KR102075181B1 - Composition for interfacial polymerizing polyamide, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module - Google Patents

Abstract

The present application is directed to at least one of an amine compound and an acyl halide compound; Amine-based hydrophilic additives; And a composition for polyamide interfacial polymerization comprising a metal chelate compound, a method for preparing a reverse osmosis membrane using the same, and a reverse osmosis membrane.

Description

COMPOSITION FOR INTERFACIAL POLYMERIZING POLYAMIDE, METHOD FOR PREPARING REVERSE OSMOSIS MEMBRANE USING THE SAME, AND REVERSE OSMOSIS MEMBRANE AND WATER TREATMENT MODULE}

The present specification relates to a composition for polyamide interfacial polymerization and a method for producing a reverse osmosis membrane using the same. The present specification also relates to a reverse osmosis membrane prepared using the polyamide interfacial polymerization composition and a water treatment module including the reverse osmosis membrane.

Osmotic phenomenon is the movement of a solvent through a membrane from a solution of low solute concentration to a high solution between two solutions separated by a semi-permeable membrane. Is called osmotic pressure. By applying an external pressure higher than the osmotic pressure, the solvent moves to a solution having a lower concentration of solute. This phenomenon is called reverse osmosis. Using the reverse osmosis principle, a pressure gradient can be used as a driving force to separate various salts and organic materials through the semipermeable membrane. The water treatment membrane using the reverse osmosis phenomenon is used to separate the material of the molecular level, remove the salt from the brine or sea water to supply household water for construction, industrial use.

Representative examples of such water treatment separation membranes include polyamide-based water treatment separation membranes, and polyamide-based water treatment separation membranes are manufactured by a method of forming a polyamide active layer on a microporous layer support. A sulfonic layer is formed to form a microporous support, and the microporous support is immersed in an m-phenylene diamine (mPD) aqueous solution to form an mPD layer, which is then trimesoyl chloride (TriMesoyl Chloride, TMC) It is manufactured by the method of forming a polyamide layer by immersing in an organic solvent and making an mPD layer contact with TMC and interfacially polymerizing.

Roh et al., J. Poly. Sci. 36, 1821-1830, 1998]

The present application is intended to provide a reverse osmosis membrane having a high salt removal rate and an improved flux by adding an amine hydrophilic additive together with a metal chelate compound when forming a polyamide layer of the reverse osmosis membrane.

One embodiment of the present specification is at least one of an amine compound and an acyl halide compound; Amine-based hydrophilic additives; And it provides a composition for polyamide interfacial polymerization comprising a metal chelate compound.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive has at least one NH ₂ and at least one COOH.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

L1 is a direct bond or -NR-, R is hydrogen, an alkyl group or an aryl group,

L2 is a direct bond or -S (= O) _2- ,

L 3 is arylene unsubstituted or substituted with a direct bond or an OH group,

Ra to Rc are the same as or different from each other, and are each independently hydrogen, an alkyl group or an aryl group, a and b are each an integer of 1 to 5, c is an integer of 0 to 4, a + b + c is 6 When a, b, and c are each 2 or more, the substituents in parentheses are the same or different.

Another embodiment of the present specification comprises the steps of preparing a porous support; And it provides a method for producing a reverse osmosis membrane comprising the step of forming a polyamide active layer on the porous support using the above-described composition for polyamide interfacial polymerization.

According to one embodiment, the composition for polyamide interfacial polymerization comprises an amine compound, an amine-based hydrophilic additive, and a metal chelate compound, the polyamide by interfacial polymerization by contacting the polyamide interfacial polymerization composition with an acyl halide compound Form an active layer.

According to another example, the polyamide interfacial polymerization composition includes an acyl halide compound, an amine hydrophilic additive, and a metal chelate compound, and by interfacial polymerization by contacting the polyamide interfacial polymerization composition with an amine compound To form a polyamide active layer.

Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer includes an amine hydrophilic additive and a metal chelate compound, and the hydrophilic group of the amine hydrophilic additive may form a complex with the metal chelate compound. It provides a reverse osmosis membrane that the amine group of the amine-based hydrophilic additive can form an amide bond.

