CN107176963B - A kind of preparation method of phosphonic chloride monomer, Nano filtering composite membrane and Nano filtering composite membrane - Google Patents
A kind of preparation method of phosphonic chloride monomer, Nano filtering composite membrane and Nano filtering composite membrane Download PDFInfo
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- CN107176963B CN107176963B CN201710537173.0A CN201710537173A CN107176963B CN 107176963 B CN107176963 B CN 107176963B CN 201710537173 A CN201710537173 A CN 201710537173A CN 107176963 B CN107176963 B CN 107176963B
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- acyl chlorides
- composite membrane
- chloride
- nano filtering
- filtering composite
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- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 239000000178 monomer Substances 0.000 title claims abstract description 64
- NJLHHACGWKAWKL-UHFFFAOYSA-N ClP(Cl)=O Chemical compound ClP(Cl)=O NJLHHACGWKAWKL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000001914 filtration Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims description 74
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 47
- -1 aroyl chloride Chemical compound 0.000 claims description 44
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 34
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 23
- 235000010290 biphenyl Nutrition 0.000 claims description 19
- 239000004305 biphenyl Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229920002492 poly(sulfone) Polymers 0.000 claims description 14
- 229920000768 polyamine Polymers 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000003205 fragrance Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007873 sieving Methods 0.000 abstract description 5
- 238000001728 nano-filtration Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000460 chlorine Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 150000003009 phosphonic acids Chemical group 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010010 raising Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/42—Halides thereof
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of phosphonic chloride monomer, has structure shown in Formulas I, wherein R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5It is independent to be selected from-H ,-COCl ,-PO (Cl)2Or-OPO (Cl)2, and R1、R2、R3、R4And R5It is not simultaneously-H.The present invention also provides a kind of Nano filtering composite membranes and preparation method thereof.The present invention will have-PO (Cl)2The phosphonic chloride monomer of group is for utilizing-PO (Cl) in the preparation process of Nano filtering composite membrane2A large amount of-PO (OH) is generated in reaction process2Group realizes the purpose for increasing active layer negative charge amount.And the space structure of the phosphonic chloride monomer in the present invention makes active layer have of a relatively loose structure, finally realizes the equilibrium state an of sieving actoion and electrical charge rejection effect.While guaranteeing compared with equipment with high desalinization, permeation flux has large increase.
Description
Technical field
The invention belongs to technical field of membrane more particularly to a kind of phosphonic chloride monomers, Nano filtering composite membrane and Nano filtering composite membrane
Preparation method.
Background technique
Compared with reverse osmosis composite membrane, nanofiltration membrane have of a relatively loose active layer, therefore it have low energy consumption, ion choosing
The advantages that selecting property is high, and permeation flux is high.Currently, nanofiltration membrane has been widely used in the preparation of drinking water, sewage treatment, food
The fields such as industry and pharmaceuticals industry.
It reacts from Cadotte piperazine in 1977 with pyromellitic trimethylsilyl chloride after preparing NS-100 nanofiltration membrane, nanofiltration is compound
Membrane technology has obtained significant progress in nearly 40 years.The nanofiltration membrane being commercialized at present mainly has the NF of U.S. Dow Film Tec
Series, UTC and the TR series of Japanese Toray, the ESNA series etc. of Japanese Nitto Denco Hydronautics.These are compound
Film is substantially to be synthesized with pyromellitic trimethylsilyl chloride by interfacial polymerization with m-phenylene diamine (MPD) or piperazine, the salt rejection rate and water of composite membrane
" trade-off " effect generally existing between flux, the i.e. salt rejection rate of composite membrane and permeation flux can not reach ideal simultaneously
Effect.95% or more usually is held to the rejection of divalent salts, water flux is maintained at 40-60L/m2h.However it this kind of receives
Filter membrane be mainly composite film surface-COOH group plays the role of electrical charge rejection in the operational process of composite membrane and reaches pair
The high rejection of divalent salts.Since the dissociation constant of carboxylate radical is smaller, to keep receiving prepared by excellent salt rejection rate
Filter membrane is relatively compact.Which limits the raisings of composite membrane permeation flux.
