CN105664741A - Reverse osmosis composite film and preparation method thereof - Google Patents
Reverse osmosis composite film and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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 reverse osmosis composite film and a preparation method thereof. The reverse osmosis composite film consists of a polysulfone supporting film and a functional layer, wherein the functional layer takes polyamine as a water phase monomer and aromatic multivariate chloride as an oil phase monomer; the water phase monomer and the oil phase monomer are compounded on the polysulfone supporting film through interface polymerization; and the chemical structure of the functional layer is as shown in formula (I). The invention further provides trimesoylamidoamine for preparing the reverse osmosis composite film and a synthesis method of the reverse osmosis composite film. The novel reverse osmosis film provided by the invention has a smooth film surface and is high in hydrophilic property and excellent in anti-oxidization and anti-pollution performance; and furthermore, the trimesoylamidoamine and the synthesis method have profound significance for research on anti-oxidization and anti-pollution reverse osmosis films.
Description
(1) technical field
The present invention relates to membrane material and preparation method thereof, be specifically related to a kind of novel reverse osmosis composite membrane and preparation method thereof.
(2) background technology
Reverse osmosis is a kind of energy-efficient isolation technics, is widely used in sea-water brackish water desalination and sewage disposal as a kind of important water resource increment technique. The core of reverse osmosis technology is reverse osmosis membrane, and asymmetric reverse osmosis membrane and reverse osmosis composite membrane are two class high-performance reverse osmosis membranes of commercial applications at present, and reverse osmosis composite membrane is then the main product in current reverse osmosis membrane field.
1981, Cadotte et al., at USPatent4, was prepared for reverse osmosis composite membrane by m-diaminobenzene. (MPD) and pyromellitic trimethylsilyl chloride (TMC) through interfacial polymerization in 277,344, and its structure is shown below. Current general reverse osmosis composite membrane is also mainly this type of film, but ubiquity easily pollutes, oxidizable shortcoming.
Fouling membrane can significantly reduce reverse osmosis membrane water flux, shortens membrane lifetime, finally increases energy consumption and production cost. Therefore, one of prevention and cure of pollution problem main direction of studying being always up reverse osmosis technology of reverse osmosis membrane. The essence of the pollution course of reverse osmosis membrane is the interaction process between pollutant and film surface and pollutant and pollutant in longtime running. Therefore, the factor affecting the interphase interaction of reverse osmosis membrane and pollutant is to determine the key factor that reverse osmosis membrane pollutes, and surface hydrophilicity is reverse osmosis membrane important properties, not only affects membrane flux, and film surface contamination also plays the influence of key. Hydrophilic reverse osmosis membrane surface is often with a large amount of hydrophilic groups, its easy and hydrone formation hydrogen bond, these hydrones are in ordered arrangement state, when pollutant are close to film surface, this layer of water molecule energy plays effective inhibition, and therefore film surface is not easily pollutant-contaminated.
Film oxidation is owing to the film properties in order to suppress fouling membrane to cause changes, and usually before feed water by reverse osmosis, solution can be carried out pre-treatment, as reducing biological pollution, generally added NaClO or ClO in the solution2Deng disinfection sanitizer. But polyamide composite film is easy to, by active chlorine attack, oxidative degradation is occurred, and causes film properties degradation.Film oxidation shortens the service life of film, significantly limit the extensive use of reverse osmosis membrane. Therefore, high chlorine resistance complex reverse osmosis membrane is developed on the basis of research crosslinking aromatic polyamide membrane chlorizating depolymerization mechanism and there is highly important theoretical and practical significance.
