KR20020061690A - Composite polyamide reverse osmosis membrane and method of producing the same - Google Patents

Abstract

PURPOSE: A polyamide composite reverse osmosis membrane which can be used in industrial water purification plant used for changing seawater to freshwater and domestic water purifier is provided to get a large amount of quantity of water and the high removing rate of salinity even in the condition of low pressure. CONSTITUTION: By mixing water solution which contains multi-functional amine on the porous support and the solution of organic solvent containing amine reacted compound selected from multi-functional acyl halide, multi-functional sulfonyl halide and multi-functional isocyanate, polyamide reverse osmosis membrane composite can be produced. The water solution contains the mixture of the ternary multi-functional amine base which is produced by mixing the ternary multi-functional amine and acid with the rate of 1:0 to 1:1 by mole and the free ternary multi-functional amine.

Description

Polyamide reverse osmosis membrane and method of producing the same

The present invention relates to a new reverse osmosis composite membrane used for industrial water, agricultural water, household water, etc. through salt removal of water such as brine or seawater, and a method of manufacturing 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 salt water and seawater desalination process using reverse osmosis membrane removes salts, ions and particles by contacting the brine to the reverse osmosis membrane, so that salts and dissociated ions and particles do not pass through the membrane and only pure water passes through them. As the osmotic pressure increases, at least 97% of salt removal rate is required for the application of brine and seawater desalination, so the reverse osmosis membrane must have a high salt removal coefficient and relatively high water can pass through the membrane even at relatively low pressure. Must have the ability to be present, i.e. high flow characteristics. In general, flux of membrane is required for seawater desalination condition, 10 gallon / ft ² day (gfd) at 800 psi, brine condition, 220gfd, and high flow rate is more important than salt removal rate, or vice versa. have.

The general type of reverse osmosis membrane consists 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 Cadette, 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 coated with m-phenylenediamine on a microporous polysulfone supporter, and then the excess metaphenylenediamine solution is removed, and then trimezoyl chloride dissolved in Freon (trichlorotrifluoroethane) is used. It is prepared by reacting with (TMC), wherein the contact time of interfacial polymerization is 10 seconds and the reaction proceeds in 1 second. Although Cadette's membrane shows excellent flow rate and salt removal rate, various studies have been conducted to increase the flow rate and increase the salt removal rate of polyamide reverse osmosis composite membranes, and to improve the chemical resistance of the membrane. Most studies have been the main method of using various additives in the solution used in interfacial polymerization.

For example, Tomashke, US Patent 4,872,984 (registered in October 1989) (a) contains an aromatic polyfunctional polyamine having at least two amine functional groups and an amine salt to form a liquid layer on a microporous support layer. Applying a microporous support with an aqueous solution to (b) an organic solvent solution of an aromatic amine reactive reactant, wherein the amine reactive reactant has, on average, at least about 2.2 acyl halides per molecule of the reactant, and consists of a polyfunctional acyl halide or mixture thereof And a method of preparing a reverse osmosis membrane comprising (c) drying the product at an oven temperature of 60 to 110 ° C. for 1 to 10 minutes to form a permeable osmotic membrane.

The amine salt of Tomaski is trialkylamine, 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 ; Of benzyltrialkylammonium hydroxides such as benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltripropylammonium hydroxide and mixtures of at least one quaternary amine and strong acid selected from It is a water soluble salt.

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, the porous support contains a polar aprotic solvent which does not react with an amine, a polyhydric material and an acid acceptor. Contact with aqueous polyamine solution, wherein the polyhydric material is a long carbon atom containing ethylene glycol, propylene glycol, glycerin and glycol, present in the aqueous solution in an amount of 0.1 to 50%. Subsequently, the excess solution of the coated support is removed and then contacted with the polyacyl halide organic solution, at which time the polymerization product is allowed to form on the support, and the resulting complex is hydroxypolycarboxylic acid, polyaminoalkylene poly After treating with a carboxylic acid, a salt consisting of an acid and an amine, sulfuric acid, an amino acid, an amino acid salt, a polymeric acid, an organic acid, and the like, it is dried to obtain a reverse osmosis composite membrane.