Therefore how in the case where keeping effectively salt rejection rate, the water flux of composite membrane is improved, to reach saving energy
The purpose in source is the project of a very worth research.
Summary of the invention
The purpose of the present invention is to provide the preparation method of a kind of phosphonic chloride monomer, Nano filtering composite membrane and Nano filtering composite membrane,
The Nano filtering composite membrane being prepared using the phosphonic chloride monomer in present invention permeation flux with higher and higher de- simultaneously
Salt rate.
The present invention provides a kind of phosphonic chloride monomer, has structure shown in Formulas I:
Wherein, R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5It is independent to be selected from-H ,-COCl ,-PO (Cl)2
Or-OPO (Cl)2, and R1、R2、R3、R4And R5It is not simultaneously-H.
Preferably, the phosphonic chloride monomer has shown in Formula II -1~II~16,
The present invention provides a kind of Nano filtering composite membrane, including nonwoven layer, the supporting layer being compounded in the nonwoven layer and
The active separating layer being compounded on the supporting layer；
The active separating layer is obtained by polyamine, aroyl chloride and phosphonic chloride monomer reaction described above；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
Preferably, the polyamine includes one of m-phenylene diamine (MPD), p-phenylenediamine, piperazine and polyethyleneimine or several
Kind.
Preferably, the polynary acyl chlorides of the biphenyl type includes 2,2 ', 4,4 '-biphenyl, four acyl chlorides, 3,3 ', 5,5 '-biphenyl, four acyl
Chlorine, 2,2 ', 5,5 '-biphenyl, four acyl chlorides, 2,3 ', 4,5 '-biphenyl, four acyl chlorides and 2,4,4 ', one of four acyl chlorides of 6- biphenyl or several
Kind.
Preferably, the mass concentration ratio of phosphonic chloride monomer described above and aroyl chloride is 2:8~8:2.
Preferably, the mass ratio of the gross mass and the polyamine of phosphonic chloride monomer described above and aroyl chloride is
1:20~1:40.
The present invention provides a kind of preparation method of Nano filtering composite membrane, comprising the following steps:
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution successively) are coated in support layer surface, is reacted, it is multiple to obtain nanofiltration
Close film；
The acyl chlorides mixture solution includes aroyl chloride and phosphonic chloride monomer above；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
Preferably, the mass-volume concentration of the polynary amine aqueous solution is 1~4%.
Preferably, the mass-volume concentration of the acyl chlorides mixture solution is 0.04~0.3%.
The present invention provides a kind of phosphonic chloride monomer, has structure shown in Formulas I, wherein R is-PO (Cl)2Or-OPO (Cl)2,
R1、R2、R3、R4And R5It is independent to be selected from-H ,-COCl ,-PO (Cl)2Or-OPO (Cl)2, and R1、R2、R3、R4And R5Be not simultaneously-
H.Separating mechanism of the present invention according to nanofiltration membrane sieving actoion and electrical charge rejection, by the way that-PO (Cl) will be had2The phosphonic chloride of group
Monomer is for utilizing-PO (Cl) in the preparation process of Nano filtering composite membrane2A large amount of-PO (OH) is generated in reaction process2Group is real
Now increase the purpose of active layer negative charge amount.And the space structure of the phosphonic chloride monomer in the present invention makes active layer have phase
To loose structure, the equilibrium state an of sieving actoion and electrical charge rejection effect is finally realized.It is larger to the size of high price
Ion have excellent retention, the ion of the small size of unit price can permit by it passes through, and there has also been very for permeation flux
Big raising.The experimental results showed that in 0.48MPa, 2000ppm variety classes inorganic salts, under 25 DEG C of test condition, nanofiltration membrane
99.0% or more can achieve to the salt rejection rate of divalent salts, pure water flux is in 70~90L/m2H, it is close with current commercialization rejection
As nanofiltration membrane compare, water flux improves 17%~50%.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the hydrogen spectrum and phosphorus spectrogram of the monomer prepared in the embodiment of the present invention 1；
Fig. 2 is the model configuration figure of 5- (dichloro phosphono) m-phthaloyl chloride made from the embodiment of the present invention 1；
Fig. 3 is the infared spectrum of the embodiment of the present invention 1 and 3 and comparative example 1；
Fig. 4 is the hydrogen spectrum and phosphorus spectrogram of the monomer prepared in the embodiment of the present invention 7.
