KR20010018000A - Composite polyamide reverse osmosis membrane and method of producing the same - Google Patents

Abstract

PURPOSE: Provided is a polyamide reverse osmosis multi-membrane which has high flow rate and excellent salt exclusion rate at low pressure. Also a method thereof is provided. CONSTITUTION: The polyamide reverse osmosis multi-membrane is characterized by obtaining reaction of organic solution comprising: aqueous solution composed of salt containing compound composed of multi-functional amine, at least one polar solvent, at least one aminate functional group and at least amine functional group; and amine reactive reactant selected from multi-functional acylhalide, multi-functional sulfonyl halide and multi-functional isocyanate group. The method thereof comprises; the step of coating aqueous solution containing multi-functional amine, at least one polar solvent and compound of reaction product of strong acid and multi-functional tertiary amine on the porous supporter; the step of forming crosslinked polyamide layer at the interface on the supporter by contacting multi-functional amine reactive reactant selected from multi-functional acylhalide, multi-functional sulfonyl halide and multi-functional isocyanate for condensing; and the step of drying the product.

Description

Polyamide reverse osmosis membrane and method of producing the same

The present invention relates to a new reverse osmosis composite membrane used for desalination of a lot of water, such as industrial water and agricultural water, by desalting water such as brine or seawater, and a method for producing the same.

Dissociated materials can be separated from the solvent using several optional membranes, such as microfiltration membranes, ultrafiltration membranes and reverse osmosis membranes. Initially, reverse osmosis membranes used for brine and seawater desalination were useful for supplying large amounts of industrial and domestic water. The brine and seawater desalination process using reverse osmosis membrane removes salts, ions and particles when only salt water is dissolved and dissociated ions and particles do not pass through the membrane and pure water passes through the membrane. If the osmotic pressure is increased, at least 97% of salt removal rate is required for the application of saline and seawater desalination. There must be a capability, that is, a characteristic of high flow. Generally, the flux of membrane is required for seawater desalination condition, 10 gallon / ft ² day (gfd), salt water condition, 220gfd at 800psi, and high flow rate is more important than salt removal rate, or vice versa. have.

As a reverse osmosis membrane, the composite membrane is composed of a porous support layer and a polyamide-based composite thin film on the support layer. Typical polyamide membranes can be obtained by interfacial polymerization of polyfunctional amines and polyfunctional acyl halides.

U.S. Patent 4,277,344, previously filed by Cadotte, discloses aromatic polyamides obtained by interfacial polymerization of aromatic polyfunctional amines containing two primary amine substituents and aromatic acyl halides having three or more acyl halide functional groups. Techniques for thin films have been proposed. In this case, the reverse osmosis membrane is prepared by coating m-phenylenediamine on a microporous polysulfone support, and then reacting an excess of metaphenylenediamine solution with dissolved trimezoyl chloride (TMC), which has excellent performance. It is announced. Although Cadette's membranes show good flow rates and salt removal rates, various studies have been conducted to increase the flow rates and improve the salt removal rate of polyamide reverse osmosis composite membranes. It has been continued.

For example, Tomashke's U.S. Patent 4,872,984 (registered in October 1989) (a) to form a liquid layer on a microporous support layer (1) is essentially an aromatic polyamine of monomers having at least two amine functional groups. Applying a microporous support as an aqueous solution consisting of the reactant and (2) an amine salt of the monomer, (b) the amine reactive reactant on average has at least about 2.2 acyl halides per molecule of the reactant, and the polyfunctional acyl halide or mixture thereof Contacting the liquid layer with an organic solvent solution of an aromatic amine reactive reactant consisting essentially of monomers and (c) drying the product in two steps to form the permeable osmosis membrane. It was.

Examples of the amine salt of Tomaske include trialkylamines such as trimethylamine, triethylamine and tripropylamine; N-alkylcyclic substituted amines such as 1-methylpiperidine; N, N-dialkanamines such as N, N-dimethylethylamine, N, N-diethylmethylamine; N, N-dialkylethanolamines such as N, N-dimethylethanolamine; Two cyclic tertiary amines such as 3-quinuclidinol and mixtures thereof or tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropyl ammonium hydroxide ; Benzyl trialkyl ammonium hydroxide, such as benzyl trimethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, benzyl tripropyl ammonium hydroxide, and the like.

