CN105664741B - A kind of reverse osmosis composite membrane and preparation method thereof - Google Patents

A kind of reverse osmosis composite membrane and preparation method thereof Download PDF

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CN105664741B
CN105664741B CN201610128324.2A CN201610128324A CN105664741B CN 105664741 B CN105664741 B CN 105664741B CN 201610128324 A CN201610128324 A CN 201610128324A CN 105664741 B CN105664741 B CN 105664741B
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reverse osmosis
membrane
composite membrane
diaminourea
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CN105664741A (en
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刘立芬
陈晓林
周勇
高从堦
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes

Abstract

The invention provides a kind of reverse osmosis composite membrane and preparation method thereof, described reverse osmosis composite membrane is made up of polysulfones support membrane and functional layer, described functional layer is using polyamine as aqueous phase monomers, using aromatic polyvalent acyl chlorides as oil phase monomer, it is compound in by interfacial polymerization on polysulfones support membrane, shown in the chemical constitution such as formula (I) of the functional layer；Present invention also offers a kind of equal benzene trimethamide amine and its synthetic method for being used to prepare the reverse osmosis composite membrane；New reverse osmosis membrane provided by the present invention, film surface is smooth, good hydrophilic property, has excellent resistance to oxidation antifouling property；And the research of benzene trimethamide amine and its synthetic method to resistance to oxidation anti-pollution reverse osmosis membrane disclosed in this invention has far-reaching significance.

Description

A kind of reverse osmosis composite membrane and preparation method thereof
(1) technical field
The present invention relates to membrane material and preparation method thereof, and in particular to a kind of new reverse osmosis composite membrane and its preparation side Method.
(2) background technology
Counter-infiltration is a kind of energy-efficient isolation technics, is widely used as a kind of important water resource increment technique In sea-water brackish water desalination and sewage disposal.The core of reverse osmosis technology is reverse osmosis membrane, asymmetric reverse osmosis membrane and counter-infiltration Composite membrane is the two class high-performance reverse osmosis membranes for having been commercialized application at present, and reverse osmosis composite membrane is then current reverse osmosis membrane neck The main product in domain.
1981, Cadotte et al. passed through m-phenylene diamine (MPD) (MPD) and equal benzene front three in US Patent 4,277,344 Acyl chlorides (TMC) is prepared for reverse osmosis composite membrane through interfacial polymerization, and its structure is shown below.Current general reverse osmosis composite membrane Mainly such film, but the shortcomings that generally existing easily pollutes, be oxidizable.
Fouling membrane can significantly reduce reverse osmosis membrane water flux, shorten membrane lifetime, final to increase energy consumption and production cost.Cause This, the prevention and cure of pollution problem of reverse osmosis membrane is always one of main direction of studying of reverse osmosis technology.The pollution of reverse osmosis membrane The essence of journey is the interaction process in longtime running between pollutant and film surface and pollutant and pollutant.Therefore, The factor for influenceing reverse osmosis membrane and the interphase interaction of pollutant is to determine the key factor of reverse osmosis membrane pollution, surface hydrophilicity It is reverse osmosis membrane important properties, not only influences membrane flux, and the influence of key is also played to film surface contamination.Parent Water-based reverse osmosis membrane surface is often with a large amount of hydrophilic radicals, and it easily forms hydrogen bond with hydrone, and these hydrones are in orderly Ordered state, when pollutant is close to film surface, this layer of water molecule energy plays effective inhibition, therefore film surface is not easy It is pollutant-contaminated.
Film oxidation is due to change to suppress film properties caused by fouling membrane, usually can be before feed water by reverse osmosis to solution Pre-treatment is carried out, such as to reduce biological pollution, can typically add NaClO or ClO in the solution2Deng disinfection sanitizer.But polyamides Amine composite membrane is easy to that oxidative degradation occurs by Active Chlorine attack, causes film properties degradation.Film oxidation shortens film Service life, it significantly limit the extensive use of reverse osmosis membrane.Therefore, it is crosslinked aromatic polyamide membrane chlorizating depolymerization machine in research High chlorine resistance complex reverse osmosis membrane is developed on the basis of reason has highly important theoretical and practical significance.