Specific embodiment
The present invention provides a kind of phosphonic chloride monomers, and structure is shown in formula I,
Wherein, R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5It is independent to be selected from-H ,-COCl ,-PO (Cl)2
Or-OPO (Cl)2, and R1、R2、R3、R4And R5It is not simultaneously-H.
Preferably, the phosphonic chloride monomer has structure shown in Formula II -1~Formula II -16,
It is furthermore preferred that the phosphonic chloride monomer in the present invention is the monomer of both structures of Formula II -1 and Formula II -2, i.e. 5- (two
Chlorine phosphono) m-phthaloyl chloride (Formula II -1) and 3,5- dichloro Fonnylphenyl phosphonic chloride (Formula II -2).
The present invention preferably prepares 5- (dichloro phosphono) isophthalic diformazan according to following synthetic route (formula III) and synthetic method
Acyl chlorides:
100g, the 5- iodine dimethyl isophthalate of 312mmol, 3.50g, 16mmol are added into the there-necked flask of 500mL
NiBr2With the triethyl phosphite of 300mL.Vacuum nitrogen gas three times after, be slowly warming up to 160 DEG C under magnetic stirring,
175 DEG C are warming up to after reaction 4h.After the reaction was continued 10h, diethyl phosphonate base isophthalic diformazan is obtained with the method for vacuum distillation
Dimethyl phthalate.20g diethyl phosphonate base dimethyl isophthalate is weighed later, it is cold with 120 DEG C of 50ml concentrated hydrochloric acid reaction 10h
But it is filtered to room temperature, obtains the M-phthalic acid of phosphonic acids substitution.Finally the M-phthalic acid thionyl chloride that phosphonic acids replaces is existed
12h is reacted under conditions of reflux, obtains 5- (dichloro phosphono) m-phthaloyl chloride.
The present invention preferably synthesizes 3,5- dichloro Fonnylphenyl phosphine according to synthetic route shown in formula IV and synthetic method
Acyl chlorides,
The 5- Hydroxy M Phthalic Acid for weighing 20g, adds it in the single port bottle of 250mL, and bottle is placed in ice bath
In be cooled to 0 DEG C.Then the phosphorus pentachloride of 2.0equiv is added thereto.Under magnetic stirring, tail excuse with drying tube and
Nitrogen protection.5h is stirred at 0 DEG C, reaction system becomes colorless and transparent solution, and then system is warming up at 100 DEG C and is stirred
2h further removes the hydrogen chloride of reaction system.Cool down later to reaction system.Pure 3,5- is obtained with the method for vacuum distillation
Dichloro Fonnylphenyl phosphonic chloride.
The present invention also provides a kind of Nano filtering composite membranes, including nonwoven layer, the supporting layer being compounded in the nonwoven layer
With the active separating layer being compounded on the supporting layer；
The active separating layer is reacted to obtain by polyamine and acyl chlorides mixture；
The acyl chlorides mixture includes aroyl chloride and phosphonic chloride monomer described above；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
In the present invention, the nonwoven layer is preferably polyester non-woven fabric；The supporting layer is preferably polysulfone supporting layer, this
Invention does not have special limitation to the thickness and size of the nonwoven layer and supporting layer.Specifically, in the present invention, the nonwoven
The thickness of layer of cloth is preferably 120~150 μm；The thickness of the supporting layer is preferably 40~60 μm；The thickness of the active separating layer
Degree is preferably 100~300nm.
In the present invention, the active separating layer is reacted to obtain by polyamine and acyl chlorides mixture, and the present invention is by phosphonic chloride
It is introduced into Nano filtering composite membrane active layer, utilizes phosphonic chloride tetrahedral structure and the high feature susceptible to hydrolysis of reactivity, system
The nanofiltration membrane of the standby open structure with phosphonyl group out；The stronger phosphate groups of negative electricity are also introduced into composite membrane simultaneously
In, and the effective aperture of composite membrane is increased, so that high valence ion salt rejection rate is realized, the system with high permeating flux nanofiltration membrane
It is standby.