In US Pat. No. 4,983,291, inventor Chau et al. Proposed a membrane prepared by interfacial polymerization on a porous support. According to this patent, a polyamine aqueous solution containing a polar solvent, a polyhydric material, and an acid acceptor that does not react with the amine Wherein the polyhydric material is a long carbon atom containing ethylene glycol, propylene glycol, glycerin and glycol, with an aqueous solution content of 0.1 to 50%. The excess solution of the coated support was removed and then contacted with the polyacyl halide organic solution, with sufficient time for the polymerization product to form on the support, the resulting complex being hydroxypolycarboxylic acid, polyaminoalkylene polycarboxyl After treatment with an acid, salt consisting of acid and amine, sulfuric acid, amino acid, amino acid salt, polymeric acid, organic acid and the like, it is dried to obtain a reverse osmosis composite membrane.

In addition, in the US patent 5,576,057, inventor Hirose et al. (A) coating a solution containing a compound having at least two amino groups on the porous support and then contacting the (b) solution containing a polyfunctional halogen acid reverse osmosis complex A method of preparing the membrane was presented, wherein the difference in solubility constant between solution (a) and solution (b) was 7 to 15 (cal / cm 3) ^1/2 .

The solvent of the solution (A) is ethanol, propanol, butanol, 1-pentanol, t-amyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, 2-ethylbutanol, 2-ethylhexanol, Octanol, cyclohexanol, tetrahydroxypearlfuryl alcohol, neopentigol, t-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, ethylene glycol Mixtures of alcohol and water, such as diethylene glycol, triethylene glycol, tetraethylene glycol, propanediol, butanediol, pentanediol, hexanediol, glycerol, nitromethane, formamide, methylformamide, acetonitrile, dimethylformamide, It is a mixture of nitrogen compounds and water such as ethylformamide and the like.

And, in US Pat. No. 5,614,099, Hirose et al. Presented a reverse osmosis composite membrane in which the average surface roughness of the polyamide layer is at least 55 nm. Wherein the polyamide surface layer is prepared by reaction with a polyfunctional halogen acid compound having an amino group and a halogen acid group and the polymer film is a solution containing m-phenylenediamine in a porous polysulfone support such that a solution layer is formed on the support. After contact with, the film is prepared by placing the film in a dryer such that the trimezoyl chloride solution is contacted to form a polymer film on the support. The surface of the polyamide layer can be treated with a quaternary amine salt and coated with an organic crosslinked polymer having a positive charge.

However, the reverse osmosis composite membranes prepared by the above methods have not reached a satisfactory level in terms of physical properties, and development of more economic methods is required.

It is an object of the present invention to provide a polyamide reverse osmosis composite membrane having higher performance than that of the above-described methods, that is, having high salt rejection and high flow characteristics even at low pressure.

FIELD OF THE INVENTION The present invention relates to polyamide membranes and methods of preparation, that is, (a) polyfunctional amines, aqueous solutions containing at least one polar solvent, at least one salt consisting of at least one amine salt functional group and at least one amine functional group, and (b) a polypipe. The present invention relates to a polyamide reverse osmosis composite membrane obtained by the reaction of an organic solution composed of an amine reactive reactant selected from a functional acyl halide, a polyfunctional sulfonyl halide, and a polyfunctional isocyanate.

In the above, the amine salt functional group is a tertiary amine salt functional group, the amine functional group is a tertiary amine functional group, and the salt is preferentially a reaction product of a strong acid and a polyfunctional tertiary amine, wherein examples of the strong acid are ethanesulfonic acid, toluenesulfonic acid, Camphorsulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and the like, and examples of the polyfunctional tertiary amine include 1,4-diazabicyclo "2,2,2" octane and 1,8-diazabicyclo "5,4,0" undecylenate; -7-ene, N, N, N ', N'-tetramethylethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N, N ', N', N "-pentanemethyldiethylenetriamine, 1,1,3,3-tetramethylguanidine, N, N, N'N'-tetramethylethylenediamine, 1,2-dimethylimidazole And imidazole substituents including the 1-alkyl-imidazole substituents and mixtures thereof.

One or more polar solvents include ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives and urea derivatives, and specific examples of such polar solvents are 2-methoxy. Ethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, alkoxyethanol and 1-pentanol, 1-butanol, di (ethylene glycol) t-butylmethyl ether, di (ethylene glycol) hexyl Ether, propylene glycol butyl ether, propylene glycol propyl ether, 1,3-heptanediol, 2-ethyl-1,3-hexanediol, 1,3-hexanediol, 1,3-pentanediol, dimethylsulfoxide, tetramethylene Sulfoxide, butyl sulfoxide, methylphenyl sulfoxide, tetramethylene sulfone, butyl sulfone, acetonitrile and 1,3-dimethyl-2-imidazolidinnan. The content of at least one polar solvent contained in the aqueous solution is preferably in the range of 0.01 to 8% by weight.