Hoek et al. mentions aliphatic secondary amine in USPatent61,748,431 and aromatic series acyl chlorides connects the compound formed and has fine chlorine-resistant voltinism. DAP (DAP) is a kind of aliphatic amine, has good linear structure, and has good hydrophilic containing hydroxyl, has good resistance to oxidation stain resistance with pyromellitic trimethylsilyl chloride by the reverse osmosis membrane that interfacial polymerization is made. But the 1 of binary, 3-diaminourea-2-propanol diffuses into oil phase from aqueous phase and is polymerized formation nascent state film with the pyromellitic trimethylsilyl chloride of ternary, course of reaction has the acid chloride groups on a small amount of pyromellitic trimethylsilyl chloride and can generate carboxyl with water molecule reaction, thus can be easier to generate linear structure. The generation of these linear structures can make film be prone under high pressure by densification, causes that permeation flux is very low.
It is an object of the invention to provide a kind of new anti-pollution antioxidation reverse osmosis composite membrane, and there is better permeation flux and salt rejection rate. Based on this purpose, the present invention designs and has synthesized a kind of equal benzene trimethamide-amine of novel dendritic macromole polyamine monomer, equal benzene trimethamide-amine has the phenyl ring of rigidity and the dendrimer structure of multiple hydroxyl, the permeation flux making its reverse osmosis membrane prepared with aromatic polyvalent acyl chlorides interfacial polymerization is greatly improved, although rejection declines to some extent, but the reverse osmosis membrane prepared with aromatic polyvalent acyl chlorides interfacial polymerization again after it being mixed with diamino alcohol compounds has better permeation flux and salt rejection rate.
(3) summary of the invention
The invention provides a kind of novel trans osmosis composite membrane and preparation method thereof, adopt the following technical scheme that
A kind of reverse osmosis composite membrane, is made up of polysulfones support membrane and functional layer, and described functional layer is with polyamine for aqueous phase monomers, with aromatic polyvalent acyl chlorides for oil phase monomer, is compound on polysulfones support membrane by interfacial polymerization;
Described polyamine is selected from one of following: the mixture of all diamino alcohol compounds shown in benzene trimethamide-amine, formula (II) and equal benzene trimethamide-amine shown in formula (III) shown in diamino alcohol compounds shown in formula (II), formula (III), it is preferable that the mixture of diamino alcohol compounds shown in formula (II) and equal benzene trimethamide-amine mass ratio 1:1 shown in formula (III);
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, it is preferable that pyromellitic trimethylsilyl chloride;
Shown in the chemical constitution of described functional layer such as formula (I):
In formula (I),
X is CO NH, NH CO NH or OCO NH;
Y is COOH, NHCOOH, NH2Or OH;
Shown in the chemical constitution such as formula (II) of described diamino alcohol compounds:
Shown in the chemical constitution such as formula (III) of described equal benzene trimethamide-amine:
In formula (I), formula (II) or formula (III), m, n, q, z each stand alone as the integer of one of 1～6. Furthermore, it is desirable to illustrate, in formula (I), formula (II) or formula (III), same letter m, n, q or z independently of one another can be optionally identical or different in the scope of integer 1～6.
The preparation method of reverse osmosis composite membrane of the present invention is:
Aqueous solution 1～10min by polysulfones support membrane single-contact polyamine (aqueous phase monomers), then drain, again with the n-hexane solution single-contact of aromatic polyvalent acyl chlorides (oil phase monomer), carry out interface polymerization reaction 40～120s, dry in the shade in atmosphere afterwards, thermally treated, EDI water rinsing successively, prepares described reverse osmosis composite membrane again.
In the aqueous solution of described polyamine, the mass concentration of polyamine is 1.0%～3.0%, possibly together with 0.15wt% dodecyl sodium sulfate, 4wt% camphorsulfonic acid, 2wt% triethylamine in the aqueous solution of described polyamine.
In the n-hexane solution of described aromatic polyvalent acyl chlorides, the mass concentration of aromatic polyvalent acyl chlorides is 0.05%～0.15%.