In addition, in the US patent 5,576,057, the inventor Hirose et al. (A) coating a solution containing a compound having at least two amino groups on a porous support and then contacting the (b) solution containing a polyfunctional halogen acid to reverse osmosis complex A method of preparing a membrane was presented, wherein the difference between the dissolution coefficients of the solution (a) and the solution (b) was 7-15 (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, tetrahydropulfuryl alcohol, neopentyl glycol, t-butanol, benzyl alcohol, 4-methyl-2-pentanol, 3-methyl-2-butanol, pentyl alcohol, allyl alcohol, ethylene glycol, A mixture of alcohol and water, such as diethylene glycol, and a mixture of water and nitrogen compounds such as nitromethane, formamide, methylformamide, acetonitrile, dimethylformamide, ethylformamide, and the like. Here, Hirose et al. Exemplify that the mixing ratio of water / ethanol is selected in the range of 60 to 90/40 to 10 with respect to the ratio of (a) to water and other solutions.

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 is treated with a quaternary ammonium salt and coated with an organic crosslinked polymer having a positive charge.

On the other hand, in the U.S. Patent No. 6,063,278, the inventor of the present invention, such as Gu Ja-young, is a polyfunctional tertiary amine in which an amine-reactive compound (b) selected from polyfunctional amine (a), polyfunctional acyl halide, polyfunctional sulfonyl halide and polyfunctional isocyanate It was announced that the polyamide composite membrane having high salt bezel ratio and high flow rate characteristics can be obtained even under low pressure by reacting in the presence of salt (c), a reaction product of peracid, wherein the reaction molar ratio of polyfunctional tertiary amine and strong acid It is described that is preferably equal to or larger than 1: 1.

It is an object of the present invention to provide a polyamide reverse osmosis composite membrane having high salt rejection rate and high flow rate even under low pressure.

Another object of the present invention is the molar ratio of the polyfunctional tertiary amine and acid during the interfacial reaction of the polyfunctional amine and the amine-reactive compound, as presented in the United States Patent No. 6,63,278 filed in the United States and patented by the inventor Gu Ja-young et al. To provide a method different from that of adding 1: 1 or more, and has a high salt rejection rate and a high flow rate even when the molar ratio of the polyfunctional tertiary amine and the acid is added in a range of less than 1: 1. To provide a polyamide reverse osmosis composite membrane.

The present invention contacts an aqueous solution (1) containing a polyfunctional amine on a porous support, and an organic solvent solution (2) containing an amine reactive compound selected from polyfunctional acyl halides, polyfunctional sulfonyl halides, and polyfunctional isocyanates. In the preparation of the polyamide reverse osmosis composite membrane by interfacial polymerization, the polyfunctional tertiary amine solution (1) is a polyfunctional tertiary amine alone, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and A polyamide reverse osmosis composite membrane containing an additive selected from a mixture of a polyfunctional tertiary amine, a polar solvent, a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, wherein the polyfunctional tertiary amine The mixture of salt and free polyfunctional tertiary amine is made by mixing the polyfunctional tertiary amine with an acid in a molar ratio of greater than 1: 0 and less than 1: 1. will be.

Hereinafter, the present invention will be described in detail.

The porous support used in the present invention is not a specific microporous support 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. 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. Materials used for 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 participating in the interfacial reaction in the present invention is essentially a monomeric amine having at least two or more amine functional groups, wherein the amine functional group is a primary or secondary amine functional group.

Examples of suitable polyfunctional amines for the present invention include metaphenylenediamine, paraphenylenediamine, and alkyl substituent groups such as methyl or ethyl, alkoxy substituent groups such as methoxy or ethoxy, hydroxyalkyl groups, hydroxy groups, Metaphenylenediamine and paraphenylenediamine derivatives substituted with halogen atoms and the like, and other examples include alkanediamines such as 1,3-propanediamine and 1,3-propanediamine and cycloaliphatic such as cyclohexane diamine. Cycloaliphatic secondary diamines such as primary diamines, piperazine or piperazine derivatives, N, N'-dimethyl-1,3-phenylenediamine, N, N'-diphenylethylene diamine, benzidine, xylene diamine Such aromatic secondary diamines and derivatives thereof. Among these, aromatic primary diamine is more preferable, and metaphenylenediamine is especially preferable.

In the present invention, the polyfunctional amine aqueous solution contains approximately 0.1-20 wt% (more preferably 0.5-8.0 wt%) of the polyfunctional amine, 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 acceptor in the range of 0.001 to 5% by weight. Examples of the acid acceptor include trialkylamines as well as hydroxides, carboxylates, carbonates, borates, and phosphates of alkali metals.