Hoek et al. mentions aliphatic secondary amine in US Patent 61,748,431 and connects shape with aromatic series acyl chlorides Into compound there is fine resistance to chlorination.DAP (DAP) is a kind of aliphatic amine, has preferable line Property structure, and there is preferable hydrophily containing hydroxyl, have with pyromellitic trimethylsilyl chloride by reverse osmosis membrane made of interfacial polymerization There is good resistance to oxidation stain resistance.But the 1,3- diaminourea -2- propyl alcohol of binary diffuses into oil phase and ternary from aqueous phase Pyromellitic trimethylsilyl chloride polymerize to form nascent state film, and acid chloride groups meeting and water on a small amount of pyromellitic trimethylsilyl chloride are had in course of reaction Molecule reaction generation carboxyl, thus can be easier to generate linear structure.The generation of these linear structures can cause film to be easy to By densification under high pressure, cause permeation flux very low.
It is an object of the invention to provide a kind of anti-oxidant reverse osmosis composite membrane of new anti-pollution, and have and preferably ooze Saturating flux and salt rejection rate.Based on this purpose, it is equal that present invention design has synthesized a kind of polynary amine monomers of novel dendritic macromolecular Benzene trimethamide-amine, there is in equal benzene trimethamide-amine the dendrimer structure of rigid phenyl ring and multiple hydroxyls, make it The permeation flux of the reverse osmosis membrane prepared with the interfacial polymerization of aromatic polyvalent acyl chlorides greatly improves, although rejection has declined, But the reverse osmosis membrane prepared again with the interfacial polymerization of aromatic polyvalent acyl chlorides after it is mixed with diaminourea alcohol compound has More preferable permeation flux and salt rejection rate.
(3) content of the invention
The invention provides a kind of new reverse osmosis composite membrane and preparation method thereof, adopt the following technical scheme that：
A kind of reverse osmosis composite membrane, it is made up of polysulfones support membrane and functional layer, described functional layer is using polyamine as aqueous phase Monomer, using aromatic polyvalent acyl chlorides as oil phase monomer, it is compound in by interfacial polymerization on polysulfones support membrane；
Described polyamine is selected from one of following：Diaminourea alcohol compound shown in formula (II), equal benzene three shown in formula (III) The mixture of diaminourea alcohol compound shown in formamide-amine, formula (II) and equal benzene trimethamide-amine shown in formula (III), preferably Diaminourea alcohol compound shown in formula (II) and equal benzene trimethamide-amine mass ratio 1 shown in formula (III)：1 mixture；
Described aromatic polyvalent acyl chlorides is selected from one of following：Pyromellitic trimethylsilyl chloride, 5- isocyanates-isophthaloyl chlorine, 5- Chloromethane acyl-oxygen-different peptide acyl chlorides, preferably pyromellitic trimethylsilyl chloride；
Shown in the chemical constitution of the functional layer such as formula (I)：
In formula (I),
X be-CO-NH-,-NH-CO-NH-or-OCO-NH-；
Y is-COOH ,-NHCOOH ,-NH2Or-OH；
Shown in the chemical constitution such as formula (II) of the diaminourea alcohol compound：
The chemical constitution such as formula (III) of described benzene trimethamide-amine is shown：
In formula (I), formula (II) or formula (III), m, n, q, z each stand alone as one of 1~6 integer.Furthermore, it is desirable to illustrate , in formula (I), formula (II) or formula (III), same alphabetical m, n, q or z independently of one another can be in the range of integers 1~6 It is optionally identical or different.
The preparation method of reverse osmosis composite membrane of the present invention is：
By 1~10min of the aqueous solution of polysulfones support membrane single-contact polyamine (aqueous phase monomers), then drain, then with virtue The normal hexane solution single-contact of the fragrant polynary acyl chlorides of race (oil phase monomer), 40~120s of interface polymerization reaction is carried out, afterwards in sky Dried in the shade in gas, then thermally treated, EDI water rinsing successively, described reverse osmosis composite membrane is made.