Described heat treatment is process 8～10min 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 all benzene trimethamide-amine shown in described formula (III), have two kinds:
Synthetic method A
(1)N2Under protection, chloroform and pyromellitic trimethylsilyl chloride are mixed, the mixed liquor of stirring lower dropping methanol and chloroform, 20～30min is reacted under room temperature, it is warming up to 60 DEG C of backflow 3～4h afterwards, then under ice bath, diamino alcohol compounds shown in dropping formula (II), triethylamine, DMF mixing is dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, 2～3h is reacted under room temperature, reactant liquor is through washing afterwards, anhydrous sodium sulfate dries, filter, filtrate desolvation, residue dissolves with chloroform again, add ethyl acetate and precipitate out solid, filter, filter cake ethyl acetate is washed, dry to obtain crude product, gained crude product obtains midbody compound (3a) through column chromatography for separation,
In step (1), the ratio of described methanol and the amount of substance of pyromellitic trimethylsilyl chloride is 2～2.5:1 (preferred 2.5:1), shown in described pyromellitic trimethylsilyl chloride and formula (II), the ratio of the amount of substance of diamino alcohol compounds is 2:1, and the ratio of described triethylamine and the amount of substance of pyromellitic trimethylsilyl chloride is 3～3.3:1 (preferred 3.3:1);
(2) by diamino alcohol compounds, methanol mixed shown in step (1) gained midbody compound (3a), formula (II), reflux 24h at 60 DEG C, solvent is evaporated off afterwards, adds ethanol and precipitate out solid, filter, after filtration cakes torrefaction, with water dissolution, add ethanol and again precipitate out solid, filter, filtration cakes torrefaction, obtains equal benzene trimethamide-amine shown in product formula (III);
In step (2), the ratio of the amount of substance of diamino alcohol compounds shown in described formula (II) and midbody compound (3a) is 5.0～5.79:1 (preferred 5.49:1).
Route A:
Synthetic method B
(a)N2Under protection; by THF, benzene tricarbonic acid's diethylester, triphosgene (BTC) stirring mixing; then under ice-water bath, drip composite catalyst (pyridine/imidazole mixture) be dissolved in the solution of THF; drip off in room temperature reaction 12h; filter afterwards; filtrate steaming removal solvent, is dissolved in chloroform by residue, at N2Under protection, 0～5 DEG C of condition, diamino alcohol compounds shown in dropping formula (II), triethylamine, DMF mixing is dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, then under room temperature, react 2～3h, afterwards reactant liquor dry through washing, anhydrous sodium sulfate, filter, filtrate desolvation, residue, through column chromatography for separation, obtains midbody compound (3b);
In step (a), the ratio of described benzene tricarbonic acid's diethylester and the amount of substance of triphosgene is 0.5～1.5:1, the mass ratio of described composite catalyst and triphosgene is 0.08～0.2:1, in described composite catalyst, imidazoles is 1:3～4 with the mass ratio of pyridine, the ratio of diamino alcohol compounds shown in described formula (II) and the amount of substance of benzene tricarbonic acid's diethylester is 1:2, and the ratio of described benzene tricarbonic acid's diethylester and the amount of substance of triethylamine is 0.5～3:1;
B () is by diamino alcohol compounds, methanol mixed shown in step (a) gained midbody compound (3b), formula (II), reflux 24h at 60 DEG C, solvent is evaporated off afterwards, adds ethanol and precipitate out solid, filter, after filtration cakes torrefaction, with water dissolution, add ethanol and again precipitate out solid, filter, filtration cakes torrefaction, obtains equal benzene trimethamide-amine shown in product formula (III);
In step (b), the ratio of the amount of substance of diamino alcohol compounds shown in described formula (II) and midbody compound (3b) is 5.0～5.79:1 (preferred 5.49:1).
Route B
The beneficial effects of the present invention is: equal benzene trimethamide-amine shown in diamino alcohol compounds, formula (III) or the diamino alcohol compounds novel trans permeable membrane that the mixture of equal benzene trimethamide-amine is prepared through interfacial polymerization with polynary acyl chlorides with shown in formula (III) shown in formula (II) shown in formula (II), face is smooth, good hydrophilic property, has the resistance to oxidation antifouling property of excellence. Shown in formula (III), all benzene trimethamide-amine synthetic method B adopts triphosgene to be chloride reagent, compared to advantages such as the active height of other chloride reagents, operation safety, synthetic method A is compared to synthetic method B reaction condition milder, simple to operate, convenient post-treatment, and there is higher economical in reaction, the research of resistance to oxidation anti-pollution reverse osmosis membrane is had profound significance.
