CN107176963A - 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
- Publication number
- CN107176963A CN107176963A CN201710537173.0A CN201710537173A CN107176963A CN 107176963 A CN107176963 A CN 107176963A CN 201710537173 A CN201710537173 A CN 201710537173A CN 107176963 A CN107176963 A CN 107176963A
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- CN
- China
- Prior art keywords
- acyl chlorides
- chloride
- composite membrane
- nano filtering
- phosphonic
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- 239000012528 membrane Substances 0.000 title claims abstract description 89
- 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 54
- 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 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 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 46
- -1 aroyl chloride Chemical compound 0.000 claims description 43
- 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 24
- 239000004305 biphenyl Substances 0.000 claims description 23
- 235000010290 biphenyl Nutrition 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 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 8
- 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
- 230000004907 flux Effects 0.000 abstract description 22
- 238000007873 sieving Methods 0.000 abstract description 5
- 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 16
- 238000001228 spectrum Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 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
- 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
- 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
- 238000010792 warming Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-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
- 238000000034 method Methods 0.000 description 4
- 238000001728 nano-filtration Methods 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
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 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
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 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
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction 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
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 238000005481 NMR spectroscopy Methods 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
- 125000002252 acyl group Chemical group 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
- 238000010612 desalination reaction 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
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003003 phosphines Chemical class 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
- 150000004885 piperazines Chemical class 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
- 238000000425 proton nuclear magnetic resonance spectrum Methods 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
- 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
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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of phosphonic chloride monomer, with structure shown in Formulas I, wherein, R is PO (Cl)2Or OPO (Cl)2, R1、R2、R3、R4And R5Independent is selected from H, COCl, PO (Cl)2Or OPO (Cl)2, and R1、R2、R3、R4And R5It is asynchronously H.Present invention also offers a kind of Nano filtering composite membrane and preparation method thereof.The present invention will carry PO (Cl)2The phosphonic chloride monomer of group is used in the preparation process of Nano filtering composite membrane, utilizes PO (Cl)2Substantial amounts of PO (OH) is produced in course of reaction2Group realizes the purpose of increase active layer negative charge amount.And the space structure of the phosphonic chloride monomer in the present invention causes active layer to have of a relatively loose structure, the poised state that a sieving actoion is acted on electrical charge rejection is finally realized.While ensureing 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 monomer, Nano filtering composite membrane and Nano filtering composite membrane
Preparation method.
Background technology
Compared with reverse osmosis composite membrane, NF membrane has of a relatively loose active layer, therefore it has energy consumption low, ion choosing
Selecting property is high, the advantages of permeation flux is high.At present, NF membrane has been widely used in the preparation of drinking water, sewage disposal, food
The field such as industry and pharmaceuticals industry.
Prepared from Cadotte piperazines in 1977 with pyromellitic trimethylsilyl chloride reaction after NS-100 NF membranes, nanofiltration is combined
Membrane technology has obtained significant progress in nearly 40 years.The NF membrane of current commercialization mainly has U.S. Dow Film Tec NF
Series, Japanese Toray UTC and TR series, Japanese Nitto Denco Hydronautics ESNA series etc..These are combined
Film is substantially to be synthesized with m-phenylene diamine (MPD) or piperazine with pyromellitic trimethylsilyl chloride by interfacial polymerization, the salt rejection rate and water of composite membrane
Generally existing " trade-off " effect, the i.e. salt rejection rate of composite membrane can not reach ideal simultaneously with permeation flux between flux
Effect.Rejection generally to divalent salts is held at more than 95%, and water flux is maintained at 40-60L/m2h.But this kind of receive
Filter membrane be mainly composite film surface-COOH group plays a part of electrical charge rejection in the running of composite membrane and reaches pair
The high rejection of divalent salts.Because the dissociation constant of carboxylate radical is smaller, therefore to keep receiving prepared by excellent salt rejection rate
Filter membrane is relatively compact.Which limits the raising of composite membrane permeation flux.
Therefore how in the case where keeping effectively salt rejection rate, the water flux of composite membrane is improved, so as to reach saving energy
The purpose in source is the problem of a very worth research.
The content of the invention
It is an object of the invention 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 that is prepared using the phosphonic chloride monomer in the present invention is while have higher permeation flux and higher de-
Salt rate.
The present invention provides a kind of phosphonic chloride monomer, with structure shown in Formulas I：
Wherein, R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5Independent is selected from-H ,-COCl ,-PO (Cl)2
Or-OPO (Cl)2, and R1、R2、R3、R4And R5It is asynchronously-H.
