CN100457241C - Method for preparing multilayer polyamide composite film - Google Patents
Method for preparing multilayer polyamide composite film Download PDFInfo
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- CN100457241C CN100457241C CNB2006100533088A CN200610053308A CN100457241C CN 100457241 C CN100457241 C CN 100457241C CN B2006100533088 A CNB2006100533088 A CN B2006100533088A CN 200610053308 A CN200610053308 A CN 200610053308A CN 100457241 C CN100457241 C CN 100457241C
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Abstract
The invention relates to a method for preparing multilayer polyamide composite film. Wherein, it emerges polyamide composite film (PA) used in reverse osmosis (RO) in the water solution of 0.5-2.5wt% m-phenylenediamine for 10-30min; then emerges it in the skellysolve B solution whose mesitylene chlorine density is 0.3-1.0wt% for 10-30s; then croslinking it to form one layer of PA film; repeats, to obtain the multilayer PA composite film. The multilayer PA composite film with 5 times of polycondensation separates PV on the water mixture whose alcohol isopropylicum density is 88.2%, the water content of osmosis material can reach 51.04-97.53%, the osmosis flux can reach 25.66-575.85g/m2, while the reaction is quick. The invention has simple process.
Description
Technical field
The present invention relates to by polymer chemistry reaction the carrying out preparation of multilayer polyamide (PA) composite membrane.The PA composite membrane that specifically utilizes water treatment counter-infiltration (RO) desalination to use prepares the method for infiltration evaporation (PV) diffusion barrier by interfacial polycondensation technology repeatedly.This multilayer polyamide (PA) composite membrane is as the PV diffusion barrier of organic aqueous solution.
Background technology
Polyamide (PA) is a kind of separation membrane material of function admirable.By compound filming technology, industrial water treatment desalination counter-infiltration (RO) film, technology maturation, and widely use.But for research and the application still rare finding of infiltration evaporation with the PA film.
" Desalination " (148 phases: 43-48,2002) and " Journal of Membrane Science " (185 phases: 193-200, calendar year 2001) reported respectively with 2,2-two [4-(4-amino-benzene oxygen) benzene] HFC-236fa (BAPPH) and 2, a series of fluorine-containing aromatic polyamide membrane that 2-two [4-(4-amino-benzene oxygen) benzene] propane (BAPPP) is synthetic with different aromatic diacids.This film is used for infiltration evaporation (PV) method Separation of Benzene/cyclohexylamine mixture and ethanol dehydration.
" Journal of Membrane Science " (131 phases: 249-259,1997) reported with isophathalic acid respectively with 2,2-two [4-(4-amino-benzene oxygen) benzene] HFC-236fa and 2,2-two [4-(4-amino-benzene oxygen) benzene] propane carries out polycondensation reaction in than the solution of coughing up alkane and obtains two kinds of aromatic polyamide membranes containing triphenyl phosphite, pyrimidine and N-methyl-2-: F-aromatic polyamide membrane and H-aromatic polyamide membrane, these films all are used for PV method ethanol dehydration process.
" European Polymer Journal " (36 phases: 663-672,2000) have been reported at aramid surfaces acrylamide in the plasma technique grafting, and this graft copolymer membrane can be used for PV separating alcohol/aqueous mixtures.
The inventor is once at " Journal of Applied Polymer Science " (Vol.92:1005-1010,2004) and Chinese patent (the solvent modified method of polyamide composite film, application number in July, 03141702.2,2003) disclosing PA composite membrane that the RO of asymmetry uses on respectively becomes the dense film of the PV separation of organic substances aqueous solution by the solvent processing method modification.This method of modifying is the PA composite membrane used of the RO with commodity through the step of soaking in the solvent solution of PA, drying under the rinsing in the deionized water, room temperature condition, obtains the fine and close PA composite membrane that the PV of modification uses.Solvent modified processing procedure be solvent molecule with the PA macromolecular chain contact and the PA film in the outside process of motion of micro-capsule inner macromolecule segment, cause the PA membrane structure more fine and close, form the PV film that can be used for the organic-compound system separation.
The present invention is based on the high molecular polymerization technology, the PA film preparation that proposes RO to be used with different before this preparation technologies becomes the repeatedly polycondensation method of PV diffusion barrier.
