KR100973831B1 - Amine aqueous solution for forming an active layer of polyamide reverse osmosis composite membrane, polyamide reverse osmosis composite membrane prepared thereby, and preparation method thereof - Google Patents

Abstract

The present invention relates to an aqueous amine solution for forming a polyamide reverse osmosis composite membrane active layer, a polyamide reverse osmosis composite membrane using the same, and a method for preparing the same, more specifically, formed by the reaction of a polyfunctional tertiary amine with a polyfunctional acid. The present invention relates to an aqueous amine solution for forming an active layer of a polyamide reverse osmosis composite membrane including a tertiary amine salt multimer, a polyamide reverse osmosis composite membrane using the same, and a method of manufacturing the same.

The aqueous amine solution of the present invention enables the preparation of a polyamide reverse osmosis composite membrane having an improved water permeability and salt excretion rate, including an amine salt multimer, so that the polyamide reverse osmosis composite membrane prepared by the production method of the present invention has a high flow rate. It can be easily applied to the field requiring both and high salt rejection rate.

Polyamide, reverse osmosis composite membrane, polyfunctional tertiary amine, polyfunctional acid, tertiary amine salt multimer

Description

Amine aqueous solution for forming polyamide reverse osmosis composite membrane active layer, polyamide reverse osmosis composite membrane using same, and method for preparing the same PREPARATION METHOD THEREOF}

The present invention relates to an aqueous amine solution for forming a polyamide reverse osmosis composite membrane active layer, a polyamide reverse osmosis composite membrane using the same, and a method for preparing the same, and more particularly, to a polyamide reverse osmosis composite membrane having a high water permeability and a salt excretion ratio. The present invention relates to an aqueous amine solution for forming an active layer of a polyamide reverse osmosis composite membrane, a polyamide reverse osmosis composite membrane using the same, and a method for preparing the same.

Water is an essential resource for all living things including human beings along with air, and its quantity and quality have a great influence on not only human beings but also the life of the earth. Moreover, given the fact that the utilization of water resources is getting wider and the importance of water resources is increasing due to the development of science and industry, securing high quality water resources is a very important problem in maintaining the life of the earth. At present, the world is running on a double road of water shortages and water pollution, and its use continues to increase, making it more difficult to secure practically available water resources. According to a UN study, 1.2 billion people, or one fifth of the world's population, suffer from a shortage of safe drinking water, more than twice as many as 2.4 billion people drink without water. Due to poor management of these water resources, more than 3 million people worldwide die every year from unsanitary water.

Meanwhile, seawater is reported to account for over 70% of the world's water. However, since seawater contains a large amount of impurities such as salt and various salts, seawater cannot be directly used for industrial water, agricultural water, household water, drinking water and the like. Therefore, the process of desalination by removing impurities such as salts or various salts from seawater or salt water is essential for humans to use them for various purposes. The reverse osmosis composite membrane is used as a core part in such desalination processes.

The general polyamide reverse osmosis composite membrane is composed of two layers. Looking at its structure, the reverse osmosis composite membrane is composed of a porous polymer support that maintains mechanical strength and a polyamide active layer formed thereon that determines permeability and salt rejection performance. In particular, the polyamide active layer is formed by interfacial polymerization of a polyfunctional amine and a reactive compound such as polyfunctional acyl halide. Examples of such polyamide reverse osmosis composite membranes are described in US Pat. No. 4,277,344 to Cadette, 1981. This patent describes a polyamide active layer formed by interfacial polymerization of a polyfunctional aromatic amine having at least two primary amine groups and a polyfunctional acyl halide having at least three or more acyl halide groups. Cadette's polyamide reverse osmosis composite membrane prepared by this method showed high permeability and salt rejection performance, but since then, many studies have been conducted to improve the permeability and salt rejection performance by various methods.

The methods for improving water permeability of polyamide reverse osmosis composite membranes reported to date can be classified as follows. First, a method of adding an amine salt monomer to an aqueous amine solution, second, a method of adding an alcohol or a polar aprotic solvent to an aqueous amine solution, third, a method of adding a polyfunctional alcohol amine salt monomer, and finally prepared polyamide reverse osmosis composite Post-treatment methods have been reported in which the membrane is contacted with an acid-containing solution, an aqueous amine solution or a polyfunctional tertiary alcohol amine and dried at a constant temperature for a certain time.

The method of performing interfacial polymerization by adding an amine aqueous solution to the amine salt monomer will be described in detail.

In 1989, U.S. Patent No. 4,872,984, Tomasschke used a polyfunctional aromatic amine monomer having at least two reactive amine groups, an aqueous amine solution containing an amine salt monomer and an aromatic polyfunctional acyl halide compound. The containing organic solution was contacted on the surface of the porous support to prepare a polyamide reverse osmosis composite membrane by interfacial polymerization. At this time, the amine salt monomer added to the aqueous amine solution is mainly a tertiary amine salt monomer or quaternary amine salt formed by tertiary amine and strong acid. Specifically, tertiary amines are trialkylamines such as trimethylamine, triethylamine and tripropylamine; 1-methylpiperidine which is N-alkylcycloaliphaticamines; N, N-dimethylethylamine and N, N-diethylmethylamine which are N, N-dialkylamines; N, N-dimethylethanolamine which is N, N-dialkylethanolamines was illustrated. As quaternary amines, tetramethylammonium hydroxide and tetraethylammonium hydroxide which are tetraalkylammonium hydroxides; Benzyltriethylammonium hydroxide and benzyl tripropyl hydroxide which were benzyl trialkyl ammonium hydroxides were illustrated. In addition, the strong acid specifically presented camphorsulfonic acid, methanesulfonic acid, trifluoroacetic acid and the like.