According to the present invention, other polyamide membranes may be selected from a group consisting of (a) an aqueous solution containing a polyfunctional amine, a salt having at least one polar solvent and a compound, and (b) a polyfunctional acyl halide, a polyfunctional sulfonyl halide, and a polyfunctional isocyanate. As a reverse osmosis composite membrane obtained by the reaction of an organic solution composed of an amine reactive reactant having a compound, a salt having a compound at this time is obtained by reaction of a strong acid with a polyfunctional tertiary amine.

The polyfunctional tertiary amine has n tertiary amine functional groups, n is 2 or more, and the polyfunctional tertiary amine and the strong acid are preferably reacted at a molar ratio of 1: 1 or more and 1: n or less, respectively. More preferably, the reaction is carried out under the condition that the molar ratio of the polyfunctional tertiary amine and the strong acid is 1: (0.9).

Another polyamide membrane of the present invention optionally comprises (a) an aqueous solution containing a polyfunctional amine, an amine salt and at least one polar solvent, and (b) a group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate. A reverse osmosis composite membrane obtained by reaction of an organic solution composed of an amine reactive reactant having at least one polar solvent, 2-ethyl-1,3-hexanediol; 2-ethyl-1,3-hexanediol and dimethylsulfoxide Combination of the side; di (ethylene glycol) hexyl ether; combination of di (ethylene glycol) hexether and dimethyl sulfoxide; di (ethylene glycol) t-butyl methyl ether; combination of alcohol ethanol and dimethyl sulfoxide; propylene glycol butyl Ether; propylene glycol propyl ether; triethylene glycol dimethyl ether; 1,3-dimethyl-2-imidazolidinan; combination of 2-ethyl-1,3-hexanediol and acetonitrile; Tetramethylene sulfoxide; Butyl sulfoxide; methylphenyl sulfoxide; butyl sulfone and mixtures thereof.

In addition, the amine salt is selected from quaternary ammonium salt and the reaction product of strong acid and tertiary salt, and the tertiary amine is a monofunctional tertiary amine or a polyfunctional tertiary amine.

Another membrane of the polyamide of the present invention optionally comprises (a) an aqueous solution containing a polyfunctional amine, an amine salt and at least one polar solvent, and (b) a group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate. A reverse osmosis composite membrane obtained by reaction of an organic solution composed of an amine reactive reactant having a solvent content of 0.05 to 4 wt% alkoxyethanol, 0.01 to 8 wt% dimethyl sulfoxide, and 0.05 to 4 wt% alkoxyethanol And 0.01-8% by weight dimethyl sulfoxide combination, 0.01-2% by weight 1-butanol, 0.01-3% by weight, 1-butanol, 0.01-4% by weight tetramethylenesulfone.

In the present invention, the porous support layer is not a specific microporous support layer, but is made of a general polymer material, and the pores are large enough to not impede permeability but have a size not too large to prevent the formation of an ultrathin film on the support layer. Used. Specifically, the pore size of the support layer is preferably in the range of 1 to 500 nanometers, but when the diameter is larger than 500 nanometers, the ultra-thin film is recessed into the pores to obtain the desired flat membrane. Examples of the microporous support layer include various halogenated polymers such as polysulfone, polyether, polyimide, polyamide, polypropylene, polyvinylidene fluoride, and the like.

The thickness of the microporous support layer is not specified in the present invention, but is preferably about 25 to 125 탆 (more preferably 40 to 75 탆).

The polyfunctional amine reactant used in the present invention is essentially a monomeric amine having at least two or more amine functional groups, where the amine functional groups are primary or secondary amine functional groups.

Examples of suitable polyamines for the present invention include metaphenylenediamine, paraphenylenediamine, paraphenylenediamine, and alkyl substituent groups such as methyl or ethyl, alkoxy substituent groups such as methoxy or ethoxy, hydroxyalkyl groups, and hydroxides. Metaphenylenediamine and paraphenylenediamine derivatives substituted with oxy groups, halogen atoms and the like, and other examples thereof include 1,3-propanediamine and 1,3-propanediamine as basic skeletons, and N-alkyl or Alkanediamines such as substituents with or without N-aryl substituents, cycloaliphatic primary diamines such as cyclohexane diamine, cycloaliphatic secondary diamines such as piperazine or piperazine derivatives, N, N'-dimethyl-1, 3-phenylenediamine, N, N'-diphenylethylene diamine, benzidine, xylene diamine or xylene diamine derivatives. Of these, aromatic primary diamines are preferred, and metaphenylenediamine is particularly preferred.

In the present invention, the polyamine aqueous solution contains approximately 0.1-20 wt% (more preferably 0.5-8.0 wt%) of polyamine, and the pH of the solution is in the range of 7-13. At this time, the pH is adjusted by adding a basic acid receptor in the range of 0.001 to 5% by weight. The acid acceptor includes not only trialkylamines but also hydroxides, carboxylates, carbonates, borates, phosphate salts and the like of alkali metals.

