Art
[1]This application claims the benefit of Korea Patent Application No. 10-2017-0050529 filed in Korea Intellectual Property Office submitted on April 19, 2017, and all its contents are incorporated herein by reference.
[2]Herein it relates to a process for preparing a water treatment separation membrane and its.
BACKGROUND
[3]Recently, due to severe water shortages and pollution of the water environment it has emerged as an urgent challenge to develop new water sources. Research on water pollution and has a good life and industrial water, various kinds of domestic sewage and industrial wastewater treatment to the target, there is a heightened interest in water treatment processes using the separator having the advantage of energy conservation. In addition, the strengthening of environmental regulations and is expected to accelerate to accelerate the activation of membrane technology. Traditional water treatment processes are being strengthened to meet the himdeuna regulations, in the case of membrane technology because it guaranteed an excellent treatment efficiency and stable processing are expected to become the dominant technology in the future water treatment applications.
[4]
Liquid separation is classified as microfiltration (Micro Filtration), UF (Ultra Filtration), nanofiltration (Nano Filtration), RO (Reverse Osmosis), couch, active transport, and electrodialysis, etc., depending on the membrane pores. Then in the reverse osmosis method is water permeable, however, be the melting salt to use a semi-permeable membrane showing impermeable to say a process for the desalting operation the high pressure number that for a salt inlet on one side of the semipermeable membrane, the pure salt is removed It is come to the other side to low pressure.
[5]
Specifically, a typical example of such a water treatment membrane is a polyamide-based membrane may be made of water, to form a polysulfonic poncheung over a non-woven fabric to form a microporous support, the microporous support the m- phenylenediamine (m-Phenylene immersing the Diamine, mPD) aqueous solution to form a mPD layer, by dipping or coating it back to trimesoyl chloride (TriMesoylChloride, TMC) the organic solution by contacting the mPD layer with TMC by interfacial polymerization by the method of forming the polyamide active layer It may have been manufactured.
[6]
In the study of what raising the same polyamide-based composite membrane salt rejection and the flux it is being continuously made to.
Detailed Description of the Invention
SUMMARY
[7]
Herein it is to provide for a water treatment separation membrane and manufacturing method thereof having an improved filtration performance.
Problem solving means
[8]
An exemplary embodiment of the present disclosure
[9]
A porous support; And
[10]
In the water treatment separation membrane comprising a polyamide active layer it is provided on the porous support,
[11]
The polyamide active layer provides a water treatment separation membrane comprises at least one selected from units represented by the following formula (1) units to the unit, to to, and units represented by the formula (3) formula (4) represented by the formula (2) represented by the do.
[12]
Formula 1
[13]
[14]
[Formula 2]
[15]
[16]
[Formula 3]
[17]
[18]
[Formula 4]
[19]
[20]
In the above Chemical Formulas 1 to 4,
[21]
U 1 and U 2 are the same or, each independently represent a substituted or unsubstituted divalent aliphatic group-substituted 2 different from each other; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic ring a divalent group,
[22]
U 3 is a substituted or unsubstituted aliphatic group unsubstituted trivalent; A substituted or unsubstituted trivalent alicyclic group; Or a substituted or unsubstituted aromatic ring a trivalent group,
[23]
A 1 to A 9 are represented by any one which is the same or different and each is independently selected from the formula to 5 to 7 with each other,
[24]
A 10 is represented by the general formula (5) or to 8,
[25]
[Formula 5]
[26]
[27]
[Chemical Formula 6]
[28]
[29]
[Chemical Formula 7]
[30]
[31]
[Chemical Formula 8]
[32]
[33]
In the above Chemical Formula 5 to 8,
[34]
V 1 and V 2 are the same or different from each other, and each independently represent a substituted or unsubstituted phenylene ring,
[35]
V 3 is a group substituted or non-substituted divalent benzene ring with 3 ring,
[36]
However, A 1 to A 3 one, A 4 and A 5 one, A 6 and A 7 one, and A 8 and A 9 one of which is represented by the formula (5).
[37]
In addition, an exemplary embodiment of the present disclosure is a porous support; And comprising a polyamide as a water treatment separation membrane containing an active layer, the water treatment separation membrane is an acid or base dissociation before and after the 1H-NMR analysis of the benzene ring peak between 6.8ppm to 7.8ppm (peak) is provided on the porous support It provides a water treatment separation membrane.
[38]
In addition, an exemplary embodiment of the present disclosure is a porous support; And as a water treatment separation membrane comprising a polyamide active layer is provided on the porous support, the water separation membrane is an acid or base dissociation before and after the IR analysis C = N bond and which comprises a peak (peak) of the NCN combined treatment It provides a separation membrane.
[39]
In addition, an exemplary embodiment of the present disclosure is a porous support; And comprises a polyamide as a water treatment separation membrane containing an active layer, the water treatment separation membrane is an acid or base dissociation after the MS analysis showed that the m / z values ​​277, 193, 178, 102, 85 or 60 provided on the porous support It provides a water treatment separation membrane.
[40]
In addition, an exemplary embodiment of the present disclosure includes the steps of: preparing a porous substrate; And
[41]
A method of manufacturing a water treatment separation membrane including forming a polyamide active layer on the porous support,
[42]
The forming of the polyamide active layer comprises the interfacial polymerization using an organic solution comprising an aqueous solution and the acyl halide compounds, including amine compounds,
[43]
The amine at least one of an organic solution containing the aqueous solution and the acyl halide compound containing compound to contain the by at least one guanidine compound represented by the formula 9 or formula 10,
[44]
By the guanidine compound also provides a manufacturing method of a water treatment separation membrane to form a polyamide in the active layer, an amine compound or an acyl halide compound with a covalent bond:
[45]
[Chemical Formula 9]
[46]
[47]
[Formula 10]
[48]
[49]
For Formula 9, and 10,
[50]
U 4 is a substituted or unsubstituted divalent aliphatic group with ring 2; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic ring a divalent group,
[51]
T 1 to T 4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A hydroxyl group; An acyl halide group; An isocyanate group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl tiok group; Substituted or unsubstituted aryl tiok group; A substituted or unsubstituted alkyl sulfoxide group; Substituted or unsubstituted aryl sulfoxide group ring; Substituted or unsubstituted amine groups; A substituted or unsubstituted alicyclic group; Or a substituted or unsubstituted aromatic ring group.
[52]
In addition, an exemplary embodiment of the present disclosure provides a water treatment module including the above-described water separation membrane.
Effects of the Invention
[53]
According to an exemplary embodiment of the present disclosure, prepared by the conventional method the water treatment separation membrane preparation, one selected from units represented by the unit represented by Chemical Formula 1, the unit, the unit and the formula (4) represented by the formula (3) represented by the formula (2) water separation membrane having a polyamide active layer comprising at least has an effect to improve the salt rejection and / or flux properties.
[54]
Further, according to one embodiment of the disclosure, prepared by the conventional method the water treatment separation membrane preparation, formula (9) or an amine-based aqueous solution containing a compound and / or an acyl halide comprising the bi-guanidine compound at least one kind represented by the formula (10) a water treatment separation membrane comprising a polyamide active layer is formed by interfacial polymerization of an organic solution containing the compound has an effect to improve the salt rejection and / or flux properties.
Brief Description of the Drawings
[55]
Figure 1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present disclosure.
[56]
Figure 2 shows the acid or base dissociation before and after the 1H-NMR spectrum of the water separation membrane in accordance with one embodiment of the present disclosure.
[57]
Figure 3 is after dissociation of the acid or base treatment membrane according to one embodiment of the present disclosure shows the ESI-MS spectrum.
[58]
4 is a diagram showing the 13C-NMR analysis based on compound A and PHB polymer.
[59]
Reference Numerals
[60]
100: Non-woven
[61]
200: a porous support layer
[62]
300: polyamide active layer
[63]
400: brine
[64]
500: Water
[65]
600: concentrated
Best Mode for Carrying Out the Invention
[66]
When that member which is positioned "on" the other element herein, it also includes a case member which is in contact with the other members, as well as if the other member exists between the two members.
[67]
Assuming that any part "includes" a certain component in the present specification, which is not to exclude other components not specifically described are the opposite means that may further contain other components.
[68]
Water separator according to one embodiment of the present specification, the porous support; And comprising a polyamide active layer is provided on the porous support, the polyamide active layer is represented by the following formula (1) units to the unit, to the unit and the formula 4 of the formula (3) represented by the formula (2) represented by the It may include one or more of the selected unit:
[69]
Formula 1
[70]
[71]
[Formula 2]
[72]
[73]
[Formula 3]
[74]
[75]
[Formula 4]
[76]
[77]
In the above Chemical Formulas 1 to 4,
[78]
U 1 and U 2 are the same or, each independently represent a substituted or unsubstituted divalent aliphatic group-substituted 2 different from each other; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic ring a divalent group,
[79]
U 3 is a substituted or unsubstituted aliphatic group unsubstituted trivalent; A substituted or unsubstituted trivalent alicyclic group; Or a substituted or unsubstituted aromatic ring a trivalent group,
[80]
A 1 to A 9 are represented by any one which is the same or different and each is independently selected from the formula to 5 to 7 with each other,
[81]
A 10 is represented by the general formula (5) or to 8,
[82]
[Formula 5]
[83]
[84]
[Chemical Formula 6]
[85]
[86]
[Chemical Formula 7]
[87]
[88]
[Chemical Formula 8]
[89]
[90]
In the above Chemical Formula 5 to 8,
[91]
V 1 and V 2 are the same or different from each other, and each independently represent a substituted or unsubstituted phenylene ring,
[92]
V 3 is a group substituted or non-substituted divalent benzene ring with 3 ring,
[93]
However, A 1 to A 3 one, A 4 and A 5 one, A 6 and A 7 one, and A 8 and A 9 one of which is represented by the formula (5).
[94]
Usually by the addition of guanidine compounds as additives to prepare a water treatment separation membrane, the analysis results are shown in the main chain is the functional group was introduced by a covalent bond is not present, when the group-by-guanidine is used as the additive that exists inside the polyamide active layer, or the outgoing washed there is a disadvantage if you can not see. However, the water separation membrane in accordance with one embodiment of the present specification, a water separation membrane by the guanidine compound is present as a covalent bond to a polyamide active layer, it is possible to verify this by the results described in this Example.
[95]
According to an exemplary embodiment of the present disclosure, the polyamide active layer is comprising a by-guanidine compounds in which nitrogen is contained at least three, the two ends of the bi-guanidine compound is a polyamide active layer an amine-based compound in the or acyl halide compounds Share made a bond is bonded to the main chain. Thus, the membrane can exhibit a high contrast, salt removal ratio, which does not include the separation membrane and, by guanidine compounds, including by-guanidine compounds as additives in the polyamide active layer.
[96]
More specifically, when the by-guanidine compound is included as an additive, a polyamide in a state (embedding), which lodged by the guanidine compound in the active layer to represent fully the specific functional groups of active, in which case the by-guanidine compounds other monomers in the polyamide active layer or polymer there may be hidden by the structure. However, according to an exemplary embodiment of the present disclosure, by the guanidine compound and the amine-based compounds or acyl halide compounds and if stably present in the polyamide active layer through covalent, high salt rejection and the boron rejection, regardless of the operating time and conditions It can be maintained. Further, due to the covalent bond formed when the flow rate also increases the effect to increase the free volume of the water separation membrane (free volume). Flow synergistic effect due to the increase in free volume as the effect it does not appear when you introduce a bi-guanidine as an additive when introducing the bi-guanidine as an additive rather it can be confirmed that empirically that the flow rate is falling.
[97]
According to yet an embodiment of the present disclosure, the porous support; And a water treatment separation membrane comprising a polyamide active layer is provided on the porous support may comprise a peak (peak) of the benzene ring in the acid or base dissociation between before and after the 1H-NMR analysis 6.8ppm to 7.8ppm.
[98]
Specifically, it is possible to between 6.8ppm to 7.8ppm includes four peaks (peak) of the benzene ring.
[99]
Conventional water treatment separation membrane comprising a polyamide active layer is a 1H-NMR analysis, but to obtain a peak as described above, the unit represented by the aforementioned formula (1) units represented by the formula (2) units and formula (4) represented by the formula (3) a water treatment separation membrane comprising a polyamide active layer including at least one selected from units represented may include a peak (peak) of the benzene ring between the 1H-NMR analysis 6.8ppm to 7.8ppm, after acid or base dissociation equal to 1H-NMR analysis before and dissociation results may include a peak (peak) of the benzene ring between 6.8ppm to 7.8ppm.
