WO2022127637A1 - 复合反渗透膜及其制备方法 - Google Patents

复合反渗透膜及其制备方法 Download PDF

Info

Publication number
WO2022127637A1
WO2022127637A1 PCT/CN2021/135779 CN2021135779W WO2022127637A1 WO 2022127637 A1 WO2022127637 A1 WO 2022127637A1 CN 2021135779 W CN2021135779 W CN 2021135779W WO 2022127637 A1 WO2022127637 A1 WO 2022127637A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
polyethylene glycol
porous support
polylactic acid
support layer
Prior art date
Application number
PCT/CN2021/135779
Other languages
English (en)
French (fr)
Inventor
梁松苗
胡利杰
赵连瑞
金焱
吴宗策
Original Assignee
沃顿科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 沃顿科技股份有限公司 filed Critical 沃顿科技股份有限公司
Priority to US18/257,789 priority Critical patent/US20240307829A1/en
Publication of WO2022127637A1 publication Critical patent/WO2022127637A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present disclosure relates to the technical field of reverse osmosis membranes, in particular to a composite reverse osmosis membrane for seawater desalination and a preparation method thereof.
  • the preparation method of the present disclosure can realize the preparation of a composite reverse osmosis membrane with high flux, high salt rejection rate, high boron rejection rate and high pollution resistance in a simple and easy operation and high reaction efficiency manner.
  • composite reverse osmosis membrane As one of the core materials of membrane separation technology, composite reverse osmosis membrane has been widely used in the fields of sewage treatment, drinking water standard improvement, reclaimed water reuse and seawater desalination. It plays an increasingly important role in promoting high-quality economic development and ensuring ecological environment. more important role. In the face of increasingly harsh application environment and operating cost control and the diversification of polluted water bodies, higher requirements are also put forward for reverse osmosis membrane systems and membrane materials in terms of energy consumption, desalination rate and pollution resistance.
  • Seawater desalination composite reverse osmosis membrane is one of the branches with the highest technical level, the most difficult production and the most extensive application in reverse osmosis membrane materials. In addition to the above requirements, it also involves the removal of boron in seawater.
  • researchers often pay attention to the water flux, desalination rate, anti-pollution ability and boron removal ability of membrane materials at the same time. We strive to provide a membrane product that can meet the above four requirements at the same time. Therefore, the development and production of composite reverse osmosis membranes for seawater desalination is more complicated than that of ordinary low-pressure composite reverse osmosis membranes.
  • patent application CN201680025296.X discloses a method for increasing the flux of composite reverse osmosis membranes by using metal chelates containing metal atoms or metal ions and bidentate ligands, However, the composite reverse osmosis membrane prepared by this method has a low desalination rate;
  • patent application CN201510988458.7 discloses an anti-pollution composite multi-layer polymer separation membrane and a preparation method thereof.
  • the membrane adopts a support layer and is formed on it.
  • the multi-layer structure of the hydrophilic interception functional layer is composed of polysulfone block copolymers containing hydrophilic blocks.
  • the purpose of the present disclosure is to solve the above problems existing in the prior art, and to provide a composite reverse osmosis membrane and a preparation method thereof, so as to realize the preparation of high flux, high rejection rate, high Composite reverse osmosis membrane with boron removal rate and high pollution resistance.
  • the inventors of the present disclosure and others have conducted intensive research and found that by forming an amphiphilic block copolymer modified layer on the surface of the polymer porous support layer, the amine can be effectively regulated in the subsequent interfacial polymerization reaction.
  • the binding force between the two thereby improving the desalination rate of the composite reverse osmosis membrane; by introducing the ether with a cyclic structure into the polyamide network by physical doping or chemical bonding through in-situ interfacial polymerization, so that the amphiphilic
  • a hybrid polyamide functional layer also known as a hybrid polyamide desalination layer
  • a hybrid polyamide desalination layer containing an ether with a cyclic structure is formed on the polymer porous support layer modified by the cyclic block copolymer, which can effectively improve the affinity of the desalination layer. water, thereby improving the water flux and anti-fouling ability of the composite reverse osmosis membrane.
  • One aspect of the present disclosure relates to a composite reverse osmosis membrane comprising: a non-woven layer, a polymeric porous support layer, an amphiphilic block copolymer modified layer, and a hybrid polyamide functional layer, wherein the amphiphilic
  • the functional block copolymer comprises a hydrophilic block and a lipophilic block
  • the hybrid polyamide functional layer comprises an ether with a cyclic structure, and the ether with a cyclic structure is physically doped or chemically bonded way present in the hybrid polyamide functional layer.
  • the polymer porous support layer is a polysulfone porous support layer, a polyethersulfone porous support layer, a polyacrylonitrile porous support layer, a polyethyleneimine porous support layer, a polyaryl ether
  • the polyamide is aromatic polyamide and/or aliphatic polyamide.
  • the composite reverse osmosis membrane of the present disclosure wherein the amphiphilic block copolymer has an HLB value of 3 to 40.
  • amphiphilic block copolymer modified layer comprises one or more of the following block copolymers: polystyrene-b-polyethylene glycol, DL type poly Lactic acid-b-polyacrylic acid, polyglycolide-b-polyethylene glycol-polyglycolide, polystyrene-b-DL type polylactic acid, polystyrene-b-L type polylactic acid, polyethylene glycol-b -polyethyleneimine, polycaprolactone-b-polyethyleneimine, polylactic acid-glycolic acid-b-polylysine, polyethylene glycol-b-polylactic acid-polycaprolactone, polylactic acid-poly Caprolactone-b-polyethylene glycol-maleimide, polylactic acid-polycaprolactone-b-polyethylene glycol-amino, polylactic acid-polycaprolactone-b-polyethylene glycol-carbox
  • ether with a cyclic structure is a cyclic ether comprising a structural unit (CH 2 CH 2 Y) n , wherein Y is selected from heteroatoms O, N, S, P At least one of, n is an integer and 3 ⁇ n ⁇ 10.
  • Another aspect of the present disclosure relates to a preparation method of a composite reverse osmosis membrane, comprising the following steps:
  • the non-woven fabric on which the amphiphilic block copolymer modified layer and the polymer porous support layer are formed are sequentially mixed with an aqueous phase solution containing an amine monomer as the second solution, and an acid chloride monomer-containing solution as the third solution.
  • the composite reverse osmosis membrane is obtained after post-treatment and drying.
  • the polymer porous support layer is a polysulfone porous support layer, a polyethersulfone porous support layer, a polyacrylonitrile porous support layer, a polyethyleneimine porous support layer, One or more of a polyarylethersulfoneketone porous support layer, a polyvinylidene fluoride porous support layer and a sulfonated polyethersulfone porous support layer;
  • the polyamide is an aromatic polyamide and/or an aliphatic polyamide.
  • the first solution comprises an amphiphilic block copolymer and a first solvent
  • the amphiphilic block copolymer comprises a hydrophilic block and a lipophilic block segment
  • the HLB value of the amphiphilic block copolymer is 3 to 40
  • the first solvent is methanol, ethanol, propanol, butanol, acetone, tetrahydrofuran, dimethyl sulfoxide, sulfolane, N,N- Dimethylformamide, N,N-dimethylacetamide, water, toluene, xylene, chloroform, ISOPAR-G, ISOPAR-E, ISOPAR-L, n-butane, n-heptane, cyclohexane and ethyl acetate one or more of cyclohexane; preferably, the concentration of the amphiphilic block copolymer in the first
  • the ether with a cyclic structure is a cyclic ether comprising a structural unit (CH 2 CH 2 Y) n , wherein Y is selected from heteroatoms O, N, At least one of S and P, n is an integer and 3 ⁇ n ⁇ 10; preferably, the concentration of the ether having a cyclic structure in at least one of the second solution and the third solution is 0.01wt% to 10wt%.
  • amine monomers are aniline, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1, 2,4-Triaminobenzene, 3,5-Diaminobenzoic acid, 2,4-Diaminotoluene, 2,4-Diaminoanisole, Amiphene, Xylylenediamine, 1,4- Cyclohexanediamine, 1,2-cyclohexanediamine, piperazine, ethylene glycol amine, ethylene diamine, propylene diamine, butanediamine, hexanediamine, ethanolamine, polyethyleneimine, triethylamine, triethylamine (2-aminoethyl)amine, diethylenetriamine, N-(2-hydroxyethyl)ethylenediamine, 1,3-cyclohexanediamine, 1,3-bispiperid
  • the acid chloride monomers are phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, biphthaloyl chloride, trimesoyl chloride, and tribasic acid chlorides having a structure represented by the following general formula (1) one or more of:
  • R 1 , R 2 , and R 3 are each independently at least one of the following groups
  • the concentration of the acid chloride monomer is 0.05wt% to 5wt%.
  • the composite reverse osmosis membrane provided by the present disclosure has a removal rate of sodium chloride higher than 99.85%, a removal rate of boron higher than 93%, and a water flux of 20-30 GFD, and has excellent anti-pollution ability.