In the present invention, the polyamine include one of m-phenylene diamine (MPD), p-phenylenediamine, piperazine and polyethyleneimine or
It is several；The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type；The polynary acyl chlorides of biphenyl type includes 2,
2 ', 4,4 '-biphenyl, four acyl chlorides, 3,3 ', 5,5 '-biphenyl, four acyl chlorides, 2,2 ', 5,5 '-biphenyl, four acyl chlorides, 2,3 ', 4,5 '-biphenyl four
Acyl chlorides and 2,4,4 ', one or more of four acyl chlorides of 6- biphenyl.
In the present invention, the mass concentration ratio of the phosphonic chloride monomer and aroyl chloride is preferably 2:8~8:2, specifically,
In an embodiment of the present invention, 2:8,4:6,6:4,7:3 or 8:2 be can be；Total matter of the phosphonic chloride monomer and aroyl chloride
Amount and the mass ratio of the polyamine are preferably 1:20~1:40, more preferably 1:25~1:35, specifically, of the invention
In embodiment, 1:20,1:25 or 1:33 can be.
The present invention also provides a kind of preparation methods of Nano filtering composite membrane, comprising the following steps:
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution successively) are coated in support layer surface, is reacted, it is multiple to obtain nanofiltration
Close film；
The acyl chlorides mixture solution includes aroyl chloride and phosphonic chloride monomer of any of claims 1 or 2；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
The present invention first prepares polysulfones solution according to the following steps, then scratches polysulfones solution scraper in non-woven fabrics table
Face, then be dipped in poor solvent, be supported layer；
The preparation of polysulfones solution: polysulfones, perforating agent and surfactant are dissolved in good solvent, obtain polysulfones solution, institute
It states pore-foaming agent and preferably includes one or more of glycol monoethyl ether, polyvinylpyrrolidone and polyethylene glycol；The surface
Activating agent includes alkyl phenol polyoxy ethyl ester phosphonate ester, one or more of dodecane sulfonate and polyvinyl alcohol；It is described good
Solvent preferably includes n,N-Dimethylformamide, one or more of n,N-dimethylacetamide and N-Methyl pyrrolidone.
In the polysulfones solution, the mass concentration of polysulfones is preferably 10~30%, and more preferably 14~24%；The quality of the pore-foaming agent
Concentration is preferably 10~20%, and more preferably 10~18.5%；The mass concentration of the surfactant is preferably 0.01~
0.05%, more preferably 0.02~0.04%.
In the present invention, the poor solvent is preferably water, and present invention preferably uses hot water washings repeatedly, to remove residual
Solvent.Supporting layer aperture obtained is 30~70nm, molecular cut off 10w.
It is supported after film, polynary amine aqueous solution is preferably poured on support film surface and keeps 1.5~3min by the present invention, then
The polynary amine aqueous solution of support membrane excess surface is outwelled, the droplet of film surface is wiped with filter paper, is dried, then by acyl chlorides mixture
Solution is poured on film surface, carries out interface polymerization reaction with polyamine, obtains Nano filtering composite membrane.
In the present invention, the polynary amine aqueous solution is preferably polynary amine aqueous solution, the type of the polyamine with above
The type of polyamine is consistent, and details are not described herein；(quality is divided by volume, g/ for the mass-volume concentration of the polynary amine aqueous solution
It mL) is preferably 1~4%, more preferably 2~3%.
In the present invention, the acyl chlorides mixture solution is preferably the Isopar G solution of acyl chlorides mixture, described
Isopar G solution is isomeric alkane hydro carbons solvent naphtha, and the acyl chlorides mixture includes aroyl chloride and phosphonic chloride list above
Body, the type and use of the type and dosage of the aroyl chloride and phosphonic chloride monomer and above aroyl chloride and phosphonic chloride monomer
Amount is consistent, and details are not described herein.The mass-volume concentration of the acyl chlorides mixture solution is preferably 0.04~0.3%, more preferably
Be 0.06~0.2%, most preferably 0.08~0.1%, specifically, in an embodiment of the present invention, can be 0.06% or
0.08%.
In the present invention, the interface polymerization reaction preferably carries out at room temperature, and the reaction time is preferably 10~30s, more
Preferably 20s.