It is preferred that, 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 that is compounded in the nonwoven layer and
It is compounded in the active separating layer 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.
It is preferred that, the polyamine includes one kind or several in m-phenylene diamine (MPD), p-phenylenediamine, piperazine and polyethyleneimine
Kind.
It is preferred that, the polynary acyl chlorides of biphenyl type includes 2,2 ', 4, the acyl chlorides of 4 '-biphenyl four, 3,3 ', 5, the acyl of 5 '-biphenyl four
One kind or several in chlorine, 2,2 ', the acyl chlorides of 5,5 '-biphenyl four, the acyl chlorides of 2,3 ', 4,5 '-biphenyl four and the acyl chlorides of 2,4,4 ', 6- biphenyl four
Kind.
It is preferred that, phosphonic chloride monomer described above and the mass concentration ratio of aroyl chloride are 2:8~8:2.
It is preferred that, phosphonic chloride monomer described above and the gross mass of aroyl chloride and the mass ratio of the polyamine are
1:20~1:40.
The present invention provides a kind of preparation method of Nano filtering composite membrane, comprises the following steps：
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution) are coated successively in support layer surface, is reacted, and are obtained nanofiltration and are answered
Close film；
Phosphonic chloride monomer of the acyl chlorides mixture solution including aroyl chloride and above；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
It is preferred that, the mass-volume concentration of the polynary amine aqueous solution is 1~4%.
It is preferred that, 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, with structure shown in Formulas I, wherein, R is-PO (Cl)2Or-OPO (Cl)2,
R1、R2、R3、R4And R5Independent is selected from-H ,-COCl ,-PO (Cl)2Or-OPO (Cl)2, and R1、R2、R3、R4And R5Be asynchronously-
H.The present invention is according to NF membrane sieving actoion and the separating mechanism of electrical charge rejection, by that will carry-PO (Cl)2The phosphonic chloride of group
Monomer is used in the preparation process of Nano filtering composite membrane, utilizes-PO (Cl)2Substantial amounts of-PO (OH) is produced in course of reaction2Group 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 causes active layer to have phase
To loose structure, the poised state that a sieving actoion is acted on electrical charge rejection is finally realized.Size to high price is larger
Ion have excellent retention, it can be allowed to pass through for the ion of small size of unit price, and permeation flux there has also been very
Big raising.Test result indicates that, in 0.48MPa, 2000ppm variety classes inorganic salts, under 25 DEG C of test condition, NF membrane
Salt rejection rate to divalent salts can reach more than 99.0%, and pure water flux is in 70~90L/m2H, it is near with current commercialization rejection
As NF membrane compare, water flux improves 17%~50%.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
The hydrogen of monomers of the Fig. 1 to be prepared in the embodiment of the present invention 1 is composed and phosphorus spectrogram；
Fig. 2 is the model configuration figure of 5- made from the embodiment of the present invention 1 (dichloro phosphono) m-phthaloyl chloride；
Fig. 3 is the infared spectrum of the embodiment of the present invention 1 and 3 and comparative example 1；
The hydrogen of monomers of the Fig. 4 to be prepared in the embodiment of the present invention 7 is composed and phosphorus spectrogram.
Embodiment
The invention provides a kind of phosphonic chloride monomer, structure shown in formula I,
Wherein, R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5Independent is selected from-H ,-COCl ,-PO (Cl)2
Or-OPO (Cl)2, and R1、R2、R3、R4And R5It is asynchronously-H.
It is preferred that, 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 chlorides (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, 312mmol 5- iodine DMIPs, 3.50g, 16mmol are added into 500mL there-necked flask
NiBr2With 300mL triethyl phosphite.After vacuum nitrogen gas three times, 160 DEG C are slowly warming up under magnetic stirring,
175 DEG C are warming up to after reaction 4h.Continue to react after 10h, diethyl phosphonate base isophthalic diformazan is obtained with the method for vacuum distillation
Dimethyl phthalate.20g diethyl phosphonate base DMIPs are weighed afterwards, and with 50ml concentrated hydrochloric acids, 120 DEG C are reacted 10h, cold
But filtered to room temperature, obtain 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 backflow, 5- (dichloro phosphono) m-phthaloyl chloride is obtained.