  • FIG. 1 is a scanning electron microscope image of a cross-section of the composite reverse osmosis membrane prepared in Example 1 of the disclosure.
  • Example 2 is a scanning electron microscope image of the surface of the composite reverse osmosis membrane prepared in Example 1 of the disclosure.
  • the present disclosure relates to a composite reverse osmosis membrane comprising: a non-woven fabric layer, a polymer porous support layer, an amphiphilic block copolymer modified layer and a hybrid polyamide functional layer, wherein the amphiphilic block
  • the copolymer comprises a hydrophilic block and a lipophilic block
  • the hybrid polyamide functional layer comprises an ether with a cyclic structure
  • the ether with a cyclic structure exists in the form of physical doping or chemical bonding in the hybrid polyamide functional layer.
  • the technical idea of the composite reverse osmosis membrane of the present disclosure is to form an amphiphilic block copolymer modified layer on the surface of the polymer porous support layer, so as to effectively control the amine monomer and the acid chloride monomer in the subsequent interfacial polymerization reaction.
  • the two-way diffusion of the body thereby preparing a polyamide functional layer (also known as a polyamide desalination layer) with a higher degree of crosslinking and a thicker thickness, thus improving the bonding force between the polyamide desalination layer and the polymer porous support layer, thereby improving the The salt rejection rate of composite reverse osmosis membranes; and by introducing ethers with cyclic structures into the polyamide network by physical doping or chemical bonding via in situ interfacial polymerization, so as to be modified by amphiphilic block copolymers.
  • a polyamide functional layer also known as a polyamide desalination layer
  • a hybrid polyamide functional layer (also known as a hybrid polyamide desalination layer) containing an ether with a cyclic structure is formed on the polymer porous support layer, which effectively improves the hydrophilicity of the desalination layer, thereby improving the composite reaction. Water flux and fouling resistance of permeable membranes.
  • the composite reverse osmosis membrane of the present disclosure wherein the polymer porous support layer is a polysulfone porous support layer, a polyethersulfone porous support layer, a polyacrylonitrile porous support layer, a polyethyleneimine porous support layer, and a polyarylethersulfone ketone.
  • the porous support layer, the polyvinylidene fluoride porous support layer and the sulfonated polyethersulfone porous support layer; the polyamide is aromatic polyamide and/or aliphatic polyamide.
  • the composite reverse osmosis membrane of the present disclosure wherein the weight average molecular weight of the amphiphilic block copolymer is in the range of 1 ⁇ 10 3 to 1 ⁇ 10 9 , preferably in the range of 1 ⁇ 10 3 to 1 ⁇ 10 7 , more preferably in the range of 1 ⁇ 10 4 to 1 ⁇ 10 6 ; the HLB value (hydrophilic-lipophilic balance value) of the amphiphilic block copolymer is 3 to 40, preferably 10 to 40, more preferably 10 to 20.
  • the HLB value is lower than 3, the hydrophobicity of the amphiphilic block copolymer is too strong, it is difficult to effectively control the diffusion process of interfacial polymerization, and it cannot improve the binding force between the polyamide desalination layer and the polymer porous support layer;
  • the HLB value is higher than 40, the amphiphilic block copolymer may dissolve in the water phase due to excessive hydrophilicity, and it is difficult to achieve the purpose of the present disclosure.
  • amphiphilic block copolymer modified layer comprises one or more of the following block copolymers: polystyrene-b-polyethylene glycol, DL type polylactic acid- b-polyacrylic acid, polyglycolide-b-polyethylene glycol-polyglycolide, polystyrene-b-DL polylactic acid, polystyrene-b-L polylactic acid, polyethylene glycol-b-poly Ethyleneimine, polycaprolactone-b-polyethyleneimine, polylactic acid-glycolic acid-b-polylysine, polyethylene glycol-b-polylactic acid-polycaprolactone, polylactic acid-polycaprolactone Ester-b-polyethylene glycol-maleimide, polylactic acid-polycaprolactone-b-polyethylene glycol-amino, polylactic acid-polycaprolactone-b-polyethylene glycol-maleimide, polylactic acid-polycaprolactone-b
  • the amphiphilic block copolymer modified layer more preferably comprises one or more of the following block copolymers: polystyrene-b-polyethylene glycol, polylactic acid-polyallyllactide-b - polyethylene glycol-amino.
  • ether with a cyclic structure is a cyclic ether comprising a structural unit (CH 2 CH 2 Y) n , wherein Y is selected from heteroatoms O, N, S, P At least one, n is an integer and 3 ⁇ n ⁇ 10, preferably, n is 4, 5, 6, 8.
  • the ether having a cyclic structure is preferably one or more selected from the following substances: aza-18-crown-6, 18-crown-6, 15-crown Ether-5, fluorine-containing crown ether, thia crown ether, naphthylmethyl aza crown ether, carbonyl calixarene crown ether, 2-hydroxymethyl-12-crown ether-4, 2-hydroxymethyl-18- Crown ether-6, dicyclohexyl-18-crown-6, tetrastyrene double crown ether, benzomonoazepine 15-crown-5, bis(benzazepine 15-crown-5), triazine Hetero15-crown-5, diazepine 18-crown-6, dibenzo-18-crown-6, benzo-18-crown-6, dibenzo-24-crown-8, bicyclic Hexano-18-crown (ether)-6, 12-crown
  • the content of the ether having a cyclic structure is 0.01 wt % to 50 wt %, preferably 0.1 wt % to 20 wt %.
  • the content of ether with a cyclic structure is too low, which has limited influence on the structure and performance of the functional layer; when the content is higher than 50wt%, the continuous network structure of the functional layer will be destroyed, making The degree of polyamide crosslinking decreases and the desalination layer becomes thin and loose, thereby affecting the performance of the membrane.
  • the preparation method of the composite reverse osmosis membrane of the present disclosure comprises the following steps:
  • the non-woven fabric on which the amphiphilic block copolymer modified layer and the polymer porous support layer are formed are sequentially mixed with an aqueous phase solution containing an amine monomer as the second solution, and an acid chloride monomer-containing solution as the third solution.
  • the composite reverse osmosis membrane is obtained after post-treatment and drying.
  • the polymer porous support layer is a polysulfone porous support layer, a polyethersulfone porous support layer, a polyacrylonitrile porous support layer, a polyethyleneimine porous support layer, a polyarylene One or more of ether sulfone ketone porous support layer, polyvinylidene fluoride porous support layer and sulfonated polyether sulfone porous support layer;
  • the polyamide is aromatic polyamide and/or aliphatic polyamide.
  • the polymer porous support layer may be formed by coating a polymer solution as a casting liquid on the non-woven fabric layer.
  • the polymer solution comprises a polymer and a solvent, the polymer being polysulfone, polyethersulfone, polyacrylonitrile, polyethyleneimine, polyarylethersulfoneketone, polyvinylidene fluoride, and sulfonated polyethersulfone one or more of.
  • it is polysulfone, polyethersulfone, more preferably polysulfone.
  • the polysulfone used in the present disclosure is not particularly limited, and may be bisphenol A-type PSF (ie, so-called PSF), polyarylsulfone, and polyethersulfone.
  • PSF bisphenol A-type PSF
  • a single polysulfone can be used alone or any combination of polysulfones can be used.
  • the mass ratio of the different kinds of polysulfones is not particularly limited.
  • the solvent contained in the polymer solution used in the present disclosure is not particularly limited, and the solvent may be N,N-dimethylformamide DMF, N,N-dimethylpyrrolidone, N,N-dimethylacetamide , one or more of dimethyl sulfoxide, n-hexane, cyclohexane, n-heptane, isoparaffin solvent Isopar G, chloroform, chloroform, toluene, benzene, methanol and propanol.
  • the concentration of the polymer in the polymer solution is from 10 wt% to 25 wt%.
  • the quality of the produced membrane (such as membrane strength, pore size, etc.) is more excellent.
  • the concentration of the polymer in the casting solution is lower than 10wt%, the concentration of the casting solution is too low, the structure of the prepared membrane is too loose, resulting in a decrease in the strength of the membrane, which is easily damaged, and the pore size is too large to achieve the interception effect, or even The viscosity of the casting liquid is too low to form a film.
  • the concentration of the polymer in the casting solution exceeds 25wt%, the concentration of the casting solution is too high, the viscosity is too high, and the prepared membrane structure is too dense, resulting in lower porosity, lower roughness, more defects in the membrane, and higher retention performance. poor. It is preferably 10wt% to 20wt%, more preferably 16wt% to 20wt%, which can further improve the quality of the obtained membrane material.
  • the preparation method of the composite reverse osmosis membrane of the present disclosure wherein the first solution comprises an amphiphilic block copolymer and a first solvent, the amphiphilic block copolymer comprises a hydrophilic block and a lipophilic block,
  • the amphiphilic block copolymer comprises a hydrophilic block and a lipophilic block
  • the first solvent is methanol, ethanol, propanol, butanol, acetone, tetrahydrofuran, dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, water, toluene , one or more of xylene, chloroform, ISOPAR-G, ISOPAR-E, ISOPAR-L, n-butane, n-heptane, cyclohexane and ethylcyclohexane.