(4) detailed description of the invention
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to that
Embodiment 1: all synthesis of benzene trimethamide-amine
In 100mL equipped with magnetic agitation, thermometer, reflux condensing tube there-necked flask in, N2Under protection; successively add 30mL chloroform and 4.00g (0.015mol) pyromellitic trimethylsilyl chloride, in material liquid, drip 1.20g methanol (being dissolved in 10mL chloroform) under stirring, react under room temperature after 25min; 60 DEG C of backflow 3～4h, high performance liquid chromatography monitoring reaction. Then by 0.69g (0.0075mol) 1,3-diaminourea-2-propanol, 5.00g (0.05mol) triethylamine and 1mLDMF mixing are dissolved in 30mL chloroform, under ice bath, (0～5 DEG C) is slowly added dropwise to there-necked flask reaction 30min, 2～3h, thin plate chromatography (TLC) monitoring reaction is reacted under room temperature. React complete, reaction mixture is washed twice, gained organic facies anhydrous sodium sulfate dries, filters, filtrate is dissolved with a small amount of (5mL) chloroform after sloughing solvent again, add 50mL ethyl acetate and precipitate out solid, filter, filter cake ethyl acetate is washed, dry to obtain thick product, intermediate 1 is obtained through the column chromatography for separation mixed liquor of petrol ether/ethyl acetate volume ratio 1:1 (eluant be) after, 3-bis-[(3,5-dicarboxylic acid methyl ester) Benzoylamide]-2-propanol 2.30g.
C25H26N2O11[530.15]1HNMR(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).
Adding 60ml methanol, 2.00g1,3-diaminourea-2-propanol, 2.10g1,3-bis-[(3,5-dicarboxylic acid methyl ester) Benzoylamide]-2-propanol in 100mL single port flask, reflux at 60 DEG C 24h. Reacting complete, rotation is evaporated off solvent, adds 50mL ethanol and precipitates out white solid, filters, dry, and filter cake, with a small amount of (5mL) water dissolution, again precipitates out solid in 50mL ethanol, and filtration drying obtains the equal benzene trimethamide-amine 3.00g of white solid product.
C33H50N10O11[762.37]; Mp:100-103 DEG C;1HNMR (500MHz, DMSO) δ 8.78 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); HRMScalculatedforC33H51N10O11[M+1]: 763.3733; Found:763.3717.
Embodiment 2: all synthesis of benzene trimethamide-amine
Add 40mLTHF in 100ml there-necked flask, under nitrogen protection, add benzene tricarbonic acid diethylester 1.3g (0.005mol); 3.0g (0.01mol) triphosgene, stirring, 0.3g pyridine and 0.1g imidazoles are dissolved in 20mLTHF; it is slowly added dropwise to there-necked flask under ice-water bath; reacting 12h after dripping off under room temperature, reactant liquor is become blue again by the colourless milky that becomes, and blueness fades away; stopped reaction; filtering, rotation is evaporated off solvent THF and phosgene, obtains yellow liquid. Yellow liquid is dissolved in 30ml chloroform; under nitrogen protection; ice-water bath controls temperature 0～5 DEG C, dropping 0.23g1,3-diaminourea-2-propanol (0.0025mol); 1.0g (0.01mol) triethylamine; 1mlDMF mixing is dissolved in the mixed liquor of 10ml chloroform, dropwises, and ice-water bath continues to keep 30min; remove ice-water bath, under room temperature, react 2～3h. Reacting complete, reactant liquor washes with water twice, and anhydrous sodium sulfate dries, and filters. Filtrate is spin-dried for solvent, the column chromatography for separation mixed liquor of petrol ether/ethyl acetate volume ratio 1:1 (eluant be), obtains 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).