Summary of the invention
The invention provides a kind of interfacial polycondensation reaction of passing through repeatedly, make the PA monomer solution on support membrane, form the method for fine and close multilayer polyamide (PA) composite membrane.The PA composite membrane that makes commerical grade counter-infiltration (RO) usefulness through polycondensation repeatedly to adapt to the needs of infiltration evaporation (PV).
The basic principle of the inventive method is that the PA film with commerical grade counter-infiltration (RO) usefulness is a support membrane, in the aqueous solution and pyromellitic trimethylsilyl chloride (TMC) hexane solution of m-phenylene diamine (MPD) (m-PDA), through repeatedly polycondensation reaction and processing, on support membrane, form PA film fine and close, that be suitable for the separatory sandwich construction of PV.
The preparation method of the multilayer polyamide composite film of technical solution of the present invention is characterized in that, its processing step comprises:
1), the preparation of condensation polymerization monomer solution
One is m-phenylene diamine (MPD) (m-PDA) aqueous solution of 0.5wt%～2.5wt% with the deionized water compound concentration; Its two, be pyromellitic trimethylsilyl chloride (TMC) hexane solution of 0.3wt%-1.0wt% with the n-hexane compound concentration;
2), the interfacial polycondensation of polyamide (PA) composite membrane reaction
At first, RO is immersed in the m-PDA aqueous solution with the PA composite membrane, soak time is 10～30 minutes, then takes out, air-dry, it is immersed in the TMC hexane solution again, and it is standby that soak time is that 10-30 took out after second;
3), the heat treatment of composite membrane
To heat-treat at ambient temperature or under the raising temperature through the PA composite membrane of organic monomer immersion treatment, make organic monomer finish cross-linking reaction and form new one deck PA film;
4), repeat above-mentioned steps 2)-3) operation, make the PA composite membrane carry out repeatedly interfacial polycondensation reaction more than 2 times or 2 times, make multilayer polyamide composite film at last.
The concentration of above-described m-phenylene diamine (MPD) (m-PDA) aqueous solution is 2.5wt%; Pyromellitic trimethylsilyl chloride (TMC) hexane solution concentration is 0.8wt%.
The number of times of above-described repeatedly interfacial polycondensation reaction is 6 times.
Above-described soak time in m-phenylene diamine (MPD) (m-PDA) aqueous solution is 20 minutes; Soak time in pyromellitic trimethylsilyl chloride (TMC) hexane solution was 20 seconds.
It is raw material with the PA composite membrane that the inventive method is only used commerical grade counter-infiltration (RO), add the chemical reagent of small quantities of usual, for have certain basis particularly the manufacturing enterprise of composite membrane need not to increase membrane equipment and macromolecular material can be produced, preparation technology is simple, easy to operate and safe, condition is easily controlled.
Owing to only be that repeatedly polycondensation reaction is carried out on the separating layer PA film surface of RO composite membrane, therefore to the structure and the not influence of physical and mechanical properties thereof of porous support layer polysulfones (PS) film of composite membrane, the original chemical stability of composite membrane can not change yet.Polycondensation process is rapid, and repeatedly the compact structure of the diffusion barrier of polycondensation is good.Realized will the organic matter aqueous mixtures not being had the preparation becoming of PA composite membrane colory multilayer polyamide (PA) composite membrane, i.e. the PV diffusion barrier of commerical grade counter-infiltration (RO) usefulness of separating power.
Description of drawings
Fig. 1 is a process frame chart.
Fig. 2 is the PA membrane superficial tissue form comparison diagram before and after the repeatedly polycondensation reaction.
SEM (SEM) take the photograph (* 5K)
Wherein: (a) the PA film used of RO; (b) the PA film of interfacial polycondensation 1 time; (c) the PA film of interfacial polycondensation (40 ℃) 6 times
Fig. 3 is the PA membrane superficial tissue form comparison diagram before and after the repeatedly polycondensation reaction.
AFM (AFM) is taken the photograph
Wherein: (a) the PA film used of RO; (b) the PA film of interfacial polycondensation 1 time; (c) the PA film of interfacial polycondensation (40 ℃) 6 times
Fig. 4 PA film is the 3D rendering of the AFM on film surface, polycondensation reaction front and back repeatedly.