  • the concentration of the amphiphilic block copolymer in the first solution is 0.01 wt% to 10 wt%, preferably 0.1 wt% to 2 wt%.
  • concentration is lower than 0.01 wt%, the content of the amphiphilic block copolymer is too small to form a modified layer, which cannot effectively control the bidirectional diffusion properties of amine monomers and acid chloride monomers during the interfacial polymerization process, and cannot simultaneously improve the polymerization.
  • the ether with a cyclic structure is a cyclic ether comprising a structural unit (CH 2 CH 2 Y) n , wherein Y is selected from heteroatoms O, N, S, at least one of P, n is an integer and 3 ⁇ n ⁇ 10; the concentration of the ether having a cyclic structure in at least one of the second solution and the third solution is 0.01wt% to 10wt%, It is preferably 0.1 wt % to 8 wt %.
  • the content of ether with a cyclic structure is too low, and the structure and performance control of the functional layer is limited; when the content is higher than 10wt%, the continuous network structure of the functional layer will be destroyed, making The degree of polyamide crosslinking is reduced, and the desalination layer becomes loose and thin, thereby affecting the performance of the membrane.
  • the ether having a cyclic structure is contained in at least one of the second solution and the third solution, and the ether having a cyclic structure may be added to the aqueous solution as the second solution or to the third solution.
  • the oil phase solution whether it is added to the water phase or the oil phase, it can achieve excellent technical effects, and the membrane prepared by adding it to the water phase has better overall performance.
  • amine monomers are aniline, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2, 4-Triaminobenzene, 3,5-Diaminobenzoic acid, 2,4-Diaminotoluene, 2,4-Diaminoanisole, Amiphene, Xylylenediamine, 1,4-Cyclohexyl Diamine, 1,2-cyclohexanediamine, piperazine, glycolamine, ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, ethanolamine, polyethyleneimine, triethylamine, tris(2 -aminoethyl)amine, diethylenetriamine, N-(2-hydroxyethyl)ethylenediamine, 1,3-cyclohexanediamine, 1,3-bispiperidin
  • the amine monomer is one or more of m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, p-toluenediamine, m-toluenediamine, o-toluenediamine and biphenylenediamine kind.
  • the concentration of the amine monomer is 0.5wt% to 10wt%, preferably 2wt% to 5wt%.
  • the preparation method of the composite reverse osmosis membrane of the present disclosure wherein the acid chloride monomers are phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, biphthaloyl chloride, trimesoyl chloride and have the following One or more of the tribasic acid chlorides of the structure represented by the general formula (1):
  • R 1 , R 2 , and R 3 are each independently at least one of the following groups
  • the acid chloride monomer is one or more of phthaloyl chloride, isophthaloyl chloride and trimesoyl chloride.
  • the concentration of the acid chloride monomer is 0.05wt% to 5wt%, preferably 0.1wt% to 2wt%.
  • the solvent in the third solution can be at least one of n-hexane, cyclohexane, n-heptane, and isoparaffin solvent Isopar G.
  • the first solution with an amphiphilic block copolymer concentration of 0.01wt% to 10wt% is coated on a polysulfone porous support membrane to form an amphiphilic block copolymer modified layer;
  • a second solution having a concentration of 0.01 wt to 10 wt % and an amine monomer concentration of 0.5 wt to 10 wt % and a third solution having an acid chloride monomer concentration of 0.05 wt to 5 wt % are contacted to perform interfacial polymerization to form an interfacial polymerization reaction.
  • the post-treatment is preferably to remove the excess solution on the surface of the composite reverse osmosis membrane, and then clean, for example, using deionized water. More preferably, the moisturizing treatment is performed using an aqueous solution with a glycerin concentration of 10 wt %. Then drying is performed, and the drying temperature is not particularly limited, usually 30°C to 100°C; the drying time is also not particularly limited, usually 1 to 20 minutes.
  • the polysulfone ultrafiltration support layer was immersed in an aqueous solution with a concentration of 3.5wt% m-phenylenediamine, the pH of the aqueous solution was 11, the temperature of the aqueous solution was 30°C, and the soaking time was 5min, and then taken out using an air knife at room temperature
  • the table below is dry.
  • the surface-dried polysulfone ultrafiltration support layer was immersed in a cyclohexane solution containing 0.2 wt% trimesoyl chloride for interfacial polymerization, the reaction temperature was 25 °C, and the reaction time was 30 s, and then taken out and kept at 50 °C. drying.
  • the dried composite membrane was moisturised with an aqueous solution with a glycerol concentration of 10 wt % and dried at 100° C. to obtain a composite reverse osmosis membrane of a comparative example.
  • the first solution is uniformly coated on the polysulfone porous support membrane, and dried at 30°C to prepare a polysulfone porous support membrane with an amphiphilic block copolymer modified layer, and then soaked in the second solution, wherein
  • the concentration of m-phenylenediamine is 3.5wt%
  • the content of aza-12-crown-4 is 2wt%
  • the solvent is water
  • the pH value of the second solution is 11
  • the temperature of the second solution is 30°C
  • the soaking time is 5min, then take out and dry at room temperature with an air knife.
  • the dried composite membrane is subjected to moisturizing treatment with an aqueous solution with a concentration of 10 wt % of glycerin and dried at 100° C. to finally obtain a composite reverse osmosis membrane.
  • the prepared first solution was uniformly coated on the polysulfone porous support membrane, and dried at 30°C to prepare a polysulfone porous support membrane with an amphiphilic block copolymer modified layer.
  • the modified polysulfone ultrafiltration support membrane was soaked in the second solution, wherein the concentration of m-phenylenediamine was 4.0 wt %, the solvent was water, the solution temperature was 30 ° C, and the soaking time was 5 min, and then taken out using an air knife Dry at room temperature.
  • the surface-dried film was immersed in a cyclohexane solution containing 0.2wt% trimesoyl chloride and 1wt% aza-12-crown-4 for reaction at a reaction temperature of 25°C and a reaction time of 30s.
  • the dried composite membrane is subjected to moisturizing treatment with an aqueous solution with a concentration of 10 wt % of glycerol and dried at 100°C to finally obtain a composite reverse osmosis membrane.
  • the composite reverse osmosis membranes obtained in Examples 1-2 were tested for flux, salt rejection, boron rejection and anti-pollution performance.
  • the raw water is 32000ppm NaCl aqueous solution
  • the solution temperature is 25 °C
  • the pH value is 6.5-7.5. Solute removal rate.
  • the solute removal rate (R) refers to the difference between the solute concentration (C) of the feed solution and the solute concentration (Cp) in the permeate under certain operating conditions, and then divided by the solute concentration of the feed solution.
  • the calculation formula is:
  • R is the solute removal rate, also known as the desalination rate (%)
  • C is the solute concentration of the feed solution, that is, the mass concentration of the original solution
  • Cp is the solute concentration of the permeate, that is, the mass concentration of the permeate solution.
  • Water flux (F) refers to the volume (V) of water permeating unit membrane area (S) in unit time (t) under certain operating conditions, and the unit of water flux (F) is L m - 2 ⁇ h -1 (LMH); V is the volume of permeate (unit is L); S is the effective surface area of the membrane (unit is m 2 ); t is the permeation time (unit is h).
  • the deboronation rate of the diaphragm is tested according to the national standard GBT 5750.6-2006, page 5, 1.4 inductively coupled plasma emission spectrometry.
  • the raw water is 0.2wt% BSA (bovine serum albumin) aqueous solution
  • the solution temperature is 25°C
  • the pH value is 6.5-7.5. Decay rate of water flux F BSA (%) after 10 hours of operation.
  • the initial flux of the composite reverse osmosis membrane provided by the present disclosure is significantly improved, the water flux is 20-30 GFD, and the flux decay rate is significantly reduced, It can be as low as 10.2%, so it shows excellent anti-pollution performance, and the desalination (NaCl) rate and boron removal rate are also significantly improved.
  • the removal rate of sodium chloride can be as high as 99.85% or more, and the removal rate of boron can be Up to more than 93%, and has excellent anti-pollution ability.
  • FIG. 1 shows a scanning electron microscope image of the cross-section of the composite reverse osmosis membrane prepared in Example 1
  • Fig. 1 shows that the thickness of the desalination layer can reach 362 nm to 457 nm and the thickness distribution is uniform
  • FIG. 2 shows a scanning electron microscope image of the surface of the composite reverse osmosis membrane prepared in Example 1, and it can be seen from FIG. 2 that the surface of the desalination layer on the surface is smooth.
  • the preparation method of the present disclosure can realize the preparation of a composite reverse osmosis membrane with high flux, high rejection rate and high pollution resistance in a simple and easy operation and high reaction efficiency manner.
  • the composite reverse osmosis membrane prepared in the present disclosure can be advantageously used for desalination of seawater.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Laminated Bodies (AREA)