As another example, a method for preparing a polyamide reverse osmosis composite membrane proposed by Ja-Young Koo in US Patent No. 6,063,278 in 2000 is as follows. Salt-containing compounds having an organic solution comprising an amine reactive compound selected from a polyfunctional acyl halide, a polyfunctional sulfonyl halide or a polyfunctional isocyanate and a polyfunctional amine, at least one tertiary amine group and at least one tertiary amine salt group An aqueous amine solution containing a salt-containing compound was contacted at the surface of the porous support to prepare a polyamide reverse osmosis composite membrane by interfacial polymerization. Salt-containing compounds set forth in this patent are formed by the reaction of strong acids with polyfunctional tertiary amines. At this time, the polyfunctional tertiary amine includes at least two tertiary amine groups, and some tertiary amine groups react with strong acids to form tertiary amine salt monomers, and other tertiary amine groups act as reaction catalysts in the interfacial polymerization reaction. Characterized in that. Specific polyfunctional tertiary amines are N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N , N ', N'-pentamethyldiethylenetriamine, 1,1,3,3-tetramethylguanidine, N, N, N', N'-tetramethylenediamine or mixtures thereof are exemplified.

As another example, in 2001 US Pat. No. 6,245,234, Ja-Young Koo discloses an aromatic polyfunctional amine monomer having at least two reactive amine groups, a polyfunctional tertiary amine, an aqueous amine solution and a polytube in which a strong acid is dissolved. A method for preparing a polyamide reverse osmosis composite membrane by contacting an organic solution containing an amine reactive compound of a functional acyl halide, a polyfunctional sulfonyl halide or a polyfunctional isocyanate on the surface of a porous support is proposed. In this case, as the type of the polyfunctional tertiary amine included in the aqueous solution, N, N, N ', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-tetramethyl-1,4 -Butanediamine, N, N, N ', N'-tetramethyl-2-butene-1,4-diamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N , N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,8-octanediamine, N, N, N ', N'-tetramethyl- 1,7-heptane diamine, N, N, N ', N'-tetramethyl-1,5-pentanediamine, N, N, N', N'-tetraethyl-1,4-butanediamine, N, N , N ', N'-tetraethyl-1,3-butanediamine, N, N, N', N'-tetraethyl-1,3-propanediamine, 1,4-dimethylpiperazine, N, N, N ', N'-tetraethylethylenediamine is preferred, wherein the reaction molar ratio of the polyfunctional tertiary amine and the strong acid is in the range of 1: 0 to less than 1: 1. The structural feature of the multifunctional tertiary amines set forth in this patent is that alkanes of 2 to 10 carbon atoms in the main chain or to 3 to 10 ring hydrocarbons of reducing and include at least two or more tertiary amines.

In addition, in 2002 U.S. Patent No. 6,368,507, Koo Ja-Young described a salt-containing compound comprising water, a polyfunctional amine, at least one tertiary amine salt group and at least one tertiary amine group in preparing a polyamide reverse osmosis composite membrane. preparing a polyamide reverse osmosis composite membrane by interfacial polymerization of an aqueous amine solution containing a salt-containing compound and at least one polar solvent with an organic solution containing a polyfunctional acyl halide, a polyfunctional sulfonyl halide or a polyfunctional isocyanate It was presented how to. At this time, the polar solvent proposed in the patent, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, di (ethylene glycol), t-butyl methyl ether, di (ethylene glycol ) Hexyl ether, 1,3-hexanediol, 1,3-propanediol, 2-ethyl-1,3-hexanediol, dimethyl sulfoxide, tetramethylene sulfoxide, butyl sulfoxide, methylphenyl sulfoxide, tetramethyl sulfone, Butyl sulfone, 1,3-dimethyl-2-imidazolidinone, and the like. In addition, the polyfunctional tertiary amines are specifically N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N , N, N ', N'-pentamethyldiethylenetriamine, 1,1,3,3-tetramethylguanidine, N, N, N', N'-tetramethylenediamine are illustrated.

The method of adding a tertiary amine salt monomer to an aqueous primary bath amine solution in order to improve the water permeability of the membrane prepared in the conventional polyamide reverse osmosis composite membrane as described above, the addition of tertiary amine and strong acid to the primary aqueous amine solution To form a tertiary amine salt monomer or a polyfunctional tertiary amine composed of two or more tertiary amines and a strong acid to form a polyfunctional tertiary amine salt monomer.

Compared to the polyamide reverse osmosis composite membrane prepared by the reaction of the conventional polyfunctional amine and polyfunctional acyl halide, the above-described production method was able to obtain a water permeability improvement effect, but not as much as desired. There is a need for a polyamide reverse osmosis composite membrane production technique having better water permeability and salt rejection performance.