AFM (AFM) is taken the photograph
Wherein: (a) the PA film used of RO; (b) the PA film of interfacial polycondensation 1 time; (c) the PA film of interfacial polycondensation (40 ℃) 6 times
The specific embodiment
The process frame chart of the inventive method embodiment is shown in Fig. 1:
With commerical grade counter-infiltration (RO) polyamide (PA) composite membrane, at first be immersed in certain density m-phenylene diamine (MPD) (m-PDA) aqueous solution, dry through taking out behind the dipping of time a few minutes, put into certain density pyromellitic trimethylsilyl chloride-n-hexane (TMC) solution then, after soaking several seconds, take out to place under certain temperature rapidly and heat-treat, finish course of reaction.So repeatedly repetitive operation (dotted portion among Fig. 1), the last good multilayer PA composite membrane of obtained performance.
For the purpose of the present invention, interfacial polycondensation is meant that support membrane is a RO PA composite membrane, successively with the aqueous solution in organic monomer and with organic solvent in the polycondensation reaction carried out of the monomer of (water insoluble), be the process that on porous supporting body, forms PA macromolecule thin layer.Carrying out repeatedly of interfacial polycondensation course of reaction can obtain the PA composite membrane that PV separates that is used for of sandwich construction.
The PA that forms multilayer film is synthesized through interfacial polycondensation by m-PDA and TMC, and its chemical structural formula is:
Multilayer PA film is used for the PV separating experiment, measures the separating property of film.The PV experiment condition is: 20～30 ℃ of room temperatures, and film downstream vacuum 300～600Pa, feed side pressure 0.05～0.1MPa, feed liquid is that isopropyl alcohol (IPA) is that 88.2wt% and water are the IPA/ aqueous mixtures of 11.8wt%.Usually, the PV separating property characterizes with permeation flux (J) and separation factor (α):
J＝W/(A·t) (1)
α＝(Y
w/Y
IPA)/(X
w/X
IPA) (2)
In the formula (1), W is for seeing through liquid weight (g), and A is effective film area (m
2), t is sample acquisition time (h).In the formula (2), Y
wAnd Y
IPABe respectively the mass fraction of water and IPA in the penetrating fluid; X
wAnd X
IPABe respectively the mass fraction of water and IPA in the material liquid.
The PA composite membrane repeatedly PV separating property of interfacial polycondensation front and back relatively sees the following form.
Show repeatedly the Pervaporation Separation of interfacial polycondensation front and back polyamide composite film
*The soak time of PA film in the m-PDA aqueous solution that RO uses is 30 minutes, and the soak time in the TMC hexane solution was 30 seconds; The concentration of the m-PDA aqueous solution is 1.0wt%, and the concentration of TMC hexane solution is 0.5wt%.
*Permeation flux " very big " is illustrated in and feed liquid seepage phenomenon promptly occurs after the PV experimentation is opened vavuum pump and vacuumized.
Show in the table that through behind the interfacial polycondensation repeatedly, multilayer PA composite membrane all has PV separating property preferably to the IPA aqueous solution, and effect is very obvious.When under 40 ℃, when the number of times of organic monomer interfacial polycondensation reaction reached 6 times, the water content in the penetrant can reach more than 97%.This be since repeatedly commerical grade counter-infiltration (RO) the PA composite membrane that PA film surface ratio is original after the polycondensation reaction want fine and close, and along with the increase of polycondensation reaction number of times, PA is big, and packing of molecules density increases (see figure 2) significantly, the film surface average roughness increases (see figure 3), the PA macromolecule thin layer height on 6 polycondensation reaction caudacoria surfaces reaches 400nm, cause whole PA polymeric membrane separating layer to become more abundant, the loose structure of the PA composite membrane that RO uses disappears.
Fig. 2,3 and 4 brief description are as follows:
PA film (* 5K) the PA film used of photo: a, RO of the SEM (SEM) on film surface before and after the polycondensation reaction repeatedly among Fig. 2; The PA film that b, interfacial polycondensation are 1 time; The PA film that c, interfacial polycondensation (40 ℃) are 6 times.Contrast these three SEM and show film surface compact degree: c 〉=b ≌ a.
Repeatedly AFM (AFM) photo: a on film surface, the PA film that RO uses before and after the polycondensation reaction of PA film among Fig. 3; The PA film that b, interfacial polycondensation are 1 time; The PA film that c, interfacial polycondensation (40 ℃) are 6 times.Contrast these three AFM and show film surface average roughness (RMS): c=65.03nm＞b=53.61nm＞a=44.45nm.