Adding 60ml methanol, 1.0g1,3-diaminourea-2-propanol, 0.60g1,3-bis-[(3,5-dicarboxylic acid methyl ester) Benzoylamide]-2-propanol in 100mL single port flask, reflux at 60 DEG C 24h. Reacting complete, rotation is evaporated off solvent, adds 50mL ethanol and precipitates out white solid, filters, dry, and filter cake, with a small amount of (5mL) water dissolution, again precipitates out solid in 50mL ethanol, and filtration drying obtains the equal benzene trimethamide-amine 0.80g of white solid product.
C33H50N10O11[762.37]; Mp:100-103 DEG C;1HNMR (500MHz, DMSO) δ 8.78 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); HRMScalculatedforC33H51N10O11[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 the aqueous solution of 2% m-diaminobenzene. (MPD) about 2 minutes by (embodiment 3-1), in this aqueous solution possibly together with the dodecyl sodium sulfate of 0.15%, 4% camphorsulfonic acid, 2% triethylamine.After draining aqueous solution, treat that film surface drains, then carry out interface polymerization reaction 60 seconds with the n-hexane solution single-contact of the pyromellitic trimethylsilyl chloride (TMC) of 0.1%. The nascent state composite membrane of gained dries in the shade 2 minutes in atmosphere, and then through heat treatment at 60 DEG C 8 minutes, EDI water rinsed, and prepares reverse osmosis composite membrane MPD-TMC.
Polysulfone porous support membrane one side is immersed in 2%1 by (embodiment 3-2), in the aqueous solution of 3-diaminourea-2-propanol (DAP) about 1 minute, in this aqueous solution possibly together with the dodecyl sodium sulfate of 0.15%, 4% camphorsulfonic acid, 2% triethylamine. After draining aqueous solution, treat that film surface drains, then carry out interface polymerization reaction 60 seconds with the n-hexane solution single-contact of the pyromellitic trimethylsilyl chloride (TMC) of 0.1%. The nascent state composite membrane of gained dries in the shade 2 minutes in atmosphere, and then through heat treatment at 60 DEG C 10 minutes, EDI water rinsed, and prepares reverse osmosis composite membrane DAP-TMC.
Polysulfone porous support membrane one side is immersed in equal benzene trimethamide-amine (TMAAM) aqueous solution of 2% about 10 minutes by (embodiment 3-3), in this aqueous solution possibly together with the dodecyl sodium sulfate of 0.15%, 4% camphorsulfonic acid, 2% triethylamine. After draining aqueous solution, treat that film surface drains, then carry out interface polymerization reaction 60 seconds with the n-hexane solution single-contact of the pyromellitic trimethylsilyl chloride (TMC) of 0.15%. Gained nascent state composite membrane dries in the shade 2 minutes in atmosphere, and then through heat treatment at 60 DEG C 10 minutes, EDI water rinsed, and prepares reverse osmosis composite membrane TMAAM-TMC.
Polysulfone porous support membrane one side is immersed the equal benzene trimethamide-amine (TMAAM) of mixed amine monomer 1% and the 1 of 1% by (embodiment 3-4), 3-diaminourea-2-propanol (DAP) aqueous solution about 5 minutes, in this aqueous solution possibly together with the dodecyl sodium sulfate of 0.15%, 4% camphorsulfonic acid, 2% triethylamine. After draining aqueous solution, treat that film surface drains, then carry out interface polymerization reaction 60 seconds with the n-hexane solution single-contact of the pyromellitic trimethylsilyl chloride (TMC) of 0.15%. Gained nascent state composite membrane dries in the shade 2 minutes in atmosphere, and then through heat treatment at 60 DEG C 10 minutes, EDI water rinsed, and prepares reverse osmosis composite membrane DAP/TMAAM-TMC.