According to the embodiments described herein, the amine group of the amine-based hydrophilic additive not only improves the salt removal rate by amide bonding with the acyl halide compound, but also increases the permeate flow rate by increasing the partial pore structure by strong bonding with the metal chelate compound. You can improve flux.

In this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part "includes" a certain component, this means that the component may further include other components, except for the case where there is no description to the contrary.

One embodiment of the present specification is at least one of an amine compound and an acyl halide compound; Amine-based hydrophilic additives; And it provides a composition for polyamide interfacial polymerization comprising a metal chelate compound. Here, the amine hydrophilic additive is a compound different from the amine compound.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive has at least one COOH as a hydrophilic group.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive has at least one NH ₂ and at least one COOH.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

L1 is a direct bond or -NR-, R is hydrogen, an alkyl group or an aryl group,

L2 is a direct bond or -S (= O) _2- ,

L 3 is arylene unsubstituted or substituted with a direct bond or an OH group,

Ra to Rc are the same as or different from each other, and are each independently hydrogen, an alkyl group or an aryl group, a and b are each an integer of 1 to 5, c is an integer of 0 to 4, a + b + c is 6 When a, b, and c are each 2 or more, the substituents in parentheses are the same or different.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive is represented by the following formula (2).

[Formula 2]

In the formula (2), the substituent is as defined in formula (1).

According to another exemplary embodiment of the present specification, the amine-based hydrophilic additive may be represented by one of the following Chemical Formulas 2-1 to 2-4, and may include one kind or two or more kinds.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Chemical Formulas 2-1 to 2-4,

R 'and R "are each hydrogen, an alkyl group or an aryl group.

In the present specification, the alkyl group is a straight or branched chain alkyl group having 1 to 20 carbon atoms.

In the present specification, the aryl group is a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

According to yet an embodiment of the present disclosure, the amine-based hydrophilic additive may be selected from the following structural formula.

According to an exemplary embodiment, the polyamide interfacial polymerization composition is an aqueous solution including an amine compound, an amine hydrophilic additive, and a metal chelate compound, and the amine hydrophilic additive is 0.1-0.6 wt% based on 100 wt% of the total composition. Preferably, it may be included in 0.275% by weight. At this time, the composition may be an aqueous solution. According to one embodiment, the weight ratio of the amine compound, such as mPD (m-phenylenediamine) to the amine hydrophilic additive, may be from 8: 1 to 12: 1, preferably 10: 1, in which case maintaining the salt removal rate High permeation flux can be achieved.

According to another exemplary embodiment of the present specification, the metal chelate compound may be a metal chelate compound including a metal atom or a metal ion and a bidentate ligand. Wherein the metal may be a Group 2-15 metal on the IUPAC Periodic Table. According to one example, the metal may be a Group 2 or 13 metal on the IUPAC Periodic Table. According to one example, the metal may be selected from the group consisting of alkaline earth metals such as beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba). The bidentate ligand can be selected from the following structural formulas, for example.

및

And

Wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently C ₁ -C ₁₀ alkyl, halogenated C ₁ -C ₁₀ alkyl, 5- or 6-membered aromatic ring, condensed 6- Aromatic bicyclic systems containing two ring members and aromatic bicyclic systems containing a 5-membered ring condensed to a 6-membered aromatic ring. Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be individually selected from C ₁ -C ₆ alkyl and halogenated C ₁ -C ₆ alkyl. Any one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a C ₃ -C ₅ aromatic ring containing 1 to 4 heteroatoms selected from phenyl, benzyl, N, O and S and N, O and It may be selected from a C ₅ -C ₉ bicyclic aromatic ring system containing 1 to 4 hetero atoms selected from S. Any one of R ¹ , R ² , R ³ , R ⁴ or R ⁵ is furanyl, pyrrolyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, phenyl, pyridinyl, Pyrazinyl, pyrimidinyl, pyridazinyl, purinyl, benzoxazolyl, benzothiazolyl, benzisoxazolyl, benzimidazolyl, benzothiophenyl, indazolyl, benzo [c] -thiophenyl, iso Indolyl, isobenzofuranyl, naphthaleneyl, quinolinyl, quinoxalinyl, quinazolinyl and isoquinolinyl.