Abstract

本公开涉及一种复合反渗透膜及其制备方法，本公开的制备方法能够实现以简便易操作、反应效率高的方式制备兼具高通量、高脱盐率、高脱硼率和高抗污染性的复合反渗透膜。

Description

复合反渗透膜及其制备方法 技术领域
本公开涉及反渗透膜技术领域，特别涉及一种海水淡化复合反渗透膜及其制备方法。本公开的制备方法能够实现以简便易操作、反应效率高的方式制备兼具高通量、高脱盐率、高脱硼率和高抗污染性的复合反渗透膜。
背景技术
复合反渗透膜作为膜分离技术的核心材料之一，已广泛应用于污水处理、饮用水提标、中水回用和海水淡化等领域，为促进经济高质量发展和保障生态环境发挥着越来越重要的作用。面对日益苛刻的应用环境和运营成本控制以及被污染水体的多样化，对反渗透膜系统及膜材料在能耗、脱盐率和抗污染性等方面也提出了更高的要求。
海水淡化复合反渗透膜作为反渗透膜材料中技术水平要求最高、生产难度最大和应用最为广泛的分支之一，除了上述要求之外，还涉及到海水中硼的脱除问题。鉴于此，在海水淡化复合反渗透膜的设计开发和产业化过程中，作为共性系统的要求，研究者往往会同时关注膜材料的水通量、脱盐率、抗污染能力和脱硼能力等方面的性能要求，力求提供一种能够同时符合以上四大需求的膜产品。因此，海水淡化复合反渗透膜的研发生产较之普通低压型复合反渗透膜更为复杂。
在提升复合渗透膜的水通量方面，专利申请CN201680025296.X中公开了一种用含有金属原子或金属离子、以及二齿配体的金属螯合物提升复合反渗透膜的通量的方法，但该方法制备的复合反渗透膜的脱盐率较低；专利申请CN201510988458.7中公开了一种抗污染复合多层聚合物分离膜及其制备方法，该膜采用了支撑层和形成于其上的亲水截留功能层的多层结构，亲水截留功能层为含有亲水嵌段的聚砜类嵌段共聚物组成，尽管膜的亲水性增强，但由于未引入聚酰胺脱盐层，膜的脱盐率仍然处于较低的水平。
综上所述，开发一种兼具高通量、高脱盐率、高脱硼率和高抗污染性的复合反渗透膜势在必行。
发明内容
发明要解决的问题
本公开的目的在于解决现有技术中存在的以上问题，提供一种复合反渗透膜及其制备方法，实现以简便易操作、反应效率高的方式制备兼具高通量、高脱盐率、高脱硼率和高抗污染性的复合反渗透膜。
用于解决问题的方案
本公开的发明人等为了实现以上目的，进行锐意研究之后发现，通过在聚合物多孔支撑层的表面上形成两亲性嵌段共聚物修饰层，可有效地调控在后续的界面聚合反应中胺类单体和酰氯类单体的双向扩散，从而制备交联程度更高和厚度更厚的聚酰胺功能层(又称聚酰胺脱盐层)，因此提高聚酰胺脱盐层与聚合物多孔支撑层之间的结合力，从而提高复合反渗透膜的脱盐率；通过将具有环状结构的醚借助原位界面聚合反应以物理掺杂或化学键合的方式引入至聚酰胺网络中，从而在经两亲性嵌段共聚物修饰后的聚合物多孔支撑层上形成包含具有环状结构的醚的杂化的聚酰胺功能层(又称杂化的聚酰胺脱盐层)，可以有效地提升脱盐层的亲水性，从而提高复合反渗透膜的水通量和抗污染能力。
本公开的一个方面涉及一种复合反渗透膜，其包括：无纺布层、聚合物多孔支撑层、两亲性嵌段共聚物修饰层和杂化的聚酰胺功能层，其中所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，所述杂化的聚酰胺功能层包含具有环状结构的醚，所述具有环状结构的醚以物理掺杂的方式或者化学键合的方式存在于所述杂化的聚酰胺功能层。
本公开所述的复合反渗透膜，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
本公开所述的复合反渗透膜，其中所述两亲性嵌段共聚物的HLB值为3至40。
本公开所述的复合反渗透膜，其中所述两亲性嵌段共聚物修饰层包含以下嵌段共聚物中的一种或多种：聚苯乙烯-b-聚乙二醇、DL型聚乳酸-b-聚丙烯酸、聚乙交酯-b-聚乙二醇-聚乙交酯、聚苯乙烯-b-DL型聚乳酸、聚苯乙烯-b-L型聚乳酸、聚乙二醇-b-聚乙烯亚胺、聚己内酯-b-聚乙烯亚胺、聚乳酸-羟基乙酸-b-聚赖氨酸、聚乙二醇-b-聚乳酸-聚己 内酯、聚乳酸-聚己内酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇-氨基、聚乳酸-聚己内酯-b-聚乙二醇-羧基、聚乳酸-聚己内酯-b-聚乙二醇-活化酯、聚乳酸-b-聚乙二醇氨基、聚乳酸-b-聚乙二醇羧基、聚乳酸-b-聚乙二醇羟基、聚乳酸-聚己内酯-b-聚乙二醇-叶酸、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇、聚丙烯酸-b-聚丙烯酰胺、聚丙烯酸-b-聚甲基丙烯酸甲酯、聚丙烯酸正丁酯-b-聚丙烯酸、聚丙烯酸正丁酯-b-聚丙烯酰胺、聚甲基丙烯酸叔丁酯-b-聚氧乙烯、聚甲基丙烯酸甲酯-b-聚丙烯酸、聚新戊酯-b-聚甲基丙烯酸、聚氧乙烯-b-聚丙烯酸、聚氧乙烯-b-聚丙烯酰胺、聚四氢呋喃-b-聚氧化丁烯、聚氧乙烯-b-聚己内酯、聚氧乙烯-b-聚乳酸、聚氧乙烯-b-聚环氧丙烷、聚氧乙烯-b-聚甲基丙烯酸硝基苄酯、聚氧乙烯-b-聚N-异丙基丙烯酰胺、聚氧乙烯-b-聚丙烯酸叔丁酯、聚氧乙烯-b-聚甲基丙烯酸叔丁酯、聚氧乙烯-b-聚甲基噁唑啉、聚氧乙烯-b-聚丙交酯、聚异丁烯-b-聚丙烯酸、聚异丁烯-b-聚氧乙烯、聚苯乙烯-b-聚丙烯酰胺、聚苯乙烯-b-聚丙烯酸、聚苯乙烯-b-聚甲基丙烯酸、聚苯乙烯-b-聚丙烯酸钠、聚苯乙烯-b-聚丙基丙烯酸、聚苯乙烯磺酸-b-聚甲基丁烯、聚4-苯乙烯磺酸钠盐-b-聚氧乙烯、聚二甲基硅氧烷-b-聚氧乙烯、聚二甲基硅氧烷-b-聚甲基丙烯酸、聚乙烯基吡啶-b-聚氧乙烯、聚甲基丙烯酸-b-聚新戊酯、聚甲基丙烯酸-b-聚甲基丙烯酸羟乙酯、聚甲基丙烯酸-b-聚己内酯、聚苯乙烯-b-聚丙烯酸苄酯、聚苯乙烯-b-聚乳酸、聚苯乙烯-b-聚甲基丙烯酸乙酯、聚苯乙烯-b-聚甲基丙烯酸丁酯、聚苯乙烯-b-聚甲基丙烯酸羟丙酯、聚苯乙烯-b-聚甲基丙烯酸羟乙酯、聚乳酸羟基乙酸-b-聚乙二醇马来酰亚胺、聚乳酸羟基乙酸-b-聚乙二醇羧基、聚乳酸羟基乙酸-b-聚乙二醇氨基、聚乳酸羟基乙酸共聚物-b-聚乙二醇羟基、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇生物素、聚乳酸羟基乙酸共聚物-b-聚乙二醇叠氮、聚乳酸羟基乙酸共聚物-b-聚乙二醇磷脂、聚乳酸羟基乙酸共聚物-b-聚乙二醇醛基、聚乳酸羟基乙酸共聚物-b-聚乙二醇丙烯酯和聚乳酸羟基乙酸共聚物-b-聚乙烯亚胺。
本公开所述的复合反渗透膜，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10。
本公开的另一个方面涉及一种复合反渗透膜的制备方法，其包括以下步骤：
制备基膜，所述基膜包括在无纺布层上的聚合物多孔支撑层；
制备两亲性嵌段共聚物溶液作为第一溶液涂覆在聚合物多孔支撑层以形成两亲性嵌段共聚物修饰层；
将形成有两亲性嵌段共聚物修饰层、聚合物多孔支撑层的无纺布依次与作为第二溶液的包含胺类单体的水相溶液、作为第三溶液的含有酰氯类单体的油相溶液接触，在第二溶液和第三溶液的至少一者中包含具有环状结构的醚，以形成包含具有环状结构的醚的杂化的聚酰胺功能层；
经后处理、烘干后得到复合反渗透膜。
本公开所述的复合反渗透膜的制备方法，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
本公开所述的复合反渗透膜的制备方法，其中所述第一溶液包含两亲性嵌段共聚物和第一溶剂，所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，所述两亲性嵌段共聚物的HLB值为3至40，所述第一溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、四氢呋喃、二甲亚砜、环丁砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲苯、二甲苯、氯仿、ISOPAR-G、ISOPAR-E、ISOPAR-L、正丁烷、正庚烷、环己烷和乙基环己烷中的一种或多种；优选地，所述两亲性嵌段共聚物在所述第一溶液中的浓度为0.01wt％至10wt％。
本公开所述的复合反渗透膜的制备方法，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10；优选地，所述具有环状结构的醚在第二溶液和第三溶液的至少一者中的浓度为0.01wt％至10wt％。
本公开所述的复合反渗透膜的制备方法，其中所述胺类单体为苯胺、间苯二胺、对苯二胺、邻苯二胺、1,3,5-三氨基苯、1,2,4-三氨基苯、3,5-二氨基苯甲酸、2,4-二氨基甲苯、2,4-二氨基苯甲醚、阿米酚、苯二甲基二胺、1,4-环己二胺、1,2-环己二胺、哌嗪、乙二醇胺、乙二胺、丙二胺、丁二胺、己二胺、乙醇胺、聚乙烯亚胺、三乙胺、三(2-氨乙基)胺、二乙烯三胺、N-(2-羟乙基)乙二胺、1,3-环己二胺、1,3-双哌啶基丙烷、4-氨基甲 基哌嗪、乙醇胺、二乙醇胺、己二醇胺和二甘醇胺中的一种或多种，在所述第二溶液中，所述胺类单体的浓度为0.5wt％～10wt％；
所述酰氯类单体为邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯、联苯二甲酰氯、均苯三甲酰氯和具有以下通式(1)表示的结构的三元酰氯中的一种或多种：
Figure PCTCN2021135779-appb-000001
其中R 1、R 2、R 3各自独立地为以下基团中的至少一种
Figure PCTCN2021135779-appb-000002
在所述第三溶液中，所述酰氯类单体的浓度为0.05wt％～5wt％。
发明的效果