Therefore, in the present invention, in preparing a polyamide reverse osmosis composite membrane, a new amine aqueous solution, a method for preparing a polyamide reverse osmosis composite membrane using the same, has been proposed, and has improved water permeability and salt rejection rate as compared with the conventional reverse osmosis composite membrane. To prepare a reverse osmosis composite membrane.

To solve the above problems, an object of the present invention is to use a tertiary amine salt multimer formed from a polyfunctional tertiary amine composed of two or more tertiary amine groups and a polyfunctional acid composed of two or more acid groups. It is to provide an amine aqueous solution for forming an active layer of a polyamide reverse osmosis composite membrane which enables the production of a polyamide reverse osmosis composite membrane having high water permeability and excellent salt rejection ratio.

Another object of the present invention is to provide a polyamide reverse osmosis composite membrane prepared by using the aqueous amine solution and a method of manufacturing the same.

The present invention to achieve the above object,

Provided is an aqueous amine solution for forming a polyamide reverse osmosis composite membrane active layer comprising a tertiary amine salt multimer formed by the reaction of a polyfunctional tertiary amine with a polyfunctional acid.

In addition, the present invention,

In the method for producing a polyamide reverse osmosis composite membrane by interfacial polymerization,

(1) A porous support coated with a tertiary amine salt multimer formed by the reaction of a polyfunctional tertiary amine with a polyfunctional acid, an aqueous amine solution containing a polyfunctional aromatic amine monomer and water, and then coated with the aqueous amine solution. Obtaining a support;

(2) contacting an organic solution containing at least one amine-reactive compound selected from the group consisting of polyfunctional acyl halides, polyfunctional sulfonyl halides and polyfunctional isocyanates on a porous support coated with an aqueous amine solution to form a polyamide active layer. Obtaining; And

(3) drying step

It provides a method for producing a polyamide reverse osmosis composite membrane comprising a.

The present invention also provides a polyamide reverse osmosis composite membrane prepared by the above method.

The present invention enables the preparation of polyamide reverse osmosis composite membranes having high water permeability and excellent salt rejection rate by using tertiary amine salt multimers which have not been used conventionally.

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

The present invention forms a tertiary amine salt multimer from a polyfunctional tertiary amine and a polyfunctional acid, which has not been used conventionally, and preferably uses a tertiary amine salt multimer represented by Formula 1 in an aqueous amine solution:

[Formula 1]

(상기 화학식 1에서,
R₁ 내지 R₄는 서로 동일하거나 상이할 수 있으며, 각각 독립적으로 수소원자; -OH로 치환 또는 미치환된 C1∼C10의 직쇄 또는 측쇄의 알킬기; -Q¹R¹; -R²Q¹R³; 및 이들의 조합으로 이루어진 군으로부터 선택되는 1종이고, 또는 상기 R₁-R₂, R₁-R₃, R₂-R₄, 및 R₃-R₄가 서로 결합하여 고리를 형성하거나, N-R₁, N-R₂, N-R₃, 및 N-R₄가 서로 결합하여 포화 또는 불포화 고리를 형성하거나, 또는 N-N이 직접 결합하여 포화 또는 불포화 고리를 형성하고;
이때 상기 Q¹는 -O-, -SO₂-, -CO-, -S-, -CF₂ - 및 이들의 조합으로 이루어진 군으로부터 선택되는 1종이며, 상기 R¹ 및 R³는 서로 동일하거나 상이할 수 있으며, 각각 독립적으로 C1∼C10의 직쇄 또는 측쇄의 알킬기이고, 상기 R²는 C1∼C10의 직쇄 또는 측쇄의 알킬렌기이고;
Ra는 C1∼C10의 포화 또는 불포화 직쇄 또는 측쇄의 알킬렌기; C3∼C10의 시클로알킬렌기;

; -C(=NH)-;

및 이들의 조합으로 이루어진 군으로부터 선택된 1종이고, 또는 Ra-R₂, Ra-R₄가 서로 결합하여 포화 또는 불포화 고리를 형성하고;
상기 Rb 및 Rc는 서로 동일하거나 상이할 수 있으며, 각각 독립적으로 -OH로 치환 또는 미치환된 C1∼C10의 직쇄 또는 측쇄의 알킬렌기이고,
상기 R₅는 -OH로 치환 또는 미치환된 C1∼C10의 직쇄 또는 측쇄의 알킬기이고,
HX는 산 관능기를 나타내며, 이때 HX는 서로 동일하거나 상이할 수 있으며 -COOH, -SO₃H 및 이들의 조합으로 이루어진 군으로부터 선택되는 1종이고,
Rd는 C1∼C10의 직쇄 또는 측쇄의 알킬렌기; C1∼C10의 직쇄 또는 측쇄의 디아미노알킬렌기, C1∼C10의 직쇄 또는 측쇄의 알킬이미노기, 비페닐기 및 이들의 조합으로 이루어진 군으로부터 선택되는 1종이고,

