KR20210051614A - Composition for interfacial polymerizing polyamide and method for manufacturing water-treatment membrane using same - Google Patents

Abstract

The present invention relates to: a composition for interfacial polymerization of polyamide, which contains a compound represented by chemical formula 1 and an acyl halide compound, and contains 20 mol% or more to less than 100 mol% of the compound represented by the chemical formula 1, based on 100 mol% of the acyl halide compound; a method for manufacturing a water treatment separation membrane using the composition; and a water treatment separation membrane. When a water treatment separation membrane is manufactured using the polyamide interfacial polymerization composition according to an exemplary embodiment of the present specification, the permeate flow rate increases as a crosslinking density of a polyamide active layer decreases.

Description

A composition for polyamide interfacial polymerization and a method of manufacturing a water treatment separation membrane using the same {COMPOSITION FOR INTERFACIAL POLYMERIZING POLYAMIDE AND METHOD FOR MANUFACTURING WATER-TREATMENT MEMBRANE USING SAME}

The present specification relates to a composition for polyamide interfacial polymerization, a method of manufacturing a water treatment separation membrane using the same, and a water treatment separation membrane manufactured thereby.

The phenomenon that the solvent moves through the separation membrane from the solution with the low solute concentration to the high solution between the two solutions separated by the semi-permeable membrane is called the osmotic phenomenon.At this time, the pressure acting on the solution side with the high solute concentration due to the movement of the solvent Is called osmotic pressure. However, when an external pressure higher than the osmotic pressure is applied, the solvent moves toward a solution with a low solute concentration, and this phenomenon is called reverse osmosis. Using the reverse osmosis principle, various salts or organic substances can be separated through a semi-permeable membrane using a pressure gradient as a driving force. Water treatment separation membranes using the reverse osmosis phenomenon are used to separate substances at the molecular level, remove salts from salt water or seawater, and supply water for household, construction, and industrial use.

A representative example of such a water treatment separation membrane may be a polyamide-based water treatment separation membrane, and the polyamide-based water treatment separation membrane is manufactured by forming a polyamide active layer on a microporous layer (porous support), and more specifically, A polysulfone layer is formed on the nonwoven fabric to form a microporous layer, and the microporous layer is immersed in an m-phenylenediamine (mPD) aqueous solution to form an mPD layer, which is again trimesoyl chloride ( Trimesoyl Chloride, TMC) It is manufactured by immersing in an organic solvent and interfacial polymerization of the mPD layer in contact with TMC to form a polyamide layer.

In the water treatment separation membrane, the salt removal rate and the permeate flow rate are used as important indicators for the performance of the membrane.

Korean Patent Publication No. 10-1999-0019008

The present specification is to provide a composition for polyamide interfacial polymerization, a method of manufacturing a water treatment separation membrane using the same, and a water treatment separation membrane manufactured thereby.

An exemplary embodiment of the present specification

A compound represented by the following formula (1); And an acyl halide compound, wherein the content of the compound represented by Formula 1 is 20 mol% or more and less than 100 mol% based on 100 mol% of the acyl halide compound.

[Formula 1]

In Formula 1,

R1 to R5 are the same as or different from each other, and each independently hydrogen; Or, it is an electron donating group.

In addition, an exemplary embodiment of the present specification

Preparing a porous layer; And

It provides a method of manufacturing a water treatment separation membrane comprising the step of interfacial polymerization of the composition for interfacial polymerization of the polyamide and an aqueous solution containing an amine compound to form a polyamide active layer on the porous layer.

In addition, an exemplary embodiment of the present specification provides a water treatment separation membrane manufactured by the method of manufacturing the water treatment separation membrane.

In addition, an exemplary embodiment of the present specification provides a water treatment module including at least one water treatment separation membrane.

When a water treatment separation membrane is manufactured using the polyamide interfacial polymerization composition according to an exemplary embodiment of the present specification, as the crosslinking density of the polyamide active layer decreases, the permeation flow rate increases.

1 shows a water treatment separation membrane according to an exemplary embodiment of the present specification.

Hereinafter, the present specification will be described in more detail.

In an exemplary embodiment of the present specification, the composition for polyamide interfacial polymerization is a compound represented by the following formula (1); And an acyl halide compound, wherein the content of the compound represented by Formula 1 is 20 mol% or more and less than 100 mol% based on 100 mol% of the acyl halide compound.