Fig. 4 PA film is the 3D rendering photo of the AFM (AFM) on film surface, polycondensation reaction front and back repeatedly: the PA film that a, RO use; The PA film that b, interfacial polycondensation are 1 time; The PA film that c, interfacial polycondensation (40 ℃) are 6 times.Contrast the height that these three AFM show film surface PA macromolecule thin layer: c=400nm＞b=200nm ≌ a=200nm.
This shows, adopt repeatedly the method for interfacial polycondensation can realize the good PV diffusion barrier of PA composite membrane preparation becoming that not to have the commodity RO of separating power to use to the organic matter aqueous mixtures.
Embodiments of the invention are as follows:
Embodiment 1:
Getting the PA composite membrane that commerical grade RO uses is to soak 20 minutes in 2.5wt% m-phenylene diamine (MPD) (m-PDA) aqueous solution in the concentration that is mixed with deionized water, after taking-up is dried, be to soak for 20 seconds in pyromellitic trimethylsilyl chloride (TMC) hexane solution of 0.8wt% in the concentration that is mixed with n-hexane again, taking-up places under 25 ℃ of the room temperatures dries, about 5 minutes, more than operation repeated 5 times.Obtain dark brown multilayer polyamide composite film.
The PV test determination, the performance that this multilayer PA composite membrane is used for the separating isopropanol aqueous mixtures is: permeation flux 92.53g/m
2H, water content 37.70wt% in the penetrant.
Embodiment 2:
As the processing step of embodiment 1, wherein, only change the PA composite membrane of handling through the organic monomer solvent soaking and under 40 ℃ infrared lamp, heat-treat, the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained is: permeation flux 27.60g/m
2H, water content 95.57wt% in the penetrant.
Embodiment 3:
All the other conditions only change 70 ℃ of heat treatment temperatures with embodiment 2, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 21.82g/m
2H, water content 96.08wt% in the penetrant.
Embodiment 4:
All the other conditions only change the concentration 0.5wt% of the m-PDA aqueous solution with embodiment 2, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 575.85g/m
2H, water content 51.04wt% in the penetrant.
Embodiment 5:
All the other conditions only change the concentration 1.5wt% of the m-PDA aqueous solution with embodiment 2, and the performance of the modified polyamide composite membrane PV separating isopropanol aqueous mixtures of gained is: permeation flux 50.41g/m
2H, water content 80.79wt% in the penetrant.
Embodiment 6:
All the other conditions only change the concentration 2.5wt% of the m-PDA aqueous solution with embodiment 2, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 25.66g/m
2H, water content 97.53wt% in the penetrant.
Embodiment 7:
Processing step as embodiment 1, getting the commodity polyamide reverse osmosis composite film soaked 20 minutes in the 1.5wt%m-PDA aqueous solution, after taking-up is dried, in 0.3wt%TMC solution, soaked for 20 seconds again, take out and under 40 ℃ infrared light, heat-treat, more than operation repeats 5 times, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 188.00/m
2H, water content 48.47wt% in the penetrant.
Embodiment 8:
All the other conditions only change the concentration 1.0wt% of TMC solution with embodiment 7, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 48.35g/m
2H, water content 84.87wt% in the penetrant.
Embodiment 9:
Processing step as embodiment 1, getting the commodity polyamide reverse osmosis composite film soaked 20 minutes in the 1.0wt%m-PDA aqueous solution, after taking-up is dried, in 0.5wt%TMC solution, soaked for 20 seconds again, taking-up places under the room temperature dries, more than operation repeats 5 times, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 381.95g/m
2H, water content 21.11wt% in the penetrant.
Embodiment 10:
All the other conditions are with embodiment 9, only change the soak time 10 minutes in the m-PDA aqueous solution, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 602.60g/m
2H, water content 15.73wt% in the penetrant.
Embodiment 11:
All the other conditions are with embodiment 9, only change the soak time 30 minutes in the m-PDA aqueous solution, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 385.80g/m
2H, water content 21.18wt% in the penetrant.
Embodiment 12:
All the other conditions only change 10 seconds of soak time in TMC solution with embodiment 9, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 585.65g/m
2H, water content 14.22wt% in the penetrant.
Embodiment 13:
All the other conditions only change 30 seconds of soak time in TMC solution with embodiment 9, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 386.45g/m
2H, water content 21.11wt% in the penetrant.