[100]
In the specification, 1H-NMR analysis was performed at room temperature using the NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple 0 people 5mm probe (probe). NMR solvent for measurement (D 2 a O) was used to dilute the analyte to be about 10mg / ml the degree of concentration.
[101]
In the present specification, 13C-NMR analysis was performed at room temperature using the NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple 0 people 5mm probe (probe). NMR solvent for measurement (D 2 a O) was used to dilute the analyte to be about 10mg / ml the degree of concentration. That is, 13C-NMR analysis is measured by 1H-NMR analysis device with the same device, was determined by setting only the different measurement pulse sequence.
[102]
According to yet an embodiment of the present disclosure, the porous support; And it may include a peak (peak) of the combined polyamide-water separator including an active layer that is an acid or base dissociation before and after the IR analysis C = N bond and NCN provided on the porous support.
[103]
In the present specification, IR analysis of the spectrum was determined over the ATR mode by using FT-IR spectroscopy. Method of measuring the separation membrane surface with an acid or a base, the dried film after dissociation was carried out in two ways for measuring mixed with KBr.
[104]
In the case of a water treatment separation membrane introduced into the bi-guanidine compounds as an additive, by measuring the membrane surface, but can receive the (embedding) by a bi-guanidine C = N and NCN peak which lodged in the water separation membrane, an acid or when a base dissociation is by guanidine compound this dissociates disappear peak (peak). However, the water separation membrane in accordance with one embodiment of the present disclosure is left with a by-guanidine combines shared in polyamide I and the by-guanidine compound covalently bound in the active layer, an acid or a polyamide active layer after nucleotide dissociation, C = N and NCN peak is It is displayed.
[105]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) before and after, and the acid or base dissociation comprises at least one selected of the units may include a peak (peak) of the benzene ring between the 1H-NMR analysis 6.8ppm to 7.8ppm.
[106]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) before and after, and the acid or base dissociation comprises at least one selected of the units may include a peak (peak) of the combined result of IR analysis C = N bond and NCN.
[107]
Water separator according to one embodiment of the present disclosure is a porous support; And a peak (peak) of the benzene ring among the Polyamide The polyamide active layer, comprising an active layer is an acid or base dissociation before and after the 1H-NMR analysis 6.8ppm to 7.8ppm provided on the porous support, and then an acid or a base before dissociation can include a peak (peak) of the combined result of IR analysis C = N bond and NCN.
[108]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) comprises at least one selected of the units, and acid or base dissociation before and after the 1H-NMR analysis results to contain 6.8ppm peak (peak) of the benzene ring between 7.8ppm, acid or base dissociation before and after the IR analysis C = N may include a peak (peak) of the coupling and coupling NCN.
[109]
According to yet an embodiment of the present disclosure, the porous support; And a water treatment separation membrane comprising a polyamide active layer is provided on the porous support may be to include after the acid or base dissociation the MS analysis showed that the m / z values ​​277, 193, 178, 102, 85 and / or 60.
[110]
For example, the m / z values ​​when an amine compound contained in the polyamide active layer according to an exemplary embodiment of the present disclosure are combined with bi-guanidine group two are covalently bonded to the both ends of mPD, acid or base of the water separator Harry after a value a result of MS analysis calculated for cleavage (cleavage) molecular Weight (m / z) is.
[111]
In the present specification, MS analysis using ESI positive ionization method, the LC / MS analysis as C18 column was carried out at 40 ℃.
[112]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) and then, an acid or base dissociation comprises at least one selected of the units can be the MS analysis showed that the m / z values ​​include 277, 193, 178, 102, 85 and / or 60.
[113]
Water separator according to one embodiment of the present disclosure is a porous support; And a peak (peak) of the benzene ring among the Polyamide The polyamide active layer, comprising an active layer is an acid or base dissociation before and after the 1H-NMR analysis 6.8ppm to 7.8ppm provided on the porous support, after the acid or base dissociation may be the MS analysis showed that the m / z values ​​include 277, 193, 178, 102, 85 and / or 60.
[114]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) including the peak (peak) of the benzene ring in between including at least one, and acid or base dissociation before and after the 1H-NMR analysis 6.8ppm to 7.8ppm selected in a unit, and the acid or base dissociation after MS analysis showed that the m / the z value can include 277, 193, 178, 102, 85 and / or 60.
[115]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, the acid or base dissociation after MS analysis showed that the m / z value is included in the 277, 193, 178, 102, 85 and / or 60, acid or base dissociation before and the post may include a peak (peak) of the IR analysis C = N bond and NCN bond.
[116]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) comprises at least one selected of the units, and acid or base dissociation after MS analysis showed that the m / z value of 277, 193, 178, 102, 85, and / or including 60, and acid or base dissociation before and after the IR analysis C = N may include a peak (peak) of the coupling and coupling NCN.
[117]
Water separator according to one embodiment of the present disclosure is a porous support; And a peak (peak) of the benzene ring among the Polyamide The polyamide active layer, comprising an active layer is an acid or base dissociation before and after the 1H-NMR analysis 6.8ppm to 7.8ppm provided on the porous support, after the acid or base dissociation MS analysis showed that the m / z value is coupled 277, 193, 178, 102, 85, and / or including 60, and acid or base dissociation before and after the IR analysis C = N bond with the NCN of the peak ( It may include peak).
[118]
Water separator according to one embodiment of the present disclosure is a porous support; And comprising a polyamide active layer is provided on the porous support, in which the polyamide active layer is expressed in units, units of the formula (3) units and formula (4) represented by the represented by the above formula 2 of the formula (1) including the peak (peak) of the benzene ring in between including at least one, and acid or base dissociation before and after the 1H-NMR analysis 6.8ppm to 7.8ppm selected in a unit, and the acid or base dissociation after MS analysis showed that the m / the z value of 277, 193, and 178 include, 102, 85 and / or 60, acid or base dissociation before and after may comprise a peak (peak) of the combined result of IR analysis C = N bond and NCN.
[119]
In the present specification, or the like, and the acid or base upon dissociation, the acid is hydrochloric acid, nitric acid, sulfuric acid, etc. The base may be sodium hydroxide, potassium hydroxide, and the like.
[120]
In the present specification, the term "substituted" means that the change in the hydrogen atom of another substituent bonded to a carbon atom of the compound, and that the substitution position is position is substituted the hydrogen atom that is, the substituent is not limited if the substitutable position (s), 2 If the above substituted, two or more substituents may be the same or different from each other.
[121]
In the present specification, the term "substituted or unsubstituted" are deuterium; A halogen group; A nitrile group; A hydroxyl group; Alkyl group; Cycloalkyl group; Alkenyl; Alkoxy group; An amine group; Arylamine group; An aryl group; And N, O, S, substituted with Se and substituent substituted by one or more, or 2 substituents selected from the group consisting of a heterocyclic ring containing one or more of the Si atoms or the two or more of the above-exemplified substituents substituent attached or, or any It means having no substituent FIG.
[122]
In the present specification, examples of the halogen groups include fluorine, chlorine, bromine, or iodine.
[123]
In the present specification, the aliphatic group refers to an alkyl group; Alkenyl; Or alkynyl group, an alicyclic group refers to a cycloalkyl group; Or an aliphatic heterocyclic group containing N, O, and at least one of S, the aromatic group is an aryl group; Or a heteroaryl group.
[124]
In the present specification, the alkyl group may be straight linear or branched, number of carbon atoms is preferably, but not particularly limited to the range of 1 to 30. Specifically, it is preferable that 1 to 20 carbon atoms. More specifically, it is preferable that 1 to 10 carbon atoms. Specific examples are methyl; ethyl; profile; n- propyl; Isopropyl; Butyl; n- butyl; Isobutyl; tert- butyl; sec- butyl; 1-methylbutyl; 1-ethyl-butyl; Pentyl; n- pentyl; Isopentyl; Neopentyl; tert- pentyl; Cyclohexyl; n- hexyl; 1-methylpentyl; 2-methylpentyl; 4-methyl-2-pentyl; 3,3-dimethylbutyl; 2-ethylbutyl; Heptyl; n- heptyl; 1-methyl-hexyl; Cyclopentylmethyl; Cyclohexylmethyl; Octyl; n- octyl; tert- octyl; 1-methyl-heptyl; 2-ethylhexyl; 2-propyl-pentyl; n- nonyl; 2,2-dimethyl-heptyl; 1-ethylpropyl; 1,1-dimethylpropyl; Isohexyl; 2-methylpentyl; 4-methyl-hexyl; Or 5-methylhexyl, etc., but is not limited to this.
[125]
In the present specification, a cycloalkyl group is not specifically limited, but is preferably a carbon number of 3 to 30, more preferably from 3 to 20 carbon atoms. Specifically, cyclopropyl; Cyclobutyl; Cyclopentyl; 3-methyl-cyclopentyl; 2,3-dimethyl-cyclopentyl; Cyclohexyl; 3-methylcyclohexyl; 4-methylcyclohexyl; 2,3-dimethylcyclohexylamine; 3,4,5-trimethyl-cyclohexylamine; 4-tert- butylcyclohexyl; Cycloheptyl; Or the like, but cyclooctyl, and the like.
[126]
In the present specification, the alkoxy group is a straight-chain, branched-chain or ring can swaeil. The number of carbon atoms of the alkoxy group is preferably not particularly limited, the carbon number of 1 to 30. Specifically, it is preferable that 1 to 20 carbon atoms. More specifically, it is preferable that 1 to 10 carbon atoms. Specifically, methoxy; Ethoxy; n- propoxy; Isopropoxy; i- propyloxy; n- butoxy; Isobutoxy; tert- butoxycarbonyl; sec- butoxy; n- pentyloxy; Neo-pentyloxy; Iso-pentyloxy; n- hexyloxy; 3,3-dimethyl-butyloxy; 2-ethyl-butyloxy; n- octyloxy; n- nonyl oxy; n- decyloxy; Benzyloxy; Or p- methylbenzyl, but it may be such as oxy, and the like.
[127]
In this specification, the amine group -NH 2 ; Alkylamine group; N- alkyl arylamine group; Arylamine group; N- heteroaryl, aryl amine group; N- alkyl heterocyclic arylamine group; And may be selected from the heteroaryl group consisting of amine groups, the number of carbon atoms is not particularly limited, but preferably ranges from 1 to 30. Specific examples of the amine groups are methyl amine; Dimethyl amine; Amine group; Diethyl amine; Phenylamine group; Naphthylamine group; Biphenyl amine group; Anthracenyl amine group; 9-methyl-anthracenyl amine group; Diphenyl amine; N- phenyl-naphthyl amine; Ditolyl amine group; N- phenyl tolyl amine group; Triphenylamine group; N- phenyl-biphenyl amine group; N- phenyl-naphthyl amine; N- biphenyl-naphthyl amine; N- naphthyl, fluorenyl amine group; N- phenyl phenanthrenyl amine group; N- biphenyl-phenanthrenyl amine group; N- phenyl-fluorenyl amine group; N- phenyl-terphenyl amine group; N- phenanthrenyl fluorenyl amine group; Or N- biphenyl-fluorenyl group, but an amine group, and the like, and the like.
[128]
In the present specification, an alkyl amine group, N- aryl amine group, a tiok alkyl group, an alkyl sulfoxide group, an N- alkyl-heteroaryl group in the amine group is the same as the example of the above-described alkyl group. Specifically alkylthio oxy groups include methyl tiok group; Tiok ethyl group; tiok tert- butyl group; Tiok hexyl group; Tiok octyl and the like at this time, an alkyl sulfoxide group is mesyl; Ethyl sulfoxide group; Profile sulfoxide group; Although the like butyl sulfoxide group, and the like.
[129]
In the present specification, and be straight alkenyl group straight or branched, number of carbon atoms is not particularly limited, and preferably 2 to 30, more specifically, preferably from 2 to 20 carbon atoms. Specific examples thereof include vinyl; 1-propenyl; Isopropenyl; 1-butenyl; 2-butenyl; 3-butenyl; 1-pentenyl; 2-pentenyl; 3-pentenyl; 3-methyl-1-butenyl; 1,3-butadienyl; Allyl; 1-phenylvinyl-1-yl; 2-phenylvinyl-1-yl; 2,2-diphenylvinyl-1-yl; 2-phenyl-2- (naphthyl-1-yl) vinyl-1-yl; 2,2-bis (diphenyl-1-yl) vinyl-1-yl; Still beret group; Or the like, but styryl group LES, and the like.
[130]
In the present specification, the aryl group is not particularly limited, but is preferably a group having 6 to 30 carbon atoms, more preferably a group having 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic. If the aryl group is a monocyclic aryl group having a carbon number is preferably not particularly limited, the carbon number of 6 to 30. More specifically, a monocyclic aryl group is a phenyl group; A biphenyl group; Emitter, but it may be a phenyl group and the like, and the like. If the aryl group is a polycyclic aryl group having a carbon number is not specifically limited. It is a group having 10 to 30 carbon atoms are preferred. Specifically, the polycyclic aryl group is a naphthyl group; An anthracenyl group; Phenanthryl; Tree phenyl group; Les Pies group; Tenerife nalre group; Perylenyl group; Cry hexenyl group; Fluorenyl fluorenyl group and the like can be, but is not limited to this.
[131]