[Formula 1]

In Formula 1,

R1 to R5 are the same as or different from each other, and each independently hydrogen; Or, it is an electron donating group.

In order to improve the permeation flow rate of the water treatment separation membrane, it is necessary to lower the cross-linking density of the polyamide active layer. When an alcoholic additive is added to the aqueous amine compound solution, the dielectric constant of the aqueous solution is adjusted, and this affects the diffusion of the amine compound during interfacial polymerization, thereby lowering the crosslinking density. However, in this case, there is a problem in that delamination may occur between the porous layer and the active layer because the alcohol additives affect the porous layer.

In order to solve this problem, the inventors of the present invention introduced the compound represented by Formula 1 into an organic solution containing an acyl halide compound, and when forming the polyamide active layer of the water treatment separation membrane, the acyl halide in the organic solution and the compound represented by Formula 1 were It was found that by forming ester bonds, the ratio of amide bonds in the active layer is reduced, so that the crosslinking density decreases and, ultimately, the permeate flow rate can be increased without a significant decrease in the salt removal rate.

In addition, when the content of the compound represented by Formula 1 relative to 100 mol% of the acyl halide compound is 20 mol% or more and 100 mol% or less, preferably more than 20 mol% and less than 100 mol%, more preferably 30 mol% or more and 90 mol% or less, Formula 1 It was found that the effect of the compound represented by is sufficient, so that the effect of improving the permeation flow rate can be expected, and the effect of preventing the phenomenon that the salt removal rate is excessively decreased.

In the present specification, when a member is positioned'on' another member, this includes not only a case in which a member is in contact with another member, but also a case in which another member exists between the two members.

In the present specification, when a part'includes' a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, iso Pentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl , 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylhexyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the electron donating group means that the Hammett sigma constant (σ) value is less than 0. The Hammet Sigma constant value can be obtained by measuring the degree of ionization of benzoic acid according to the change of the substituent based on benzoic acid, and is established between the substituent of the meta-substituted benzene derivative and the reaction rate constant or the equilibrium constant. It can be obtained through log(k/k ₀ ) = ρХσ or log(K/K _{0) = ρХσ.} The Hammet constant value of the hydrogen atom is defined as zero. In the above formula, k is the rate constant of the benzene derivative without a substituent, k ₀ is the rate constant of the benzene derivative substituted with the substituent, K is the equilibrium constant of the benzene derivative without the substituent, and K ₀ is the equilibrium of the benzene derivative substituted with the substituent The constant, ρ, represents the reaction constant determined by the type and condition of the reaction. The Hammet Sigma constant value of the hydrogen atom is zero.

In the present specification, the electron donating group is an alkyl group.

In an exemplary embodiment of the present specification, R1 to R5 are each hydrogen.

In an exemplary embodiment of the present specification, at least one of R1 to R5 is an electron donor.

In an exemplary embodiment of the present specification, any one of R1 to R5 is an electron donor, and the other four are each hydrogen.

In the exemplary embodiment of the present specification, R1 is an electron donating group, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is an alkyl group, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is a straight-chain alkyl group, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 10 carbon atoms, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 5 carbon atoms, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is a straight-chain alkyl group having 1 to 3 carbon atoms, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R1 is an ethyl group, and R2 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is an electron donating group, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is an alkyl group, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is a linear alkyl group, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is a linear alkyl group having 1 to 10 carbon atoms, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is a straight-chain alkyl group having 1 to 5 carbon atoms, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is a straight-chain alkyl group having 1 to 3 carbon atoms, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R2 is an ethyl group, and R1 and R3 to R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is an electron donating group, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is an alkyl group, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is a straight-chain alkyl group, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is a straight-chain alkyl group having 1 to 10 carbon atoms, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is a straight-chain alkyl group having 1 to 5 carbon atoms, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is a straight-chain alkyl group having 1 to 3 carbon atoms, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, R3 is an ethyl group, and R1, R2, R4, and R5 are each hydrogen.

In the exemplary embodiment of the present specification, the compound represented by Formula 1 is a phenol unsubstituted or substituted with an alkyl group.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is phenol or an alkylphenol having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is phenol or an alkylphenol having 1 to 5 carbon atoms.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is phenol or an alkylphenol having 1 to 3 carbon atoms.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is phenol or ethylphenol.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is phenol or 4-ethylphenol.