(In Formula 1,
R ₁ to R ₄ may be the same as or different from each other, and each independently hydrogen atom; C1-C10 linear or branched alkyl group unsubstituted or substituted with -OH; -Q ¹ R ¹ ; -R ² Q ¹ R ³ ; And a combination thereof, or the R ₁ -R ₂ , R ₁ -R ₃ , R ₂ -R ₄ , and R ₃ -R ₄ combine with each other to form a ring, or NR ₁ , NR ₂ , NR ₃ , and NR ₄ combine with each other to form a saturated or unsaturated ring, or NN directly bonds to form a saturated or unsaturated ring;
Wherein Q ¹ is ^one selected from the group consisting of —O—, —SO ₂ —, —CO—, —S—, —CF ₂ —, and a combination thereof, wherein R ¹ and R ³ are the same as each other; It may be different, each independently represent a C1 to C10 linear or branched alkyl group, R ² is a C1 to C10 linear or branched alkylene group;
Ra is a C1 to C10 saturated or unsaturated linear or branched alkylene group; C3-C10 cycloalkylene group;

; -C (= NH)-;

And combinations thereof, or Ra-R ₂ , Ra-R ₄ , combine with each other to form a saturated or unsaturated ring;
Rb and Rc may be the same as or different from each other, and are each independently a C1-C10 linear or branched alkylene group substituted or unsubstituted with -OH,
R ₅ is a C1-C10 linear or branched alkyl group unsubstituted or substituted with -OH,
HX represents an acid functional group, wherein HX may be the same or different from each other and is one kind selected from the group consisting of -COOH, -SO ₃ H, and combinations thereof,
Rd is a C1-C10 linear or branched alkylene group; C1 to C10 linear or branched diaminoalkylene group, C1 to C10 linear or branched alkylimino group, biphenyl group, and a combination thereof.

Is an integer of 2≤n≤10)

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Preferably, the multifunctional tertiary amine is selected from 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] unde-7-cene, 1 , 5-diazabicyclo [4,3,0] no-5-ene, 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, 1,1,3,3- Tetramethylguanidine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N, N ' , N'-tetramethyl-2-butene-1,4-diamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl -1,3-propanediamine, N, N, N ', N'-tetramethyl-1,8-octanediamine, N, N, N', N'-tetramethyl-1,7-heptandiamine, N, N, N ', N'-tetramethyl-1,5-pentanediamine, N, N, N', N'-tetraethyl-1,4-butanediamine, N, N, N ', N'-tetraethyl -1,3-butanediamine, N, N, N ', N'-tetraethyl-1,3-propanediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N ', N'-tetramethyl-1,2-cyclohexanediamine, N, N, N ', N'-tetramethyl-1,3-cyclohexanediamine, N, N, N', N'-tetramethyl-1,4-cyclohexanediamine, N, N, N ', N '-Tetramethyl-1,2-cyclohexanebis (methylenediamine), N, N, N', N ', N "-pentamethyldiethylenetriamine, N, N, N', N'-tetrakis ( 2-hydroxypropyl) ethylenediamine, N, N, N'N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ', N' ', N' ''-pentakis (2 One selected from the group consisting of -hydroxypropyl) diethylenetriamine, 1,1 '-((3- (dimethylamino) propyl) imino) bis-2-propanol and mixtures thereof.

Preferably, the polyfunctional acid has two or more acid functional groups, 1,4-butanedicarboxylic acid, 1,2-diaminopropane-N, N, N ', N'-tetraacetic acid, 1,6- Diaminohexane-N, N, N ', N'-tetraacetic acid, N- (2-carboxyethyl) iminodiacetic acid, and 1,1'-biphenyl-4,4'-disulfonic acid It is preferable to use one.

The tertiary amine salt multimer represented by the formula (1) is preferably formed by forming a polyfunctional tertiary amine and a polyfunctional acid in a molar ratio of 1: 1.

In this case, when the reaction molar ratio of the polyfunctional tertiary amine and the polyfunctional acid is less than 1: 1, formation of tertiary amine salt multimers is insignificant.On the contrary, when the reaction molar ratio is more than 1: 1, the unreacted polyfunctional tertiary There exists a problem that the water permeability and salt rejection performance of the polyamide reverse osmosis composite membrane manufactured by the presence of an amine or a polyfunctional acid are reduced.

Such tertiary amine salt multimers enable the production of polyamide reverse osmosis composite membranes having improved salt excretion rate and high permeability through interfacial polymerization, and specific methods are as follows.

(1) porous support coating step

A tertiary amine salt multimer formed from a polyfunctional tertiary amine and a polyfunctional acid, a polyfunctional aromatic amine monomer, and water are uniformly mixed to prepare an aqueous amine solution, which is coated on at least one side or both sides of the porous support.

Wherein the polyfunctional aromatic amine monomer is 1,4-phenylenediamine, 1,3-phenylenediamine, 2,5-diaminotoluene, N, N'-diphenylethylene diamine, 4-methoxyphenylenediamine and One kind selected from the group consisting of mixtures thereof is possible.

Such polyfunctional aromatic amine monomers are used at 0.1 to 20% by weight in aqueous amine solution. In this case, if the content is less than the above range, the polyamide active layer may not be properly formed. On the contrary, if the content exceeds the above range, the water permeability of the polyamide reverse osmosis composite membrane may be reduced or a large amount of unreacted polyfunctional aromatic amine monomer may be present. It can cause problems.