通过本公开提供的复合反渗透膜在标准测试条件下，对氯化钠的脱除率高于99.85％，对硼的脱除率高于93％，水通量为20～30GFD，同时具有优异的抗污染能力。
附图说明
图1为本公开实施例1制备的复合反渗透膜的截面的扫描电子显微镜图像。
图2为本公开实施例1制备的复合反渗透膜的表面的扫描电子显微镜图像。
具体实施方式
本公开涉及一种复合反渗透膜，其包括：无纺布层、聚合物多孔支撑层、两亲性嵌段共聚物修饰层和杂化的聚酰胺功能层，其中所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，所述杂化的聚酰胺功能层包含具有环状结构的醚，所述具有环状结构的醚以物理掺杂的方式或者化学键合的方式存在于所述杂化的聚酰胺功能层。
本公开的复合反渗透膜的技术构思在于，在聚合物多孔支撑层的表面上形成两亲性嵌段共聚物修饰层，有效地调控在后续的界面聚合反应中胺类单体和酰氯类单体的双向扩散，从而制备交联程度更高和厚度更厚的聚酰胺功能层(又称聚酰胺脱盐层)，因此提高聚酰胺脱盐层与聚合物多孔支撑层之间的结合力，从而提高复合反渗透膜的脱盐率；并且通过将具有环状结构的醚借助原位界面聚合反应以物理掺杂或化学键合的方式引入至聚酰胺网络中，从而在经两亲性嵌段共聚物修饰后的聚合物多孔支撑层上形成包含具有环状结构的醚的杂化的聚酰胺功能层(又称杂化的聚酰胺脱盐层)，有效地提升脱盐层的亲水性，从而提高复合反渗透膜的水通量和抗污染能力。
本公开的复合反渗透膜，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
本公开的复合反渗透膜，其中所述两亲性嵌段共聚物的重均分子量在1×10 3至1×10 9的范围内，优选在1×10 3至1×10 7的范围内，更优选在1×10 4至1×10 6的范围内；所述两亲性嵌段共聚物的HLB值(亲水亲油平衡值)为3至40，优选为10至40，更优选为10至20。当HLB值低于3时，则两亲性嵌段共聚物的疏水性太强，难以有效调控界面聚合的扩散过程，也不能提高聚酰胺脱盐层与聚合物多孔支撑层之间的结合力；当HLB值高于40时，两亲性嵌段共聚物由于亲水性过强可能会溶于水相中，难以达成本公开的目的。
本公开的复合反渗透膜，其中所述两亲性嵌段共聚物修饰层包含以下嵌段共聚物中的一种或多种：聚苯乙烯-b-聚乙二醇、DL型聚乳酸-b-聚丙烯酸、聚乙交酯-b-聚乙二醇-聚乙交酯、聚苯乙烯-b-DL型聚乳酸、聚苯乙烯-b-L型聚乳酸、聚乙二醇-b-聚乙烯亚胺、聚己内酯-b-聚乙烯亚胺、聚乳酸-羟基乙酸-b-聚赖氨酸、聚乙二醇-b-聚乳酸-聚己内酯、聚乳酸-聚己内酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇-氨基、聚乳酸- 聚己内酯-b-聚乙二醇-羧基、聚乳酸-聚己内酯-b-聚乙二醇-活化酯、聚乳酸-b-聚乙二醇氨基、聚乳酸-b-聚乙二醇羧基、聚乳酸-b-聚乙二醇羟基、聚乳酸-聚己内酯-b-聚乙二醇-叶酸、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇、聚丙烯酸-b-聚丙烯酰胺、聚丙烯酸-b-聚甲基丙烯酸甲酯、聚丙烯酸正丁酯-b-聚丙烯酸、聚丙烯酸正丁酯-b-聚丙烯酰胺、聚甲基丙烯酸叔丁酯-b-聚氧乙烯、聚甲基丙烯酸甲酯-b-聚丙烯酸、聚新戊酯-b-聚甲基丙烯酸、聚氧乙烯-b-聚丙烯酸、聚氧乙烯-b-聚丙烯酰胺、聚四氢呋喃-b-聚氧化丁烯、聚氧乙烯-b-聚己内酯、聚氧乙烯-b-聚乳酸、聚氧乙烯-b-聚环氧丙烷、聚氧乙烯-b-聚甲基丙烯酸硝基苄酯、聚氧乙烯-b-聚N-异丙基丙烯酰胺、聚氧乙烯-b-聚丙烯酸叔丁酯、聚氧乙烯-b-聚甲基丙烯酸叔丁酯、聚氧乙烯-b-聚甲基噁唑啉、聚氧乙烯-b-聚丙交酯、聚异丁烯-b-聚丙烯酸、聚异丁烯-b-聚氧乙烯、聚苯乙烯-b-聚丙烯酰胺、聚苯乙烯-b-聚丙烯酸、聚苯乙烯-b-聚甲基丙烯酸、聚苯乙烯-b-聚丙烯酸钠、聚苯乙烯-b-聚丙基丙烯酸、聚苯乙烯磺酸-b-聚甲基丁烯、聚4-苯乙烯磺酸钠盐-b-聚氧乙烯、聚二甲基硅氧烷-b-聚氧乙烯、聚二甲基硅氧烷-b-聚甲基丙烯酸、聚乙烯基吡啶-b-聚氧乙烯、聚甲基丙烯酸-b-聚新戊酯、聚甲基丙烯酸-b-聚甲基丙烯酸羟乙酯、聚甲基丙烯酸-b-聚己内酯、聚苯乙烯-b-聚丙烯酸苄酯、聚苯乙烯-b-聚乳酸、聚苯乙烯-b-聚甲基丙烯酸乙酯、聚苯乙烯-b-聚甲基丙烯酸丁酯、聚苯乙烯-b-聚甲基丙烯酸羟丙酯、聚苯乙烯-b-聚甲基丙烯酸羟乙酯、聚乳酸羟基乙酸-b-聚乙二醇马来酰亚胺、聚乳酸羟基乙酸-b-聚乙二醇羧基、聚乳酸羟基乙酸-b-聚乙二醇氨基、聚乳酸羟基乙酸共聚物-b-聚乙二醇羟基、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇生物素、聚乳酸羟基乙酸共聚物-b-聚乙二醇叠氮、聚乳酸羟基乙酸共聚物-b-聚乙二醇磷脂、聚乳酸羟基乙酸共聚物-b-聚乙二醇醛基、聚乳酸羟基乙酸共聚物-b-聚乙二醇丙烯酯和聚乳酸羟基乙酸共聚物-b-聚乙烯亚胺。
所述两亲性嵌段共聚物修饰层更优选包含以下嵌段共聚物中的一种或多种：聚苯乙烯-b-聚乙二醇、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基。
本公开的复合反渗透膜，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10，优选 地，n为4、5、6、8。
本公开的复合反渗透膜，所述具有环状结构的醚优选为选自以下物质中的一种或多种：氮杂-18-冠醚-6、18-冠醚-6、15-冠醚-5、含氟冠醚、硫杂冠醚、萘甲基氮杂冠醚、碳基杯芳烃冠醚、2-羟甲基-12-冠醚-4、2-羟甲基-18-冠醚-6、二环己基并-18-冠醚-6、四苯乙烯双冠醚、苯并单氮杂15-冠-5、双(苯并氮杂15-冠-5)、三氮杂15-冠-5、双氮杂18-冠-6、二苯并-18-冠醚-6、苯并-18-冠醚-6、二苯并-24-冠醚-8、二环己烷并-18-冠(醚)-6、12-冠醚-4、氮杂-12-冠醚-4、苯并-15-冠醚-5、1,4,7-三氮杂环壬烷18-冠醚-6、轮环藤宁(又称1,4,7,10-四氮杂环十二烷)、1,3-二甲氧基冠醚(不具有结构单元(CH2CH2Y)n)、1,4,8,11-四氮杂环十四烷、二环己烷并-18-冠醚-6、三蝶烯衍生物三冠醚、五蝶烯衍生物单冠醚、4,4-二苯并-24-冠醚-8、2,3-萘并-15-冠醚-5、1,1-二甲基硅杂-17-冠醚-6、4-乙烯基苯并-18-冠醚-6和4’-氨基苯并-18-冠醚-6。
所述包含具有环状结构的醚的杂化的聚酰胺功能层中，所述具有环状结构的醚的含量为0.01wt％至50wt％，优选为0.1wt％至20wt％。当含量低于0.01wt％时，则具有环状结构的醚的含量过低，对功能层的结构和性能影响有限；当含量高于50wt％时，则会破坏功能层的连续网络结构，使得聚酰胺交联度降低、脱盐层变得薄且疏松，从而影响膜的性能。
本公开的复合反渗透膜的制备方法，其包括以下步骤：
制备基膜，所述基膜包括在无纺布层上的聚合物多孔支撑层；
制备两亲性嵌段共聚物溶液作为第一溶液涂覆在聚合物多孔支撑层以形成两亲性嵌段共聚物修饰层；
将形成有两亲性嵌段共聚物修饰层、聚合物多孔支撑层的无纺布依次与作为第二溶液的包含胺类单体的水相溶液、作为第三溶液的含有酰氯类单体的油相溶液接触，在第二溶液和第三溶液的至少一者中包含具有环状结构的醚，以形成包含具有环状结构的醚的杂化的聚酰胺功能层；
经后处理、烘干后得到复合反渗透膜。
本公开的复合反渗透膜的制备方法，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支 撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
任选地，所述聚合物多孔支撑层可以通过在无纺布层上涂覆作为铸膜液的聚合物溶液而形成。任选地，聚合物溶液包含聚合物和溶剂，所述聚合物为聚砜、聚醚砜、聚丙烯腈、聚乙烯亚胺、聚芳醚砜酮、聚偏氟乙烯和磺化聚醚砜中的一种或多种。优选地，为聚砜、聚醚砜，更优选地为聚砜。
在本公开中使用的聚砜没有特别限定，可以是双酚A型PSF(即通常所说的PSF)、聚芳砜和聚醚砜。可以单独使用一种聚砜或使用多种聚砜的任意组合。当使用多种不同的聚砜的组合时，对于不同种类的聚砜的质量比没有特别限定。
在本公开中使用的聚合物溶液包含的溶剂没有特别限定，所述溶剂可以为N,N-二甲基甲酰胺DMF、N,N-二甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基亚砜、正己烷、环己烷、正庚烷、异构烷烃溶剂Isopar G、氯仿、三氯甲烷、甲苯、苯、甲醇、丙醇中的一种或多种。
优选地，所述聚合物在所述聚合物溶液中的浓度为10wt％至25wt％。当浓度在该范围内时，制得的膜的品质(如膜的强度、孔径大小等)更优异。如果聚合物在铸膜液中的浓度低于10wt％，铸膜液浓度太低，制备所得的膜的结构过于疏松导致膜的强度下降，容易损坏，且孔径太大，无法达到截留效果，甚至铸膜液黏度太低导致不能成膜。如果聚合物在铸膜液中的浓度超过25wt％，则铸膜液浓度太高，黏度较大，制备所得的膜结构过于致密导致孔隙率降低、粗糙度降低、膜的缺陷较多，截留性能较差。优选为10wt％至20wt％，更优选为16wt％至20wt％，可以进一步提升制得的膜材料的品质。
本公开的复合反渗透膜的制备方法，其中所述第一溶液包含两亲性嵌段共聚物和第一溶剂，所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，对于两亲性嵌段共聚物的具体描述参见在上述关于复合反渗透膜的部分中所记载的。