In the exemplary embodiment of the present specification, R1 to R5 are each hydrogen, and the content of the compound represented by Formula 1 is 70 mol% or more and less than 100 mol%, preferably 80 mol%, based on 100 mol% of the acyl halide compound. It is more than or equal to 90 mol%.

In the exemplary embodiment of the present specification, at least one of R1 to R5 is an electron donating group, and the content of the compound represented by Formula 1 is more than 20 mol% and less than 50 mol% based on 100 mol% of the acyl halide compound. More specifically, any one of R1 to R5 is an alkyl group and the other four are hydrogen, and the content of the compound represented by Formula 1 is 30 mol% or more and less than 50 mol% based on 100 mol% of the acyl halide compound.

In the exemplary embodiment of the present specification, when each of R1 to R5 is hydrogen (phenol), and when at least one of R1 to R5 is an electron donating group (alkylphenol), acyl halide because the acidity is different from each other. Since the reactivity with the compound is also different, the optimum content range is different.

In the exemplary embodiment of the present specification, the acyl halide compound is an aromatic compound having two or three carboxylic acid halides, for example, trimesoyl chloride (TMC), isophthaloyl chloride, and terephthaloyl chloride. It is at least one selected, preferably trimesoyl chloride (TMC).

In the exemplary embodiment of the present specification, the content of the acyl halide compound is 0.05wt% to 1wt%, preferably 0.08wt% to 0.8wt%, more preferably based on 100wt% of the polyamide interfacial polymerization composition. It may be from 0.08wt% to 0.6wt%. When the content of the acyl halide compound is in the above range, it is possible to prepare a uniform polyamide active layer.

In the exemplary embodiment of the present specification, the composition for interfacial polymerization of the polyamide further includes an organic solvent that does not participate in the interfacial polymerization reaction as a solvent, and an aliphatic hydrocarbon solvent, for example, freon, has 5 to 12 carbon atoms. It may include at least one selected from an alkane and an isoparaffin-based solvent that is a mixture of alkanes. Specifically, 1 selected from hexane, heptane, octane, nonane, decane, undecan, dodecane, cyclohexane, IsoPar (Exxon), IsoPar G (Exxon), ISOL-C (SK Chem) and ISOL-G (Exxon) More than one type of organic solvent may be used, but is not limited thereto.

In an exemplary embodiment of the present specification, all the remainder of the polyamide interfacial polymerization composition except for the acyl halide compound and the compound represented by Formula 1 may be the solvent, and additional substances may be further included if necessary. have.

In an exemplary embodiment of the present specification, a method of manufacturing a water treatment separation membrane comprises: preparing a porous layer; And interfacial polymerization of the composition for interfacial polymerization of the polyamide and an aqueous solution containing an amine compound to form a polyamide active layer on the porous layer.

In one embodiment of the present specification, the step of preparing the porous layer may be performed by coating a polymer material on the nonwoven fabric, and the type, thickness, and porosity of the nonwoven fabric may be variously changed as needed. In the present specification, the porous layer may serve as a support.

Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethylchloride and polyvinylidene fluoride. Etc. can be used.

In one embodiment of the present specification, the polymer material is polysulfone.

In the exemplary embodiment of the present specification, the forming of the polyamide active layer may include forming an aqueous solution layer including an amine compound on the porous layer; And contacting the composition for interfacial polymerization of the polyamide on the aqueous solution layer.

When the aqueous solution layer containing the amine compound and the composition for interfacial polymerization of the polyamide are contacted, the amine compound coated on the surface of the porous layer and the acyl halide compound react to produce polyamide by interfacial polymerization, and a microporous layer Is adsorbed on to form a thin film. The contact method may be a method such as immersion, spray, or coating.

In the exemplary embodiment of the present specification, a method of forming an aqueous solution layer including the amine compound on the porous layer is not particularly limited, and any method capable of forming an aqueous solution layer on the porous layer may be used without limitation. . Specifically, spraying, application, immersion or dripping, etc. are mentioned.