Polysulfone porous support membrane one side is immersed in the 1 of 1% by (embodiment 3-5), 3-diaminourea-2-propanol (DAP) aqueous solution about 1 minute, after draining aqueous solution, treat that film surface drains, be again dipped in equal benzene trimethamide-amine (TMAAM) aqueous solution of 1% about 3 minutes, in above two aqueous solution each respectively possibly together with the dodecyl sodium sulfate of 0.15%, 4% camphorsulfonic acid, 2% triethylamine. After draining aqueous solution, treat that film surface drains, then carry out interface polymerization reaction 60 seconds with the n-hexane solution single-contact of the pyromellitic trimethylsilyl chloride (TMC) of 0.15%. Gained nascent state composite membrane dries in the shade 2 minutes in atmosphere, and then through heat treatment at 60 DEG C 10 minutes, EDI water rinsed, and prepares reverse osmosis composite membrane DAP-TMAAM-TMC.
The test of reverse osmosis composite membrane
With the NaCl aqueous solution of 2000ppm, it is 1.6Mpa, temperature test 5 class films salt rejection rate and flux when being 25 DEG C at operation pressure. Test result is following table such as:
Embodiment 4: the preparation of reverse osmosis composite membrane and test
The method adopting embodiment 3 prepares reverse osmosis composite membrane, with the MgCl of 2000ppm2Aqueous solution, is 1.6Mpa, temperature test 5 class films salt rejection rate and flux when being 25 DEG C at operation pressure. Test result is following table such as:
Embodiment 5: the preparation of reverse osmosis composite membrane and test
The method adopting embodiment 3 prepares reverse osmosis composite membrane, with the Na of 2000ppm2SO4Aqueous solution, is 1.6Mpa, temperature test 5 class films salt rejection rate and flux when being 25 DEG C at operation pressure.Test result is following table such as:
Claims (10)
1. a reverse osmosis composite membrane, it is characterized in that, described reverse osmosis composite membrane is made up of polysulfones support membrane and functional layer, and described functional layer is with polyamine for aqueous phase monomers, with aromatic polyvalent acyl chlorides for oil phase monomer, it is compound on polysulfones support membrane by interfacial polymerization;
Described polyamine is selected from one of following: the mixture of all diamino alcohol compounds shown in benzene trimethamide-amine, formula (II) and equal benzene trimethamide-amine shown in formula (III) shown in diamino alcohol compounds shown in formula (II), formula (III);
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;
Shown in the chemical constitution of described functional layer such as formula (I):
In formula (I),
X is CO NH, NH CO NH or OCO NH;
Y is COOH, NHCOOH, NH2Or OH;
Shown in the chemical constitution such as formula (II) of described diamino alcohol compounds:
Shown in the chemical constitution such as formula (III) of described equal benzene trimethamide-amine:
In formula (I), formula (II) or formula (III), m, n, q, z each stand alone as the integer of one of 1～6.
2. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described polyamine is diamino alcohol compounds shown in formula (II) and the mixture of equal benzene trimethamide-amine mass ratio 1:1 shown in formula (III).
3. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described aromatic polyvalent acyl chlorides is pyromellitic trimethylsilyl chloride.
4. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that in described formula (I), formula (II) or formula (III), m, n, q, z are 1.
5. reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described reverse osmosis composite membrane is Flat Membrane, hollow-fibre membrane or tubular membrane.
6. the preparation method of a reverse osmosis composite membrane as claimed in claim 1, it is characterised in that described preparation method is:
Aqueous solution 1～10min by polysulfones support membrane single-contact polyamine, then drain, again with the n-hexane solution single-contact of aromatic polyvalent acyl chlorides, carry out interface polymerization reaction 40～120s, dry in the shade in atmosphere afterwards, thermally treated, EDI water rinsing successively, prepares described reverse osmosis composite membrane again;
In the aqueous solution of described polyamine, the mass concentration of polyamine is 1.0%～3.0%, possibly together with 0.15wt% dodecyl sodium sulfate, 4wt% camphorsulfonic acid, 2wt% triethylamine in the aqueous solution of described polyamine;
In the n-hexane solution of described aromatic polyvalent acyl chlorides, the mass concentration of aromatic polyvalent acyl chlorides is 0.05%～0.15%.