Embodiment 14:
Getting the commodity polyamide reverse osmosis composite film soaked 20 minutes in the 1.0wt%m-PDA aqueous solution, after taking-up is dried, in 0.5wt%TMC solution, soaked for 20 seconds again, take out and under 40 ℃ infrared light, heat-treat, more than operation repeats 3 times, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 120.08g/m
2H, water content 27.12wt% in the penetrant.
Embodiment 15:
All the other conditions only change the interfacial polycondensation reaction times 5 times with embodiment 14, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 62.15g/m
2H, water content 68.38wt% in the penetrant.
Embodiment 16:
All the other conditions only change the interfacial polycondensation reaction times 6 times with embodiment 14, and the performance of the multilayer PA composite membrane PV separating isopropanol aqueous mixtures of gained modification is: permeation flux 18.00g/m
2H, water content 97.16wt% in the penetrant.
Claims (5)
1, a kind of preparation method of multilayer polyamide composite film is characterized in that, its processing step comprises:
1), the preparation of condensation polymerization monomer solution
One is the m-phenylene diamine (MPD) aqueous solution of 0.5wt%～2.5wt% with the deionized water compound concentration; Its two, be the pyromellitic trimethylsilyl chloride hexane solution of 0.3wt%-1.0wt% with the n-hexane compound concentration;
2), the interfacial polycondensation of polyamide composite film reaction
At first, to be immersed in the m-phenylene diamine (MPD) aqueous solution with polyamide composite film as the counter-infiltration of support membrane, soak time is 10～30 minutes, then takes out, dries, it is immersed in the pyromellitic trimethylsilyl chloride hexane solution, soak time is that 10-30 took out rapidly after second again;
3), the heat treatment of composite membrane
To handle at normal temperatures or at high temperature through the polyamide composite film of organic monomer immersion treatment, make it to finish cross-linking reaction and form new one deck PA membrane;
4), repeat above-mentioned steps 2)-3) operation, make PA membrane through the reaction of the repeatedly interfacial polycondensation more than 2 times or 2 times, make multilayer polyamide composite film at last.
2, the preparation method of multilayer polyamide composite film as claimed in claim 1, the concentration that it is characterized in that the described m-phenylene diamine (MPD) aqueous solution is 2.5wt%; Pyromellitic trimethylsilyl chloride hexane solution concentration is 0.8wt%.
3, the preparation method of multilayer polyamide composite film as claimed in claim 1 is characterized in that the number of times of described repeatedly interfacial polycondensation reaction is 6 times.
4, the preparation method of multilayer polyamide composite film as claimed in claim 1 is characterized in that described soak time in the m-phenylene diamine (MPD) aqueous solution is 20 minutes; Soak time in the pyromellitic trimethylsilyl chloride hexane solution was 20 seconds.
5, the preparation method of multilayer polyamide composite film as claimed in claim 1 is characterized in that described heat treatment temperature is 25～70 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11724234B2 (en) | 2016-08-31 | 2023-08-15 | South Dakota Board Of Regents | Multilayer thin film nanocomposite membranes prepared by molecular layer-by-layer assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101185849B (en) * | 2007-09-11 | 2011-01-05 | 浙江工商大学 | Method for preparing separating layer which is multi-layer alternate composite polyamide/polyvinyl alcohol/polyamide compound film |
| CN101462025B (en) * | 2008-08-13 | 2011-09-21 | 贵阳时代汇通膜科技有限公司 | Double-layer polyamide surface layer composite reverse osmosis membrane and preparation method thereof |
| CN102210982B (en) * | 2011-06-10 | 2013-01-02 | 南京帝膜净水材料开发有限公司 | Method for preparing polyamide reverse osmosis composite membrane |
| CN102302901A (en) * | 2011-06-10 | 2012-01-04 | 南京帝膜净水材料开发有限公司 | Method for enhancing water flux of polyamide reverse-osmosis composite membrane |
| BR112014025143B1 (en) * | 2012-04-09 | 2021-04-20 | University Of Connecticut | thin film composite membrane structures and method for producing a thin film composite membrane structure |
| CN108452689A (en) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | Highly selective full alicyclic polyamide NF membrane of one kind and preparation method thereof |
| CN109157986B (en) * | 2018-10-16 | 2021-03-26 | 中国石油大学(华东) | Pervaporation composite membrane with step crosslinking degree and preparation method thereof |
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