The bidentate ligand may be acetylacetonate (aca) or fluorinated acetylacetonate. The bidentate ligand may be beta-diketonate or fluorinated beta-diketonate. For example, bidentate ligands include pentane-2,4-dionate; 1,5-difluoropentane-2,4-dionate; 1,1,5,5-tetrafluoropentane-2,4-dionate; 1,1,1,5,5,5-hexafluoropentane-2,4-dionate; Propane-1,3-dionate; Butane-1,3-dionate; 4-fluorobutane-1,3-dionate; 4,4-difluoro-butane-1,3-dionate; 4,4,4-trifluorobutane-1,3-dionate; Heptane-3,5-dionate; 1-fluoro-hexane-2,4-dionate; 1,5-difluoropentane-2,4-dionate; 1,1,5-trifluoropentane-2,4-dionate; 1,1,5,5-tetrafluoropentane-2,4-dionate; 1,1,1,5,5-pentafluoropentane-2,4-dionate; 1,1,1,5,5,5-hexafluoropentane-2,4-dionate; And octane-3,5-dionate and combinations thereof.

In some embodiments, the metal chelate additive containing a bidentate ligand and a metal atom or metal ion is Al (acac) ₃ , Al (F ₆ acac) ₃ , Be (acac) ₂ , Be (F ₆ acac) ₂ , Ca (acac) ₂ , Ca (F ₆ acac) ₂ , Cd (acac) ₂ , Cd (F ₆ acac) ₂ , Ce (acac) ₃ , Ce (F ₆ acac) ₃ , Cr (acac) ₃ , Co ( acac) ₃ , Cu (acac) ₂ , Cu (F ₆ acac) ₂ , Dy (acac) ₃ , Er (acac) ₃ , Fe (acac) ₂ , Fe (acac) ₃ , Ga (acac) ₃ , Hf ( acac) ₄ , In (acac) ₃ , K (acac), Li (acac), Mg (acac) ₂ , Mg (F ₆ acac) ₂ , Mn (acac) ₂ , Mn (acac) ₃ , MoO ₂ (acac ) ₂ , MoO ₂ (F ₆ acac) ₂ , Na (acac), Nd (acac) ₃ , Nd (F ₆ acac) ₃ , Ni (acac) ₂ , Ni (F ₆ acac) ₂ , Pd (acac) ₂ , Pr (acac) ₃ , Pr (F ₆ acac) ₃ , Ru (acac) ₃ , Ru (F ₆ acac) ₃ , Sc (acac) ₂ , Sc (F ₆ acac) ₂ , Sm (acac) ₃ , Sn (acac) ₂ , Sn (acac) ₂ Cl ₂ , t-butyl-Sn (acac) ₂ , t-butyl-Sn (acac) ₂ Cl ₂ , Sn (F ₆ acac) ₂ , Sr (acac) ₂ , Sr (F ₆ acac) ₂ , Tb (acac) ₃ , V (acac) ₃ , Y (acac) ₃ , Y (F ₆ acac) ₃ , Zn (acac) ₂ , Zn (F ₆ acac) ₂ , and Zr ( acac) can be selected from ₄ , F ₆ acac refers to 1,1,1,5,5,5-hexafluoroacetyl-acetonate.

According to one embodiment, the composition for polyamide interfacial polymerization is an aqueous solution containing an amine compound, an amine-based hydrophilic additive and a metal chelate compound, wherein the metal chelate compound is 0.02-0.05 based on 100% by weight of the total composition. Wt%, preferably 0.025 wt%. At this time, the composition may be an aqueous solution.

The amine compound is not limited as long as it can be used for polymerization of polyamide, but specific examples include m-phenylenediamine (mPD), p-phenylenediamine (PPD), and 1,3,6-benzenetriamine (TAB ), 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine or mixtures thereof may be preferably used. The content of the amine compound may be 0.1 wt% or more and 20 wt% or less with respect to 100 wt% of the composition.

