art upon reading the contents of the present application, and such equivalent forms are also within the scope of the present application.

[0038] Before further describing the specific embodiments of the present application, it should be understood that the scope of protection of the present application is not limited to the following specific embodiments; it should also be understood that the terms used in the embodiments of the present application are for the purpose of describing the specific embodiments, and are not intended to limit the scope of protection of the present application. Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as generally understood by those skilled in the art. Unless otherwise specified, the test methods in the following examples are generally carried out under conventional conditions, or under the conditions recommended by the manufacturers. In addition to the specific methods, equipment, and materials used in the examples, any method, equipment, and material of the prior art similar or equivalent to the methods, equipment, and materials described in the examples of the present application can also be used to implement the present application according to the prior art mastered by those skilled in the art and the description of the present application.

[0039] Example 1

[0040] The sulfonated polyaromatic (sulphur) ether composite reverse osmosis membrane containing a water-soluble resorcinol / formaldehyde co-deposited microporous interlayer is prepared by the following method, which specifically includes the following steps:

[0041] Step (1): 1.0 g of aquaphenol was dissolved in a sodium hydroxide aqueous solution with a molar concentration of 0.25 mol / L, 3 g of polyethyleneimine (molar mass: 70,000 g / mol) was added, and stirring was performed to prepare an aquaphenol / polyethyleneimine co-deposition alkaline solution, the concentration of aquaphenol in the aquaphenol / polyethyleneimine co-deposition alkaline solution was 10 g / L, and the concentration of polyethyleneimine was 30 g / L, a polysulfone ultrafiltration base membrane was immersed in the aquaphenol / polyethyleneimine co-deposition alkaline solution, the immersion time was 20 seconds, and an aquaphenol / polyethyleneimine co-deposition microporous intermediate layer was prepared, the surface average pore size was 10.8 nm, and the pure water flux was 69.5 L·m -2 ·h -1 ·bar -1 .

[0042] Step (2): sulfonated poly (arylene ether sulfone) (sulfonation degree: 30%) and tetrabutylammonium chloride were added to ethylene glycol monomethyl ether, stirring and dissolving to obtain a mixed solution, the mass fractions of sulfonated poly (arylene ether sulfone), tetrabutylammonium chloride and ethylene glycol monomethyl ether in the mixed solution were 0.5 parts, 0.5 parts and 99 parts respectively, the mixed solution was filtered with qualitative filter paper to prepare a coating solution;

[0043] Step (3): the coating solution was poured on the aquaphenol / polyethyleneimine co-deposition microporous intermediate layer and shaken uniformly for 2 minutes to ensure that the coating solution fully wetted the surface of the polysulfone ultrafiltration base membrane, then the excess coating solution was poured off, and the composite membrane was placed in a 60°C oven for drying for 4 minutes to prepare a sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing an aquaphenol / polyethyleneimine co-deposition microporous intermediate layer, the pure water flux was 2.3 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate was 82%.

[0044] The chemical structural formula of the sulfonated poly (arylene ether sulfone) is as follows:

[0045]

[0046] Example 2

[0047] The difference from Example 1 is that in step (1), the polysulfone ultrafiltration base membrane is immersed in the aquaphenol / polyethyleneimine co-deposition alkaline solution for 40 seconds, and the prepared aquaphenol / polyethyleneimine co-deposition microporous intermediate layer has a surface average pore size of 9.7 nm and a pure water flux of 69.5 L·m -2 ·h -1 ·bar -1 ;

[0048] The pure water flux of the sulfonated poly (aromatic (sulfo) arther) composite reverse osmosis membrane comprising the water-wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 2.1 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 83%.

[0049] The rest is the same as example 1.

[0050] Example 3

[0051] The difference from example 1 is that the immersion time of the polysulfone ultrafiltration base membrane in the water-wheel phenol / polyethyleneimine co-deposited alkaline solution in step (1) is 60 seconds, and the surface average pore size of the water-wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared is 7.4 nanometers, and the pure water flux is 69.0 L·m -2 ·h -1 ·bar -1 ;

[0052] The pure water flux of the sulfonated poly (aromatic (sulfo) arther) composite reverse osmosis membrane comprising the water-wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.8 LL·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 92.3%.

[0053] The rest is the same as example 1.

[0054] Example 4

[0055] The difference from example 1 is that the immersion time of the polysulfone ultrafiltration base membrane in the water-wheel phenol / polyethyleneimine co-deposited alkaline solution in step (1) is 300 seconds, and the surface average pore size of the water-wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared is 6.8 nanometers, and the pure water flux is 68.6 L·m -2 ·h -1 ·bar -1 ;

[0056] The pure water flux of the sulfonated poly (aromatic (sulfo) arther) composite reverse osmosis membrane comprising the water-wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.3 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 98%.