In the aqueous solution of the polyamine, the mass concentration of polyamine is 1.0%~3.0%, the polyamine it is water-soluble Also containing 0.15wt% dodecyl sodium sulfates, 4wt% camphorsulfonic acids, 2wt% triethylamines in liquid.
In the normal hexane solution of the aromatic polyvalent acyl chlorides, the mass concentration of aromatic polyvalent acyl chlorides for 0.05%~ 0.15%.
Described heat treatment is that 8~10min is handled at 50~70 DEG C.
Reverse osmosis composite membrane prepared by the present invention can be Flat Membrane, hollow-fibre membrane or tubular membrane.
Present invention also offers the synthetic method of equal benzene trimethamide-amine shown in the formula (III), there are two kinds：
Synthetic method A
(1)N2Under protection, chloroform and pyromellitic trimethylsilyl chloride are mixed, stir the lower mixed liquor that methanol and chloroform is added dropwise, room Temperature 20~30min of lower reaction, is warming up to 60 DEG C of 3~4h of backflow, then under ice bath, diamino alcohol shown in formula (II) is added dropwise afterwards Class compound, triethylamine, DMF mixing are dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, then at reaction 2 at room temperature~ 3h, afterwards reaction solution dissolved again with chloroform through washing, anhydrous sodium sulfate drying, filtering, filtrate desolvation, residue, add Ethyl acetate separates out solid, and filtering, filter cake is washed with ethyl acetate, dry that crude product, gained crude product obtain through column chromatography for separation Midbody compound (3a)；
In step (1), the ratio between amount of material of the methanol and pyromellitic trimethylsilyl chloride is 2~2.5：1 (preferably 2.5：1), The ratio between amount of material of diaminourea alcohol compound shown in the pyromellitic trimethylsilyl chloride and formula (II) is 2：1, the triethylamine with The ratio between amount of material of pyromellitic trimethylsilyl chloride is 3~3.3：1 (preferably 3.3：1)；
(2) diaminourea alcohol compound shown in step (1) gained midbody compound (3a), formula (II), methanol are mixed, Flow back 24h at 60 DEG C, and solvent is evaporated off afterwards, adds ethanol and separates out solid, filtering, after filtration cakes torrefaction, is dissolved, added with water Ethanol separates out solid again, filtering, filtration cakes torrefaction, produces equal benzene trimethamide-amine shown in product formula (III)；
In step (2), the amount of diaminourea alcohol compound shown in the formula (II) and the material of midbody compound (3a) The ratio between be 5.0~5.79：1 (preferably 5.49：1).
Route A：
Synthetic method B
(a)N2Under protection, THF, benzene tricarbonic acid's diethylester, triphosgene (BTC) are stirred, then dripped under ice-water bath Add composite catalyst (pyridine/imidazole mixture) to be dissolved in THF solution, drip off in room temperature reaction 12h, filter afterwards, filtrate is steamed Except solvent, residue is dissolved in chloroform, in N2Protect, under the conditions of 0~5 DEG C, diaminourea alcohol compound shown in dropwise addition formula (II), Triethylamine, DMF mixing are dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, then react 2~3h at room temperature, afterwards instead Liquid is answered to obtain intermediate compound through column chromatography for separation through washing, anhydrous sodium sulfate drying, filtering, filtrate desolvation, residue Thing (3b)；
In step (a), the ratio between amount of material of benzene tricarbonic acid's diethylester and triphosgene is 0.5~1.5：1, it is described multiple The mass ratio for closing catalyst and triphosgene is 0.08~0.2：1, the mass ratio of imidazoles and pyridine is 1 in the composite catalyst：3 ~4, the ratio between amount of material of diaminourea alcohol compound shown in the formula (II) and benzene tricarbonic acid's diethylester is 1：2, the benzene The ratio between amount of material of tricarboxylic diethyl phthalate and triethylamine is 0.5~3：1；
(b) diaminourea alcohol compound shown in step (a) gained midbody compound (3b), formula (II), methanol are mixed, Flow back 24h at 60 DEG C, and solvent is evaporated off afterwards, adds ethanol and separates out solid, filtering, after filtration cakes torrefaction, is dissolved, added with water Ethanol separates out solid again, filtering, filtration cakes torrefaction, produces equal benzene trimethamide-amine shown in product formula (III)；
In step (b), the amount of diaminourea alcohol compound shown in the formula (II) and the material of midbody compound (3b) The ratio between be 5.0~5.79：1 (preferably 5.49：1).