In the present specification, an aryloxy group, an aryl tiok group, an aryl of N- aryl amine and N- aryl-heteroaryl amine group is the same as the example of the above-described aryl group. More specifically, the aryloxy group include a phenoxy group; p- Saturday rilok time; m- Saturday rilok time; 3,5-dimethyl-phenoxy; 2,4,6-trimethyl-phenoxy; p-tert- butyl-phenoxy; 3-biphenyl group; 4-biphenyl group; 1-naphthyloxy group; 2-naphthyloxy group; 4-methyl-1-naphthyloxy group; 5-methyl-2-naphthyloxy group; Trill 1-oxy eyes; 2-anthryl group; 9-anthryl group; 1-phenanthryl group; 3-phenanthryl group; Or 9-phenanthryl oxide and the time or the like, the aryl group is phenyl tiok tea oxy group; Tiok 2-methylphenyl group; Or 4-tert- butylphenyl tiok and the period, etc., sulfoxides aryl groups include benzene sulfoxide group; Or p- toluene but this time including sulfoxide, and the like.
[132]
In the present specification, as including heteroaryl groups than those non-carbon atom, 1 heteroatom, the heteroatom can be specifically comprises an atom selected from the group consisting of O, N and S, such as greater than or equal to 1. Carbon atoms is not specifically limited, but is preferably a carbon number of 2 to 30, that the carbon number of 2 to 20 may be more preferable, and the heteroaryl group is a monocyclic or polycyclic. Examples of heteroaryl groups are thiophene group; Furanoid group; Blood rolgi; Group imidazolyl; A thiazolyl group; Oxazolyl group; Oxadiazolyl group; A pyridyl group; By a pyridyl group; US pyridyl group; Group possess triazole; Triazolyl group; Acridine group-; A pyridazinyl group; Pyrazolyl group possess; Quinolinyl group; Quinazolinyl group; Quinoxalinyl group; Phthalazine groups possess; Pyrido pyridyl US; Pyrido group also pyrazinyl; Group possess pyrazino pyrazole; Isoquinolinium group; Indolyl group; Carbazolyl group; Benzoxazolyl group; Benzimidazolyl group; Benzothiazolyl group; Benzo-carbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzo furanoid group; Fe nansseu Raleigh group (phenanthroline); Iso-oxazolyl group; A thiadiazolyl group; Phenothiazine thiazinyl group; And the like, but dibenzo furanoid group, and the like.
[133]
In the present specification, it refers to a alkylene group ahkil groups that have two binding positions, i.e., 2 to the top. It may be applied to the description of the above-described alkyl group, except that each of the second top.
[134]
In the present specification, the arylene group means an aryl group to which more and the binding position, i.e. 2 to the top. It may be applied to the description of the above-mentioned aryl group, except that each of the two top.
[135]
In this specification, as comprising the aliphatic heterocyclic group is a non-carbon atom, a heteroatom cut more than 1, specifically, the heteroatom is O, a cyclic alkyl group one containing at least one atom selected from the group consisting of N and S, etc. can. The number of carbon atoms is not particularly limited, a carbon number is preferably from 2 to 30, and that the carbon number of 2 to 20 may be more preferable, and the more preferable, and the group of the aliphatic heterocyclic monocyclic or polycyclic group having from 2 to 10 carbon atoms. Specifically, the epoxide group; Or the like, but ahjiri dingi, and the like.
[136]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different, each independently represent a substituted or unsubstituted alkylene group with one another; A substituted or unsubstituted divalent alkenyl group unsubstituted 2; A substituted or unsubstituted divalent cycloalkyl group; A substituted or unsubstituted group divalent aliphatic heterocyclic ring; Or a substituted or unsubstituted arylene group.
[137]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different, each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms with each other; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms in the ring. The alkylene group is a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptyl group, an octyl group, a nonadecyl carbonyl group or a decanyl group and the like, an arylene group is a phenylene group, biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a perylenyl carbonyl group, a fluoran-butenyl group, a triphenylmethyl alkylenyl group, a pie alkylenyl group or a fluorenyl group, but the like, and the like.
[138]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each is independently a hydroxy group, a halogen group, or an amine group substituted or unsubstituted alkylene group with one another; Group or a hydroxy group, a halogen group, or an amine is a substituted or unsubstituted arylene group ring.
[139]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each independently represent a substituted or unsubstituted arylene group, with each other.
[140]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each is independently a hydroxy group, a halogen group, or an amine group substituted or unsubstituted arylene group, each ring.
[141]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each is independently a substituted or unsubstituted phenylene group each other.
[142]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each is independently a hydroxy group, a halogen group, or an amine group substituted or unsubstituted phenylene group each other.
[143]
According to an exemplary embodiment of the present disclosure, U 1 and U 2 are the same or different and each is independently a hydroxy group, a fluorine group or an amine group substituted or unsubstituted phenylene group each other.
[144]
According to an exemplary embodiment of the present disclosure, U 3 is a substituted or unsubstituted trivalent group; Substituted or non-substituted divalent cycloalkyl group the ring 3; Substituted or non-substituted aliphatic group of trivalent heterocyclic ring; Or a substituted or unsubstituted divalent unsubstituted 3-aryl.
[145]
According to an exemplary embodiment of the present disclosure, U 3 is an aryl group, a substituted or unsubstituted divalent unsubstituted 3.
[146]
According to an exemplary embodiment of the present disclosure, U 3 is a substituted or unsubstituted divalent phenyl group unsubstituted 3.
[147]
According to an exemplary embodiment of the present disclosure, U 3 is a group trivalent benzene ring.
[148]
According to an exemplary embodiment of the present disclosure, V 1 and V 2 are the same or different and each is independently a substituted or unsubstituted phenylene group each other.
[149]
According to an exemplary embodiment of the present disclosure, V 1 and V 2 are the same or different and each is independently a halogen group, or an amine group substituted or unsubstituted phenylene group each other.
[150]
According to an exemplary embodiment of the present disclosure, V 1 and V 2 are the same or different and each independently a phenylene group unsubstituted or substituted with a group or an amine group fluorophenyl each other.
[151]
According to an exemplary embodiment of the present disclosure, V 3 represents a substituted or unsubstituted divalent benzene ring with three rings.
[152]
According to an exemplary embodiment of the present disclosure, V 3 is a trivalent group of benzene ring.
[153]
According to an exemplary embodiment of the present disclosure, the above formula (2) may be represented by any one of formulas 2-1 to 2-6.
[154]
[Chemical Formula 2-1]
[155]
[156]
[Formula 2-2]
[157]
[158]
[Chemical Formula 2-3]
[159]
[160]
[Chemical Formula 2-4]
[161]
[162]
[Chemical Formula 2-5]
[163]
[164]
[Chemical Formula 2-6]
[165]
[166]
For Formula 2-1 to 2-6, A 4 and A 5 definitions are the same as defined in the formula (2).
[167]
According to an exemplary embodiment of the present disclosure, the above formula (3) may be represented by formula 3-1 or 3-2.
[168]
[Chemical Formula 3-1]
[169]
[170]
[Chemical Formula 3-2]
[171]
[172]
For Formula 3-1 and 3-2, A 6 and A 7 definitions are the same as defined in the formula (3).
[173]
According to an exemplary embodiment of the present disclosure, the general formula (4) may be represented by Formula 4-1 below.
[174]
[Chemical Formula 4-1]
[175]
[176]
In the above formula 4-1, A 8 to A 10 definitions are the same as defined in the formula (4).
[177]
According to an exemplary embodiment of the present disclosure, at least one selected from the polyamide active layer of the unit represented by the formula (1) unit, unit, unit and the formula (4) shown by the above formula (3) represented by the above formula (2) represented by the the content may be 0.01% to 10% by weight.
[178]
According to an exemplary embodiment of the present disclosure, at least one selected from units represented by the formula (1) unit, unit, unit and the formula (4) shown by the above formula (3) represented by the above formula (2) represented by the form the copolymer can do.
[179]
According to an exemplary embodiment of the present disclosure, the copolymer comprising at least one selected from units represented by the formula (1) unit of the formula (II) unit, the unit and the formula (4) shown by the above formula (3) represented by the represented by the is the weight average molecular weight of 100g / mol to about 1,200g / mol, preferably from 200g / mol to about 1,000g / mol, more preferably from 400g / mol to about 950g / mol.
[180]
According to an exemplary embodiment of the present specification, the weight average molecular weight of the copolymer 100g / mol or more, if, due to the exit washed away little by little, without remaining on the copolymer film can be prevented salt rejection reduction phenomenon of the use time of the membrane and, if less than 1,200g / mol, and has an effect that the molecular weight can be lowered due to the phenomenon of the water soluble higher prevent phenomena that are not dispersed in an aqueous solution, an effect capable of ensuring an appropriate salt rejection caused by remaining in the active layer have.
[181]
Figure 1 illustrates a water treatment separation membrane according to an exemplary embodiment of the present disclosure. Specifically, as Fig. 1 shows a water treatment separation membrane comprising a nonwoven fabric 100, the porous support 200 and a polyamide active layer 300 is in sequence, are a brine 400 is introduced into the polyamide active layer (300), can be discharged through the purified water 500 is non-woven fabric 100, the concentration 600 may not pass through the polyamide active layer 300 is discharged to the outside. Here, one selected from units represented by the polyamide active layer 300, the embodiment unit represented by the formula (I) according to the unit represented by the Formula (2), the unit represented by Formula 3 and Formula 4 described above in It is included above. However, not limited to the structure of the first water separator according to an embodiment of the present disclosure, it may be further included a further configuration.
[182]
According to an exemplary embodiment of the present specification, the salt rejection of the water separation membrane of 97% or more, preferably 98% or more, more preferably 99%, more preferably at least more preferably 99.83% 99.80% or more, can.
[183]
According to an exemplary embodiment of the present specification, flux (flux) of the water separator 5gfd least 20gfd or less, preferably more than 10gfd 20gfd or less, and more preferably may be less than or more 15gfd 20gfd.
[184]
In addition, avoid multiple According to an exemplary embodiment of the present disclosure, the thickness of the water separation membrane may be up to more than 250㎛ 100㎛, the thickness of the water separator, the decrease in the flux and salt rejection of the membrane or more 100㎛ If it has the effect, that not more than 250㎛ to have the effect of preventing the phenomenon of reducing the salt rejection of the membrane.
[185]
According to an exemplary embodiment of the present disclosure, the thickness of the porous support may be a 60㎛ to 100㎛, not limited to this may be adjusted as needed. In addition, the pore size of the porous support is preferably a one 1㎚ 500㎚ to, but is not limited to such.
[186]
In addition, an exemplary embodiment of the present disclosure includes the steps of: preparing a porous substrate; And a method for manufacturing a water treatment separation membrane including forming a polyamide active layer on the porous support, the forming of the polyamide active layer with an organic solution comprising an aqueous solution and the acyl halide compound containing the amine-based compound an interfacial polymerization, a water treatment separation membrane comprises the amine-based compound aqueous solution and the acyl halide compound the organic solution at least one of to of the general formula (9) or by a guanidine compound at least one kind represented by the formula (10) comprising a containing It provides a process for producing the same.
[187]
[Chemical Formula 9]
[188]
[189]
[Formula 10]
[190]
[191]
For Formula 9, and 10,
[192]
U 4 is a substituted or unsubstituted divalent aliphatic group with ring 2; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic ring a divalent group,
[193]
T 1 to T 4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A hydroxyl group; An acyl halide group; An isocyanate group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl tiok group; Substituted or unsubstituted aryl tiok group; A substituted or unsubstituted alkyl sulfoxide group; Substituted or unsubstituted aryl sulfoxide group ring; Substituted or unsubstituted amine groups; A substituted or unsubstituted alicyclic group; Or a substituted or unsubstituted aromatic ring group.
[194]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted alkylene group; A substituted or unsubstituted divalent alkenyl group unsubstituted 2; A substituted or unsubstituted divalent cycloalkyl group; Or a substituted or unsubstituted arylene group.
[195]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms in the ring. The alkylene group is a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptyl group, an octyl group, a nonadecyl carbonyl group or a decanyl group and the like, an arylene group is a phenylene group, biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a perylenyl carbonyl group, a fluoran-butenyl group, a triphenylmethyl alkylenyl group, a pie alkylenyl group or a fluorenyl group, but the like, and the like.
[196]
According to an exemplary embodiment of the present disclosure, U 4 is a hydroxy group, an acyl halide group, a halogen group or an amine group substituted or unsubstituted alkyl group; Or a hydroxy group, an acyl halide group, a halogen group or a substituted or unsubstituted arylene group, an amine group.
[197]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted arylene group.
[198]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted arylene group, a hydroxy group, acyl halide group, a halogen group, or an amine.
[199]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted phenylene group.
[200]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted phenylene group, a hydroxy group, acyl halide group, a halogen group, or an amine.