After the completion of polymerization reaction, obtained composite membrane is preferably placed in convection oven and dries by the present invention, drying temperature
Preferably 80~90 DEG C of degree, the time of drying is preferably 4~7min, and composite membrane is followed by placed in aqueous sodium carbonate by drying
2~4min is impregnated, is then cleaned for several times, is saved spare in deionized water with 80 DEG C of deionized water.
The preparation method of Nano filtering composite membrane of the present invention is simple, has wide applicability, can be applied to sea water desalination, bitter salty
The fields such as water desalination, municipal tap water purifying and drink water purifying.
The present invention provides a kind of phosphonic chloride monomer, has structure shown in Formulas I, wherein R is-PO (Cl)2Or-OPO (Cl)2,
R1、R2、R3、R4And R5It is independent to be selected from-H ,-COCl ,-PO (Cl)2Or-OPO (Cl)2, and R1、R2、R3、R4And R5Be not simultaneously-
H.Separating mechanism of the present invention according to nanofiltration membrane sieving actoion and electrical charge rejection, by the way that-PO (Cl) will be had2The phosphonic chloride of group
Monomer is for utilizing-PO (Cl) in the preparation process of Nano filtering composite membrane2A large amount of-PO (OH) is generated in reaction process2Group is real
Now increase the purpose of active layer negative charge amount.And the space structure of the phosphonic chloride monomer in the present invention makes active layer have phase
To loose structure, the equilibrium state an of sieving actoion and electrical charge rejection effect is finally realized.It is larger to the size of high price
Ion have excellent retention, the ion of the small size of unit price can permit by it passes through, and there has also been very for permeation flux
Big raising.The experimental results showed that in 0.48MPa, 2000ppm variety classes inorganic salts, under 25 DEG C of test condition, nanofiltration membrane
99.0% or more can achieve to the salt rejection rate of divalent salts, pure water flux is in 70~90L/m2H, it is close with current commercialization rejection
As nanofiltration membrane compare, water flux improves 17%~50%.
In order to further illustrate the present invention, with reference to embodiments to a kind of phosphonic chloride monomer provided by the invention, nanofiltration
The preparation method of composite membrane and Nano filtering composite membrane is described in detail, but cannot be understood as the limit to the scope of the present invention
It is fixed.
Water flux: at a particular pressure, the volume that the unit time passes through the water of per membrane area.It can be indicated with following formula.
(V (L)-permeates the volume of water, A (m2The effective area of)-film, t (h)-time)
Salt rejection rate: after solute passes through nanofiltration membrane, the percentage that can always have solubility impurity concentration is removed from system water inlet.It can
To be indicated with following formula:
(CfFeeding liquid concentration, CpPenetrating fluid concentration)
In the examples below, pure water flux test condition is as follows: 25 DEG C of operation temperature, the variety classes of 2000ppm without
The aqueous solution of machine salt, the operating pressure of 0.48Mpa.The permeation flux of nanofiltration membrane is indicated with pure water flux at this pressure.It surveys
Before the permeation flux for trying nanofiltration membrane, composite membrane precompressed 4h at 0.48Mpa guarantees the stability of test data.Every kind of formula
Composite membrane test 6 data, be averaged.
Comparative example 1
Configuring polysulfones mass concentration is 14%, and glycol monoethyl ether mass concentration is 13.5%, dodecyl sodium sulfate matter
Measure the N,N-dimethylformamide solution that concentration is 0.03%.Then it is scratched on polyester non-woven fabric with scraper.Finally, leaching
Enter to obtain the supporting layer that aperture is 60nm or so into poor solvent.It is washed repeatedly with hot water, removes remaining solvent.
Mass-volume concentration (g/ml) is poured in polysulfone supporting layer film surface and is kept for 2% m-phenylene diamine (MPD) aqueous solution
2min.Then the m-phenylenediamine solution of support membrane excess surface is outwelled, is wiped the apparent droplet of film surface with filter paper, in sky
It is dried in gas 3 minutes.The Isopar G solution of mass-volume concentration (g/ml) four acyl chlorides of biphenyl for being 0.06% is toppled over later
Interfacial polymerization, reaction time 20s are carried out in film surface.Finally the composite membrane of preparation is placed in 90 DEG C of convection oven and is handled
4min.Then reverse osmosis composite membrane is placed in the aqueous solution of sodium carbonate and impregnates 3min, cleaned for several times with 80 DEG C of deionized water,
It saves spare in deionized water.