The present invention preferably synthesizes 3,5- dichloro Fonnylphenyl phosphines according to the synthetic route shown in formula IV and synthetic method
Acyl chlorides,
Weigh in 20g 5- Hydroxy M Phthalic Acids, the single port bottle for adding it to 250mL, and bottle is placed in ice bath
In be cooled to 0 DEG C.Then 2.0equiv phosphorus pentachloride is added thereto.Under magnetic stirring, tail excuse drying tube and
Nitrogen is protected.5h is stirred at 0 DEG C, reaction system becomes the solution of water white transparency, then system is warming up at 100 DEG C and stirred
2h, further removes the hydrogen chloride of reaction system.Reaction system is cooled afterwards.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 membrane, including nonwoven layer, the supporting layer that is compounded in the nonwoven layer
With the active separating layer being compounded on the supporting layer；
The active separating layer is obtained by polyamine and the reaction of 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 obtained by polyamine and the reaction of acyl chlorides mixture, of the invention by phosphonic chloride
Be incorporated into Nano filtering composite membrane active layer, using phosphonic chloride tetrahedral structure and reactivity it is high susceptible to hydrolysis the characteristics of, system
For the NF membrane for going out the open structure with phosphonyl group；The stronger phosphate groups of negative electricity are also incorporated into composite membrane simultaneously
In, and the effective aperture of composite membrane is increased, it is achieved thereby that high valence ion salt rejection rate, the system with high permeating flux NF membrane
It is standby.
In the present invention, the polyamine include m-phenylene diamine (MPD), p-phenylenediamine, piperazine and polyethyleneimine in one kind 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,
The acyl chlorides of 2 ', 4,4 '-biphenyl four, the acyl chlorides of 3,3 ', 5,5 '-biphenyl four, the acyl chlorides of 2,2 ', 5,5 '-biphenyl four, 2,3 ', 4,5 '-biphenyl four
One or more in acyl chlorides and 2,4,4 ', the acyl chlorides of 6- biphenyl four.
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, can be 2:8,4:6,6:4,7：3 or 8:2；Total matter of the phosphonic chloride monomer and aroyl chloride
Measure and the mass ratio of the polyamine is preferably 1:20~1:40, more preferably 1:25~1:35, specifically, the present invention's
Can be 1 in embodiment:20、1:25 or 1:33.
Present invention also offers a kind of preparation method of Nano filtering composite membrane, comprise the following steps：
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution) are coated successively in support layer surface, is reacted, and are obtained nanofiltration and are answered
Close film；
The acyl chlorides mixture solution includes the phosphonic chloride monomer described in aroyl chloride and claim 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 following steps, then scratches polysulfones solution in non-woven fabrics table with scraper
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, polysulfones solution, institute is obtained
State pore-foaming agent and preferably include one or more in glycol monoethyl ether, polyvinylpyrrolidone and polyethylene glycol；The surface
Activating agent includes the one or more in alkyl phenol polyoxy ethyl ester phosphonate ester, dodecane sulfonate and polyvinyl alcohol；It is described good
Solvent preferably includes the one or more in DMF, DMA and 1-METHYLPYRROLIDONE.
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, present invention preferably uses hot wash repeatedly, to remove residual
Solvent.Obtained supporting layer aperture is 30~70nm, and molecular cut off is 10w.
It is supported after film, polynary amine aqueous solution is preferably poured on support membrane surface and keeps 1.5~3min by the present invention, then
The polynary amine aqueous solution of support membrane excess surface is outwelled, the globule on film surface is wiped with filter paper, 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 species of the polyamine with above
The species of polyamine is consistent, will not be repeated here；Mass-volume concentration (quality divided by the volume, g/ of the polynary amine aqueous solution
ML it 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, phosphonic chloride list of the acyl chlorides mixture including aroyl chloride and above
Body, the species and consumption of aroyl chloride and the phosphonic chloride monomer and the species and use of above aroyl chloride and phosphonic chloride monomer
Amount is consistent, will not be repeated here.The mass-volume concentration of the acyl chlorides mixture solution is preferably 0.04~0.3%, more preferably
For 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 is preferably carried out at room temperature, and the reaction time is preferably 10~30s, more
Preferably 20s.
After the completion of polymerisation, obtained composite membrane is preferably placed in convection oven by the present invention is dried, drying temperature
Degree is preferably 80~90 DEG C, and the time of drying is preferably 4~7min, and composite membrane is followed by placed in aqueous sodium carbonate by drying
2~4min is soaked, is then cleaned for several times, preserved standby in deionized water with 80 DEG C of deionized water.