[0057] The rest is the same as example 1.

[0058] Example 5

[0059] The difference from Example 4 is that the molar mass of polyethyleneimine in step (1) is 10000 g / mol, and the surface average pore size of the prepared waterwheel phenol / polyethyleneimine co-deposited microporous intermediate layer is 6.2 nm, and the pure water flux is 66.5 L·m -2 ·h -1 ·bar -1 ;

[0060] The pure water flux of the sulfonated polyaromatic (thio) ether composite reverse osmosis membrane containing the waterwheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) of the application is 0.89 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 98.5%.

[0061] The rest is consistent with Example 4.

[0062] Example 6

[0063] The difference from Example 1 is that the molar mass of polyethyleneimine in step (1) is 1800 g / mol, and the surface average pore size of the prepared waterwheel phenol / polyethyleneimine co-deposited microporous intermediate layer is 5.5 nm, and the pure water flux is 59.3 L·m -2 ·h -1 ·bar -1 ;

[0064] The pure water flux of the sulfonated polyaromatic (thio) ether composite reverse osmosis membrane containing the waterwheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) of the application is 0.76 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 99%.

[0065] The rest is consistent with Example 1.

[0066] Example 7

[0067] The difference from Example 4 is that no tetrabutylammonium chloride is added in step (2), and the mass fraction of sulfonated polyaromatic ether sulfone and ethylene glycol monomethyl ether in the mixed solution is 0.5 parts and 99.5 parts, respectively.

[0068] The pure water flux of the sulfonated polyaromatic (thio) ether composite reverse osmosis membrane containing the waterwheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) of the application is 1.8 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 91%.

[0069] The rest is consistent with Example 4.

[0070] Example 8

[0071] The difference from Example 4 is that the mass fractions of sulfonated poly (arylene ether sulfone), tetrabutylammonium chloride and ethylene glycol monomethyl ether in the mixed solution in step (2) are 0.3 parts, 0.5 parts and 99.2 parts, respectively.

[0072] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing a hydroxy naphthol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.67 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 94.5%.

[0073] The rest is consistent with Example 4.

[0074] Example 9

[0075] The difference from Example 4 is that the mass fractions of sulfonated poly (arylene ether sulfone), tetrabutylammonium chloride and ethylene glycol monomethyl ether in the mixed solution in step (2) are 0.7 parts, 0.5 parts and 98.8 parts, respectively.

[0076] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing a hydroxy naphthol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.27 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 99%.

[0077] The rest is consistent with Example 4.

[0078] Example 10

[0079] The difference from Example 4 is that the sulfonation degree of sulfonated poly (arylene ether sulfone) in step (2) is 20%, and the chemical structural formula of sulfonated poly (arylene ether sulfone) is as follows:

[0080]

[0081] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing a hydroxy naphthol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 0.23 L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 99%.

[0082] The rest is consistent with Example 4.

[0083] Example 11

[0084] The difference between the example 4 is that the mixed solution in step (2) is sulfonated poly (arylene ether ketone) (sulfonation degree: 30%), tetrabutylammonium chloride, ethylene glycol monomethyl ether, and the mass fraction is 0.5 parts, 0.5 parts, 99 parts respectively; the chemical structural formula of sulfonated poly (arylene ether ketone) is as follows:

[0085]

[0086] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing the water wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.37L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 97.8%.

[0087] The rest is consistent with example 4.

[0088] Example 12

[0089] The difference between the example 4 is that the mixed solution in step (2) is sulfonated poly (arylene ether ketone) (sulfonation degree: 30%), tetrabutylammonium chloride, ethylene glycol monomethyl ether, and the mass fraction is 0.5 parts, 0.5 parts, 99 parts respectively; the chemical structural formula of sulfonated poly (arylene ether ketone) is as follows:

[0090]

[0091] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing the water wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.37L·m -2 ·h -1 ·bar -1 , and the sodium chloride rejection rate is 97.8%.

[0092] The rest is consistent with example 4.

[0093] Example 13

[0094] The difference between the example 4 is that the mixed solution in step (2) is sulfonated poly (arylene ether ketone) (sulfonation degree: 30%), tetrabutylammonium chloride, ethylene glycol monomethyl ether, and the mass fraction is 0.5 parts, 0.5 parts, 99 parts respectively; the chemical structural formula of sulfonated poly (arylene ether ketone) is as follows:

[0095]

[0096] The pure water flux of the sulfonated poly (aromatic (sulfur) ether) composite reverse osmosis membrane containing the water wheel phenol / polyethyleneimine co-deposited microporous intermediate layer prepared in step (3) is 1.37L·m -2 ·h -1 ·bar -1The sodium chloride rejection was 98%.