In the exemplary embodiment of the present specification, the aqueous solution layer may be additionally subjected to a step of removing an aqueous solution containing an excess amine compound, if necessary. The aqueous solution layer formed on the porous layer may be non-uniformly distributed when there is too much aqueous solution present on the porous layer. If the aqueous solution is non-uniformly distributed, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization. have. Therefore, it is preferable to remove the excess aqueous solution after forming the aqueous solution layer on the porous layer. The removal of the excess aqueous solution is not particularly limited, but may be performed using, for example, a sponge, an air knife, blowing nitrogen gas, air drying, or a compression roll.

In the exemplary embodiment of the present specification, the amine compound is not limited as long as it can be used for polymerization of polyamide, but m-phenylenediamine (mPD), p-phenylenediamine (PPD), 1,3,6- It may be one or more selected from benzenetriamine (TAB), 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, and 3-chloro-1,4-phenylenediamine, Preferably it may be m-phenylenediamine (mPD).

In an exemplary embodiment of the present specification, the content of the amine compound may be 0.1 wt% to 20 wt% based on 100 wt% of the aqueous solution containing the amine compound, preferably 1 wt% to 15 wt%, more preferably It may be 3wt% to 10wt%. When the content of the amine compound is in the above range, it is possible to prepare a uniform polyamide layer.

In the exemplary embodiment of the present specification, the aqueous solution containing the amine compound may further include a surfactant.

During the interfacial polymerization of the polyamide active layer, polyamide is rapidly formed at the interface between the aqueous solution layer and the organic solution layer.At this time, the surfactant makes the layer thin and uniform so that the amine compound present in the aqueous solution layer easily moves to the organic solution layer. A uniform polyamide active layer is formed.

In the exemplary embodiment of the present specification, the surfactant may be selected from nonionic, cationic, anionic and amphoteric surfactants. According to an exemplary embodiment of the present specification, the surfactant is sodium lauryl sulfate (SLS); Alkyl ether sulfates; Alkyl sulfates; Olefin sulfonates; Alkyl ether carboxylates; Sulfosuccinates; Aromatic sulfonates; Octylphenol ethoxylates; Ethoxylated nonylphenols; Alkyl poly(ethylene oxide); Copolymers of poly(ethylene oxide) and poly(propylene oxide); Alkyl polyglucosides such as octyl glucoside and decyl maltoside; Fatty acid alcohols such as cetyl alcohol, oleyl alcohol, cocamide MEA, cocamide DEA, alkyl hydroxyethyl dimethyl ammonium chloride, cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride; And alkyl betaines. Specifically, the surfactant may be SLS, octylphenol ethoxylates, or ethoxylated nonylphenols.

In particular, when sodium lauryl sulfate (SLS) is used as the surfactant, SLS has a high degree of affinity for water and oil (Hydrophile-Lipophile Balance, HLB), so that it is well soluble in water, and the critical Michelle concentration (Critical Michelle Concentration) is high. , CMC) is also high, so even if an excessive amount is added, the formation of the polyamide active layer is not inhibited.

In the exemplary embodiment of the present specification, the content of the surfactant may be 0.01wt% to 1wt% based on 100wt% of the aqueous solution containing the amine compound.

In the exemplary embodiment of the present specification, the remainder of the aqueous solution containing the amine compound except for the amine compound and the surfactant may be water, and additional substances may be further included if necessary.

Each configuration of the method for manufacturing the water treatment separation membrane may refer to the description of the above-described polyamide interfacial polymerization composition.

In one embodiment of the present specification, the water treatment separation membrane is manufactured by the method of manufacturing the water treatment separation membrane described above.

Each configuration of the water treatment separation membrane may refer to the description of the above-described polyamide interfacial polymerization composition and a method of manufacturing the water treatment separation membrane.

1 shows a water treatment separation membrane according to an exemplary embodiment of the present specification. Specifically, FIG. 1 shows a water treatment separation membrane in which a nonwoven fabric 100, a porous layer 200, and a polyamide active layer 300 are sequentially provided, and the raw water 400 containing impurities as the polyamide active layer 300 Is introduced, the purified water 500 is discharged through the nonwoven fabric 100, and the concentrated water 600 is discharged to the outside without passing through the polyamide active layer 300. However, the water treatment separation membrane according to the exemplary embodiment of the present specification is not limited to the structure of FIG. 1, and an additional configuration may be further included.