The preparation method of Nano filtering composite membrane of the present invention is simple, with wide applicability, can be applied to desalinization, 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, with structure shown in Formulas I, wherein, R is-PO (Cl)2Or-OPO (Cl)2,
R1、R2、R3、R4And R5Independent is selected from-H ,-COCl ,-PO (Cl)2Or-OPO (Cl)2, and R1、R2、R3、R4And R5Be asynchronously-
H.The present invention is according to NF membrane sieving actoion and the separating mechanism of electrical charge rejection, by that will carry-PO (Cl)2The phosphonic chloride of group
Monomer is used in the preparation process of Nano filtering composite membrane, utilizes-PO (Cl)2Substantial amounts of-PO (OH) is produced in course of reaction2Group 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 causes active layer to have phase
To loose structure, the poised state that a sieving actoion is acted on electrical charge rejection is finally realized.Size to high price is larger
Ion have excellent retention, it can be allowed to pass through for the ion of small size of unit price, and permeation flux there has also been very
Big raising.Test result indicates that, in 0.48MPa, 2000ppm variety classes inorganic salts, under 25 DEG C of test condition, NF membrane
Salt rejection rate to divalent salts can reach more than 99.0%, and pure water flux is in 70~90L/m2H, it is near with current commercialization rejection
As NF 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 of the invention provided, nanofiltration
The preparation method of composite membrane and Nano filtering composite membrane is described in detail, but can not be understood as the limit to the scope of the present invention
It is fixed.
Water flux：At a particular pressure, the volume for the water that the unit interval passes through per membrane area.It can be represented with following formula.
(volume of V (L)-infiltration water, A (m2The effective area of)-film, t (h)-time)
Salt rejection rate：After solute is by NF membrane, the percentage that can always have solubility impurity concentration is removed from system water inlet.Can
To be represented with following formula：
(Cf- feeding liquid concentration, Cp- penetrating fluid concentration)
In the examples below, pure water flux test condition is as follows：25 DEG C of operation temperature, 2000ppm variety classes without
The aqueous solution of machine salt, 0.48Mpa operating pressure.The permeation flux of NF membrane is represented with pure water flux at this pressure.Survey
Before the permeation flux for trying NF membrane, composite membrane precompressed 4h under 0.48Mpa, it is ensured that the stability of test data.Every kind of formula
Composite membrane test 6 data, average.
Comparative example 1
It is 14% to configure polysulfones mass concentration, 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 scratched with scraper on polyester non-woven fabric.Finally, soak
Enter to obtain supporting layer of the aperture for 60nm or so into poor solvent.With hot wash repeatedly, the solvent of residual is removed.
Mass-volume concentration (g/ml) is poured on polysulfone supporting layer film surface and kept for the 2% m-phenylene diamine (MPD) aqueous solution
2min.Then the m-phenylenediamine solution of support membrane excess surface is outwelled, wiped the obvious globule in film surface with filter paper, in sky
Dried in gas 3 minutes.The Isopar G solution by mass-volume concentration (g/ml) for 0.06% acyl chlorides of biphenyl four is toppled over afterwards
Interfacial polymerization is carried out on film surface, the reaction time is 20s.Finally the composite membrane of preparation is placed in 90 DEG C of convection oven and handled
4min.Then reverse osmosis composite membrane is placed in the aqueous solution of sodium carbonate and soaks 3min, cleaned for several times with 80 DEG C of deionized water,
Preserve standby in deionized water.
Embodiment 1
100g, 312mmol 5- iodine DMIPs, 3.50g, 16mmol are added into 500mL there-necked flask
NiBr2With 300ml triethyl phosphite.After vacuum nitrogen gas three times, 160 DEG C are slowly warming up under magnetic stirring,
175 DEG C are warming up to after reaction 4h.Continue to react after 10h, diethyl phosphonate base isophthalic diformazan is obtained with the method for vacuum distillation
Dimethyl phthalate.20g diethyl phosphonate base DMIPs are weighed afterwards, with the 120 degrees Celsius of reactions of 50ml concentrated hydrochloric acids
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 backflow, obtains target product.
Obtained target product is subjected to proton nmr spectra and phosphorus spectrum detection, as a result as shown in figure 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 obtained 5- (dichloro phosphono) m-phthaloyl chloride.