In the present invention, as described above, the aqueous solution contains a polyfunctional tertiary amine or a polyfunctional tertiary amine salt in addition to the polyfunctional amine, wherein the polyfunctional amine salt is a polyfunctional tertiary amine and an acid or a polyfunctional tertiary amine and an acid. Obtained by reacting anhydride. Such a polyfunctional tertiary amine or a polyfunctional tertiary amine salt serves to increase the flux of the membrane formed by addition to the aqueous solution. In this case, the polyfunctional tertiary amine salt added to the aqueous solution may be added after mixing the polyfunctional tertiary amine and the acid (or acid anhydride) in advance, or may be separately added to the aqueous solution.

The first example of the polyfunctional tertiary amine usable in the present invention is 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'-tetramethyl-1,4-butanediamine, N, N, N ' , N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetraethylethylenedimine N, N, N ', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine and the like are preferable, and N, N, N ', N'-tetramethyl-1,6-hexanediamine is more preferable.

As a second example of the polyfunctional tertiary amine, N, N, N ', N'-tetramethyl-1, n-cyclohexanediamine (n is 2 to 4) N, N, N', N'-tetramethyl-1 and n-cyclohexanebis (methylamine) (n is 2 to 4). As a third example of the polyfunctional tertiary amine is 1,4-dimethylpiperazine.

The content of such polyfunctional tertiary amine is preferably 0.05-6 wt% of the aqueous solution (more preferably 0.1-3 wt% of the aqueous solution), and the weight ratio of the polyfunctional and polyfunctional tertiary amines added to the aqueous solution is 1.5: The range of 1-10: 1 is preferred.

In addition, a polyfunctional tertiary amine salt is obtained by reaction of a polyfunctional tertiary amine with an acid (or an acid anhydride). Examples of suitable acids for the present invention include aromatic sulfonic acid, aliphatic sulfonic acid, cyclic aliphatic sulfonic acid, sulfuric acid, trifluoroacetic acid, nitric acid, hydrochloric acid, phosphoric acid, alkylphosphoric acid, arylphosphoric acid, carboxylic acid and mixtures thereof. Examples of acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, hexanoic anhydride, benzoic anhydride, sulfonic anhydride and mixtures thereof.

In the present invention, when the multifunctional tertiary amine and the acid are simultaneously used as additives, the preferred molar ratio is greater than 1: 0 and less than 1: 1 (more preferably greater than 1: 0 and less than 1: 0.9). In addition, when a polyfunctional tertiary amine and an acid anhydride are used simultaneously as additives, a range larger than 1: 0 and less than 1: 1 can be used, but it is particularly preferable to add a polyfunctional tertiary amine and an acid anhydride in a range larger than 1: 0 and smaller than 1: 5. Excellent addition effect.

In the present invention, the polyfunctional tertiary amine salt is preferably such that the total content in the aqueous solution is 0.1 to 12% by weight (more preferably, 0.1 to 9% by weight).

As described above, in addition to the polyfunctional tertiary amine and / or the polyfunctional tertiary amine salt, the polyfunctional amine aqueous solution (1) may be prepared by further adding one or two or more polar solvents. Ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide derivatives, sulfone derivatives, nitrile derivatives, ketone derivatives, urea derivatives, and mixtures thereof, and the like, which also increase the flow rate of the resulting membrane. do.

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, (2-methoxy ethyl) ether, (2-ethoxyethyl) ether, and the like. Examples of 1,3-propane diol include 1,3-heptanediol, 2-ethyl-1,3 -Hexanediol, 1,3-hexanediol, 1,3-pentanediol, and the like.

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, dimethyl sulfone, tetramethylene sulfone, butyl sulfone and the like are useful.

In the present invention, the nitrile derivative is preferably selected from the group consisting of acetonitrile and propionitrile, and urea derivatives include 1,3-dimethyl-2-imidazolidinnan, and ketone derivatives include acetone and 2- Butanone, 2-hexanone 3-hexanone, 3-pentanone, cyclohexanone, cyclopentanone and the like.

The total content of the polar solvent alone or in an aqueous solution of two or more mixed solvents is preferably in the range of 0.01-8% by weight.