Route B
The beneficial effects of the present invention are：Diaminourea alcohol compound, equal benzene front three shown in formula (III) as shown in formula (II) Shown in diaminourea alcohol compound shown in amide-amine or formula (II) and formula (III) the mixture of benzene trimethamide-amine with The new reverse osmosis membrane that polynary acyl chlorides is prepared through interfacial polymerization, film surface is smooth, good hydrophilic property, has excellent resistance to oxidation antipollution Performance.Equal benzene trimethamide-amine synthetic method B uses triphosgene as chloride reagent shown in formula (III), compared to other acyl chlorides Change the advantages such as the active height of reagent, safe operation, synthetic method A is compared to synthetic method B reaction conditions milder, operation letter It is single, convenient post-treatment, and there is higher economical in reaction, the research to resistance to oxidation anti-pollution reverse osmosis membrane has far-reaching meaning Justice.
(4) embodiment
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to that
Embodiment 1：The synthesis of equal benzene trimethamide-amine
In 100mL equipped with magnetic agitation, thermometer, reflux condensing tube three-necked flask in, N2Under protection, successively add 30mL chloroforms and 4.00g (0.015mol) pyromellitic trimethylsilyl chloride, 1.20g methanol is added dropwise into material liquid under stirring and (is dissolved in 10mL Chloroform), after reacting 25min at room temperature, 60 DEG C of 3~4h of backflow, high performance liquid chromatography monitoring reaction.Then by 0.69g (0.0075mol) DAP, 5.00g (0.05mol) triethylamines and 1mL DMF mixing are dissolved in 30mL chloroforms, ice (0~5 DEG C) is slowly added dropwise into three-necked flask and reacts 30min under bath, and then at 2~3h is reacted at room temperature, thin plate chromatography (TLC) is supervised Control reaction.Reaction is finished, and reaction mixture is washed twice, and gained organic phase anhydrous sodium sulfate drying, filtering, filtrate is sloughed molten Dissolved again with a small amount of (5mL) chloroform after agent, add 50mL ethyl acetate and separate out solid, filtering, filter cake is washed with ethyl acetate, is done Dry to obtain crude product, most through column chromatography for separation, (eluant, eluent is petrol ether/ethyl acetate volume ratio 1 afterwards：1 mixed liquor) obtain centre Body 1,3- bis- [(3,5- dicarboxylic acid methyl esters) benzamide] -2- propyl alcohol 2.30g.
C25H26N2O11[530.15]1H NMR(500MHz,CDCl3)：δ 8.77 (t, J=1.5Hz, 2H), 8.68 (t, J= 2.3Hz, 4H), 7.64 (t, J=6.1Hz, 2H), 4.44-4.39 (m, 1H), 4.13 (d, J=7.2Hz, 1H), 3.98 (d, J= 5.5Hz,12H),3.72–3.65(m,4H)。
60ml methanol, 2.00g DAPs, 2.10g 1,3- bis- are added in 100mL single-necked flasks [(3,5- dicarboxylic acid methyl ester) benzamide] -2- propyl alcohol, flow back at 60 DEG C 24h.Reaction finishes, and revolving removes solvent, adds 50mL ethanol separates out white solid, filters, and dries, and filter cake is dissolved with a small amount of (5mL) water, is separated out again in 50mL ethanol solid Body, filtration drying obtain the equal benzene trimethamide-amine 3.00g of white solid product.