Mass-volume concentration (g/ml) is poured on polysulfone supporting layer film surface and kept for the 2% m-phenylene diamine (MPD) aqueous solution
2min.Then the m-phenylenediamine solution of support membrane excess surface is outwelled, wiped the obvious globule in film surface with filter paper, in sky
Dried in gas 3 minutes.Afterwards by the acyl chlorides of biphenyl four that mass-volume concentration (g/ml) is 0.06% and obtained 5- (dichloro phosphonos
Base) the Isopar G solution of m-phthaloyl chloride is poured over film surface and carries out interfacial polymerization, the wherein acyl chlorides of biphenyl four and 5- (dichloros
Phosphono) m-phthaloyl chloride mass-volume concentration ratio be 8:2, the reaction time is 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 soaks 3min, with 80
DEG C deionized water cleaning for several times, preserve it is standby in deionized water.
Embodiment 2
By the acyl chlorides of biphenyl four and two kinds of acyl chlorides of 5- made from embodiment 1 (dichloro phosphono) m-phthaloyl chloride collectively as
Acyl chlorides monomer prepares NF membrane with m-phenylene diamine (MPD) reaction.Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.06%.Wherein
The concentration ratio of the acyl chlorides of biphenyl four and 5- (dichloro phosphono) m-phthaloyl chloride is 6:4.The preparation condition of other films and embodiment 1
It is identical.
Embodiment 3
By the acyl chlorides of biphenyl four and two kinds of acyl chlorides of 5- made from embodiment 1 (dichloro phosphono) m-phthaloyl chloride collectively as
Acyl chlorides monomer prepares NF membrane with m-phenylene diamine (MPD) reaction.Total acyl chlorides monomer mass volumetric concentration (g/ml) is 0.06%.Wherein
The concentration ratio of the acyl chlorides of biphenyl four and 5- (dichloro phosphono) m-phthaloyl chloride is 4:6.The preparation condition of other films and embodiment 1
It is identical.
The present invention tests its pure water flux and salt rejection rate to the composite membrane that embodiment 1~3 and comparative example 1 are obtained, 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 the embodiment of the present invention 1~3 of table 1 and comparative example 1
The present invention has carried out infrared detection to the NF membrane that embodiment 1 and 3 and comparative example 1 are obtained, as a result such as Fig. 3 institutes
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-1Occur in that 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, the intensity at the two peaks is as phosphonic chloride content of monomer then increases and gradually strengthens.
The present invention has carried out surface-element analysis to the NF membrane that comparative example 1 and embodiment 1~3 are obtained, as a result such as the institute of table 2
Show, table 2 is the surface-element composition for the NF membrane that comparative example 1 of the present invention and embodiment 1~3 are obtained,
The surface-element composition for the NF membrane that the comparative example 1 of the present invention of table 2 and embodiment 1~3 are obtained
As can be seen from Table 2, the P element content of composite film surface gradually increases with the increase of phosphono chlorinity, enters
One step demonstrates phosphonic chloride monomer and is introduced in active layer.
Comparative example 2
Reacted with mass-volume concentration (g/ml) for 0.08% pyromellitic trimethylsilyl chloride as acyl chlorides monomer and m-phenylene diamine (MPD)
Prepare NF membrane.Other preparation conditions are same as Example 1.
Embodiment 4
Pyromellitic trimethylsilyl chloride is made jointly with 5- made from embodiment 1 (dichloro phosphono) two kinds of acyl chlorides of m-phthaloyl chloride
It is that acyl chlorides monomer and m-phenylene diamine (MPD) reaction prepare NF membrane.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
Apply example 1 identical.
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 prepares NF membrane with m-phenylene diamine (MPD) reaction.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 prepares NF membrane with m-phenylene diamine (MPD) reaction.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 present invention tests pure water flux and salt rejection rate to the NF membrane that embodiment 4~6 and comparative example 2 are obtained, as a result such as
Shown in table 3, table 3 is the performance data for the NF membrane that the embodiment of the present invention 4~6 and comparative example 2 are obtained.
The performance data for the NF membrane that the embodiment of the present invention 4~6 of table 3 and comparative example 2 are obtained
Embodiment 7
Weigh in 20g 5- Hydroxy M Phthalic Acids, the single port bottle for adding it to 250ml, and bottle is placed in ice bath
In be cooled to 0 degree Celsius.Then 2.0equiv phosphorus pentachloride is added thereto.Under magnetic stirring, tail excuse drying tube
And nitrogen protection.5h is stirred under 0 degree Celsius, reaction system becomes the solution of water white transparency, system then is warming up into 100 takes the photograph
2h is stirred under family name's degree, the hydrogen chloride of reaction system is further removed.Reaction system is cooled afterwards.Obtained with the method for vacuum distillation
To pure target product.
The present invention has carried out hydrogen spectrum and the 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 chlorides.