The porous support may be a polymer material generally used as a composite membrane, and the type of the porous support is not particularly limited. Typically, polysulfone, polyethersulfone, polyimide, polypropylene, polyvinylidene fluoride, polyamide, polyetherimide, polyacrylonitrile, polymethylmethacrylate, polyethylene, polyolefin and the like are possible.

The porosity and thickness of the porous support depends on the field to be applied, and for example, the pore size is preferably 1 to 500 nm and thickness is 25 to 125 μm.

The coating is preferably a wet coating method, for example, a known method such as dip coating, spin coating, bar coating, spray coating is possible. At this time, by adjusting the content of water in the aqueous amine solution to adjust the viscosity to suit each coating method, for example, 0.1 to 20% by weight of polyfunctional aromatic amine monomer, 0.1 to 20% by weight of tertiary amine salt multimer of formula 1 and water 40 To 99.7% by weight is used in combination.

The content of such tertiary amine salt multimer is used in an amount of 0.1 to 20% by weight, preferably 0.5 to 5% by weight in an aqueous amine solution. In this case, if the content is less than the above range, there is a problem that the effect due to the addition is insignificant, on the contrary, if it exceeds the above range, there is a problem that the polyamide reverse osmosis composite membrane salt rejection performance is lowered due to the influence on the interfacial polymerization reaction.

(2) polyamide active layer forming step

Next, at least one side of the porous support coated with the amine aqueous solution is contacted with an organic solution containing an amine reactive compound to form a polyamide active layer.

The polyamide active layer is formed by interfacial polymerization by a reaction between a polyfunctional aromatic amine monomer in an aqueous amine solution coated on a porous support and an amine reactive compound in an organic solution.

The amine-reactive compound may be one selected from the group consisting of polyfunctional acyl halides, polyfunctional sulfonyl halides and polyfunctional isocyanates so as to perform interfacial polymerization with the polyfunctional amine. Preferably the amine reactive compound uses trimezoyl chloride, terephthaloyl chloride, isophthaloyl chloride or mixtures thereof.

The content of such an amine reactive compound is used in 0.01 to 10% by weight, preferably 0.05 to 2.0% by weight of the organic solution. In this case, if the content is less than the above range, the polyamide active layer formation is insignificant. On the contrary, if the content exceeds the above range, the water permeability of the polyamide reverse osmosis composite membrane may be reduced or a large amount of unreacted amine-reactive compound may be present. .

The organic solvent in which the amine reactive compound is dissolved may be any one as long as it is commonly used. Typically, a mixed organic solution of hexane, cyclohexane, heptane, alkane having 8 to 12 carbon atoms, a halogen substituted hydrocarbon of Freon or a mixture thereof is used.

(3) drying step

Subsequently, the polyamide active layer formed on the porous support by the interfacial polymerization method is dried to prepare a polyamide reverse osmosis composite membrane.

At this time, the drying conditions are not particularly limited in the present invention, but are carried out under conditions that can sufficiently remove the reactants, water and organic solvents that are not used in the interfacial polymerization. Preferably it is carried out at 30 to 150 ℃, if necessary under reduced pressure.

1 is a scanning electron micrograph of a cross section of a polyamide reverse osmosis composite membrane prepared according to Example 1. FIG.

Referring to FIG. 1, the polyamide reverse osmosis composite membrane 1 has a structure in which a polyamide active layer 3 is formed on a porous support 2. At this time, the polyamide active layer is formed on one side of the porous support, but can be formed on both sides of the porous support according to the application to be applied.

Through these steps, it is possible to prepare a polyamide reverse osmosis composite membrane according to the present invention, and has improved water permeability and salt rejection rate than the composite membrane prepared by a conventional manufacturing method.

Hereinafter, preferred examples and comparative examples of the present invention are described. The following examples and comparative examples are described for the purpose of more clearly expressing the present invention, but the contents of the present invention are not limited to the following examples and comparative examples.

(Example 1)

A tertiary amine salt multimer (2 ≦ n ≦ 10) was prepared by reacting 1,4-diazabicyclo [2,2,2] octane and 1,4-butanedicarboxylic acid in a molar ratio of 1: 1.

Aqueous amine solution was prepared by mixing 3.0 wt% of tertiary amine salt multimer prepared above, 2.0 wt% of 1,3-phenylenediamine, and 95 wt% of water.

Then, the polysulfone polymer solution was coated on the nonwoven fabric to prepare the polyamide reverse osmosis composite membrane, and then the porous support prepared by the phase transfer method was immersed in the prepared amine aqueous solution for 1 minute. The excess aqueous amine solution on the porous support was removed with a rubber roller, immersed in an isopar (Exxon) solution containing 0.1% by weight of trimezoyl chloride for 30 seconds, and then dried in an oven at 95 ° C. for 5 minutes to carry out a polyamide reverse osmosis composite. The membrane was prepared.