[201]
According to an exemplary embodiment of the present disclosure, U 4 is a substituted or unsubstituted phenylene group, a hydroxy group, acyl halide group, a fluorine group or an amine.
[202]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A hydroxyl group; An acyl halide group; An isocyanate group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl tiok group; Substituted or unsubstituted aryl tiok group; A substituted or unsubstituted alkyl sulfoxide group; Substituted or unsubstituted aryl sulfoxide group ring; Substituted or unsubstituted amine groups; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aliphatic heterocyclic group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group rings.
[203]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A hydroxyl group; An acyl halide group; An isocyanate group; Alkoxy group; Aryloxy; Tiok alkyl group; Tiok aryl group; An alkyl sulfoxide group; An aryl sulfoxide group; An amine group; Arylamine group; Hetero arylamine group; Aliphatic heterocyclic group containing N, O, and one or more of S; An aryl group; Or a heteroaryl group.
[204]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 are the same or group different and each is a nitrile, independently of each other, a halogen group, hydroxyl group, acyl halide group, an isocyanate group, an alkoxy group, an aryloxy group, an alkyl tiok group, aryl tiok a group, an alkyl sulfoxide group, an aryl sulfoxide group and an amine group substituted by one or more from the group consisting or unsubstituted aryl group.
[205]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 are the same or group different and each is a nitrile, independently of each other, a halogen group, hydroxyl group, acyl halide group, an isocyanate group, an alkoxy group, an aryloxy group, an alkyl tiok group, aryl tiok group, an alkyl sulfoxide group, an aryl sulfoxide group and a substituted from the group consisting of an amine group with one or more or unsubstituted aryl group having 6 to 20 ring, the aryl group is a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl Tre group, a perylenyl group, a fluoran te group, a triphenylmethyl group les, pie LES group or fluorenyl may carbonyl date, but is not limited to this.
[206]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 are the same or group different and each is a nitrile, independently of each other, a halogen group, hydroxyl group, acyl halide group, an isocyanate group, an alkoxy group, an aryloxy group, an alkyl tiok group, aryl is tiok group, an alkyl sulfoxide group, an aryl sulfoxide group and a substituted or unsubstituted phenyl group one or more from the group consisting of amine groups.
[207]
According to an exemplary embodiment of the present disclosure, T 1 to T 4 is an amino group (-NH 2 a).
[208]
According to an exemplary embodiment of the present specification, the formula (9) may be represented by Formula 9-1, Formula 10 can be represented by the following formula 10-1 to.
[209]
[Chemical Formula 9-1]
[210]
[211]
[Chemical Formula 10-1]
[212]
[213]
According to an exemplary embodiment of the present disclosure, the method comprising the polyamide active layer is formed in the aqueous layer containing the amine-based compound on the porous support; And contacting the organic solution containing the acyl halide compound in the aqueous layer containing the amine-based compound may be formed through the step of forming the polyamide active layer. At this time, at least one of an organic solution containing the aqueous solution and the acyl halide compound containing the amine-based compounds include guanidine compounds by one or more kinds represented by the above formula 9, or 10.
[214]
According to an exemplary embodiment of the present disclosure, by the guanidine compound at least one kind represented by the formula 9 or 10 is in the range of 0.01% to 10% by weight in an organic solution comprising an aqueous solution or the acyl halide compound containing the amine compound It may be included in the content. Preferably it may be included to 2% by weight to 10% by weight of the content. When satisfying the above range, the My presence by the guanidine compound to a water treatment separation membrane, and the amine compound or an acyl salt by residues without leaving washed away due to the covalent bond between the halide removal ratio and boron removal ratio maintained, a water treatment due to the covalent bond formation flow increase effect by increasing the free volume (free volume) of the separator is also shown.
[215]
According to an exemplary embodiment of the present specification, the salt of the case by the guanidine compound is less than 0.01% by weight in the aqueous solution or the organic solution, the failure to ensure the proper copolymer content in the polyamide active water treatment separation membrane represented by the formula 9, or 10 It can not prevent the removal rate reduction phenomenon, when the amount exceeds 10% by weight, the lower the flux nopahdo the salt removal can not ensure the function of the separation membrane. In particular, when more than 10% by weight, is formed a non-transparent state with respect to the aqueous solution or organic solution is effective to avoid the problem of contaminating the film production equipment and precipitation occurs.
[216]
According to an exemplary embodiment of the present specification, forming an aqueous layer containing the amine-based compound is not particularly limited, if the method capable of forming a solution layer on the porous support can be used without limitation. Specifically, the method of forming an aqueous layer containing the amine-based compound on the porous support may include spraying, coating, dipping, dropping or the like.
[217]
According to an exemplary embodiment of the present disclosure, the amine based on contact of the organic solution containing the acyl halide and the aqueous layer containing the compound, while the amine-based compound and the acyl halide compound is coated on the surface reaction by the interfacial polymerization generating a polyamide, and is adsorbed by the microporous support is formed with a thin film. Further, according to an exemplary embodiment of the present disclosure, the contact may form an active layer by a method such as dipping, spraying or coating.
[218]
According to an exemplary embodiment of the present disclosure, the aqueous layer may be subjected to additional steps to remove the aqueous solution containing the amine-based compound of the excess, if necessary. Aqueous layer formed on the porous support when the aqueous solution present on the support is too large, may be unevenly distributed, and may be the aqueous solution if unevenly distributed, the one active non-uniform by the interfacial polymerization of a later formed. Therefore, it is desirable to remove the excess aqueous solution after formation of the aqueous layer on the support. Removal of the excess aqueous solution is not specifically limited, for example, can be performed by using a sponge, an air knife, a nitrogen gas blowing, air drying, or compression rolls.
[219]
According to an exemplary embodiment of the present disclosure, to the porous support, it may be used on the non-woven fabric having a coating layer of a polymer material. To the polymer material, e.g., polysulfone, polyether sulfone, polycarbonate, polyethylene oxide, polyimide, polyether imide, polyether ether ketone, polypropylene, polymethylpentene, polyvinyl chloride, and polyvinylidene fluoride However the fluoride be used such as, but are not necessarily limited to these. Specifically, it is possible to use a polysulfone as the polymer material.
[220]
According to an exemplary embodiment of the present specification, the preparation of the porous support, forming a polyamide active layer on the porous support, that is, prior to application of the aqueous solution containing the amine-based compound on the support, TEACSA (triethylammonium camphorsulfonate) and It may comprise the step of further coating the same additives.
[221]
According to an exemplary embodiment of the present disclosure, if the amine of the amine-based compound in an aqueous solution containing compounds if the amine-based compound used in the manufacture of a water treatment separation membrane, but not limited to their kind, and costs a specific example, m- phenylenediamine selected from diamines, p- phenylene diamine, 1,3,6- benzene triamine, 4-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylenediamine, and mixtures thereof is one member or more is preferred.
[222]
According to an exemplary embodiment of the present disclosure, wherein the acyl halide compound is not particularly restricted but includes, for example, an aromatic compound having 2 to 3 carboxylic acid halide, trimesoyl chloride, isophthaloyl chloride, terephthaloyl roil can be a chloride and at least one mixture selected from the group consisting of a mixture thereof.
[223]
According to an exemplary embodiment of the present disclosure, the amount of amine compound is the amine may be up to 15% by weight of at least 0.1% by weight relative to the aqueous solution containing the compound, and preferably may be less than 10% by weight of at least 0.1% by weight . Is the amine, if the content of the compound is less than 0.1% by weight, can not be achieved a smooth reaction with the organic solution containing the acyl halide compound, 15 if the weight% amine-based compound is stably dissolved in the aqueous solution It can be difficult
[224]
Further, according to an exemplary embodiment of the present disclosure, the amount of the acyl halide compounds can be up to 0.1% by weight 0.5% by weight based on the organic solution containing the acyl halide compound. That is, prevent the phenomenon that, according to an exemplary embodiment of the present disclosure, if the amount of the acyl halide compound at least 0.1 wt% based on the organic solution containing the acyl halide compound, the salt rejection and the flux of the final manufacturing separation membranes decreases If the effect, and not more than 0.5% by weight to which there is an effect that it is possible to prevent a decrease in salt rejection of the final membrane manufacturing.
[225]
According to an exemplary embodiment of the present disclosure, the aqueous solution may further comprise a surfactant.
[226]
According to an exemplary embodiment of the present disclosure, the surfactant may be selected from nonionic, cationic, anionic and amphoteric surfactants. According to an exemplary embodiment of the present disclosure, the surfactant is sodium lauryl sulfate (SLS); Alkyl ether sulfate and the like; Alkyl sulfate and the like; Olefin sulfonates; Alkyl ether carboxylates and the like; Nate during surgery pavement and the like; Aromatic sulfonate and the like; Flow rate Ethoxylated octylphenol; Ethoxylated nonyl phenol; Alkyl poly (ethylene oxide); Copolymers of poly (ethylene oxide) and poly (propylene oxide); Octyl glucoside and decyl when alkyl poly glucosides, such as malto seed Drew; Cetyl alcohol, oleyl alcohol, cocamide MEA, cocamide DEA, alkyl hydroxyethyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, fatty alcohols such as hexadecyl trimethyl ammonium bromide, and hexadecyl trimethyl ammonium chloride and the like; And it may be selected from alkyl beta humanity. Specifically, the surfactant may be a flow rate or ethoxylated nonyl phenol ethoxylate SLS, octylphenol.
[227]
According to an exemplary embodiment of the present disclosure, the amount of the surfactant can be not more than 0.5% by weight less than 0.005% by weight based on said aqueous solution.
[228]
Further, according to an exemplary embodiment of the present disclosure, the organic solution may further include an organic solvent, the organic solvents include aliphatic hydrocarbon solvents such as chlorofluorocarbons and Class of hexane carbon number of 5-12, cyclohexane , immiscible with water, such as heptane, alkanes hydrophobic liquid, for example, the number of carbon atoms is used, such as the IsoPar (Exxon), ISOL-C (SK Chem), ISOL-g (Exxon) 5 to 12 alkane and a mixture thereof It is, but is not limited thereby.
[229]
According to an exemplary embodiment of the present specification, the organic solvent may comprise less than 80 parts by weight or more and 99.499 parts by weight based on 100 parts by weight of organic solution. When the organic solvent is less than 80 parts by weight based on 100 parts by weight of the organic solution is not more than the final effective for preventing the salt rejection, and the phenomenon that the flux decrease of the produced membrane, and 99.499 parts by weight, the finally produced separator there is the effect of preventing the phenomenon of reduced salt rejection.
[230]
According to an exemplary embodiment of the present disclosure, the water separator can be used, such as microfiltration membranes (Micro Filtration), ultrafiltration membrane (Ultra Filtration), nanofiltration membrane (Nano Filtration) or reverse osmosis (Reverse Osmosis), in particular reverse osmosis membrane, It can be used.
[231]
Another embodiment of the present disclosure provides a water treatment module including the above-described water separation membrane.
[232]
Specific kind of the water treatment module is not particularly limited, and examples thereof include such as a plate (Plate & Frame) module, a tubular (Tubular) module, a hollow fiber (Hollow & Fiber) module or a spiral wound type (Spiral wound) module. In addition, the water treatment module which comprises a water separation membrane in accordance with one embodiment of the above-described herein, or other any other configuration and manufacturing method, etc. are not particularly limited, and can employ the common means known in the art, without limitation, have.
[233]
On the other hand, a water treatment module according to an exemplary embodiment of the present disclosure are salt rejection, and the flux is excellent, and the chemical stability can be used solid and useful in water treatment devices, such as domestic / industrial water purification system, sewage system, haedam treatment system have.
[234]
It will now be described in detail the example embodiments to illustrate the present disclosure in detail. However, embodiments according to the disclosure are can be modified in many different forms, and are not construed the scope of the present disclosure be limited to the embodiments set forth herein. The practice of this specification examples are provided to more completely describe the present specification to those skilled in the art.
Mode for the Invention
[235]
Preparation of the water separator
[236]