At this time, when the alkoxy ethanol is used as a polar solvent, the total content in the aqueous solution is preferably 0.04 ~ 4.0% by weight. When 1-pentanediol is used as the polar solvent, the content in the aqueous solution is preferably 0.01 to 1.0% by weight, and when butyl sulfoxide is used as the polar solvent, the content in the aqueous solution is preferably 0.01 to 1.0% by weight, and methylphenyl When sulfoxide is used as the polar solvent, the content in the aqueous solution is preferably 0.01 to 1.0% by weight. When butyl sulfone is used as the polar solvent, the content in the aqueous solution is preferably 0.01 to 1.0% by weight, and the ketone derivative is polar. When used as a solvent, the content in the aqueous solution is preferably 0.01 to 4.0% by weight.

Such a polar solvent may be applied to the support by adding the polyfunctional tertiary amine alone or a mixture of the polyfunctional tertiary amine salt and the free polyfunctional tertiary amine to the aqueous polyfunctional amine solution (1), but the primary After applying the aqueous polyfunctional amine solution (1) to which only the polar solvent was added to the support, the polyfunctional secondary addition of the polyfunctional tertiary amine alone or a mixture of the polyfunctional tertiary amine salt and free polyfunctional tertiary amine secondary It is possible to obtain more excellent effects by using a method of further applying the amine aqueous solution 1 to the support.

On the other hand, the amine reactive compound is present in the organic solvent solution (2) which is not mixed with water, the preferred content of this amine reactive compound is 0.005 to 5% by weight (more preferably 0.01 to 0.5% by weight), the organic used Examples of the solvent include hexane, cyclohexane, heptane, alkanes having 8 to 12 carbon atoms, and halogenated hydrocarbons such as freon. The ISOPAR solvent used in the following examples is an alkanes mixture having 8 to 12 carbon atoms.

On the other hand, a specific method of preparing a reverse osmosis composite membrane by interfacial polymerization by contacting with a polyfunctional amine aqueous solution (1) containing the above additives and an organic solvent solution (2) containing an amine reactive compound is as follows. Passing methods can be used.

That is, (iii) a polyfunctional tertiary amine, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, and a polar solvent and a polyfunctional tertiary amine salt and a free polyfunctional Applying an aqueous polyfunctional amine solution (1) containing an additive selected from a mixture of tertiary amines to the porous support to form a first aqueous solution layer; (Ii) applying an aqueous solution (1) containing purely polyfunctional amine only on the first solution layer to form a second solution layer; (iii) polyfunctional acyl to cause interfacial polymerization of the aqueous solution layer formed as described above; Contacting an organic solvent solution (2) containing an amine reactive compound selected from a halide, a polyfunctional sulfonyl halide, a polyfunctional isocyanate to form a crosslinked polyamide layer on the porous support; And (iii) drying and washing with water.

In addition, (iii) applying a polyfunctional amine aqueous solution (1) containing at least one polar solvent to the porous support to form a first aqueous solution layer; (ii) a polyfunctional tertiary amine alone or a multi-tube on the first solution layer Applying a polyfunctional amine aqueous solution (1) containing a mixture of a functional tertiary amine salt and a free polyfunctional tertiary amine to form a second solution layer; (iii) interfacial polymerization of the aqueous solution layer formed as described above; Contacting the organic solvent solution containing the amine reactive compound (2) to form a crosslinked polyamide layer on the porous support; And (iii) drying and washing with water.

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

Example 1

1.6 wt% methphenylene diamine (MPD), 0.6 wt% N, N, N ', N'-tetramethyl-1,6 was applied to a support having a microporous polysulfone layer coated on a 140 μm thick nonwoven fabric. After immersion in an aqueous solution containing -hexanediamine (TMHD) for 40 seconds, the excess solution of the support layer was removed with a roll. The support layer was immersed in an Exxon Corp. solution containing 0.1 wt% trimezoyl chloride (TMC) for 1 minute and then the excess solution was removed. The prepared composite membrane was dried in air for 1 minute, and soaked in a 0.2 wt% Na ₂ CO ₃ washing solution for 30 minutes at room temperature before performance experiment. The performance of the obtained reverse osmosis composite membrane was measured by passing NaCl aqueous solution of 2000 PPM at 225 psi. As a result, the salt removal rate was 96.8% and the permeation flux was 45.8 gfd.