As mentioned above, in addition to polyamines, amine salts are added to the aqueous solution, which preferably has substituents of three or four alkyl, cycloaliphaticalkyl, benzyl, alkoxy, and / or alkanol groups at the nitrogen atom, in particular Quaternary ammonium salts or reaction products of strong acids with tertiary amines are more suitable.

Examples of quaternary ammonium salts usable in the present invention include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetrapropylammonium hydroxide; Benzyltrialkylammonium hydroxides such as benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltripropylammonium hydroxide; And mixtures of these ammonium salts.

When the amine salt is a quaternary ammonium salt or a reaction product of a strong acid and a tertiary amine, the tertiary amine may be both a monofunctional tertiary amine or a polyfunctional tertiary amine. Here, the tertiary amine of a single functional group may be trialkylamines such as trimethylamine, triethylamine, tripropylamine and the like; N-alkylcycloaliphatic amines such as 1-methylpiperidine, N, N'-dimethylethylamine, N, N'-diethylmethylamine; N, N'-dialkylethanolamines, such as N, N'-dimethylethanolamine; Etc. are suitable.

Examples of strong acids are methanesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and the like, and other aromatic, aliphatic, and cycloaliphatic sulfonic acids, trifluoroacetic acid, nitric acid, hydrochloric acid, sulfuric acid, and mixtures thereof. .

Polyfunctional tertiary amines Having n tertiary amine functional groups, when n is greater than or equal to 2 to form an amine salt, the polyfunctional tertiary amine and the strong acid have a molar ratio of 1: 1 or more and 1: n or less. Reacts at In addition, the reaction molar ratio of the polyfunctional tertiary amine to the strong acid is 1: 1 or more, and is less than or equal to 1: (0.95) n (more preferably 1: 1 or more, and 1: (0.9) n). Less than or equal to).

In the present invention, the amine salt is preferably composed of a reaction product of a polyfunctional tertiary amine and a strong acid formed by combining at least one tertiary amine salt functional group and at least one tertiary amine, respectively, which means that the tertiary amine salt functional group is poly This is because the tertiary amine functional group acts as an acid acceptor as an acid adduct formed during the interfacial polymerization reaction between the polyfunctional amine and the amine reactive compound, while this functional feature of this type is characterized by a single Significantly improves the flow rate compared to the type having tertiary amine salt functional groups and tertiary amine functional groups or amine salt functional groups of two or more tertiary amine salts and groups without tertiary amine functional groups.

Suitable examples of polyfunctional tertiary amines include 1,4-diazabicyclo [2,2,2] octane (1,4-diazabicyclo [2,2,2] octane; DABCO), 1,8-diaza Bicyclo [5,4,0] unde-7-ene (1,8-diazabicyclo [5,4,0] undec-7-ene), N, N, N ', N'-tetramethyl-1,3 -Butanediamine (N, N, N ', N'-tetramethyl-1,3-butanediamine; TMBD), N, N, N', N'-tetramethyl-1,6-hexanediamine (N, N, N ', N'-tetramethyl-1,6-hexanediamine; N, N, N', N'N "-pentamethyldiethylenetriamine (N, N, N ', N'N" -pentamethyldiethylenetriamine), 1,1 , 3,3, -tetramethylguanidine (1,1,3,3-tetramethylethylenediamine; TMGU) N, N, N ', N'-tetramethylethylenediamine (N, N, N', N'-tetramethylethylenediamine; TMED ), 1,2-dimethylimidazole (MDI), 1-alkyl-imidazole substituent, etc. These polyfunctional tertiary amines are essentially polymerized as non-monomers. Can not.

The amine salt used in the present invention is used in an amount capable of producing an aqueous polyamine solution of 0.3 to 12% by weight (preferably 0.6 to 8.0% by weight).

The aqueous solution is also made by adding one or more polar solvents in addition to the polyfunctional amines and amine salts. The polar solvents include ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives and sulfone derivatives. , Nitrile derivatives, urea derivatives, and mixtures thereof are useful.

Examples of the ethylene glycol derivative used in the present invention include 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, di (ethylene glycol) -t-butylmethyl ether, di ( Ethylene glycol) hexyl ether and the like, and examples of the propylene glycol derivatives include propylene glycol butyl ether and propylene glycol propyl ether. As the alcohol used in the present invention, 1-pentanol, 1-butanol, and the like are suitable. As derivatives of 1,3-propanediol, 1,3-heptanediol, 2-ethyl-1,3-hexanediol, 1,3-hexanediol, 1,3-pentanediol, and the like are suitable.