[237]
DMF (N, N- dimethylformamide) to put the polysulfone solid content of 18% by weight to obtain a liquid which is dissolved for more than 12 hours at 80 ℃ to 85 ℃ uniform. The solution was cast to a thickness on 150㎛ 95㎛ 100㎛ to the thickness of the non-woven polyester material. Then, into the non-woven fabric is cast in water to prepare a porous polysulfone support. At this time, the width of the support was prepared by 400㎚.
[238]
A solution comprising a porous polysulfone of 10% by weight TEACSA (triethylammonium camphorsulfonate), and water, based on the total solution on a support slot, was applied as a coating method.
[239]
Then, an aqueous solution containing m-phenylenediamine (mPD), to a 0.1% by weight of Compound A 5% by weight based on the total aqueous solution of a slot coating method, the coating on the porous polysulfone support with a 16m / min speed to form a solution layer. Furthermore, the excess aqueous solution occurred during application was removed using an air knife.
[240]
The organic solution containing the organic solvent, and TMC (IsoPar G) of 0.3% by weight based on the total organic solution onto the aqueous layer to the slot-coating was applied by the 16m / min speed. And, after dried until it evaporates all the liquid component in 95 ℃, washed with distilled water, ultra pure water (DIW) to a water treatment separation membrane was prepared. At this time, the width of the separation membrane was prepared in 380㎚.
[241]