(Examples 2 to 10)

A polyamide reverse osmosis composite membrane was manufactured in the same manner as in Example 1, except that the polyfunctional tertiary amine and the polyfunctional acid contained in the amine aqueous solution in Example 1 were used in Table 1 below.

division Polyfunctional tertiary amines Polyfunctional acid Molar ratio Example 2 N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine 1,4-butanedicarboxylic acid 1: 1 Example 3 1,8-diazabicyclo [5,4,0] unde-7-cene 1,4-butanedicarboxylic acid 1: 1 Example 4 1,5-diazabicyclo [4,3,0] no-5-ene 1,4-butanedicarboxylic acid 1: 1 Example 5 1,4-dimethylpiperazine 1,4-butanedicarboxylic acid 1: 1 Example 6 4- [2- (dimethylamino) ethyl] morpholine 1,4-butanedicarboxylic acid 1: 1 Example 7 1,1,3,3-tetramethylguanidine 1,4-butanedicarboxylic acid 1: 1 Example 8 N, N, N´, N´-tetramethyl-1,6-hexanediamine 1,4-butanedicarboxylic acid 1: 1 Example 9 N, N, N ', N'-tetramethyl-1,4-butanediamine 1,4-butanedicarboxylic acid 1: 1 Example 10 N, N, N ', N'-tetramethyl-2-butene-1,4-diamine 1,4-butanedicarboxylic acid 1: 1 Example 11 N, N, N´, N´-tetramethyl-1,3-butanediamine 1,4-butanedicarboxylic acid 1: 1 Example 12 N, N, N ', N'-tetraethyl-1,4-butanediamine 1,4-butanedicarboxylic acid 1: 1 Example 13 N, N, N´, N´-tetramethylethylenediamine 1,4-butanedicarboxylic acid 1: 1 Example 14 N, N, N ', N'-tetramethyl-1,3-cyclohexanediamine 1,4-butanedicarboxylic acid 1: 1 Example 15 N, N, N ', N'-tetramethyl-1,2-cyclohexanebis (methylenediamine) 1,4-butanedicarboxylic acid 1: 1 Example 16 N, N, N´, N´, N ″ -pentamethyldiethylenetriamine 1,4-butanedicarboxylic acid 1: 1 Example 17 N, N, N´, N´-tetramethyl-1,3-butanediamine 1,2-diaminopropane-N, N, N ', N'-tetraacetic acid 1: 1 Example 18 N, N, N´, N´-tetramethyl-1,3-butanediamine 1,6-diaminohexane-N, N, N ', N'-tetraacetic acid 1: 1 Example 19 N, N, N´, N´-tetramethyl-1,3-butanediamine 1,1'-biphenyl-4,4'-disulfonic acid 1: 1 Example 20 N, N, N´, N´-tetramethyl-1,3-butanediamine N- (2-carboxyethyl) iminodiacetic acid 1: 1

(Comparative Example 1)

The polysulfone support was immersed in an aqueous amine solution containing 2.0% by weight 1,3-phenylenediamine, and then the excess amine solution was removed from the surface of the support, followed by a Freon TF organic solution in which 0.1% by weight of trimezoyl chloride was dissolved. The polyamide reverse osmosis composite membrane was prepared by performing interfacial polymerization for 10 seconds on the surface of the substrate and the support.

(Comparative Example 2)

The polysulfone support was immersed in an aqueous amine solution containing 2.0 wt% 1,3-phenylenediamine, 2.0 wt% tetramethylammonium hardoxide, 0.1 wt% sodium dodecyl benzyl sulfate for 2 minutes, and then The aqueous amine solution was removed. Thereafter, the support was contacted with a solution of Isopar (Exxon) in which 0.05 wt% trimezoyl chloride and 0.075 wt% isophthaloyl chloride was dissolved, and then dried in an oven at 95 ° C. for 6 minutes to prepare a polyamide reverse osmosis composite membrane.

(Comparative Example 3)

The polysulfone support was immersed in an aqueous amine solution containing 1.6 wt% 1,3-phenylenediamine, 0.6 wt% N, N, N ', N'-tetramethyl-1,6-hexanediamine, 0.06 wt% toluenesulfonic acid for 40 seconds. After immersion, excess aqueous amine solution on the support surface was removed. Then, a polyamide reverse osmosis composite membrane was prepared by reacting anisopropyl C (Isopar, Exxon) organic solution in which 0.1 wt% trimesoyl chloride was dissolved for 1 minute on the support surface. The prepared polyamide reverse osmosis composite membrane was dried at room temperature for 1 minute and then washed for 30 minutes in a 0.2% by weight Na ₂ CO ₃ aqueous solution.

(Comparative Example 4)

The polysulfone support was immersed in an aqueous amine solution containing 2.0 wt% 1,3-phenylenediamine, 2.3 wt% camphorsulfonic acid, 1.1 wt% triethylamine, 2.0 wt% 2-butoxyethanol for 40 seconds, and then Excess aqueous amine solution was removed. Then, a polyamide reverse osmosis composite membrane was prepared by reacting an isopa (Isopar, Exxon) organic solution in which 0.1 wt% trimethoyl chloride was dissolved for 1 minute on the support surface. The prepared polyamide reverse osmosis composite membrane was dried at 90 ° C. for 3 minutes 30 seconds, and then washed at room temperature for 30 minutes with a 0.2 wt% Na ₂ CO ₃ aqueous solution.