所述第一溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、四氢呋喃、二甲亚砜、环丁砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲苯、二甲苯、氯仿、ISOPAR-G、ISOPAR-E、ISOPAR-L、正丁烷、正庚烷、环己烷和乙基环己烷中的一种或多种。
优选地，所述两亲性嵌段共聚物在所述第一溶液中的浓度为0.01wt％至10wt％，优 选为0.1wt％至2wt％。当浓度低于0.01wt％时，两亲性嵌段共聚物的含量太少难以形成修饰层，不能有效调控界面聚合过程中胺类单体和酰氯类单体的双向扩散性质，不能同时提高聚酰胺脱盐层与聚砜超滤支撑层之间的结合力；当浓度高于10wt％时，则修饰层会对聚合物支撑层的孔径和孔隙率产生很大影响，最终使得制备的复合膜的通量下降。
本公开的复合反渗透膜的制备方法，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10；所述具有环状结构的醚在所述第二溶液和第三溶液的至少一者中的浓度为0.01wt％至10wt％，优选为0.1wt％至8wt％。当含量低于0.01wt％时，则具有环状结构的醚的含量过低，对功能层的结构和性能调控有限；当含量高于10wt％时，则会破坏功能层的连续网络结构，使得聚酰胺交联度降低、脱盐层变疏松变薄，从而影响膜的性能。
在第二溶液和第三溶液的至少一者中包含具有环状结构的醚，具有环状结构的醚既可以添加在作为第二溶液的水相溶液中，也可以添加在作为第三溶液的油相溶液中，无论是添加于水相中还是添加于油相中均可以实现优异的技术效果，添加于水相中而制备的膜综合性能更佳。
对于具有环状结构的醚的具体描述参见在上述关于复合反渗透膜的部分中所记载的。
本公开的复合反渗透膜的制备方法，其中所述胺类单体为苯胺、间苯二胺、对苯二胺、邻苯二胺、1,3,5-三氨基苯、1,2,4-三氨基苯、3,5-二氨基苯甲酸、2,4-二氨基甲苯、2,4-二氨基苯甲醚、阿米酚、苯二甲基二胺、1,4-环己二胺、1,2-环己二胺、哌嗪、乙二醇胺、乙二胺、丙二胺、丁二胺、己二胺、乙醇胺、聚乙烯亚胺、三乙胺、三(2-氨乙基)胺、二乙烯三胺、N-(2-羟乙基)乙二胺、1,3-环己二胺、1,3-双哌啶基丙烷、4-氨基甲基哌嗪、乙醇胺、二乙醇胺、己二醇胺和二甘醇胺中的一种或多种。
优选地，所述胺类单体为间苯二胺、对苯二胺、邻苯二胺、对甲苯二胺、间甲苯二胺、邻甲苯二胺和联苯二胺中的一种或多种。
在所述第二溶液中，所述胺类单体的浓度为0.5wt％～10wt％，优选为2wt％至5wt％。
本公开的复合反渗透膜的制备方法，其中所述酰氯类单体为邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯、联苯二甲酰氯、均苯三甲酰氯和具有以下通式(1)表示的结构的 三元酰氯中的一种或多种：
Figure PCTCN2021135779-appb-000003
其中R 1、R 2、R 3各自独立地为以下基团中的至少一种
Figure PCTCN2021135779-appb-000004
优选地，所述酰氯类单体为邻苯二甲酰氯、间苯二甲酰氯、均苯三甲酰氯中的一种或多种。
在所述第三溶液中，所述酰氯类单体的浓度为0.05wt％～5wt％，优选为0.1wt％～2wt％。
所述第三溶液中的溶剂可以为正己烷、环己烷、正庚烷、异构烷烃溶剂Isopar G中的至少一种。
作为本公开的复合反渗透膜的制备方法的一个非限制性实例，其可以如下所示：
将两亲性嵌段共聚物浓度为0.01wt至10wt％的第一溶液涂覆在聚砜多孔支撑膜上以形成两亲性嵌段共聚物修饰层；随后依次与具有环状结构的醚的浓度为0.01wt至10wt％且胺类单体的浓度为0.5wt至10wt％的第二溶液、酰氯类单体的浓度为0.05wt至5wt％的第三溶液接触进行界面聚合反应以形成包含具有环状结构的醚的杂化的聚酰胺功能层。
在本公开的制备方法中，所述后处理优选为去除复合反渗透膜表面多余的溶液，然后清洗，例如采用去离子水进行清洗。更优选地，采用甘油浓度为10wt％的水溶液进行保湿处理。随后进行烘干，对于烘干温度没有特别限制，通常为30℃～100℃；对于烘干 时间也没有特别限制，通常为1～20分钟。
实施例
下面结合具体实施例进一步详细说明本公开，但本公开绝不限于以下实施例。需要说明的是，本公开实施例中采用的试剂和原料除非特别说明，皆为商购可得的常规产品。
对比例
将聚砜超滤支撑层浸泡于间苯二胺的浓度为3.5wt％的水溶液中，水溶液的pH值为11，水溶液的温度为30℃，浸泡时间为5min，然后取出采用空气风刀于室温下表干。将表干后的聚砜超滤支撑层浸泡于含0.2wt％均苯三甲酰氯的环己烷溶液中进行界面聚合反应，反应温度为25℃，反应时间为30s，然后取出并且在50℃下烘干。将烘干后的复合膜采用甘油浓度为10wt％的水溶液进行保湿并且在100℃下烘干，获得对比例复合反渗透膜。
实施例1
在室温下，将0.5g聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基分散于99.5g丙酮中，制备得到两亲性嵌段共聚物的浓度为0.5wt％的第一溶液。
将第一溶液均匀涂敷于聚砜多孔支撑膜上，并于30℃下烘干制备得到具有两亲性嵌段共聚物修饰层的聚砜多孔支撑膜，随后浸泡于第二溶液中，其中间苯二胺的浓度为3.5wt％，氮杂-12-冠醚-4含量为2wt％，溶剂为水，第二溶液的pH值为11，第二溶液的温度为30℃，浸泡时间为5min，然后取出采用空气风刀于室温下表干。接着浸泡于均苯三甲酰氯的浓度为0.2wt％的环己烷溶液中进行界面聚合反应，反应温度为25℃，反应时间为30s。
然后取出并且在50℃下烘干。将烘干后的复合膜采用甘油的浓度为10wt％的水溶液进行保湿处理并且在100℃下烘干，最终获得复合反渗透膜。
实施例2
在室温下，将1.0g聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基分散于99g丙酮中，制备两亲性双嵌段共聚物的浓度为1.0wt％的第一溶液。
将制备得到的第一溶液均匀涂敷于聚砜多孔支撑膜上，并于30℃下烘干制备得到具 有两亲性嵌段共聚物修饰层的聚砜多孔支撑膜。
将修饰得到的聚砜超滤支撑膜浸泡于第二溶液中，其中间苯二胺的浓度为4.0wt％，溶剂为水，溶液温度为30℃，浸泡时间为5min，然后取出采用空气风刀于室温下表干。将表干后的膜浸泡于含0.2wt％均苯三甲酰氯和1wt％氮杂-12-冠醚-4的环己烷溶液中进行反应，反应温度25℃，反应时间30s。
然后取出并在50℃下烘干，将烘干后的复合膜采用甘油的浓度为10wt％的水溶液进行保湿处理并且在100℃下烘干，最终获得复合反渗透膜。
将对比例和实施例1-2得到的复合反渗透膜进行通量、脱盐率、脱硼率和抗污染性能的测试。
膜片的通量和脱盐(NaCl)率的测试条件：
将膜片放在膜片检测台中，在操作压力为800psi、原水为32000ppm NaCl水溶液、溶液温度为25℃、pH值为6.5-7.5的测试条件下，测试膜片运行不同时间的水通量和溶质脱除率。
溶质脱除率(R)是指在一定操作条件下，进料液溶质浓度(C)与渗透液中溶质浓度(Cp)之差，再除以进料液溶质浓度，其计算公式为：
Figure PCTCN2021135779-appb-000005
式中，R为溶质脱除率，又名脱盐率(％)；C为进料液溶质浓度，即原液质量浓度；Cp为渗透液溶质浓度，即渗透液质量浓度。
水通量(F)是指在一定的操作条件下，单位时间(t)内透过单位膜面积(S)的水的体积(V)，水通量(F)的单位为L·m -2·h -1(LMH)；V为渗透液体积(单位为L)；S为膜的有效表面积(单位为m 2)；t为透水时间(单位为h)。
水通量(F)的计算公式为：
Figure PCTCN2021135779-appb-000006
通量的不同单位之间的换算关系为：GFD＝LMH/1.7
脱硼率的测试方法：
膜片的脱硼率按照国标GBT 5750.6-2006第5页1.4电感耦合等离子体发射光谱法进行测试。
抗污染性能的测试方法：
将膜片放在膜片检测台中，在操作压力为800psi、原水为0.2wt％BSA(牛血清白蛋白)水溶液、溶液温度为25℃、pH值为6.5-7.5的测试条件下，测试膜片运行10小时后水通量的衰减率F BSA(％)。
F BSA＝(F t＝0–F t＝10)/F t＝0×100％
其中F t＝0和F t＝10分别为膜片的初始通量及运行10小时后的通量。
表1
  初始通量(GFD) 脱盐(NaCl)率(％) 脱硼率(％) 通量衰减率(％)
对比例 17.8 99.74 87.4 42.3
实施例1 22.1 99.87 94.2 10.2
实施例2 25.6 99.85 93.3 13.8
从表1的结果可见，与对比例的复合反渗透膜相比，通过本公开提供的复合反渗透膜的初始通量显著提高，水通量为20～30GFD，并且通量衰减率明显降低，可低至10.2％，因此显示出优异的抗污染性能，并且脱盐(NaCl)率和脱硼率也显著提高，对氯化钠的脱除率可以高达99.85％以上，对硼的脱除率可高达93％以上，同时具有优异的抗污染能力。
图1示出实施例1制备的复合反渗透膜的截面的扫描电子显微镜图像，图1示出脱盐层的厚度较高可达到362nm至457nm且厚度分布均匀。图2示出实施例1制备的复合反渗透膜的表面的扫描电子显微镜图像，从图2可见位于表面的脱盐层的表面平整光滑。
产业上的可利用性
本公开的制备方法能够实现以简便易操作、反应效率高的方式制备兼具高通量、高脱盐率和高抗污染性的复合反渗透膜。本公开制备的复合反渗透膜可有利地用于海水的淡化。