[242]
In Example 1, m-phenylenediamine (mPD) of 5% by weight based on the total aqueous solution, instead of an aqueous solution which comprises 0.1% by weight of compound A, m-phenylenediamine (mPD) of 5% by weight, 0.2% by weight except of having to use an aqueous solution containing the compound a, and to prepare a water membrane in the same manner as in example 1.
[243]

[244]
In Example 1, m-phenylenediamine (mPD) of 5% by weight based on the total aqueous solution, instead of an aqueous solution which comprises 0.1% by weight of compound A, m-phenylenediamine (mPD) of 5% by weight, 0.3% by weight except of having to use an aqueous solution containing the compound a, and to prepare a water membrane in the same manner as in example 1.
[245]

[246]
In Example 1, m-phenylenediamine (mPD) of 5% by weight based on the total aqueous solution, instead of an aqueous solution which comprises 0.1% by weight of compound A, m-phenylenediamine (mPD) of 5% by weight, 0.4% by weight except of having to use an aqueous solution containing the compound a, and to prepare a water membrane in the same manner as in example 1.
[247]

[248]
In Example 1, m-phenylenediamine (mPD) of 5% by weight based on the total aqueous solution, instead of an aqueous solution which comprises 0.1% by weight of compound A, m-phenylenediamine (mPD) of 5% by weight, 0.5% by weight except of having to use an aqueous solution containing the compound a, and to prepare a water membrane in the same manner as in example 1.
[249]

[250]
DMF (N, N- dimethylformamide) to put the polysulfone solid content of 18% by weight to obtain a liquid which is dissolved for more than 12 hours at 80 ℃ to 85 ℃ uniform. The solution was cast to a thickness on 150㎛ 95㎛ 100㎛ to the thickness of the non-woven polyester material. Then, into the non-woven fabric is cast in water to prepare a porous polysulfone support. At this time, the width of the support was prepared by 400㎚.
[251]
A solution comprising a porous polysulfone of 10% by weight TEACSA (triethylammonium camphorsulfonate), and water, based on the total solution on a support slot, was applied as a coating method.
[252]
Then, an aqueous solution containing m-phenylenediamine (mPD), to a 0.1% by weight of compound B in 5% by weight based on the total aqueous solution of a slot coating method, the coating on the porous polysulfone support with a 16m / min speed to form a solution layer. Furthermore, the excess aqueous solution occurred during application was removed using an air knife.
[253]
The organic solution containing the organic solvent, and TMC (IsoPar G) of 0.3% by weight based on the total organic solution onto the aqueous layer to the slot-coating was applied by the 16m / min speed. And, after dried until it evaporates all the liquid component in 95 ℃, washed with distilled water, ultra pure water (DIW) to a water treatment separation membrane was prepared. At this time, the width of the separation membrane was prepared in 380㎚.
[254]