C33H50N10O11[762.37]；Mp:100-103℃；1H NMR(500MHz,DMSO)δ8.78–8.66(m,6H), 8.46 (t, J=9.8Hz, 6H), 3.90 (d, J=5.3Hz, 1H), 3.61-3.56 (m, 4H), 3.47-3.42 (m, 12H), 3.36–3.20(m,13H),2.62–2.59(m,4H),2.51–2.47(m,4H)；IR:582.4,711.1,961.2,1048.3, 1096.3,1291.4,1432.0,1542.6,1651.7,2930.3,3077.2,3294.6cm-1；13CNMR(126MHz, DMSO-d6)δ:165.90(2C),165.84(4C),135.02(6C),128.66(6C),70.79(4C),68.56,45.48 (6C),43.51(4C)；HRMS calculated for C33H51N10O11[M+1]:763.3733；found:763.3717.
Embodiment 2：The synthesis of equal benzene trimethamide-amine
40mL THF are added in 100ml three-necked flasks, under nitrogen protection, add benzene tricarbonic acid's diethylester 1.3g (0.005mol), 3.0g (0.01mol) triphosgene, stirring, 0.3g pyridines and 0.1g imidazoles are dissolved in 20mL THF, under ice-water bath It is slowly added dropwise into three-necked flask, drips off after reacting 12h at room temperature, reaction solution becomes au bleu again by the colourless milky that becomes, Blueness fades away, and stops reaction, filtering, and revolving removes solvent THF and phosgene, obtains yellow liquid.Yellow liquid is dissolved in 30m l chloroforms, under nitrogen protection, ice-water bath 0~5 DEG C of temperature of control, 0.23g DAPs are added dropwise (0.0025mol), 1.0g (0.01mol) triethylamine, 1ml DMF mix the mixed liquor for being dissolved in 10ml chloroforms, are added dropwise, frozen water Bath continues to keep 30min, removes ice-water bath, reacts 2~3h at room temperature.Reaction finishes, and reaction solution is washed with water twice, anhydrous slufuric acid Sodium is dried, filtering.Filtrate is spin-dried for solvent, and (eluant, eluent is petrol ether/ethyl acetate volume ratio 1 to column chromatography for separation：1 mixing Liquid), obtain white solid 0.6g.
C29H34N2O11[586.21],1HNMR(500MHz,CDCl3):δ 8.68 (t, J=1.6Hz, 2H), 8.64 (d, J= 1.6Hz,4H),7.95(m,2H),4.40-4.37(m,1H),4.36-4.19(m,8H),4.18(m,1H),3.78-3.64(m, 4H), 1.39 (t, J=7.0Hz, 12H)
The addition 60ml methanol in 100mL single-necked flasks, 1.0g DAPs, 0.60g 1,3- bis- [(3, 5- dicarboxylic acid methyl esters) benzamide] -2- propyl alcohol, flow back at 60 DEG C 24h.Reaction finishes, and revolving removes solvent, adds 50mL second Alcohol separates out white solid, filters, and dries, and filter cake is dissolved with a small amount of (5mL) water, separates out solid again in 50mL ethanol, is filtered It is dried to obtain the equal benzene trimethamide-amine 0.80g of white solid product.
C33H50N10O11[762.37]；Mp:100-103℃；1H NMR(500MHz,DMSO)δ8.78–8.66(m,6H), 8.46 (t, J=9.8Hz, 6H), 3.90 (d, J=5.3Hz, 1H), 3.61-3.56 (m, 4H), 3.47-3.42 (m, 12H), 3.36–3.20(m,13H),2.62–2.59(m,4H),2.51–2.47(m,4H)；IR:582.4,711.1,961.2,1048.3, 1096.3,1291.4,1432.0,1542.6,1651.7,2930.3,3077.2,3294.6cm-1；13CNMR(126MHz, DMSO-d6)δ:165.90(2C),165.84(4C),135.02(6C),128.66(6C),70.79(4C),68.56,45.48 (6C),43.51(4C)；HRMS calculated for C33H51N10O11[M+1]:763.3733；found:763.3717.