As the sulfoxide derivatives used in the present invention, dimethyl sulfoxide, tetramethylene sulfoxide, butyl sulfoxide, methylphenyl sulfoxide, and the like are useful. As the sulfone derivatives, tetramethylene sulfone and butyl sulfone are useful.

In the present invention, the nitrile derivative is preferably selected from the group consisting of acetonitrile propionitrile, and 1,3-dimethyl-2-imidazolidone is preferable as the urea derivative.

And two or more polar solvents include 2-ethyl-1,3-hexanediol and dimethyl sulfoxide; Di (ethylene glycol) hexyl ether and dimethyl sulfoxide; Alkoxyethanol (eg 2-butoxyethanol) and dimethyl sulfoxide; 2-ethyl-1,3-hexanediol and acetonitrile are used, and the total content of the polar solvent in the aqueous solution is preferably 0.01 to 8% by weight.

When di (ethylene glycol) hexyl ether is used as the polar solvent, the total content in the aqueous solution is preferably 0.01 to 0.3% by weight (more preferably, 0.1 to 8% by weight). In addition, when 2-ethyl-1,3-hexanediol is used as the polar solvent, the content in the aqueous solution is preferably 0.1 to 1.0% by weight. When alcohol ethanol is used as the polar solvent, the content in the aqueous solution is 0.05 to 4.0. If the 1-pentanol is used as a polar solvent, the content in the aqueous solution is preferably 0.01 to 2.0% by weight, and when 1-butanol is used as the polar solvent, the content in the aqueous solution is 0.01 to 3.0% by weight. % Is preferable, and when tetramethylene sulfone or methylphenyl sulfoxide is used as the polar solvent, the content in the aqueous solution is preferably 0.01 to 4.0% by weight, and when dimethyl sulfoxide is used as the polar solvent, the content in the aqueous solution is 0.1 to It is preferable that the content is 0.5% by weight, and when dimethyl sulfoxide is used as the polar solvent, the content in the aqueous solution is preferably 0.1 to 7.0% by weight.

In the present invention, one or more compounds selected from the group consisting of polyfunctional acyl halides, polyfunctional sulfonyl halides, and polyfunctional isocyanates are used as compounds capable of reacting with amines.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

A microporous polysulfone support formed on a 140 μm thick nonwoven fabric was prepared with 2.0 wt% metaphenylene diamine (MPD), 2.3 wt% camphorsulfonic acid (CSA) and 1.1 wt% triethylamine (TEA). ) And 2.0 wt% of 2-butoxy ethanol (BE) was immersed for 40 seconds. After removing the excess organic solution from the coated support, 0.1 wt% trimezoyl chloride was immersed in a solution layer dissolved in an isopar solvent (EXXON) for 1 minute and then the excess organic solution was removed again.

The composite membrane obtained above was heated at 90 ° C. for 3 minutes and then immersed in an aqueous 0.2% Na ₂ CO ₃ solution for 30 minutes at room temperature and then measured for performance. The measured performance was 99% salt removal and 37 GFD flow rate.

Examples 2 to 36 and Comparative Examples A to W

Except for 2wt% 2-butoxyethanol (BE) in Example 1 except for changing the polar solvent and the amount of use shown in Table 1 was carried out in the same manner as in Example 1 and the performance measurement results are shown in Table 1.

division additive Concentration (% by weight) Flow rate (GFD) Salt removal rate (%) Example 2 Dimethyl Sulfoxide (DMSO) One 40 98.2 Example 3 2-ethyl-1,3-hexanediol (EHD) 0.1 35.2 94.5 Example 4 EHD 0.2 42.6 96.6 Example 5 EHD 0.3 47.9 97.6 Example 6 EHD 0.4 47.5 97.1 Example 7 DMSO / EHD 2 / 0.3, each 75.6 93.5 Example 8 DMSO / EHD 2 / 0.2, each 76.8 92.8 Example 9 DMSO / EHD 0.5 / 0.3, each 58.4 96.6