[255]
In the above embodiment 6, the m-phenylenediamine (mPD) of 5% by weight based on the total aqueous solution, instead of an aqueous solution which comprises 0.1% by weight of compound B, m-phenylenediamine (mPD) of 5% by weight, 0.3% by weight except for the use of the aqueous solution containing compound B was prepared and a water separator in the same manner as in example 6.
[256]

[257]
In Example 1, 5% by weight based on the total aqueous solution of m-phenylenediamine (mPD), in place of an aqueous solution which comprises 0.1% by weight of compound A, 5% by weight does not include a by-guanidine compounds phenylenediamine except that an aqueous solution containing (mPD) and the water separation membrane was prepared in the same manner as in example 1.
[258]
[Compound A]
[259]
[260]
[Compound B]
[261]
[262]

[263]
DMF (N, N- dimethylformamide) to put the polysulfone solid content of 18% by weight to obtain a liquid which is dissolved for more than 12 hours at 80 ℃ to 85 ℃ uniform. The solution was cast to a thickness on 150㎛ 95㎛ 100㎛ to the thickness of the non-woven polyester material. Then, into the non-woven fabric is cast in water to prepare a porous polysulfone support. At this time, the width of the support was prepared by 400㎚.
[264]
A solution comprising a porous polysulfone of 10% by weight TEACSA (triethylammonium camphorsulfonate), and water, based on the total solution on a support slot, was applied as a coating method.
[265]
Then, an aqueous solution containing m-phenylenediamine (mPD) to the and 0.1% by weight of compound C in a 5% by weight based on the total aqueous solution of a slot coating method, the coating on the porous polysulfone support with a 16m / min speed to form a solution layer. Furthermore, the excess aqueous solution occurred during application was removed using an air knife.
[266]
The organic solution containing the organic solvent, and TMC (IsoPar G) of 0.3% by weight based on the total organic solution onto the aqueous layer to the slot-coating was applied by the 16m / min speed. And, after dried until it evaporates all the liquid component in 95 ℃, washed with distilled water, ultra pure water (DIW) to a water treatment separation membrane was prepared. At this time, the width of the separation membrane was prepared in 380㎚.
[267]

[268]
In Comparative Example 2, a 5% by weight based on the total aqueous solution of m-phenylenediamine (mPD) and m-phenylenediamine (mPD) of a 0.1 aqueous solution instead of the 5% by weight comprising a% to the weight of Compound C and 0.2% by weight to, except that the aqueous solution containing the compound C of the water separation membrane was prepared in the same manner as in Comparative example 2.
[269]

[270]
In Comparative Example 2, a 5% by weight based on the total aqueous solution of m-phenylenediamine (mPD) and 0.1 instead of the aqueous solution containing a% to the weight of compound C, 5% by weight of m-phenylenediamine (mPD) and 0.3% by weight to, except that the aqueous solution containing the compound C of the water separation membrane was prepared in the same manner as in Comparative example 2.
[271]

[272]
In Comparative Example 2, a 5% by weight based on the total aqueous solution of m-phenylenediamine (mPD) and 0.1 instead of the aqueous solution containing a% to the weight of compound C, 5% of m-phenylenediamine (mPD) and 0.4% by weight to, except that the aqueous solution containing the compound C of the water separation membrane was prepared in the same manner as in Comparative example 2.
[273]

[274]
In Comparative Example 2, a 5% by weight based on the total aqueous solution of m-phenylenediamine (mPD) and 0.1 instead of the aqueous solution containing a% to the weight of compound C, 5% of m-phenylenediamine (mPD) and 0.5% by weight to, except that the aqueous solution containing the compound C of the water separation membrane was prepared in the same manner as in Comparative example 2.
[275]
[Compound C]
[276]
[277]

[278]
1) NMR Analysis
[279]
The NMR of the water separation membrane produced by the above third embodiment are shown in the results of analysis.
[280]
1H-NMR analysis was performed at room temperature using the NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple 0 people 5mm probe (probe). NMR solvent for measurement (D 2 a O) was used to dilute the analyte to be about 10mg / ml the degree of concentration.
[281]
13C-NMR analysis was performed at room temperature using the NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple 0 people 5mm probe (probe). NMR solvent for measurement (D 2 a O) was used to dilute the analyte to be about 10mg / ml the degree of concentration.
[282]
13C-NMR analysis is measured by 1H-NMR analysis device with the same device, it was determined by setting only the different measurement pulse sequence.
[283]
By performing an acid or base dissociation method of measuring the entire membrane surface with acid (HCl) or base (NaOH) method of measuring the membrane surface after loosening two kinds of measurement and the results were shown in Table 1, 1H-NMR analysis a is shown in Fig.
[284]
When each of the dissociated acid or base, or at the same time, was similar to the measurement result even when dissociated, the acid or base treatment is meant that the strong damage (damage) on the membrane achieved a covalent bond.
[285]
TABLE 1
Condition result
1H-NMR (400 MHz, D2O) δ7.45 (t, J = 8.1 Hz, 1H, aromate: CH=CH-CH), δ7.33 (t, J = 2.0 Hz, 1H, aromate: N-C=CH-C-N), δ7.15 (dd, J = 8.1, 2.1 Hz, 2H, aromate: CH=CH-CH)
13C-NMR (400 MHz, D2O) δ163.83 (2x C=NH), δ160.34 (2x C=NH), δ140.16 (N-C=CH-CN), δ133.12 (CH=CH-CH), δ123.68 (CH=CH-CH), δ121.68 (N-C=CH-C-N)
13C-NMR (400 MHz, D2O) δ159.95 (2x C=NH)
1H-NMR (500 MHz, DMSO-d6) δ10.22-10.96 (s, NH), δ9.36-9.87 (-N-C=NH)
1H-NMR (250 MHz, DMSO-d6, 258C, TMS, d) δ1.28 (sb, 2(2H)n; g-CH2), δ1.43 (sb, 2(2H)n; b-CH2), δ3.08 (sb, 2(2H)n; a-CH2N), δ6.90-7.80(mb, 6(1H)n; NH)
13C-NMR (250 MHz, DMSO-d6, 258C, TMS, d) δ25.3 (g-CH2), δ28.5 (b-CH2), δ118.0 (a-CH2N), δ155.4160.9 (C¼N)
1H-NMR (250 MHz, DMSO-d6, 258C, TMS, d) δ3.17-3.92 (mb, 2(2H)n; a-CH2N), δ6.77-8.86 (mb, 6(1H)n; NH)

[286]
2) IR analysis
[287]
The IR of the water separation membrane produced by the above third embodiment are shown in the results of analysis.
[288]
The spectrum through the ATR mode by using FT-IR spectroscopy was measured. By performing an acid or base dissociation method of measuring the entire membrane surface with acid (HCl) or base (NaOH) and then a method of measuring dissociation was mixed with KBr, dry film 2 of measurements and the results are shown in Table 2 below.
[289]
TABLE 2
Condition result
IR (solid) Analysis: wave number (wave number; ν (cm -1 )) 3292, 3136, 1628, 1575, 1541, 1525, 1448, 1394, 1283, 781, 600, 468 cm-1
IR (solid) Analysis: wave number (wave number; ν (cm -1 )) 3319, 3160, 3111, 3034, 1686, 1627, 1153, 1078, 1029, 970, 596, 529, 472, 437 cm-1
IR (KBr) Analysis n¼3300 (s), 3204 (m; n(N-H)), 2921 (w; n(C-H)), 2177 (s; n(C=N)), 1630 (s), 1599 (m), 1560 (s; d(N-H)), 1441 (m), 1420(w; d(CH2)), 1384 (s), 1297 (m), 1150 (w), 1076 (m; n(C-N)), 779 (m; d(CH2) cm-1

[290]
3) MS analysis
[291]
After the acid or base dissociation of the water separation membrane produced by the above third embodiment it is shown in the results of analyzing the MS.
[292]
m / z analysis using ESI positive ionization method, the LC / MS analysis was performed on a C18 column 40 ℃, and are shown in Figure 3 to the result.
[293]
ESI-MS analysis: acid (HCl) or base (NaOH) Harry result, m / z = 227, 193, 178, 102, 85, 60 [M + H] +
[294]
According to the experimental example 1, a water treatment separation membrane according to an exemplary embodiment of the present specification, the 1H-NMR analysis during four benzene rings peak (peak) is found to exist between 6.8ppm to 7.8ppm.
[295]
According to the experimental example 1, a water treatment separation membrane according to an exemplary embodiment of the present specification, there is a by-guanidine compound is present as a covalent bond to a polyamide active layer is left with a by-guanidine combined share in the polyamide active layer after the acid or base dissociation it can be seen that the C = N and NCN peak (peak) appears.
[296]
However, water treatment separation membrane is manufactured by addition of by-guanidine compounds as additives, the functional group is not present an analysis result that the introduction of covalent bonds in the main chain, in the case group by guanidine used as the additive that exists inside the polyamide active layer, or wash there is a disadvantage that can not be resolved goes out. In addition, when measuring the membrane surface (solid), but may receive the (embedding) by a bi-guanidine C = N and NCN peak which lodged in the water separation membrane, acid or base dissociation when there is dissociated by-guanidine compound the peak (peak) It is lost.
[297]
According to the results of Experiment 1 as described above, a water treatment separation membrane produced by the embodiment of the present invention can be confirmed that by the guanidine compound forms the amine-based compound, or an acyl halide compound with a covalent bond.
[298]