[Examples 2 to 16 and Comparative Example A]

As shown in Table 1, except that the MPD and TMHD concentrations were different from each other, the same procedure as in Example 1 was performed, and the performance of the obtained reverse osmosis composite membrane was measured and shown in Table 1.

TABLE 1

Example 2

The permeation flux and the salt removal rate were measured in the same manner as in Example 1 except that 0.6 wt% TMHD and 0.06 wt% toluene sulfonic acid (TSA) were used instead of 0.6 wt% TMHD. 38.9 gfd and 97%, respectively.

[Examples 18-25 and Comparative Example B]

Except for using MDP, TMHD, acid (toluenesulfonic acid and acetic acid), acetic anhydride of various concentrations shown in Table 2 was carried out in the same manner as in Example 1, by measuring the performance of the prepared reverse osmosis composite membrane Table 2 shows.

TABLE 2

Example 3

Except for adding 0.2wt% 2-ethyl-1,3-hexanediol (EHD) to the aqueous solution of MPD, TMHD, TSA was carried out in the same manner as in Example 17, the performance of the prepared reverse osmosis composite membrane was measured As a result, the flux and salt removal rate were 48.7 gfd and 96.6%, respectively.

Example 27-39

Except for the use of various concentrations of MPD, TMHD, TSA, Ac ₂ O and various types of organic solvents shown in Table 3 was carried out in the same manner as in Example 1, by measuring the performance of the prepared reverse osmosis composite membrane Shown in

(In Table 3, "MEE" represents 2-methoxyethyl ether; "BUT" represents 1-butanol; "BE" represents 2-butoxyethanol; "DEGEE" represents diethyl glycol ethyl ether "CYHEX" represents cyclohexane; "DMSO" represents dimethyl sulfoxide)

TABLE 3

Example 40

1.6 wt% metaphenylenediamine (MPD), 0.6 wt% N, N, N ', N'-tetramethyl-1,6-hexanediamine instead of 1.6 wt% metaphenylenediamine (MPD), 0.5 wt% N, Except for using N, N ', N'-tetramethyl-1,6-hexanediamine was carried out in the same manner as in Example 1, the permeation flux and salt removal rate of the prepared reverse osmosis composite membrane was 32.4gfd and 96.9, respectively. Was%.

[Examples 41-53 and Comparative Examples C-F]

MPW and tertiary amines at various concentrations shown in Table 4 instead of 1.6 wt% metaphenylenediamine (MPD), 0.6 wt% N, N, N ', N'-tetramethyl-1,6-hexanediamine (TMHD) Was carried out in the same manner as in Example 1 except for using a variety of organic solvents, and the performance of the prepared reverse osmosis composite membrane is measured and shown in Table 4.

TABLE 4

As can be seen from the above examples and comparative examples, the reverse osmosis composite membrane prepared according to the present invention has high performance and high salt rejection evenly, so that industrial water purification facilities or household water purifiers used for desalination of brine or seawater. It can be used very usefully.

Claims (15)