7. preparation method as claimed in claim 6, it is characterised in that described heat treatment is process 8～10min at 50～70 DEG C.
8. for preparing equal benzene trimethamide-amine of reverse osmosis composite membrane described in claim 1, shown in its chemical constitution such as formula (III):
In formula (III), m, n, q, z each stand alone as the integer of one of 1～6.
9. 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:
(1)N2Under protection, chloroform and pyromellitic trimethylsilyl chloride are mixed, the mixed liquor of stirring lower dropping methanol and chloroform, 20～30min is reacted under room temperature, it is warming up to 60 DEG C of backflow 3～4h afterwards, then under ice bath, diamino alcohol compounds shown in dropping formula (II), triethylamine, DMF mixing is dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, 2～3h is reacted under room temperature, reactant liquor is through washing afterwards, anhydrous sodium sulfate dries, filter, filtrate desolvation, residue dissolves with chloroform again, add ethyl acetate and precipitate out solid, filter, filter cake ethyl acetate is washed, dry to obtain crude product, gained crude product obtains midbody compound (3a) through column chromatography for separation,
In step (1), the ratio of described methanol and the amount of substance of pyromellitic trimethylsilyl chloride is 2～2.5:1, shown in described pyromellitic trimethylsilyl chloride and formula (II), the ratio of the amount of substance of diamino alcohol compounds is 2:1, and the ratio of described triethylamine and the amount of substance of pyromellitic trimethylsilyl chloride is 3～3.3:1;
(2) by diamino alcohol compounds, methanol mixed shown in step (1) gained midbody compound (3a), formula (II), reflux 24h at 60 DEG C, solvent is evaporated off afterwards, adds ethanol and precipitate out solid, filter, after filtration cakes torrefaction, with water dissolution, add ethanol and again precipitate out solid, filter, filtration cakes torrefaction, obtains equal benzene trimethamide-amine shown in product formula (III);
In step (2), the ratio of the amount of substance of diamino alcohol compounds shown in described formula (II) and midbody compound (3a) is 5.0～5.79:1;
Synthetic route is:
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, by THF, benzene tricarbonic acid's diethylester, triphosgene stirring mixing, under ice-water bath, then drip composite catalyst be dissolved in the solution of THF, drip off in room temperature reaction 12h, filter afterwards, filtrate steaming removal solvent, residue is dissolved in chloroform, at N2Under protection, 0～5 DEG C of condition, diamino alcohol compounds shown in dropping formula (II), triethylamine, DMF mixing is dissolved in the mixed liquor of chloroform, drip off insulation reaction 30min, then under room temperature, react 2～3h, afterwards reactant liquor dry through washing, anhydrous sodium sulfate, filter, filtrate desolvation, residue, through column chromatography for separation, obtains midbody compound (3b);
In step (a), the ratio of described benzene tricarbonic acid's diethylester and the amount of substance of triphosgene is 0.5～1.5:1, described composite catalyst is pyridine/imidazole mixture, the mass ratio of described composite catalyst and triphosgene is 0.08～0.2:1, in described composite catalyst, imidazoles is 1:3～4 with the mass ratio of pyridine, the ratio of diamino alcohol compounds shown in described formula (II) and the amount of substance of benzene tricarbonic acid's diethylester is 1:2, and the ratio of described benzene tricarbonic acid's diethylester and the amount of substance of triethylamine is 0.5～3:1;
B () is by diamino alcohol compounds, methanol mixed shown in step (a) gained midbody compound (3b), formula (II), reflux 24h at 60 DEG C, solvent is evaporated off afterwards, adds ethanol and precipitate out solid, filter, after filtration cakes torrefaction, with water dissolution, add ethanol and again precipitate out solid, filter, filtration cakes torrefaction, obtains equal benzene trimethamide-amine shown in product formula (III);
In step (b), the ratio of the amount of substance of diamino alcohol compounds shown in described formula (II) and midbody compound (3b) is 5.0～5.79:1;
Synthetic route is:
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