Embodiment 1
100g, the 5- iodine dimethyl isophthalate of 312mmol, 3.50g, 16mmol are added into the there-necked flask of 500mL
NiBr2With the triethyl phosphite of 300ml.Vacuum nitrogen gas three times after, be slowly warming up to 160 DEG C under magnetic stirring,
175 DEG C are warming up to after reaction 4h.After the reaction was continued 10h, diethyl phosphonate base isophthalic diformazan is obtained with the method for vacuum distillation
Dimethyl phthalate.20g diethyl phosphonate base dimethyl isophthalate is weighed later, is reacted with 120 degrees Celsius of 50ml concentrated hydrochloric acid
10h is cooled to room temperature filtering, obtains the M-phthalic acid of phosphonic acids substitution.The M-phthalic acid chlorination that finally phosphonic acids is replaced
Sulfoxide reacts 12h under conditions of reflux, obtains target product.
Obtained target product is subjected to nuclear magnetic resonance spectroscopy and phosphorus spectrum detection, as a result as shown in FIG. 1, FIG. 1 is the present invention
The hydrogen spectrum and phosphorus spectrogram of the monomer prepared in embodiment 1.In Fig. 1, (a) figure is hydrogen spectrum, and (b) figure is phosphorus spectrum, as shown in Figure 1, is obtained
The target product arrived is 5- (dichloro phosphono) m-phthaloyl chloride.
Fig. 2 is the model configuration figure of 5- obtained (dichloro phosphono) m-phthaloyl chloride.
Mass-volume concentration (g/ml) is poured in polysulfone supporting layer film surface and is kept for 2% m-phenylene diamine (MPD) aqueous solution
2min.Then the m-phenylenediamine solution of support membrane excess surface is outwelled, is wiped the apparent droplet of film surface with filter paper, in sky
It is dried in gas 3 minutes.Later by mass-volume concentration (g/ml) four acyl chlorides of biphenyl for being 0.06% and obtained 5- (dichloro phosphono
Base) the Isopar G solution of m-phthaloyl chloride is poured over film surface and carries out interfacial polymerization, wherein four acyl chlorides of biphenyl and 5- (dichloro
Phosphono) m-phthaloyl chloride mass-volume concentration ratio be 8:2, reaction time 20s.Finally the composite membrane of preparation is placed on
4min is handled in 90 DEG C of convection oven.Then reverse osmosis composite membrane is placed in the aqueous solution of sodium carbonate and impregnates 3min, with 80
DEG C deionized water cleaning for several times, save it is spare in deionized water.
Embodiment 2
By two kinds of acyl chlorides of 5- (dichloro phosphono) m-phthaloyl chloride made from four acyl chlorides of biphenyl and embodiment 1 collectively as
Acyl chlorides monomer reacts preparation nanofiltration membrane with m-phenylene diamine (MPD).Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.06%.Wherein
The concentration ratio of four acyl chlorides of biphenyl and 5- (dichloro phosphono) m-phthaloyl chloride is 6:4.The preparation condition and embodiment 1 of other films
It is identical.
Embodiment 3
By two kinds of acyl chlorides of 5- (dichloro phosphono) m-phthaloyl chloride made from four acyl chlorides of biphenyl and embodiment 1 collectively as
Acyl chlorides monomer reacts preparation nanofiltration membrane with m-phenylene diamine (MPD).Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.06%.Wherein
The concentration ratio of four acyl chlorides of biphenyl and 5- (dichloro phosphono) m-phthaloyl chloride is 4:6.The preparation condition and embodiment 1 of other films
It is identical.
The composite membrane that the present invention obtains Examples 1 to 3 and comparative example 1 tests its pure water flux and salt rejection rate, as a result such as
Shown in table 1, table 1 is the performance data of the composite membrane of the embodiment of the present invention 1~3 and comparative example 1.