By obtained 3,5- dichloros Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer and isophthalic
Diamine reactant prepares NF membrane.Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloro formoxyls
The concentration ratio of Phenylphosphine acyl chlorides and pyromellitic trimethylsilyl chloride is 4:6.Remaining condition be the same as Example 1.
Embodiment 8
By 3,5- dichloros Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
NF membrane is prepared with m-phenylene diamine (MPD) reaction.Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration ratio of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride is 6:4.Remaining condition be the same as Example 1.
Embodiment 9
By 3,5- dichloros Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
NF membrane is prepared with m-phenylene diamine (MPD) reaction.Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration ratio of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride is 7:3.Remaining condition be the same as Example 1.
Embodiment 10
By 3,5- dichloros Fonnylphenyl phosphonic chloride made from embodiment 7 and pyromellitic trimethylsilyl chloride collectively as acyl chlorides monomer
NF membrane is prepared with m-phenylene diamine (MPD) reaction.Wherein the gross mass volumetric concentration (g/ml) of acyl chlorides monomer is 0.06%, 3,5- dichloros
The concentration ratio of Fonnylphenyl phosphonic chloride and pyromellitic trimethylsilyl chloride is 8:2.Remaining condition be the same as Example 1.
Comparative example 3
3,5- dichloros Fonnylphenyl phosphonic chloride made from embodiment 7 is reacted as acyl chlorides monomer and m-phenylene diamine (MPD), its
In the monomer mass-volume concentration (g/ml) be 0.06%.Remaining condition be the same as Example 1.
As shown in table 4, table 4 is the embodiment of the present invention 7~10 for the embodiment of the present invention 7~10 and the testing result of comparative example 3
With the performance data of comparative example 3.
The performance data of the embodiment of the present invention 7~10 of table 4 and comparative example 3
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of phosphonic chloride monomer, with structure shown in Formulas I：
Wherein, R is-PO (Cl)2Or-OPO (Cl)2, R1、R2、R3、R4And R5Independent is selected from-H ,-COCl ,-PO (Cl)2Or-OPO
(Cl)2, and R1、R2、R3、R4And R5It is asynchronously-H.
2. phosphonic chloride monomer according to claim 1, it is characterised in that the phosphonic chloride monomer have Formula II -1~II~
Shown in 16,
3. a kind of Nano filtering composite membrane, including nonwoven layer, the supporting layer that is compounded in the nonwoven layer and it is compounded in the branch
Support the active separating layer on layer；
The active separating layer is obtained as the phosphonic chloride monomer reaction described in polyamine, aroyl chloride and claim 1 or 2；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
4. Nano filtering composite membrane according to claim 3, it is characterised in that the polyamine includes m-phenylene diamine (MPD), to benzene two
One or more in amine, piperazine and polyethyleneimine.
5. Nano filtering composite membrane according to claim 3, it is characterised in that the polynary acyl chlorides of biphenyl type includes 2,2 ', 4,
The acyl chlorides of 4 '-biphenyl four, the acyl chlorides of 3,3 ', 5,5 '-biphenyl four, the acyl chlorides of 2,2 ', 5,5 '-biphenyl four, the acyl chlorides of 2,3 ', 4,5 '-biphenyl four
With the one or more in the acyl chlorides of 2,4,4 ', 6- biphenyl four.
6. Nano filtering composite membrane according to claim 3, it is characterised in that the phosphonic chloride list described in the claim 1 or 2
The mass concentration ratio of body and aroyl chloride is 2:8~8:2.
7. Nano filtering composite membrane according to claim 3, it is characterised in that the phosphonic chloride list described in the claim 1 or 2
The gross mass of body and aroyl chloride and the mass ratio of the polyamine are 1:20~1:40.
8. a kind of preparation method of Nano filtering composite membrane, comprises the following steps：
A polysulfones solution) is coated in nonwoven surface, be supported layer；
B polynary amine aqueous solution and acyl chlorides mixture solution) are coated successively in support layer surface, is reacted, and obtain Nano filtering composite membrane；
The acyl chlorides mixture solution includes the phosphonic chloride monomer described in aroyl chloride and claim 1 or 2；
The aroyl chloride is pyromellitic trimethylsilyl chloride and/or the polynary acyl chlorides of biphenyl type.
9. preparation method according to claim 8, it is characterised in that the mass-volume concentration of the polynary amine aqueous solution is 1
~4%.
10. preparation method according to claim 8, it is characterised in that the quality volume of the acyl chlorides mixture solution is dense
Spend for 0.04~0.3%.
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