The aqueous solution (1) containing the polyfunctional amine on the porous support and the organic solvent solution (2) containing the amine reactive compound selected from the polyfunctional acyl halide, the polyfunctional sulfonyl halide, and the polyfunctional isocyanate are brought into contact with each other. In the polyamide reverse osmosis composite membrane obtained by polymerization, the aqueous solution (1) is mixed with a polyfunctional tertiary amine alone or a polyfunctional tertiary amine and an acid in a molar ratio of greater than 1: 0 and less than 1: 1. A polyamide reverse osmosis composite membrane comprising a mixture of a polyfunctional tertiary amine salt obtained and a free polyfunctional tertiary amine. Interfacial polymerization formed by contacting an aqueous solution (1) containing a polyfunctional amine on a porous support and an organic solvent solution (2) containing an amine reactive compound selected from polyfunctional acyl halides, polyfunctional sulfonyl halides, and polyfunctional isocyanates. In the polyamide reverse osmosis composite membrane obtained by the above method, the aqueous solution (1) has a molar ratio of polyfunctional tertiary amine alone or polyfunctional tertiary amine and acid together with one or two or more polar solvents with a molar ratio of greater than 1: 0. A polyamide reverse osmosis composite membrane comprising a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine obtained by mixing in a range less than 1: 1. The polyamide reverse osmosis composite membrane according to claim 1 or 2, wherein the polyfunctional tertiary amine is contained in the range of 0.05-6% by weight of the aqueous solution (1). The polyamide reverse osmosis of claim 1 or 2, wherein the mixture of the polyfunctional tertiary amine salt and the free polyfunctional tertiary amine is contained in the range of 0.1-12% by weight of the aqueous solution (1). Composite membrane. The polyamide reverse osmosis composite membrane according to claim 1 or 2, wherein the polyfunctional amine has at least two primary or secondary amine functional groups. The polar solvent according to claim 1 or 2, wherein the polar solvent is selected from ethylene glycol derivatives, propylene glycol derivatives, 1,3-propane diol derivatives, sulfoxide derivatives, nitrile derivatives, ketone derivatives, urea derivatives, and mixtures thereof. Polyamide reverse osmosis composite membrane. The polyamide reverse osmosis composite membrane according to claim 1 or 2, wherein the polar solvent is contained in an amount of 0.01-8% by weight of the aqueous solution. 3. The polyfunctional tertiary amine of claim 1, wherein the multifunctional tertiary amine is N, N, N ', N'-tetramethyl-1,6-hexanediamine, , 4-butanediamine, N, N, N ', N'-tetramethyl-2-butene-1,4-diamine, N, N, N', N'-tetramethyl-1,3butanediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,8-octanediamine, N, N, N ', N'-tetramethyl -1,7heptanediamine, N, N, N ', N'-tetramethyl-1,5-pentanediamine, N, N, N', N'-tetramethyl-1,4-butanediamine, N, N , N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N ', N'-tetraethylethylene Diamine, N, N, N ', N'-tetramethyl-1, n-cyclohexanediamine (n is 2 to 4), N, N, N', N'-tetramethyl-1, n-cyclohexane Bis (methylamine) (n is 2 to 4), polyamide reverse osmosis composite membrane, characterized in that selected from 1,4-dimethylpiperazine. The acid according to claim 1 or 2, wherein the acid is aromatic sulfonic acid, aliphatic sulfonic acid, cyclic aliphatic sulfonic acid, sulfuric acid, trifluoroacetic acid, nitric acid, hydrochloric acid, phosphoric acid, alkylphosphoric acid, arylphosphoric acid, carboxylic acid and the like Polyamide reverse osmosis composite membrane, characterized in that selected from the mixture. The polyamide reverse osmosis composite membrane according to claim 1 or 2, wherein an acid anhydride is used instead of an acid. 11. The polyamide reverse osmosis composite membrane according to claim 10, wherein the acid anhydride is selected from acetic anhydride, propionic anhydride, butyric anhydride, hexanoic anhydride, benzoic anhydride, sulfonic anhydride and mixtures thereof. The polyamide reverse osmosis composite membrane according to claim 9, wherein the polyfunctional tertiary amine and the acid anhydride are mixed in a molar ratio of greater than 1: 0 and less than 1: 0.5. Selected from a polyfunctional tertiary amine, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, and a mixture of a polar solvent and a polyfunctional tertiary amine salt and a free tertiary amine Applying an aqueous polyfunctional amine solution (1) containing additives to the porous support; Applying an aqueous solution (1) containing purely polyfunctional amines on the solution layer; Contacting an organic solvent solution (2) containing an amine reactive reactant selected from a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate to form an interfacial polymerization, thereby forming a crosslinked polyamide layer on the porous support; And drying and washing the product with the polyamide reverse osmosis composite membrane. Applying an aqueous polyfunctional amine solution containing at least one polar solvent to the porous support; Applying a polyfunctional amine aqueous solution containing a polyfunctional tertiary amine alone or a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine mixture on the solution layer; Contacting an organic solvent solution (2) containing an amine reactive reactant selected from a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate to form an interfacial polymerization, thereby forming a crosslinked polyamide layer on the porous support; and Method for producing a polyamide reverse osmosis composite membrane consisting of drying and washing the product. 15. The mixture of claims 13 and 14 wherein the mixture of polyfunctional tertiary amine salts and free polyfunctional tertiary amines has a molar ratio of the polyfunctional tertiary amine to an acid or acid anhydride of greater than 1: 0 and less than 1: 1. Method for producing a polyamide reverse osmosis composite membrane, characterized in that obtained by mixing.