(Comparative Example 5)

The polysulfone support was immersed for 40 seconds in an aqueous amine solution containing 2.0% by weight 1,3-phenylenediamine, 1.0% by weight 1,4-diazabicyclo [2,2,2] octane and 0.85% by weight methanesulfonic acid. The excess aqueous amine solution on the support surface was then removed. Then, a polyamide reverse osmosis composite membrane was prepared by interfacial polymerization for 1 minute on an isopa (Isopar, Exxon) organic solution in which 0.1% by weight of trimezoyl chloride was dissolved and the surface of the support. The prepared polyamide reverse osmosis composite membrane was dried at 90 ° C. for 3 minutes 30 seconds, and then washed for 30 minutes with an aqueous 40% 0.2% Na ₂ CO ₃ solution.

Experimental Example

Polyamide reverse osmosis Of composite membrane Permeability and Salt rejection  Measure

The water permeation rate and salt rejection rate of the polyamide reverse osmosis composite membranes prepared in Examples 1 to 10 and Comparative Examples 1 to 5 were measured using a 2,000 ppm NaCl aqueous solution under 225 psi pressure, and the results are shown in Table 2 below.

division Permeability (L / m ² hr) Salt Exclusion Rate (%) Example 1 68.3 98.5 Example 2 70.8 98.8 Example 3 65.9 99.2 Example 4 75.5 98.8 Example 5 76.5 98.6 Example 6 77.5 99.2 Example 7 70.9 99.1 Example 8 73.2 98.5 Example 9 69.5 98.3 Example 10 69.0 98.8 Example 11 65.2 98.4 Example 12 73.5 98.5 Example 13 72.4 98.2 Example 14 75.2 98.0 Example 15 69.5 98.5 Example 16 71.5 99.0 Example 17 70.8 98.7 Example 18 68.5 98.6 Example 19 65.3 98.8 Example 20 67.2 99.2 Comparative Example 1 60.2 99.5 Comparative Example 2 34.2 99.7 Comparative Example 3 66.1 97.0 Comparative Example 4 62.9 99.0 Comparative Example 5 54.9 97.0

As shown in Table 2, the polyamide reverse osmosis composite membrane prepared according to the production method of the present invention is superior in both water permeation rate and salt rejection rate than the comparative example. Therefore, the polyamide reverse osmosis composite membrane produced by the production method of the present invention can be preferably used in the field requiring both high flow rate and high salt rejection rate.

1 is a scanning electron micrograph of the cross section of the polyamide reverse osmosis composite membrane prepared in Example 1. FIG.

Claims (10)

Amine aqueous solution for forming a polyamide reverse osmosis composite membrane active layer comprising a tertiary amine salt multimer represented by Formula 1 below: [Formula 1]

(In the formula 1, R ₁ to R ₄ may be the same as or different from each other, and each independently hydrogen atom; C1-C10 linear or branched alkyl group unsubstituted or substituted with -OH; -Q ¹ R ¹ ; -R ² Q ¹ R ³ ; And a combination thereof, or the R ₁ -R ₂ , R ₁ -R ₃ , R ₂ -R ₄ , and R ₃ -R ₄ combine with each other to form a ring, or NR ₁ , NR ₂ , NR ₃ , and NR ₄ combine with each other to form a saturated or unsaturated ring, or NN directly bonds to form a saturated or unsaturated ring; Wherein Q ¹ is ^one selected from the group consisting of —O—, —SO ₂ —, —CO—, —S—, —CF ₂ —, and a combination thereof, wherein R ¹ and R ³ are the same as each other; It may be different, each independently represent a C1 to C10 linear or branched alkyl group, R ² is a C1 to C10 linear or branched alkylene group; Ra is a C1 to C10 saturated or unsaturated linear or branched alkylene group; C3-C10 cycloalkylene group;

; -C (= NH)-;