The performance data of the composite membrane of 1 embodiment of the present invention 1~3 of table and comparative example 1
The nanofiltration membrane that the present invention obtains embodiment 1 and 3 and comparative example 1 has carried out infrared detection, as a result such as Fig. 3 institute
Show, Fig. 3 is the infared spectrum of the embodiment of the present invention 1 and 3 and comparative example 1, as seen from Figure 3, in 1197cm-1And 917cm-1There is the stretching vibration peak of phosphorus oxygen double bond and phosphonic acids hydroxyl, it was demonstrated that neoteric phosphonic chloride monomer is introduced in activity
In layer, in addition to this, the intensity at the two peaks is gradually increased as phosphonic chloride content of monomer then increases.
The present invention has carried out surface-element analysis to the nanofiltration membrane that comparative example 1 and Examples 1 to 3 obtain, as a result such as 2 institute of table
Showing, table 2 is that the surface-element for the nanofiltration membrane that comparative example 1 of the present invention and Examples 1 to 3 obtain forms,
The surface-element for the nanofiltration membrane that the comparative example 1 of the present invention of table 2 and Examples 1 to 3 obtain forms
As can be seen from Table 2, the P element content of composite film surface is gradually increased with the increase of phosphono chlorinity, into
One step demonstrates phosphonic chloride monomer and is introduced in active layer.
Comparative example 2
Using mass-volume concentration (g/ml) is that 0.08% pyromellitic trimethylsilyl chloride is reacted as acyl chlorides monomer with m-phenylene diamine (MPD)
Prepare nanofiltration membrane.Other preparation conditions are same as Example 1.
Embodiment 4
Pyromellitic trimethylsilyl chloride and 5- made from embodiment 1 (dichloro phosphono) two kinds of acyl chlorides of m-phthaloyl chloride are made jointly
Preparation nanofiltration membrane is reacted with m-phenylene diamine (MPD) for acyl chlorides monomer.Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.08%.Its
The concentration ratio of middle pyromellitic trimethylsilyl chloride and 5- (dichloro phosphono) m-phthaloyl chloride is 8:2.The preparation condition and reality of other films
It is identical to apply example 1.
Embodiment 5
By pyromellitic trimethylsilyl chloride and embodiment 1 be made two kinds of acyl chlorides of 5- (dichloro phosphono) m-phthaloyl chloride collectively as
Acyl chlorides monomer reacts preparation nanofiltration membrane with m-phenylene diamine (MPD).Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.08%.Wherein
The concentration ratio of pyromellitic trimethylsilyl chloride and 5- (dichloro phosphono) m-phthaloyl chloride is 6:4.The preparation condition of other films and implementation
Example 1 is identical.
Embodiment 6
By pyromellitic trimethylsilyl chloride and embodiment 1 be made two kinds of acyl chlorides of 5- (dichloro phosphono) m-phthaloyl chloride collectively as
Acyl chlorides monomer reacts preparation nanofiltration membrane with m-phenylene diamine (MPD).Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.08%.Wherein
The concentration ratio of pyromellitic trimethylsilyl chloride and 5- (dichloro phosphono) m-phthaloyl chloride is 4:6.The preparation condition of other films and implementation
Example 1 is identical.
The nanofiltration membrane that the present invention obtains embodiment 4~6 and comparative example 2 tests pure water flux and salt rejection rate, as a result such as
Shown in table 3, table 3 is the performance data for the nanofiltration membrane that the embodiment of the present invention 4~6 and comparative example 2 obtain.
The performance data for the nanofiltration membrane that 3 embodiment of the present invention 4~6 of table and comparative example 2 obtain
Embodiment 7
The 5- Hydroxy M Phthalic Acid for weighing 20g, adds it in the single port bottle of 250ml, and bottle is placed in ice bath
In be cooled to 0 degree Celsius.Then the phosphorus pentachloride of 2.0equiv is added thereto.Under magnetic stirring, drying tube is used in tail excuse
And nitrogen protection.5h is stirred under 0 degree Celsius, reaction system becomes colorless and transparent solution, and system is then warming up to 100 and is taken the photograph
2h is stirred under family name's degree, further removes the hydrogen chloride of reaction system.Cool down later to reaction system.It is obtained with the method for vacuum distillation
To pure target product.