Embodiment 3：The preparation of reverse osmosis composite membrane
Polysulfone porous support membrane one side is immersed in 2% m-phenylene diamine (MPD) (MPD) aqueous solution about 2 points by (embodiment 3-1) Clock, also containing 0.15% dodecyl sodium sulfate, 4% camphorsulfonic acid, 2% triethylamine in the aqueous solution.Drain water-soluble After liquid, treat that film surface drains, then gather with the normal hexane solution single-contact progress interface of 0.1% pyromellitic trimethylsilyl chloride (TMC) Close reaction 60 seconds.The nascent state composite membrane of gained dries in the shade 2 minutes in atmosphere, then through being heat-treated 8 minutes at 60 DEG C, the drift of EDI water Wash, reverse osmosis composite membrane MPD-TMC is made.
Polysulfone porous support membrane one side is immersed in the water-soluble of 2%1,3- diaminourea -2- propyl alcohol (DAP) by (embodiment 3-2) About 1 minute in liquid, also containing 0.15% dodecyl sodium sulfate, 4% camphorsulfonic acid, 2% triethylamine in the aqueous solution. After draining the aqueous solution, treat that film surface drains, then enter with the normal hexane solution single-contact of 0.1% pyromellitic trimethylsilyl chloride (TMC) Row interface polymerization reaction 60 seconds.The nascent state composite membrane of gained dries in the shade 2 minutes in atmosphere, then through being heat-treated 10 points at 60 DEG C Clock, EDI water rinsing, is made reverse osmosis composite membrane DAP-TMC.
Equal benzene trimethamide-amine (TMAAM) that polysulfone porous support membrane one side is immersed in 2% by (embodiment 3-3) is water-soluble About 10 minutes in liquid, also containing 0.15% dodecyl sodium sulfate, 4% camphorsulfonic acid, 2% three second in the aqueous solution Amine.After draining the aqueous solution, treat that film surface drains, then connect with the normal hexane solution one side of 0.15% pyromellitic trimethylsilyl chloride (TMC) Touch and carry out interface polymerization reaction 60 seconds.Gained nascent state composite membrane dries in the shade 2 minutes in atmosphere, then through being heat-treated 10 points at 60 DEG C Clock, EDI water rinsing, is made reverse osmosis composite membrane TMAAM-TMC.
(embodiment 3-4) immerses polysulfone porous support membrane one side equal benzene trimethamide-amine of mixing amine monomers 1% (TMAAM) and 1% DAP (DAP) aqueous solution about 5 minutes, also containing the ten of 0.15% in the aqueous solution Dialkyl sulfonates, 4% camphorsulfonic acid, 2% triethylamine.After draining the aqueous solution, treat that film surface drains, then with 0.15% The normal hexane solution single-contact of pyromellitic trimethylsilyl chloride (TMC) carries out interface polymerization reaction 60 seconds.Gained nascent state composite membrane exists Dried in the shade in air 2 minutes, then through being heat-treated 10 minutes at 60 DEG C, the rinsing of EDI water, reverse osmosis composite membrane DAP/TMAAM- is made TMC。
1,3- diaminourea -2- the propyl alcohol (DAP) that polysulfone porous support membrane one side is immersed in 1% by (embodiment 3-5) is water-soluble Liquid about 1 minute, after draining the aqueous solution, treat that film surface drains, be again dipped into 1% equal benzene trimethamide-amine (TMAAM) aqueous solution Middle about 3 minutes, in the above two aqueous solution each respectively also containing 0.15% dodecyl sodium sulfate, 4% camphorsulfonic acid, 2% triethylamine.After draining the aqueous solution, treat that film surface drains, then it is molten with the normal hexane of 0.15% pyromellitic trimethylsilyl chloride (TMC) Liquid single-contact carries out interface polymerization reaction 60 seconds.Gained nascent state composite membrane dries in the shade 2 minutes in atmosphere, then through hot at 60 DEG C Processing 10 minutes, EDI water rinsing, is made reverse osmosis composite membrane DAP-TMAAM-TMC.