And combinations thereof, or Ra-R ₂ , Ra-R ₄ , combine with each other to form a saturated or unsaturated ring; Rb and Rc may be the same as or different from each other, and are each independently a C1-C10 linear or branched alkylene group substituted or unsubstituted with -OH, R ₅ is a C1-C10 linear or branched alkyl group unsubstituted or substituted with -OH, HX represents an acid functional group, wherein HX may be the same or different from each other and is one kind selected from the group consisting of -COOH, -SO ₃ H, and combinations thereof, Rd is a C1-C10 linear or branched alkylene group; C1 to C10 linear or branched diaminoalkylene group, C1 to C10 linear or branched alkylimino group, biphenyl group, and a combination thereof. Is an integer of 2≤n≤10) The method of claim 1, wherein the tertiary amine salt multimer is 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] unde-7-cene, 1,5-diazabicyclo [4,3 , 0] no-5-ene, 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, 1,1,3,3-tetramethylguanidine, N, N, N´, N'-tetramethyl-1,6-hexanediamine, N, N, N ', N'-tetramethyl-1,4-butanediamine, N, N, N', N'-tetramethyl-2-butene- 1,4-diamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N ', N'-tetramethyl-1,8-octanediamine, N, N, N', N'-tetramethyl-1,7-heptanediamine, N, N, N ', N'-tetramethyl-1 , 5-pentanediamine, N, N, N ', N'-tetraethyl-1,4-butanediamine, N, N, N', N'-tetraethyl-1,3-butanediamine, N, N, N ', N'-tetraethyl-1,3-propanediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N ', N'-tetramethyl-1,2-cyclohexanediamine, N, N, N', N'-tetramethyl-1,3-cyclohexanedia , N, N, N ', N'-tetramethyl-1,4-cyclohexanediamine, N, N, N', N'-tetramethyl-1,2-cyclohexanebis (methylenediamine), N, N , N ', N', N ″ -pentamethyldiethylenetriamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N'N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ', N' ', N' ''-pentakis (2-hydroxypropyl) diethylenetriamine, 1,1 '-((3- ( 1 kind of polyfunctional tertiary amine selected from the group consisting of dimethylamino) propyl) imino) bis-2-propanol and mixtures thereof; 1,4-butanedicarboxylic acid, 1,2-diaminopropane-N, N, N ', N'-tetraacetic acid, 1,6-diaminohexane-N, N, N', N'-tetraacetic acid, N- (2-carboxyethyl) iminodiacetic acid and 1,1′-biphenyl-4,4′-disulfonic acid and one polyfunctional acid selected from the group consisting of mixtures thereof Amine aqueous solution for forming polyamide reverse osmosis composite membrane active layer. delete In the method for producing a polyamide reverse osmosis composite membrane by the interfacial polymerization method, (1) coating the porous support with an amine aqueous solution containing a tertiary amine salt multimer represented by Formula 1 below, a polyfunctional aromatic amine monomer and water to obtain a porous support coated with the amine aqueous solution; (2) contacting an organic solution containing at least one amine-reactive compound selected from the group consisting of polyfunctional acyl halides, polyfunctional sulfonyl halides and polyfunctional isocyanates on a porous support coated with an aqueous amine solution to form a polyamide active layer. Obtaining; And (3) drying step Polyamide reverse osmosis composite membrane manufacturing method comprising: [Formula 1]

(In the formula 1, R ₁ to R ₄ , Ra, HX, Rd and n are each as defined in claim 1 above) The method of claim 4, wherein the tertiary amine salt multimer is 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] unde-7-cene, 1,5-diazabicyclo [4,3 , 0] no-5-ene, 1,4-dimethylpiperazine, 4- [2- (dimethylamino) ethyl] morpholine, 1,1,3,3-tetramethylguanidine, N, N, N´, N'-tetramethyl-1,6-hexanediamine, N, N, N ', N'-tetramethyl-1,4-butanediamine, N, N, N', N'-tetramethyl-2-butene- 1,4-diamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N ', N'-tetramethyl-1,8-octanediamine, N, N, N', N'-tetramethyl-1,7-heptanediamine, N, N, N ', N'-tetramethyl-1 , 5-pentanediamine, N, N, N ', N'-tetraethyl-1,4-butanediamine, N, N, N', N'-tetraethyl-1,3-butanediamine, N, N, N ', N'-tetraethyl-1,3-propanediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetraethylethylenediamine, N, N, N ', N'-tetramethyl-1,2-cyclohexanediamine, N, N, N', N'-tetramethyl-1,3-cyclohexanedia , N, N, N ', N'-tetramethyl-1,4-cyclohexanediamine, N, N, N', N'-tetramethyl-1,2-cyclohexanebis (methylenediamine), N, N , N ', N', N ″ -pentamethyldiethylenetriamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N'N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ', N' ', N' ''-pentakis (2-hydroxypropyl) diethylenetriamine, 1,1 '-((3- ( 1 kind of polyfunctional tertiary amine selected from the group consisting of dimethylamino) propyl) imino) bis-2-propanol and mixtures thereof; 1,4-butanedicarboxylic acid, 1,2-diaminopropane-N, N, N ', N'-tetraacetic acid, 1,6-diaminohexane-N, N, N', N'-tetraacetic acid, One polyfunctional acid selected from the group consisting of N- (2-carboxyethyl) iminodiacetic acid and 1,1′-biphenyl-4,4′-disulfonic acid and mixtures thereof in a molar ratio of 1: 1 A method for producing a polyamide reverse osmosis composite membrane which is formed by reaction. The method of claim 4, wherein The polyfunctional aromatic amine monomers include 1,4-phenylenediamine, 1,3-phenylenediamine, 2,5-diaminotoluene, N, N'-diphenylethylene diamine, 4-methoxyphenylenediamine and these Method of producing a polyamide reverse osmosis composite membrane is one selected from the group consisting of a mixture of. The method of claim 4, wherein The aqueous amine solution is a method for producing a polyamide reverse osmosis composite membrane comprising 0.1 to 20% by weight of a polyfunctional aromatic amine monomer, 0.1 to 20% by weight of tertiary amine salt multimer of Formula 1, and 40 to 99.7% by weight of water. . The method of claim 4, wherein The organic solution is a method for producing a polyamide reverse osmosis composite membrane comprising an amine reactive compound in an amount of 0.01 to 10% by weight. The method of claim 4, wherein The polyfunctional acyl halide is a method for producing a polyamide reverse osmosis composite membrane is one selected from the group consisting of trimezoyl chloride, terephthaloyl chloride, isophthaloyl chloride and mixtures thereof. delete

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