Example 10 DMSO / EHD 5 / 0.3 72.4 90.7 Example 11 DMSO / EHD 7 / 0.3 69.5 86.6 Example 12 EHD / acetonitrile 0.2 / 4, each 50.7 83.5 Example 13 DMSO / 2-butoxyethanol (BE) 2/2 65.3 93.2 Example 14 DMSO / BE 0.5 / 2, each 46.0 98.0 Example 15 DMSO / BE 0.1 / 0.1 44.8 97.9 Example 16 BE 0.1 34.5 98.4 Example 17 BE 4 36.4 96.7 Comparative Example A BE 6 28.7 94.0 Comparative Example B BE 8 26.0 91.4 Example 18 2-propoxyethanol (PE) 0.1 22.1 95.1 Example 19 PE 2 43.5 97.0 Example 20 PE 4 40.6 95.4 Example 21 2-ethoxyethanol (EE) 2 39.2 96.6 Example 22 EE 4 45.7 94.5 Example 23 2-methoxyethanol (ME) 2 38.2 96.6 Example 24 ME 4 36.7 88.6 Comparative Example C Propylene glycol 2 23.1 96.9 Comparative Example D Ethylene Glycol Dimethyl Ether 2 36.3 92.9 Comparative Example E Ethylene Glycol Diethyl Ether 2 31.4 95.6 Example 25 Di (ethylene glycol) hexyl ether (DEGHE) 0.2 36.6 97.7 Comparative Example F Di (ethylene glycol) butyl ether 2 31.2 95.9 Comparative Example G Di (ethylene glycol) butyl ether 0.1 32.7 93.1 Comparative Example H Di (ethylene glycol) ethyl ether 2 34.7 96.1 Comparative Example I Di (ethylene glycol) methyl ether 2 32.5 96.4 Comparative Example J Di (ethylene glycol) diethyl ether 2 31.0 95.9 Example 26 Di (ethylene glycol) t-butyl methyl ether 2 38.2 95.6 Example 27 Propylene Glycol Butyl Ether 2 39.7 96.9 Example 28 Propylene Glycol Propyl Ether 2 37.3 94.5 Example 29 1-pentanol One 33.2 97.3 Example 30 1-butanol 2 38.3 97.1 Comparative Example K 1-propanol 2 32.4 91.2 Comparative Example L Isopropanol 3 30.8 90.7 Comparative Example M Isopropanol 10 34.7 89.4 Example 31 1,3-dimethyl-2-imidazolidinone One 54.2 92.1 Example 32 Tetramethylene sulfoxide One 46.6 94.8 Example 33 Butyl sulfoxide One 42.2 95.6 Example 34 Methylphenyl sulfoxide One 38.0 97.5 Comparative Example O Ethyl sulfone One 29.9 93.6 Example 35 Tetramethylene sulfone (TMSO) One 44.6 91.8 Example 36 Butyl sulfone 0.5 40.2 98.0 Comparative Example P N, N-dimethylformamide One 35.9 94.4 Comparative Example Q N-methylpyrrolidone 2 26.9 94.5 Comparative Example R Acetone 2 30.8 96.3 Comparative Example S - 0 26.0 98.0 Comparative Example T 1,6-hexanediol One 37.8 95.6 Comparative Example U 1,6-hexanediol 0.5 34.4 97.6 Comparative Example V 1,6-hexanediol 0.25 31.4 97.7 Comparative Example W 1,2-hexanediol One 29.3 98.0

Example 37

Example 1 uses 0.3 wt% EHD (2-ethyl-1,3-hexanediol) instead of 2.0 wt% 2-butoxyethanol and 1 wt% 1,1,3,3- instead of TEA and CSA Tetramethyl guani (TMGU) and 1.6% by weight of toluenesulfonic acid (TSA) were used in the same manner as in Example 1, and the results of the performance measurement showed a flow rate of 43.4 GFD and a salt removal rate of 96.3%.

Examples 38 to 78 and Comparative Examples X to AL

The polar solvent of Table 2 was used instead of 0.3 wt% of EHD and the amines and acids of Table 2 were used instead of TMGU and TSA, and the same procedure as in Example 37 was carried out. .

division Amine weight% / acid weight% or quaternary ammonium salt weight% Polar solvent weight% Flow rate (GFD) Salt removal rate (%) Example 38 1,2-dimethylimidazole (DMI) 1.0 / TSA 1.9 EHD 0.3 46.1 95.2 Comparative Example X TMGU 1 / TSA 1.6 - 25.4 93.3 Example 39 TMGU 1 / TSA 1.6 EHD 0.3 / DMSO 2 63.7 90.8 Example 40 TMGU 1 / TSA 1.6 DEGHE 0.2 / DMSO 2 59.5 86.9 Comparative Example Y TMGU 1 / CSA 2.0 - 26.7 97.6 Example 41 TMGU 1 / CSA 2.0 EHD 0.3 42.0 97.4 Comparative Example Z DMI 1 / TSA 1.9 - 42.8 91.5 Example 42 DMI 1 / TSA 1.9 EHD 0.3 46.1 95.2 Example 43 DMI 1 / TSA 1.9 EHD 0.3 / DMSO 4 56.6 86.9 Example 44 DMI 1 / TSA 1.9 BE 1 41.7 97.5 Example 45 DMI 1 / TSA 1.9 BE 1 / DMSO 4 49.7 90.1 Example 46 DMI 1 / CSA 2 BE 1 / DMSO 3 56.9 87.2 Example 47 DMI 1 / CSA 2 EHD 0.3 / DMSO 4 46.1 95.2 Comparative Example AA DMI 1 / CSA 2 - 38.7 89.1 Example 48 DMI 1 / CSA 2 BE 1 47.4 95.5 Example 49 DMI 1 / CSA 2 EHD 0.3 52.9 95.5 Example 50 DMI 1 / CSA 2 Triethylene glycol dimethyl ether (TEGD) 1 42.5 92.6 Comparative Example AB TMBD 1 / TSA 1.3 - 29.1 97.1 Example 51 TMBD 1 / TSA 1.3 EHD 0.3 36.7 97.8 Example 52 TMBD 1 / TSA 1.3 EHD 0.3 / DMSO 4 56.5 86.7 Example 53 TMBD 1 / TSA 1.3 BE 1 35.5 97.8 Example 54 TMBD 1 / TSA 1.3 BE 1 / DMSO 3 55.7 90.2 Comparative Example AC TMBD 1 / CSA 1.6 - 24.5 97.5