[0097] The rest was identical to Example 4.

Claims

1. A method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane, characterized in that, Includes the following steps: Step (1): Dissolve cyclophenol in an aqueous sodium hydroxide solution, add polyethyleneimine, stir to prepare a cyclophenol / polyethyleneimine co-deposition alkaline solution, impregnate the polyaromatic (sulfur) ether ultrafiltration membrane, and prepare a cyclophenol / polyethyleneimine co-deposition microporous intermediate layer. Step (2): Add sulfonated polyaromatic (sulfur) ether to ethylene glycol monomethyl ether, stir to dissolve, filter, and obtain coating solution; Step (3): The coating solution is applied to the co-deposited microporous intermediate layer of hydroxyl phenol / polyethyleneimine and dried to obtain a sulfonated polyaromatic (sulfur) ether composite reverse osmosis membrane containing the co-deposited microporous intermediate layer of hydroxyl phenol / polyethyleneimine. The sulfonated polyaromatic (sulfur) ethers mentioned in step (2) include sulfonated polyaromatic (sulfur) ether sulfones, sulfonated polyaromatic (sulfur) ether ketones, sulfonated polyaromatic (sulfur) ether nitrs, or sulfonated polyaromatic (sulfur) ether phosphine oxides; the sulfonated polyaromatic (sulfur) ethers include: The values ​​of m, p, and q are in the range of 0 to 1, and m + p + q = 1; X = O, S, N; Ar 1 Aromatic ring systems containing 1 to 2 sulfonic acid or hydrochloric acid groups, including monocyclic, bicyclic, fused-ring, or heterocyclic rings; Ar 2 Aromatic ring systems that do not contain sulfonic acid or its salt groups, whether monocyclic, bicyclic, fused-ring, or heterocyclic. Ar 3 : with Ar 2 Another type of aromatic ring system that does not contain sulfonic acid or its salt groups, including monocyclic, bicyclic, fused-ring, spirocyclic, or heterocyclic rings; Ar 4 : Bis(thio)phenol systems containing para- or meta-position monocyclic, bicyclic, fused-ring, spirocyclic, or heterocyclic rings; M=H, Group 1 alkali metal, amine NR 1 R 2 R 3 (R) 1 R 2 R 3 =H, C1-C6 alkyl or aryl); R = mono- or di-substituted aromatic substituents; having the general formula C n H 2n Non-cyclic aliphatic linear or branched substituents; having the general formula C n H 2n-2 The cyclic aliphatic substituents, where n is an integer from 1 to 12, have the following typical structures: R 4 =Aliphatic or aromatic substituents.

2. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The coating solution in step (2) also contains tetrabutylammonium chloride. Sulfonated polyaromatic (sulfur) ether and tetrabutylammonium chloride are added to ethylene glycol monomethyl ether, stirred to dissolve, filtered, and the coating solution is obtained.

3. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 2, characterized in that, The mass fraction of each component in the coating solution in step (2) is: 0.1~1.0% sulfonated polyaromatic (sulfur) ether, 0~1.0% tetrabutylammonium chloride, and the balance is ethylene glycol monomethyl ether.

4. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The polyaromatic (sulfur) ether ultrafiltration membrane mentioned in step (1) is one of polysulfone ultrafiltration membrane and polyethersulfone ultrafiltration membrane.

5. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The molar mass of polyethyleneimine in step (1) is 600~70000 g / mol; the degree of sulfonation of the sulfonated polyaromatic (sulfide) ether in step (2) is 15~50%.

6. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The impregnation of the polyaromatic (sulfur) ether ultrafiltration membrane in step (1) involves immersing the polyaromatic (sulfur) ether ultrafiltration membrane in a water-based phenol / polyethyleneimine co-deposition alkaline solution for 10 seconds to 10 minutes. The drying temperature in step (3) is 50~100℃ and the drying time is 3~6 minutes.

7. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The molar concentration of the sodium hydroxide aqueous solution in step (1) is 0.2 to 0.5 mol / L; the concentration of hydroxyl phenol in the alkaline solution of hydroxyl phenol / polyethyleneimine co-deposition is 5 to 15 g / L, and the concentration of polyethyleneimine is 15 to 45 g / L.

8. The method for preparing a sulfonated polyaromatic (sulfide) ether composite reverse osmosis membrane according to claim 1, characterized in that, The molar concentration of the sodium hydroxide aqueous solution in step (1) is 0.25 mol / L; the concentration of hydroxyl phenol in the alkaline solution of hydroxyl phenol / polyethyleneimine co-deposition is 10 g / L and the concentration of polyethyleneimine is 30 g / L.

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