Claims (10)

  1. 一种复合反渗透膜，其包括：无纺布层、聚合物多孔支撑层、两亲性嵌段共聚物修饰层和杂化的聚酰胺功能层，其特征在于，所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，所述杂化的聚酰胺功能层包含具有环状结构的醚，所述具有环状结构的醚以物理掺杂的方式或者化学键合的方式存在于所述杂化的聚酰胺功能层。
  2. 根据权利要求1所述的复合反渗透膜，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
  3. 根据权利要求1或2所述的复合反渗透膜，其中所述两亲性嵌段共聚物的HLB值为3至40。
  4. 根据权利要求1或2所述的复合反渗透膜，其中所述两亲性嵌段共聚物修饰层包含以下嵌段共聚物中的一种或多种：聚苯乙烯-b-聚乙二醇、DL型聚乳酸-b-聚丙烯酸、聚乙交酯-b-聚乙二醇-聚乙交酯、聚苯乙烯-b-DL型聚乳酸、聚苯乙烯-b-L型聚乳酸、聚乙二醇-b-聚乙烯亚胺、聚己内酯-b-聚乙烯亚胺、聚乳酸-羟基乙酸-b-聚赖氨酸、聚乙二醇-b-聚乳酸-聚己内酯、聚乳酸-聚己内酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇-氨基、聚乳酸-聚己内酯-b-聚乙二醇-羧基、聚乳酸-聚己内酯-b-聚乙二醇-活化酯、聚乳酸-b-聚乙二醇氨基、聚乳酸-b-聚乙二醇羧基、聚乳酸-b-聚乙二醇羟基、聚乳酸-聚己内酯-b-聚乙二醇-叶酸、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-氨基、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇、聚乳酸-聚烯丙基丙交酯-b-聚乙二醇-马来酰亚胺、聚乳酸-聚己内酯-b-聚乙二醇、聚丙烯酸-b-聚丙烯酰胺、聚丙烯酸-b-聚甲基丙烯酸甲酯、聚丙烯酸正丁酯-b-聚丙烯酸、聚丙烯酸正丁酯-b-聚丙烯酰胺、聚甲基丙烯酸叔丁酯-b-聚氧乙烯、聚甲基丙烯酸甲酯-b-聚丙烯酸、聚新戊酯-b-聚甲基丙烯酸、聚氧乙烯-b-聚丙烯酸、聚氧乙烯-b-聚丙烯酰胺、聚四氢呋喃-b-聚氧化丁烯、聚氧乙烯-b-聚己内酯、聚氧乙烯-b-聚乳酸、聚氧乙烯-b-聚环氧丙烷、聚氧乙烯-b-聚甲基丙烯酸硝基苄酯、聚氧乙烯-b-聚N-异丙基丙烯酰胺、聚氧乙烯-b-聚丙烯酸叔丁酯、聚氧乙烯-b-聚甲基丙烯酸叔丁酯、聚氧乙烯-b-聚甲基噁唑啉、聚氧乙烯-b-聚丙交酯、聚异丁烯-b-聚丙烯酸、聚异丁烯-b-聚氧乙烯、聚苯乙烯-b-聚丙烯酰胺、聚苯乙烯-b-聚丙烯酸、聚苯乙烯-b-聚甲基丙烯酸、聚苯乙烯-b-聚丙烯 酸钠、聚苯乙烯-b-聚丙基丙烯酸、聚苯乙烯磺酸-b-聚甲基丁烯、聚4-苯乙烯磺酸钠盐-b-聚氧乙烯、聚二甲基硅氧烷-b-聚氧乙烯、聚二甲基硅氧烷-b-聚甲基丙烯酸、聚乙烯基吡啶-b-聚氧乙烯、聚甲基丙烯酸-b-聚新戊酯、聚甲基丙烯酸-b-聚甲基丙烯酸羟乙酯、聚甲基丙烯酸-b-聚己内酯、聚苯乙烯-b-聚丙烯酸苄酯、聚苯乙烯-b-聚乳酸、聚苯乙烯-b-聚甲基丙烯酸乙酯、聚苯乙烯-b-聚甲基丙烯酸丁酯、聚苯乙烯-b-聚甲基丙烯酸羟丙酯、聚苯乙烯-b-聚甲基丙烯酸羟乙酯、聚乳酸羟基乙酸-b-聚乙二醇马来酰亚胺、聚乳酸羟基乙酸-b-聚乙二醇羧基、聚乳酸羟基乙酸-b-聚乙二醇氨基、聚乳酸羟基乙酸共聚物-b-聚乙二醇羟基、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇活性酯、聚乳酸羟基乙酸共聚物-b-聚乙二醇生物素、聚乳酸羟基乙酸共聚物-b-聚乙二醇叠氮、聚乳酸羟基乙酸共聚物-b-聚乙二醇磷脂、聚乳酸羟基乙酸共聚物-b-聚乙二醇醛基、聚乳酸羟基乙酸共聚物-b-聚乙二醇丙烯酯和聚乳酸羟基乙酸共聚物-b-聚乙烯亚胺。
  5. 根据权利要求1或2所述的复合反渗透膜，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10。
  6. 一种复合反渗透膜的制备方法，其特征在于，包括以下步骤：
    制备基膜，所述基膜包括在无纺布层上的聚合物多孔支撑层；
    制备两亲性嵌段共聚物溶液作为第一溶液涂覆在聚合物多孔支撑层以形成两亲性嵌段共聚物修饰层；
    将形成有两亲性嵌段共聚物修饰层、聚合物多孔支撑层的无纺布依次与作为第二溶液的包含胺类单体的水相溶液、作为第三溶液的含有酰氯类单体的油相溶液接触，在第二溶液和第三溶液的至少一者中包含具有环状结构的醚，以形成包含具有环状结构的醚的杂化的聚酰胺功能层；
    经后处理、烘干后得到复合反渗透膜。
  7. 根据权利要求6所述的复合反渗透膜的制备方法，其中所述聚合物多孔支撑层为聚砜多孔支撑层、聚醚砜多孔支撑层、聚丙烯腈多孔支撑层、聚乙烯亚胺多孔支撑层、聚芳醚砜酮多孔支撑层、聚偏氟乙烯多孔支撑层和磺化聚醚砜多孔支撑层中的一种或多种；所述聚酰胺为芳香族聚酰胺和/或脂肪族聚酰胺。
  8. 根据权利要求6或7所述的复合反渗透膜的制备方法，其中所述第一溶液包含两亲性嵌段共聚物和第一溶剂，所述两亲性嵌段共聚物包含亲水性嵌段和亲油性嵌段，所述两亲性嵌段共聚物的HLB值为3至40，所述第一溶剂为甲醇、乙醇、丙醇、丁醇、丙酮、四氢呋喃、二甲亚砜、环丁砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、水、甲苯、二甲苯、氯仿、ISOPAR-G、ISOPAR-E、ISOPAR-L、正丁烷、正庚烷、环己烷和乙基环己烷中的一种或多种；优选地，所述两亲性嵌段共聚物在所述第一溶液中的浓度为0.01wt％至10wt％。
  9. 根据权利要求6或7所述的复合反渗透膜的制备方法，其中所述具有环状结构的醚为包含结构单元(CH 2CH 2Y) n的环状醚，其中Y为选自杂原子O、N、S、P中的至少一种，n为整数并且3≤n≤10；优选地，所述具有环状结构的醚在第二溶液和第三溶液的至少一者中的浓度为0.01wt％至10wt％。
  10. 根据权利要求6或7所述的复合反渗透膜的制备方法，其中所述胺类单体为苯胺、间苯二胺、对苯二胺、邻苯二胺、1,3,5-三氨基苯、1,2,4-三氨基苯、3,5-二氨基苯甲酸、2,4-二氨基甲苯、2,4-二氨基苯甲醚、阿米酚、苯二甲基二胺、1,4-环己二胺、1,2-环己二胺、哌嗪、乙二醇胺、乙二胺、丙二胺、丁二胺、己二胺、乙醇胺、聚乙烯亚胺、三乙胺、三(2-氨乙基)胺、二乙烯三胺、N-(2-羟乙基)乙二胺、1,3-环己二胺、1,3-双哌啶基丙烷、4-氨基甲基哌嗪、乙醇胺、二乙醇胺、己二醇胺和二甘醇胺中的一种或多种，在所述第二溶液中，所述胺类单体的浓度为0.5wt％～10wt％；
    所述酰氯类单体为邻苯二甲酰氯、间苯二甲酰氯、对苯二甲酰氯、联苯二甲酰氯、均苯三甲酰氯和具有以下通式(1)表示的结构的三元酰氯中的一种或多种：
    Figure PCTCN2021135779-appb-100001
    其中R 1、R 2、R 3各自独立地为以下基团中的至少一种
    Figure PCTCN2021135779-appb-100002
    在所述第三溶液中，所述酰氯类单体的浓度为0.05wt％～5wt％。
PCT/CN2021/135779 2020-12-17 2021-12-06 复合反渗透膜及其制备方法 WO2022127637A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/257,789 US20240307829A1 (en) 2020-12-17 2021-12-06 Composite reverse osmosis membrane and preparation method therefor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011495171.8 2020-12-17
CN202011495171.8A CN114642974B (zh) 2020-12-17 2020-12-17 复合反渗透膜及其制备方法