The test of reverse osmosis composite membrane
With the 2000ppm NaCl aqueous solution, 5 class films are tested under conditions of operating pressure is 1.6Mpa, temperature is 25 DEG C Salt rejection rate and flux.Test result such as following table：
Embodiment 4：The preparation and test of reverse osmosis composite membrane
Reverse osmosis composite membrane is prepared using the method for embodiment 3, with 2000ppm MgCl2The aqueous solution, it is in operating pressure 1.6Mpa, temperature test the salt rejection rate and flux of 5 class films under conditions of being 25 DEG C.Test result such as following table：
Embodiment 5：The preparation and test of reverse osmosis composite membrane
Reverse osmosis composite membrane is prepared using the method for embodiment 3, with 2000ppm Na2SO4The aqueous solution, it is in operating pressure 1.6Mpa, temperature test the salt rejection rate and flux of 5 class films under conditions of being 25 DEG C.Test result such as following table：

Claims (10)

  1. A kind of 1. reverse osmosis composite membrane, it is characterised in that described reverse osmosis composite membrane is made up of polysulfones support membrane and functional layer, Described functional layer, using aromatic polyvalent acyl chlorides as oil phase monomer, is compound in using polyamine as aqueous phase monomers by interfacial polymerization On polysulfones support membrane；
    Described polyamine is selected from one of following：Diaminourea shown in equal benzene trimethamide-amine shown in formula (III) or formula (II) The mixture of alcohol compound and equal benzene trimethamide-amine shown in formula (III)；
    Described aromatic polyvalent acyl chlorides is selected from one of following：Pyromellitic trimethylsilyl chloride, 5- isocyanates-isophthaloyl chlorine, 5- chloromethanes Acyl-oxygen-different peptide acyl chlorides；
    Shown in the chemical constitution of the functional layer such as formula (I)：
    In formula (I),
    X be-CO-NH-,-NH-CO-NH-or-OCO-NH-；
    Y is-COOH ,-NHCOOH ,-NH2Or-OH；
    Shown in the chemical constitution such as formula (II) of the diaminourea alcohol compound：
    The chemical constitution such as formula (III) of described benzene trimethamide-amine is shown：
    In formula (I), formula (II) or formula (III), m, n, q, z each stand alone as one of 1~6 integer.
  2. 2. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described polyamine is diaminourea shown in formula (II) Alcohol compound and equal benzene trimethamide-amine mass ratio 1 shown in formula (III)：1 mixture.
  3. 3. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described aromatic polyvalent acyl chlorides is equal benzene front three Acyl chlorides.
  4. 4. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that in the formula (I), formula (II) or formula (III), m, N, q, z are 1.
  5. 5. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described reverse osmosis composite membrane be Flat Membrane, in Empty fiber membrane or tubular membrane.
  6. 6. a kind of preparation method of reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described preparation method is：
    By 1~10min of the aqueous solution of polysulfones support membrane single-contact polyamine, then drain, then with aromatic polyvalent acyl chlorides Normal hexane solution single-contact, carry out 40~120s of interface polymerization reaction, dry in the shade in atmosphere afterwards, then successively it is thermally treated, EDI water rinses, and described reverse osmosis composite membrane is made；
    In the aqueous solution of the polyamine, the mass concentration of polyamine is 1.0%~3.0%, in the aqueous solution of the polyamine Also containing 0.15wt% dodecyl sodium sulfates, 4wt% camphorsulfonic acids, 2wt% triethylamines；
    In the normal hexane solution of the aromatic polyvalent acyl chlorides, the mass concentration of aromatic polyvalent acyl chlorides for 0.05%~ 0.15%.
  7. 7. preparation method as claimed in claim 6, it is characterised in that described heat treatment be at 50~70 DEG C processing 8~ 10min。
  8. 8. a kind of equal benzene trimethamide-amine for being used to prepare reverse osmosis composite membrane described in claim 1, its chemical constitution such as formula (III) shown in：
    In formula (III), m, n, q, z each stand alone as one of 1~6 integer.