In the exemplary embodiment of the present specification, the water treatment separation membrane may be a micro filtration membrane, an ultra filtration membrane, a nano filtration membrane, or a reverse osmosis membrane, and specifically a reverse osmosis membrane. .

An exemplary embodiment of the present invention provides a water treatment module including at least one or more of the aforementioned water treatment separation membrane.

The specific type 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 the exemplary embodiment of the present specification has excellent salt removal rate and boron removal rate, and thus may be usefully used in water treatment devices such as household/industrial water purification devices, sewage treatment devices, and seawater desalination devices.

Hereinafter, examples will be described in detail to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Example: Preparation of water treatment separation membrane>

Comparative Example 1.

18wt% of polysulfone solid was added to DMF (N,N-dimethylformamide) solution and dissolved at 80°C to 85°C for 12 hours or longer to obtain a uniform liquid. This solution was cast to a thickness of 150 μm on a nonwoven fabric having a thickness of 95 μm to 100 μm made of polyester. Then, the cast nonwoven fabric was put in water to prepare a polysulfone porous layer having a porosity of 70%.

On the porous layer, based on 100 wt% of the total aqueous solution, m-phenylenediamine (mPD) 8 wt%, sodium lauryl sulfate (SLS, Sodium Lauryl Sulphate) 0.06 wt% as a surfactant, and an amine compound containing the remainder of water An aqueous solution was applied to form an aqueous solution layer.

Next, an organic layer was formed by applying an organic solution composition containing 0.25 wt% of trimesoyl chloride (TMC) and the remainder of Isopar-G (Exxon) based on 100 wt% of the organic solution composition on the aqueous solution layer, and interfacial polymerization A water treatment separation membrane was prepared by forming a polyamide active layer through.

Comparative Example 2.

A water treatment separation membrane was prepared in the same manner as in Comparative Example 1, except that phenyl acetate was included in the organic solution composition of Comparative Example 1 in an amount of 90 mol% relative to 100 mol% TMC.

Comparative Example 3.

A water treatment separation membrane was prepared in the same manner as in Comparative Example 1, except that methyl benzoate was included in the organic solution composition of Comparative Example 1 in an amount of 90 mol% relative to 100 mol% TMC.

Comparative Example 4.

A water treatment separation membrane was prepared in the same manner as in Comparative Example 1, except that phenol (phenol, Tokyo Chemical Industry) was included in the organic solution composition of Comparative Example 1 in an amount of 100 mol% relative to 100 mol% TMC.

Comparative Example 5.

A water treatment separation membrane was manufactured in the same manner as in Comparative Example 4, except that the content of phenol was changed to 120 mol% compared to 100 mol% of TMC.

Example 1.

A water treatment separation membrane was prepared in the same manner as in Comparative Example 1, except that phenol (phenol, Tokyo Chemical Industry) was included in the organic solution composition of Comparative Example 1 in an amount of 90 mol% relative to 100 mol% TMC.

Example 2.

A water treatment separation membrane was prepared in the same manner as in Comparative Example 1, except that 4-ethylphenol (Tokyo Chemical Industry) was included in the organic solution composition of Comparative Example 1 in an amount of 40 mol% relative to 100 mol% TMC. I did.

Example 3.

A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of phenol was changed to 80 mol% compared to 100 mol% of TMC.

<Experimental Example 1: Performance evaluation of water treatment separation membranes of Examples 1 to 3>

In order to measure the salt removal rate and permeate flow rate (GFD) of the water treatment separation membranes prepared according to Examples 1 to 3, a water treatment module including a flat plate type permeation cell, a high pressure pump, a storage tank, and a cooling device was used. The planar transmission cell had an effective transmission area of 28 cm 2 in a cross-flow method. After the water treatment separation membrane was installed in the permeation cell, preliminary operation was sufficiently performed for about 1 hour using tertiary distilled water to stabilize the evaluation equipment.

Then, after confirming that the equipment was stabilized by operating the equipment for about 1 hour at a hydraulic pressure of 150 psi and a flow rate of 4.5 L/min with a 2,000 ppm NaCl aqueous solution, the amount of water permeated at 25° C. for 10 minutes was measured and the permeate flow rate (flux: gfd (gallon/ft ² /day)) was calculated, and the salt concentration before and after permeation was analyzed using a conductivity meter, and the results of calculating the salt removal rate are shown in Table 1 below.