The acyl halide compound is not limited as long as it can be used for the polymerization of the polyamide, but is an aromatic compound having 2 to 3 carboxylic acid halides as a specific example, and may include trimezoyl chloride, isophthaloyl chloride and terephthaloyl. One or a mixture of two or more selected from the group of compounds consisting of chlorides may be preferably used. The amount of the acyl halide compound may be 0.05 wt% or more and 1 wt% or less with respect to 100 wt% of the composition.

For example, when the composition for polyamide interfacial polymerization contains an amine compound, the composition may be water, acetone, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidinone (NMP), or hexamethylphospho as a solvent. Amide (hexamethylphosphoramide, HMPA) may be further included.

For example, when the composition for polyamide interfacial polymerization includes an acyl halide compound, the composition may further include an organic solvent. The organic solvent may be an aliphatic hydrocarbon solvent, for example, a hydrophobic liquid which is not mixed with freons and water such as hexane having 5 to 12 carbon atoms, cyclohexane, heptane, and alkanes, for example, alkanes having 5 to 12 carbon atoms. And mixtures thereof IsoPar (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon) and the like can be used, but is not limited thereto.

Another embodiment of the present disclosure relates to a method for manufacturing a reverse osmosis membrane, comprising the steps of preparing a porous support; And forming a polyamide active layer on the porous support using the polyamide interfacial polymerization composition described above.

According to one embodiment, the composition for polyamide interfacial polymerization comprises an amine compound, an amine-based hydrophilic additive, and a metal chelate compound, the polyamide by interfacial polymerization by contacting the polyamide interfacial polymerization composition with an acyl halide compound Form an active layer. For example, after forming a composition layer comprising an amine compound, an amine hydrophilic additive, and a metal chelate compound on the porous support, the acyl halide compound may be contacted on the composition layer to interfacially polymerize the polyamide. The polyamide active layer can be formed by this. The acyl halide compound may be contacted on the composition layer in a state contained in an organic solvent.

According to another example, the polyamide interfacial polymerization composition includes an acyl halide compound, an amine hydrophilic additive, and a metal chelate compound, and by interfacial polymerization by contacting the polyamide interfacial polymerization composition with an amine compound To form a polyamide active layer. For example, after the amine compound layer is formed on the porous support, an acyl halide compound, an amine hydrophilic additive, and a metal chelate compound are brought into contact with the composition to interfacially polymerize the polyamide, thereby forming a polyamide active layer. Can be formed. The amine compound layer may be formed by an aqueous solution containing an amine compound.

In the above production method, upon contact between the amine compound and the acyl halide compound, the amine compound and the acyl halide compound react to form a polyamide by interfacial polymerization, and are adsorbed onto the microporous support to form a thin film. At this time, the amine-based hydrophilic additive may react with the acyl halide compound to form an amide bond. The contact may be made to the active layer through a method such as dipping, spraying or coating. Interfacial polymerization conditions may be used those known in the art.

The method of forming a composition layer including an amine compound layer or an amine compound, an amine hydrophilic additive, and a metal chelate compound on the porous support is not particularly limited. For example, a method of spraying, applying, dipping, dropping, or the like can be used.

The preparation method may additionally perform a step of removing the aqueous solution containing the excess amine compound as needed before contacting the amine compound and the acyl halide compound. When there are too many aqueous solutions containing the amine compound formed on the porous support, the composition in the aqueous solution may be nonuniform, and when the composition in the aqueous solution is nonuniform, a nonuniform active layer may be formed by subsequent interfacial polymerization. Therefore, it is preferable to remove excess aqueous solution after forming an amine aqueous solution layer on the said porous support body. The removal of the excess aqueous solution is not particularly limited, but may be performed using, for example, a sponge, air knife, nitrogen gas blowing, natural drying, a compression roll, or the like.

According to one embodiment of the present specification, as the porous support, a coating layer of a polymer material may be used on a nonwoven fabric. Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyether ether ketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluorine. Ride or the like may be used, but is not necessarily limited thereto. Specifically, polysulfone may be used as the polymer material.