Example 55 TMBD 1 / CSA 1.6 EHD 0.3 40.0 97.4 Example 56 TMBD 1 / CSA 1.6 EHD 0.3 / DMSO 4 52 93.4 Comparative Example AD TMED 1 / MSA 0.83 - 32.5 72.9 Example 57 TMED 1 / MSA 0.83 BE 1 35.6 89.1 Example 58 TMED 1 / MSA 0.83 EHD 0.3 38.7 94.6 Example 59 TMED 1 / MSA 0.83 DMSO 1 41.1 90.0 Example 60 TMED 1 / TSA 1.32 EHD 0.3 25.7 95.1 Example 61 TMED 1 / TSA 1.32 EHD 0.3 / DMSO 2 39.2 92.4 Comparative Example AE DABCO 1 / MSA 0.85 - 32.3 97.0 Example 62 DABCO 1 / MSA 0.85 BE 1 / DMSO 4 48.6 88.3 Example 63 DABCO 1 / MSA 0.85 BE 1 / TMSO 4 24.4 88.5 Example 64 DABCO 2 / MSA 1.7 BE 2 36.9 96.2 Comparative Example AF DABCO 1 / TSA 1.7 - 31.3 95.7 Example 65 DABCO 1 / TSA 1.7 BE 1 33.2 96.9 Example 66 DABCO 1 / TSA 1.7 BE 1 / DMSO 4 48.8 88.8 Example 67 DABCO 1 / TSA 1.7 EHD 0.3 30.2 95.3 Example 68 DABCO 1 / TSA 1.7 EHD 0.3 / DMSO 4 48.0 88.9 Comparative Example AG Benzyltrimethylammonium chloride (BTAC) 1.5 - 30.2 90.7 Example 69 BTAC 1.5 BE 1 / DMSO 3 46.5 91.6 Example 70 BTAC 1.5 EHD 0.3 / DMSO 3 48.0 92.3 Comparative Example AH TEA 2 / TSA 3.4 - 34.1 98.1 Example 71 TEA 2 / TSA 3.4 EHD 0.3 38.0 97.3 Example 72 TEA 2 / TSA 3.4 EHD 0.3 / DMSO 3 57.1 87.5 Example 73 TEA 2 / TSA 3.4 BE 1 45.2 97.3 Example 74 TEA 2 / TSA 3.4 BE 1 / DMSO 3 52.4 83.3 Comparative Example AL N, N-dimethylbenzylamine (DMBA) 1 / TSA 1.4 - 34.5 97.9 Example 75 DABCO 1 / TSA 1.4 EHD 0.3 32.2 96.0 Example 76 DABCO 1 / TSA 1.4 EHD 0.3 / DMSO 3 47.1 87.2 Example 77 DABCO 1 / TSA 1.4 BE 1 34.0 97.9 Example 78 DABCO 1 / TSA 1.4 BE 1 / DMSO 3 56.9 82.8

As can be seen from the above examples and comparative examples, the reverse osmosis composite membrane obtained according to the present invention has usefulness such as having both high flow rate characteristics and excellent salt rejection.