Added compound Molar ratio of added compound
(Based on TMC 1.0) Salt removal rate (%) Permeate flow
(GFD) Example 1 Phenol 0.9 99.46 22.35 Example 2 4-ethylphenol 0.4 99.39 31.62 Example 3 Phenol 0.8 99.34 21.63

From Table 1 above, it can be seen that in Examples 1 to 3 using the compound represented by Formula 1, a water treatment separation membrane having a high permeation flow rate of 20 GGFD or more while maintaining a high salt removal rate of 99.3% or more was prepared.

<Experimental Example 2: Comparison of permeation flow rate>

For the water treatment separation membranes prepared according to Comparative Examples 1 to 5 and Examples 1 to 3, the results of calculating the permeate flow rate in the same manner as in Experimental Example 1 are shown in Table 2 below.

Added compound Molar ratio of added compound
(Based on TMC 1.0) Permeate flow
(GFD) Comparative Example 1 - - 12.52 Comparative Example 2 Phenyl acetate 0.9 15.72 Comparative Example 3 Methyl benzoate 0.9 13.67 Comparative Example 4 Phenol 1.0 15.54 Comparative Example 5 Phenol 1.2 16.86 Example 1 Phenol 0.9 22.35 Example 2 4-ethylphenol 0.4 31.62 Example 3 Phenol 0.8 21.63

From the results of Table 2, it can be seen that in Examples 1 to 3, a water treatment separation membrane having a much higher permeation flow rate was prepared compared to Comparative Examples 1 to 5. In particular, it can be seen from the results of Comparative Examples 4 and 5 that even when the compound represented by Formula 1 is used, when 100 mol% or more of the acyl halide compound is used, it does not have a significant effect on the increase of the permeate flow rate.

100: non-woven
200: porous layer
300: polyamide active layer
400: raw water containing impurities
500: purified water
600: concentrated water

Claims (11)

A compound represented by the following formula (1); And an acyl halide compound,
The content of the compound represented by Formula 1 is 20 mol% or more and less than 100 mol%, based on 100 mol% of the acyl halide compound, wherein the composition for polyamide interfacial polymerization:
[Formula 1]

In Formula 1,
R1 to R5 are the same as or different from each other, and each independently hydrogen; Or, it is an electron donating group. The method according to claim 1,
Each of R1 to R5 is hydrogen,
The content of the compound represented by Chemical Formula 1 is 70 mol% or more and less than 100 mol% based on 100 mol% of the acyl halide compound. The method according to claim 1,
At least one of R1 to R5 is an electron donating group,
The content of the compound represented by Chemical Formula 1 is greater than 20 mol% and less than 50 mol% based on 100 mol% of the acyl halide compound. The method according to claim 1,
The acyl halide compound is one or more selected from trimesoyl chloride (TMC), isophthaloyl chloride, and terephthaloyl chloride. Polyamide composition for interfacial polymerization. The method according to claim 1,
The content of the acyl halide compound is from 0.05wt% to 1wt% based on 100wt% of the polyamide interfacial polymerization composition. The method according to claim 1,
Polyamide interfacial polymerization composition further comprising at least one organic solvent selected from hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, IsoPar, IsoPar G, ISOL-C and ISOL-G as a solvent . Preparing a porous layer; And
A method of manufacturing a water treatment separation membrane comprising the step of interfacial polymerization of the composition for interfacial polymerization of the polyamide according to any one of claims 1 to 6 and an aqueous solution containing an amine compound to form a polyamide active layer on the porous layer. The method of claim 7,
The amine compound is m-phenylenediamine (mPD), p-phenylenediamine (PPD), 1,3,6-benzenetriamine (TAB), 4-chloro-1,3-phenylenediamine, 6-chloro -1,3-phenylenediamine and 3-chloro-1,4-phenylenediamine at least one selected from the method for producing a water treatment separation membrane. The method of claim 7,
The content of the amine compound is 0.1wt% to 20wt% based on 100wt% of the aqueous solution, the method of manufacturing a water treatment separation membrane. A water treatment separation membrane manufactured by the manufacturing method of claim 7. A water treatment module comprising at least one water treatment separation membrane according to claim 10.

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