According to one embodiment of the present specification, the thickness of the porous support may be 60 μm to 100 μm, but is not limited thereto and may be adjusted as necessary. In addition, the pore size of the porous support is preferably 1 nm to 500 nm, but is not limited thereto.

Another embodiment of the present specification provides a reverse osmosis membrane manufactured by the method of manufacturing a reverse osmosis membrane according to the above-described embodiments. This reverse osmosis membrane comprises a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer comprises at least one of an amine compound and an acyl halide compound; Amine-based hydrophilic additives; And a composition for polyamide interfacial polymerization containing a metal chelate compound.

The amine-based hydrophilic additive and the metal chelate compound may be included in a composition containing an amine compound, such as an aqueous solution layer composition, or may be included in a composition containing an acyl halide compound, such as an organic layer composition. Preferably, the amine-based hydrophilic additive and the metal chelate compound are included in a composition containing an amine compound, such as an aqueous solution layer composition.

The polyamide active layer is formed by interfacial polymerization of the layer containing the amine compound and the layer containing the acyl halide compound, wherein the amine-based hydrophilic additive and the metal chelate compound comprise the amine compound; Or a layer comprising the acyl halide compound; Or in both layers. Preferably, the amine hydrophilic additive and the metal chelate compound are included in the layer containing the amine compound.

The hydrophilic group of the amine-based hydrophilic additive may form a complex with the metal chelate compound. In addition, the amine group of the amine-based hydrophilic additive may participate in the interfacial polymerization to form the polyamide active layer to form an amide bond.

Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer includes an amine hydrophilic additive and a metal chelate compound, and the hydrophilic group of the amine hydrophilic additive may form a complex with the metal chelate compound. It provides a reverse osmosis membrane that the amine group of the amine-based hydrophilic additive can form an amide bond.

According to one example, the amine-based hydrophilic additive and the metal chelate compound may form a complex as follows.

In addition, the amine-based hydrophilic additive may form an amide bond with an acyl halide group of an acyl halide compound such as trimezoyl chloride used for polyamide polymerization.

The reverse osmosis membrane may further include an additional layer as necessary, for example, the reverse osmosis membrane may further include an antifouling layer provided on the polyamide active layer.

One embodiment of the present invention provides a water treatment module including at least one reverse osmosis membrane.

The specific kind of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module or a spiral wound module. In addition, as long as the water treatment module includes the reverse osmosis membrane according to the exemplary embodiment of the present specification described above, other configurations and manufacturing methods are not particularly limited, and general means known in the art may be employed without limitation. .

Meanwhile, the water treatment module according to one embodiment of the present specification has excellent salt removal rate and permeate flow rate, and has excellent chemical stability, and thus may be usefully used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, seawater treatment devices, and the like. have.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

Example  1 to 3

On the nonwoven fabric with polysulfone layer, m-phenylenediamine (mPD), 3,5-diaminobenzoic acid (DABA), TEA (Triethylamine), CSA (Camphorsulfonic acid), metal chelate compound ( An aqueous solution layer was formed using a composition comprising strontium hexafluoroacetylacetonate, Strontium hexafluoroacetylacetonate), and a surfactant. Subsequently, a reverse osmosis membrane was prepared by applying a composition including trimezoyl chloride (TMC), 1,3,5-trimethylbenzene (TMB), and Isopar-G on the aqueous solution layer to form an organic layer to perform interfacial polymerization. At this time, the mPD and DABA content in the composition for forming an aqueous layer was as shown in Table 1 below. The content of the metal chelate compound in the composition for forming an aqueous solution layer was 0.025% by weight.

Comparative example  One

The same procedure as in Examples 1 to 3 was performed except that mPD was used at 2.75% by weight in the composition for forming an aqueous layer without using an amine hydrophilic additive.

Example  4

Except that ethylenediamine tetraacetic acid (EDTA) was added to the aqueous layer was carried out in the same manner as in Example 2.

Example  5

The same process as in Example 2 was performed except that an additive mesityl oxide was added to the organic layer.