[299]
The Examples 1 to 7 and Comparative Examples 1 and with respect to the water separation membrane produced according to 6, the aqueous solution of NaCl at a flow rate of 32,000ppm 800psi, 4.5L / min for about 1 hour after confirming that the stabilized by implementing the equipment operation, in 25 ℃ 10 minutes to measure the amount of water permeation flux (flux: gfd (gallon / ft 2 / day)) to calculate, and conductivity meters (conductivity meter) removal salt analyzes the transmission before and after the salt concentration by using the to the result of calculating the (Rejection) shown in Table 3.
[300]
TABLE 3
Compound contained in the polyamide active layer The content of the compound (wt%) Flux (GFD) The flux change (%) The salt rejection (%) The salt rejection change amount (%)
Example 1 Compound A 0.1 19.00 -3 99.83 0.09
Example 2 Compound A 0.2 18.38 -6 99.85 0.11
Example 3 Compound A 0.3 18.36 -6 99.88 0.14
Example 4 Compound A 0.4 17.98 -8 99.87 0.13
Example 5 Compound A 0.5 18.25 -6 99.89 0.15
Example 6 Compound B 0.1 17.51 -10 99.86 0.12
Example 7 Compound B 0.3 15.53 -20 99.90 0.16
Comparative Example 1 - 0 19.50 - 99.74 -
Comparative Example 2 Compound C 0.1 18.36 -6 99.80 0.06
Comparative Example 3 Compound C 0.2 18.94 -3 99.80 0.06
Comparative Example 4 Compound C 0.3 20.90 7 99.78 0.04
Comparative Example 5 Compound C 0.4 18.94 -3 99.79 0.05
Comparative Example 6 Compound C 0.5 17.77 -9 99.79 0.05

[301]
In Table 3, the permeation flow rate, salt removal ratio and a variation value of the Examples 1 to 7 and Comparative Examples 2 to 1-6, Comparative Example 1, compared to the base material and the flux rate, salt removal ratio change amount.
[302]
According to the results of Table 3, a water treatment separation membrane according to an exemplary embodiment of this disclosure is, in Comparative Examples 1 to 6 than the salt removal rate is not included by the guanidine compound in the polyamide layer was found improved.
[303]
This is because by the guanidine compound and the amine-based compounds or acyl halide compounds and if through a covalent bond stably present in the polyamide active layer, keeping a high salt rejection and the boron rejection, regardless of the operating time and conditions.
[304]
Further, Comparing the amount of change in the salt rejection, while Examples 1-5 are compared with Comparative Examples 2 to 6 containing a guanidine compound rate of change of the flux, including the bi-guanidine compound to a polyamide active layer is similar to the salt the effect of improving the removal rate can be seen that excellent.
[305]

[306]
The compounds A and PHB (Poly (hexamethylene biguanide) polymer (given in molecular weight from 600 to 900g / mol) in Experimental Example In a similar manner to that described in 1 13C-NMR analysis results to Figure 4 one for the case of the PHB, mPD or because the functional group that can achieve the TMC with a covalent bond exists at the terminal thereof, a polyamide to not be bonded to the active layer, but only detected C = O of TMC, the case of compound a, the amine groups are present at the terminal can achieve a covalent bond so, it is possible not only C = O of TMC see that also detected with biguanide.
[307]
[308]
Has been described with a preferred embodiment of the present invention over the above, the present invention is not limited to this can be carried out in various modifications in the description of the claims and the invention and are also within the scope of the invention .

Claims
[Claim 1]
A porous support; And in the water separation membrane comprising a polyamide active layer is provided on the porous support, the polyamide active layer is the formula to units represented by 1, the formula units represented by 2, to and a unit represented by General Formula (3) Formula a water treatment separation membrane comprises at least one selected from units represented by the 4: [formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] in the above Chemical formulas 1 to 4, U 1 and U 2 are equal to each other or different and each independently represent a substituted or unsubstituted divalent aliphatic group with ring 2; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic divalent group, and Beach, U 3 is a substituted or unsubstituted aliphatic group unsubstituted trivalent; A substituted or unsubstituted trivalent alicyclic group; Or a substituted or unsubstituted aromatic-substituted trivalent group, A 1 to A 9 are represented by any one which is the same or different and each is as to selection of the Formulas 5 to 7 independently of one another, A 10 is to the formula 5 or 8 and, [Chemical formula 5] [Chemical formula 6] [Chemical Formula 7] [Chemical Formula 8] In the above Formulas 5 to 8, V 1 and V 2 is the same or different and each independently represent a substituted or unsubstituted phenylene ring with each other, V 3 is a substituted or unsubstituted trivalent a benzene ring group, stage, a 1 to a 3 one, a 4 and a 5 one, a 6 and a 7 one, and a 8 and a 9 one of which is represented by the formula (5).
[Claim 2]
A porous support; And comprising a polyamide as a water treatment separation membrane containing an active layer, the water treatment separation membrane is an acid or base dissociation before and after the 1H-NMR analysis of the benzene ring peak between 6.8ppm to 7.8ppm (peak) is provided on the porous support water separation membrane.
[Claim 3]
The method according to claim 1, wherein the water separation membrane is an acid or base dissociation before and after the 1H-NMR analysis results to 6.8ppm water treatment separation membrane comprising a peak (peak) of the benzene ring between 7.8ppm.
[Claim 4]
The method according to claim 1, the at least one content is selected among the polyamide active layer of the unit represented by the formula (1) unit of the formula (II) unit, the unit and the formula (4) shown by the above formula (3) represented by the represented by is 0.01 % to 10 wt.% to a water treatment separation membrane.
[Claim 5]
A porous support; And as a water treatment separation membrane comprising a polyamide active layer is provided on the porous support, the water separation membrane is an acid or base dissociation before and after the IR analysis C = N bond and which comprises a peak (peak) of the NCN combined treatment Membranes.
[Claim 6]
According to one of Claims 1 to 4, wherein the water separation membrane is an acid or base dissociation before and after the IR analysis results of a water treatment separation membrane comprises a peak (peak) of the C = N bond and NCN bond.
[Claim 7]
A porous support; And comprises a polyamide as a water treatment separation membrane containing an active layer, the water treatment separation membrane is an acid or base dissociation after the MS analysis showed that the m / z values ​​277, 193, 178, 102, 85 or 60 provided on the porous support a water separator.
[Claim 8]
A method according to any one of claims 1 to 5, wherein the water separation membrane is an acid or base dissociation after MS analysis results of water separation membrane to which the m / z values ​​include 277, 193, 178, 102, 85 or 60.
[Claim 9]
Preparing a porous substrate; And a method for manufacturing a water treatment separation membrane including forming a polyamide active layer on the porous support, the forming of the polyamide active layer with an organic solution comprising an aqueous solution and the acyl halide compound containing the amine-based compound an interfacial polymerization, wherein the amine-based compound aqueous solution and the acyl organic solution at least one of which includes a halide compound comprises by guanidine compound at least one kind represented by the formula 9 or formula 10 below, and the by-guanidine compounds including It is in the polyamide active layer, a method of producing amine-based compound, or an acyl halide compound with a covalent bond of a water treatment separation membrane according to one of claims 1 to 5 and 7 to form the [formula 10] [formula 10] formula 9 and according to 10, U 4 is a substituted or unsubstituted divalent aliphatic group with ring 2; A substituted or unsubstituted divalent alicyclic group; Or a substituted or unsubstituted aromatic unsubstituted divalent group, T 1 to T 4They are the same or different from each other, and each independently hydrogen; heavy hydrogen; A nitrile group; A hydroxyl group; An acyl halide group; An isocyanate group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkyl tiok group; Substituted or unsubstituted aryl tiok group; A substituted or unsubstituted alkyl sulfoxide group; Substituted or unsubstituted aryl sulfoxide group ring; Substituted or unsubstituted amine groups; A substituted or unsubstituted alicyclic group; Or a substituted or unsubstituted aromatic ring group.
[Claim 10]
The method according to claim 9, the method of manufacturing a water treatment separation membrane will by the guanidine compound is included as the amine compound from 0.01% to 10% by weight content in the organic solution containing the aqueous solution or the acyl halide compounds, including.
[Claim 11]
The method according to claim 9, wherein the amine compound is m- phenylenediamine, p- phenylenediamine, 1,3,6- benzene triamine, 3-chloro-l 4-chloro-1,3-phenylene diamine, and, process for producing a 4-phenylenediamine, and the water separation membrane is at least one member selected from the group consisting of a mixture thereof.
[Claim 12]
The method according to claim 9, wherein the acyl halide compound is a method of manufacturing a water treatment separation membrane is at least one member selected from the group consisting of chloride, and mixtures thereof as trimesoyl chloride, isophthaloyl chloride, terephthaloyl.
[Claim 13]
Water treatment modules including a water separation membrane according to one of claims 1 to 5 and 7.