  9. 9. the synthetic method of equal benzene trimethamide-amine shown in formula (III) as claimed in claim 8, it is characterised in that described conjunction It is into method：
    (1)N2Under protection, chloroform and pyromellitic trimethylsilyl chloride are mixed, stir the lower mixed liquor that methanol and chloroform is added dropwise, at room temperature instead 20~30min is answered, 60 DEG C of 3~4h of backflow is warming up to afterwards, then under ice bath, diaminourea alcohols chemical combination shown in formula (II) is added dropwise Thing, triethylamine, DMF mix the mixed liquor for being dissolved in chloroform, drip off insulation reaction 30min, then at 2~3h is reacted at room temperature, afterwards Reaction solution is dissolved with chloroform again through washing, anhydrous sodium sulfate drying, filtering, filtrate desolvation, residue, adds ethyl acetate Solid is separated out, filtering, filter cake is washed with ethyl acetate, dry that crude product, gained crude product obtain intermediate through column chromatography for separation Compound (3a)；
    In step (1), the ratio between amount of material of the methanol and pyromellitic trimethylsilyl chloride is 2~2.5：1, the pyromellitic trimethylsilyl chloride It is 2 with the ratio between the amount of material of diaminourea alcohol compound shown in formula (II)：1, the thing of the triethylamine and pyromellitic trimethylsilyl chloride The ratio between amount of matter is 3~3.3：1；
    (2) diaminourea alcohol compound shown in step (1) gained midbody compound (3a), formula (II), methanol are mixed, in 60 Flow back 24h at DEG C, and solvent is evaporated off afterwards, adds ethanol and separates out solid, filtering, after filtration cakes torrefaction, is dissolved with water, add ethanol Solid is separated out again, is filtered, filtration cakes torrefaction, is produced equal benzene trimethamide-amine shown in product formula (III)；
    In step (2), the ratio between amount of material of diaminourea alcohol compound shown in the formula (II) and midbody compound (3a) For 5.0~5.79：1；
    Synthetic route is：
  10. 10. the synthetic method of equal benzene trimethamide-amine shown in formula (III) as claimed in claim 8, it is characterised in that described Synthetic method is：
    (a)N2Under protection, THF, benzene tricarbonic acid's diethylester, triphosgene are stirred, composite catalyzing then is added dropwise under ice-water bath Agent is dissolved in THF solution, drips off in room temperature reaction 12h, filters afterwards, filtrate steaming removal solvent, residue is dissolved in into chloroform, in N2 Protect, under the conditions of 0~5 DEG C, diaminourea alcohol compound shown in formula (II), triethylamine, DMF is added dropwise and mixes the mixing for being dissolved in chloroform Liquid, insulation reaction 30min is dripped off, then react 2~3h at room temperature, reaction solution is through washing, anhydrous sodium sulfate drying, mistake afterwards Filter, filtrate desolvation, residue obtain midbody compound (3b) through column chromatography for separation；
    In step (a), the ratio between amount of material of benzene tricarbonic acid's diethylester and triphosgene is 0.5~1.5：1, described is compound Catalyst is pyridine/imidazole mixture, and the mass ratio of the composite catalyst and triphosgene is 0.08~0.2：1, it is described compound The mass ratio of imidazoles and pyridine is 1 in catalyst：3~4, diaminourea alcohol compound shown in the formula (II) and benzene tricarbonic acid two The ratio between amount of material of ethyl ester is 1：2, the ratio between amount of material of benzene tricarbonic acid's diethylester and triethylamine is 0.5~3：1；
    (b) diaminourea alcohol compound shown in step (a) gained midbody compound (3b), formula (II), methanol are mixed, in 60 Flow back 24h at DEG C, and solvent is evaporated off afterwards, adds ethanol and separates out solid, filtering, after filtration cakes torrefaction, is dissolved with water, add ethanol Solid is separated out again, is filtered, filtration cakes torrefaction, is produced equal benzene trimethamide-amine shown in product formula (III)；
    In step (b), the ratio between amount of material of diaminourea alcohol compound shown in the formula (II) and midbody compound (3b) For 5.0~5.79：1；
    Synthetic route is：
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