The salt removal rate and permeate flow rate of the membranes prepared in Comparative Examples and Examples are shown in Table 1 below. Inferred from the results of deriving the mPD residual content in the reverse osmosis membrane prepared in Example, the residual content of the reverse osmosis membrane of DABA was about 0.24-1.42 mg / m ² . Salt removal rate and permeate flux were evaluated at 250 ppm TDS (60 dissolved solids), 60 psi, home membrane evaluation conditions.

mPD
(wt%) DABA
(wt%) Aqueous solution layer
additive
Addition
(X: no addition,
O: added) Organic layer
additive
Addition
(X: no addition,
O: added) Salt removal rate
(%) Permeate flow rate
(gfd) Comparative Example 1 2.75 0 X X 95.25 11.78 Example 1 2.6125 0.1375 X X 96.50 15.23 Example 2 2.475 0.275 X X 97.10 19.44 Example 3 2.2 0.55 X X 95.15 18.55 Example 4 2.475 0.275 O X 98.05 18.26 Example 5 2.475 0.275 O O 98.26 20.62

As shown in Table 1, it was confirmed that the permeate flow rate is increased in Examples 1 to 3, compared to the comparative example without the amine-based hydrophilic additive. In addition, in Example 5 using the additive mesityl oxide (Mesityl oxide) in the organic layer was confirmed that the increase in permeation flow rate when adding DABA. In addition, in Example 4 using ethylenediamine tetraacetic acid (EDTA) in the aqueous solution layer, it was confirmed that the permeation flux was improved when DABA was added.

Claims (20)

At least one of an amine compound and an acyl halide compound; Amine-based hydrophilic additives; And a composition for polyamide interfacial polymerization comprising a metal chelate compound,
The amine-based hydrophilic additive is a composition for polyamide interfacial polymerization, which is represented by one of the formula
[Formula 2-1]

[Formula 2-3]

[Formula 2-4]

In Chemical Formulas 2-1, 2-3, and 2-4,
R 'is hydrogen, an alkyl group or an aryl group,
R ″ is hydrogen, a hydroxy group, an alkyl group or an aryl group. delete delete delete The composition according to claim 1, wherein the amine-based hydrophilic additive is selected from the following structural formulas:

The composition according to claim 1, wherein the metal chelate compound is a metal chelate compound comprising a metal atom or a metal ion and a bidentate ligand. The composition of claim 6, wherein the metal atom or metal ion is an alkaline earth metal atom or an ion thereof. The composition according to claim 6, wherein the bidentate ligand is selected from Formulas 1 to 7 below:

And

Wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently C ₁ -C ₁₀ alkyl, halogenated C ₁ -C ₁₀ alkyl, 5- or 6-membered Aromatic rings, aromatic bicyclic systems containing two condensed 6-membered rings, and aromatic bicyclic systems containing 5-membered rings condensed to six-membered aromatic rings. Each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be individually selected from C ₁ -C ₆ alkyl and halogenated C ₁ -C ₆ alkyl. Any one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a C ₃ -C ₅ aromatic ring containing 1 to 4 heteroatoms selected from phenyl, benzyl, N, O and S and N, O and It may be selected from a C ₅ -C ₉ bicyclic aromatic ring system containing 1 to 4 hetero atoms selected from S. Any one of R ¹ , R ² , R ³ , R ⁴ or R ⁵ is furanyl, pyrrolyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, phenyl, pyridinyl, Pyrazinyl, pyrimidinyl, pyridazinyl, purinyl, benzoxazolyl, benzothiazolyl, benzisoxazolyl, benzimidazolyl, benzothiophenyl, indazolyl, benzo [c] -thiophenyl, iso Indolyl, isobenzofuranyl, naphthaleneyl, quinolinyl, quinoxalinyl, quinazolinyl and isoquinolinyl. The method of claim 6, wherein the bidentate ligand is Al (acac) ₃ , Al (F ₆ acac) ₃ , Be (acac) ₂ , Be (F ₆ acac) ₂ , Ca (acac) ₂ , Ca (F ₆ acac) ₂ , Cd (acac) ₂ , Cd (F ₆ acac) ₂ , Ce (acac) ₃ , Ce (F ₆ acac) ₃ , Cr (acac) ₃ , Co (acac) ₃ , Cu (acac) ₂ , Cu (F ₆ acac) ₂ , Dy (acac) ₃ , Er (acac) ₃ , Fe (acac) ₂ , Fe (acac) ₃ , Ga (acac) ₃ , Hf (acac) ₄ , In (acac) ₃ , K (acac ), Li (acac), Mg (acac) ₂ , Mg (F ₆ acac) ₂ , Mn (acac) ₂ , Mn (acac) ₃ , MoO ₂ (acac) ₂ , MoO ₂ (F ₆ acac) ₂ , Na (acac), Nd (acac) ₃ , Nd (F ₆ acac) ₃ , Ni (acac) ₂ , Ni (F ₆ acac) ₂ , Pd (acac) ₂ , Pr (acac) ₃ , Pr (F ₆ acac) ₃ , Ru (acac) ₃ , Ru (F ₆ acac) ₃ , Sc (acac) ₂ , Sc (F ₆ acac) ₂ , Sm (acac) ₃ , Sn (acac) ₂ , Sn (acac) ₂ Cl ₂ , t-butyl-Sn (acac) ₂ , t-butyl-Sn (acac) ₂ Cl ₂ , Sn (F ₆ acac) ₂ , Sr (acac) ₂ , Sr (F ₆ acac) ₂ , Tb (acac) ₃ , For polyamide interfacial polymerization selected from V (acac) ₃ , Y (acac) ₃ , Y (F ₆ acac) ₃ , Zn (acac) ₂ , Zn (F ₆ acac) ₂ , and Zr (acac) ₄ Composition. The composition for polyamide interfacial polymerization according to any one of claims 1 and 5 to 9, wherein the polyamide interfacial polymerization composition is an aqueous solution containing an amine compound, an amine hydrophilic additive, and a metal chelate compound. The composition of claim 10, wherein the amine-based hydrophilic additive is present in an amount of 0.1 to 0.6 wt% based on 100 wt% of the total composition. The composition of claim 10, wherein the metal chelate compound is present in an amount of 0.02 to 0.05% by weight based on 100% by weight of the total composition. The composition for polyamide interfacial polymerization according to claim 1, further comprising a solvent. Preparing a porous support; And forming a polyamide active layer on the porous support using the polyamide interfacial polymerization composition according to any one of claims 1 and 5 to 9. The polyamide interfacial polymerization composition according to claim 14, wherein the polyamide interfacial polymerization composition comprises an amine compound, an amine hydrophilic additive, and a metal chelate compound, and the polyamide is interfacially polymerized by contacting the polyamide interfacial polymerization composition with an acyl halide compound. Method for producing a reverse osmosis membrane to form an active layer. The polyamide interfacial polymerization composition according to claim 14, wherein the polyamide interfacial polymerization composition comprises an acyl halide compound, an amine hydrophilic additive, and a metal chelate compound, and the polyamide is interfacially polymerized by contacting the polyamide interfacial polymerization composition with an amine compound. Method for producing a reverse osmosis membrane to form an active layer. Reverse osmosis membrane prepared by the manufacturing method according to claim 14. Porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer includes an amine hydrophilic additive and a metal chelate compound, and the hydrophilic group of the amine hydrophilic additive may form a complex with the metal chelate compound. As the reverse osmosis membrane that the amine group of the amine-based hydrophilic additive can form an amide bond,
The amine-based hydrophilic additive is a reverse osmosis membrane that is represented by one of the following formulas 2-1, 2-3 and 2-4:
[Formula 2-1]

[Formula 2-3]

[Formula 2-4]

In Chemical Formulas 2-1, 2-3, and 2-4,
R 'is hydrogen, an alkyl group or an aryl group,
R ″ is hydrogen, a hydroxy group, an alkyl group or an aryl group. The reverse osmosis membrane according to claim 18, further comprising an antifouling layer provided on the polyamide active layer. Water treatment module comprising a reverse osmosis membrane according to claim 18 or 19.