The present invention has carried out the hydrogen spectrum and phosphorus spectrum detection of nuclear magnetic resonance to target product, as a result as shown in figure 4, Fig. 4 is this
The hydrogen spectrum and phosphorus spectrogram of the monomer prepared in inventive embodiments 7.In Fig. 4, (a) figure is hydrogen spectrum, and (b) figure is phosphorus spectrum, can by Fig. 4
Know, obtained target product is 3,5- dichloro Fonnylphenyl phosphonic chloride.
By 3,5- dichloro Fonnylphenyl phosphonic chloride obtained and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer and isophthalic
Diamine reactant prepares nanofiltration membrane.Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloro formoxyls
The concentration of Phenylphosphine acyl chlorides and pyromellitic trimethylsilyl chloride ratio is 4:6.Remaining condition is the same as embodiment 1.
Embodiment 8
By 3,5- dichloro Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
Preparation nanofiltration membrane is reacted with m-phenylene diamine (MPD).Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride ratio is 6:4.Remaining condition is the same as embodiment 1.
Embodiment 9
By 3,5- dichloro Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
Preparation nanofiltration membrane is reacted with m-phenylene diamine (MPD).Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride ratio is 7:3.Remaining condition is the same as embodiment 1.
Embodiment 10
By 3,5- dichloro Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
Preparation nanofiltration membrane is reacted with m-phenylene diamine (MPD).Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride ratio is 8:2.Remaining condition is the same as embodiment 1.
Comparative example 3
3,5- dichloro Fonnylphenyl phosphonic chloride made from embodiment 7 is reacted as acyl chlorides monomer with m-phenylene diamine (MPD),
In the monomer mass-volume concentration (g/ml) be 0.06%.Remaining condition is the same as embodiment 1.
The embodiment of the present invention 7~10 and the testing result of comparative example 3 are as shown in table 4, and table 4 is the embodiment of the present invention 7~10
With the performance data of comparative example 3.
The performance data of table 4 embodiment of the present invention 7~10 and comparative example 3
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (5)
1. a kind of Nano filtering composite membrane including nonwoven layer, the supporting layer being compounded in the nonwoven layer and is compounded in the branch
Support the active separating layer on layer；
The active separating layer is obtained by polyamine, aroyl chloride and phosphonic chloride monomer reaction；The phosphonic chloride monomer and fragrance
The mass concentration ratio of acyl chlorides is 6:4；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type；
The phosphonic chloride monomer has structure shown in Formula II -1 and Formula II -2:
The Nano filtering composite membrane is prepared according to the following steps to obtain:
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution successively) are coated in support layer surface, is reacted, obtains Nano filtering composite membrane；
The acyl chlorides mixture solution includes aroyl chloride and phosphonic chloride monomer；
The mass-volume concentration of the acyl chlorides mixture solution is 0.06~0.08%.
2. Nano filtering composite membrane according to claim 1, which is characterized in that the polyamine includes m-phenylene diamine (MPD), to benzene two
One or more of amine, piperazine and polyethyleneimine.
3. Nano filtering composite membrane according to claim 1, which is characterized in that the polynary acyl chlorides of biphenyl type includes 2,2 ', 4,
4 '-biphenyl, four acyl chlorides, 3,3 ', 5,5 '-biphenyl, four acyl chlorides, 2,2 ', 5,5 '-biphenyl, four acyl chlorides, 2,3 ', 4,5 '-biphenyl, four acyl chlorides
One or more of with 2,4,4 ', 6- biphenyl, four acyl chlorides.
4. Nano filtering composite membrane according to claim 1, which is characterized in that total matter of the phosphonic chloride monomer and aroyl chloride
Amount and the mass ratio of the polyamine are 1:20~1:40.
5. Nano filtering composite membrane according to claim 1, which is characterized in that the mass-volume concentration of the polynary amine aqueous solution is
1~4%.
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| CN111632498A (en) * | 2020-06-05 | 2020-09-08 | 上海恩捷新材料科技有限公司 | Preparation method of non-woven fabric substrate supported polyethylene nanofiltration membrane |
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