Claims (13)

(A) an aqueous solution composed of a polyfunctional amine, at least one polar solvent, a salt containing a compound consisting of at least one amine salt functional group and at least one amine functional group; A polyamide reverse osmosis composite membrane obtained by the reaction of an organic solution composed of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and an amine reactive reactant selected from a polyfunctional isocyanate group. The polyamide reverse osmosis composite membrane according to claim 1, wherein at least one amine salt functional group is at least one tertiary amine functional group. The polyfunctional amine of claim 1, wherein the polyfunctional amine is one selected from aromatic primary amines and substituted derivatives, alkane primary diamines, cyclosubstituted primary diamines, cyclosubstituted secondary diamines, aromatic secondary diamines, xylenediamines or Polyamide reverse osmosis composite membrane, characterized in that two or more compounds. The polyamide reverse osmosis composite membrane according to claim 1, wherein the amine reactive reactant is one or two or more compounds selected from isophthaloyl halide, terephthaloyl halide, and trimesoyl halide. The polyamide reverse osmium according to claim 1, wherein the one or more polar solvents are selected from ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives and urea derivatives. Osmotic membrane. An aqueous solution comprising a polyamide membrane comprising a polyfunctional amine, at least one polar solvent, and a salt containing a compound that is a reaction product of a strong acid and a polyfunctional tertiary amine; A polyamide reverse osmosis composite membrane obtained by the reaction of an organic solution comprising a polyfunctional acyl halide, a polyfunctional sulfonyl halide and an amine reactive reactant selected from a polyfunctional isocyanate. (A) an aqueous solution containing a polyfunctional amine, an amine salt and at least one polar solvent; In a polyamide reverse osmosis composite membrane obtained by reaction of an organic solution layer composed of an amine reactant selected from a group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, at least one polar solvent is 2-ethyl -1,3 hexanediol; 2-ethyl-1,3-hexanediol and dimethyl sulfoxide combination; Di (ethylene glycol) hexyl ether; Combination of di (ethylene glycol) hexyl ether and dimethyl sulfoxide; Propylene glycol butyl ether; Propylene glycol propyl ether; Triethylene glycol dimethyl ether; 1,3-dimethyl-2-imidazolidinone; Combination of 2-ethyl-1,3-hexanediol and acetonitrile; Tetramethylene sulfoxide; Butyl sulfoxide; Methylphenyl sulfoxide; Polyamide reverse osmosis composite membrane, characterized in that selected from butyl sulfone and mixtures thereof. 9. The polyamide reverse osmosis composite membrane according to claim 8, wherein the amine salt is selected from quaternary amine salts and amine salts which are reaction products of strong acids and tertiary amines. An aqueous solution composed of a polyfunctional amine, an amine salt and one or more polar solvents; In a polyamide reverse osmosis composite membrane obtained by the reaction of an organic solution containing a polyfunctional acyl halide, a polyfunctional sulfonyl halide and an amine reactive reactant selected from a polyfunctional isocyanate, at least one polar solvent is 0.05 wt% in the solution. 4.00 wt% alkoxyethanol; 0.01 wt% to 8.00 wt% of dimethyl sulfoxide; A combination of 0.05 wt% to 4.00% alkoxyethanol and 0.01 wt% to 8.00 wt% dimethyl sulfoxide; 0.01 wt% to 2.00 wt% of 1-pentanol; 0.01 wt% to 3.00 wt% of 1-butanol; Method for producing a polyamide reverse osmosis composite membrane, characterized in that it contains a polar solvent selected from 0.01wt% ~ 4.00wt% tetramethylene sulfone. Applying an aqueous solution containing a polyfunctional amine, at least one polar solvent, and a compound of a reaction product of a strong acid and a polyfunctional tertiary amine on a porous support; Contacting the polyfunctional acyl halide, the polyfunctional sulfonyl halide, and the polyfunctional amine reactive reactant selected from the polyfunctional isocyanate to form interfacial condensation to form a crosslinked polyamide layer on the support at the interface; And Polyamide reverse osmosis composite membrane production method comprising the step of drying the product. The method for producing a polyamide reverse osmosis composite membrane according to claim 10, wherein the aqueous solution contains an acid crab and the pH is in the range of 5-13. Applying a first aqueous solution containing at least one polar solvent and an amine salt to the porous support to form a solution layer on the porous support; Applying a second aqueous solution containing the polyfunctional amine to the first solution to form a second solution layer over the first solution layer; Contacting the polyfunctional acyl halide, the polyfunctional sulfonyl halide, and the polyfunctional amine reactive reactant selected from the polyfunctional isocyanate to form an interfacial crosslinked polyamide layer on the porous support to cause interfacial polymerization; And Polyamide reverse osmosis composite membrane production method comprising the step of drying the product. Applying a first aqueous solution containing at least one polar solvent to the porous support to form a solution layer on the porous support; Applying a second aqueous solution containing a polyfunctional amine and an amine salt to the first solution to form a second solution layer over the first solution layer; Contacting the polyfunctional amine reactive reactant selected from the polyfunctional acyl halide, the polyfunctional sulfonyl halide and the polyfunctional isocyanate to form an interfacial crosslinked polyamide layer on the porous support; And Polyamide reverse osmosis composite membrane production method comprising the step of drying the product.