Publications (1)

Publication Number Publication Date
WO2022127637A1 true WO2022127637A1 (zh) 2022-06-23

Family

ID=81991377

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/135779 WO2022127637A1 (zh) 2020-12-17 2021-12-06 复合反渗透膜及其制备方法

Country Status (3)

Country Link
US (1) US20240307829A1 (zh)
CN (1) CN114642974B (zh)
WO (1) WO2022127637A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115090118A (zh) * 2022-07-14 2022-09-23 重庆海通环保科技有限公司 反渗透膜功能层容液配方以及涂布工艺
CN116139698A (zh) * 2022-12-02 2023-05-23 北京纳思利万环保科技有限公司 一种反渗透膜的制备方法
CN117181002A (zh) * 2023-11-02 2023-12-08 湖南沁森高科新材料有限公司 一种海水淡化膜及其制备方法
CN118001951A (zh) * 2024-02-04 2024-05-10 同济大学 纳米笼主导传质通道的高选择性反渗透膜及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115282794B (zh) * 2022-08-19 2024-08-30 沃顿科技股份有限公司 一种耐污染海水淡化反渗透膜及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101524626A (zh) * 2008-03-07 2009-09-09 浙江欧美环境工程有限公司 外压式中空纤维纳滤膜及其制备方法
CN101874989A (zh) * 2009-12-18 2010-11-03 北京时代沃顿科技有限公司 一种耐微生物污染的复合反渗透膜及其制备方法
CN104941461A (zh) * 2014-03-27 2015-09-30 贵阳时代沃顿科技有限公司 一种海水淡化用纳滤膜及其制备方法
CN106232213A (zh) * 2014-05-01 2016-12-14 沙特基础工业全球技术有限公司 具有包含聚(亚苯基醚)和两亲聚合物的支持物的复合膜、制造方法及其分离组件
JP2018103097A (ja) * 2016-12-26 2018-07-05 三菱ケミカル株式会社 多孔質膜、及び多孔質膜の製造方法
CN110394073A (zh) * 2018-04-25 2019-11-01 华中科技大学 一种采用冠醚制备的聚酰胺复合膜、其制备和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10744748B2 (en) * 2016-02-29 2020-08-18 The Industry & Academic Cooperation In Chungnam National University (Iac) Micro nanoporous membrane, preparing method thereof and microfluidic device using thereof
CN107126851B (zh) * 2017-05-03 2018-03-06 江苏拓邦环保科技有限公司 一种复合反渗透膜及其制备方法
CN111151137B (zh) * 2020-01-03 2022-03-15 浙江工业大学 一种高通量高截盐反渗透复合膜及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101524626A (zh) * 2008-03-07 2009-09-09 浙江欧美环境工程有限公司 外压式中空纤维纳滤膜及其制备方法
CN101874989A (zh) * 2009-12-18 2010-11-03 北京时代沃顿科技有限公司 一种耐微生物污染的复合反渗透膜及其制备方法
CN104941461A (zh) * 2014-03-27 2015-09-30 贵阳时代沃顿科技有限公司 一种海水淡化用纳滤膜及其制备方法
CN106232213A (zh) * 2014-05-01 2016-12-14 沙特基础工业全球技术有限公司 具有包含聚(亚苯基醚)和两亲聚合物的支持物的复合膜、制造方法及其分离组件
JP2018103097A (ja) * 2016-12-26 2018-07-05 三菱ケミカル株式会社 多孔質膜、及び多孔質膜の製造方法
CN110394073A (zh) * 2018-04-25 2019-11-01 华中科技大学 一种采用冠醚制备的聚酰胺复合膜、其制备和应用

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115090118A (zh) * 2022-07-14 2022-09-23 重庆海通环保科技有限公司 反渗透膜功能层容液配方以及涂布工艺
CN115090118B (zh) * 2022-07-14 2023-12-01 重庆海通环保科技有限公司 反渗透膜功能层溶液配方以及涂布工艺
CN116139698A (zh) * 2022-12-02 2023-05-23 北京纳思利万环保科技有限公司 一种反渗透膜的制备方法
CN116139698B (zh) * 2022-12-02 2024-03-12 北京纳思利万环保科技有限公司 一种反渗透膜的制备方法
CN117181002A (zh) * 2023-11-02 2023-12-08 湖南沁森高科新材料有限公司 一种海水淡化膜及其制备方法
CN117181002B (zh) * 2023-11-02 2024-01-23 湖南沁森高科新材料有限公司 一种海水淡化膜及其制备方法
CN118001951A (zh) * 2024-02-04 2024-05-10 同济大学 纳米笼主导传质通道的高选择性反渗透膜及其制备方法

Also Published As

Publication number Publication date
US20240307829A1 (en) 2024-09-19
CN114642974A (zh) 2022-06-21
CN114642974B (zh) 2023-04-18

Similar Documents

Publication Publication Date Title
WO2022127637A1 (zh) 复合反渗透膜及其制备方法
US9333465B2 (en) Thin film composite membranes embedded with molecular cage compounds
EP2695670B1 (en) Composite semipermeable membrane, composite semipermeable membrane element, and method for manufacturing composite semipermeable membrane
EP2902095B1 (en) Composite semipermeable membrane
US20120201972A1 (en) Method for producing composite semipermeable membrane
US20170136422A1 (en) Composite semipermeable membrane
US10143974B2 (en) Forward osmosis-based separation membrane based on multilayer thin film, using crosslinking between organic monomers, and preparation method therefor
JP6197969B1 (ja) 複合半透膜
KR20140138651A (ko) 복합 반투막
Yang et al. Novel solvent-resistant nanofiltration membranes using MPD co-crosslinked polyimide for efficient desalination
Zhou et al. Pore size tailoring from ultrafiltration to nanofiltration with PVC-g-PDMA via rapid immersion thermal annealing
CN111686594A (zh) 一种高通量高截留的复合膜及其制备方法
EP3354333A1 (en) Water treatment membrane and method for manufacturing same
KR101971130B1 (ko) 폴리도파민 및 그래핀 옥사이드로 이루어진 중간 지지층을 포함하는 수투과도가 향상된 초박형 정삼투막 및 이의 제조 방법
US20170282129A1 (en) Composite semipermeable membrane and method for producing the same, spiral wound separation membrane element
Daneshvar et al. Tris (hydroxymethyl) aminomethane-grafted polyamine nanofiltration membrane: enhanced antifouling and pH resistant properties
US20220088542A1 (en) Composite hollow fiber membrane and composite hollow fiber membrane manufacturing method
JP7343075B1 (ja) 複合半透膜及び複合半透膜の製造方法
WO2024048695A1 (ja) 複合半透膜及び複合半透膜の製造方法
WO2023276483A1 (ja) 正浸透膜、及びそれを含む正浸透膜モジュール
WO2023048288A1 (ja) 複合半透膜
KR0123279B1 (ko) 염제거능이 우수한 복합반투막 및 그 제조방법
KR20210051805A (ko) 수처리 분리막의 제조 방법 및 이에 의하여 제조된 수처리 분리막
KR20210095428A (ko) 수처리 분리막의 제조 방법 및 이에 의하여 제조된 수처리 분리막
KR20210095476A (ko) 수처리 분리막의 제조 방법 및 이에 의하여 제조된 수처리 분리막

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21905566

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 18257789

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 21905566

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 08/08/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21905566

Country of ref document: EP

Kind code of ref document: A1