CN110527093A - A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained - Google Patents

A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained Download PDF

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CN110527093A
CN110527093A CN201910755001.XA CN201910755001A CN110527093A CN 110527093 A CN110527093 A CN 110527093A CN 201910755001 A CN201910755001 A CN 201910755001A CN 110527093 A CN110527093 A CN 110527093A
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sulfonation
polymer
polyether sulfone
amino
reverse osmosis
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张敏
郑泽军
王舜
金辉乐
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Wenzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to polymeric material fields, and in particular to a kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained.The present invention has synthesized the sulfonated polyether sulfone (SPES-NH of amino-contained water-soluble, with stiff backbone2) high molecular material, and carried out interfacial polymerization with it and m-phenylene diamine (MPD) (MPDA) mixing with trimesoyl chloride (TMC) and prepared reverse osmosis composite membrane.Sulfonated polyether sulfone-polyamide the composite layer being crosslinked is formed on polysulfone porous counterdie surface by the interface polymerization reaction of amine and polynary acyl chlorides, so that the sulfonic group of strongly hydrophilic is introduced active layer, improves water flux.Moreover, introducing the SPES-NH with the fragrant main chain of rigidity in polyamide cross-linking system for the polymer of many flexible fatty main chains2Will not salt cutoff performance on composite membrane generate apparent influence.

Description

It is the sulfonation Cardo polyether sulfone polymer and synthetic method of a kind of amino-contained, reverse osmosis multiple Close film
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of sulfonation Cardo polyether sulfone polymer of amino-contained and Synthetic method, reverse osmosis composite membrane.
Background technique
In various isolation technics, reverse osmosis technology with it without phase-change, low energy consumption；High efficiency, high reliability；Easily behaviour Make, maintenance；The advantages that inexpensive, be widely used in seawater and brackish water desalination and softening, drinking water and medicinal water preparation, Ultrapure water preparation, industry and sanitary sewage disposal etc..Reverse osmosis membrane is the core component of reverse osmosis technology, therefore is also able to Quickly development, the exploration of exploitation and filming technology including membrane material.It is reverse osmosis multiple for asymmetric reverse osmosis membrane The advantages that film is easily-controllable with its better separating property and resistance to swelling energy, structure-controllable, membrane material is abundant is closed, people are increasingly becoming The focus and emphasis of research.Reverse osmosis composite membrane is generated by porous support layer and by interfacial polymerization techniques on supporting layer Ultra-thin, fine and close isolating active layer two parts composition.Wherein, porous support layer mainly plays supporting function, up to the present most Be suitable for reverse osmosis composite membrane supporting layer is the porous bottom being prepared by bisphenol-a polysulfone (PSF) material by L-S method Film；And fine and close composite layer is the part of composite membrane most critical, it plays conclusive effect to the separating property of film, therefore, The exploitation of compound film material is particularly important.
Up to the present, the surface-active layer material haveing excellent performance is usually some linear or cross-linked polymers, and some is Reverse osmosis technology is used for by successfully exploitation, specifically includes that sulfonated poly (phenylene oxide) (SPPO), polyamide, polyureas, polyureas amide and polyethers The Film laminateds such as amide layer (TFC) material.Wherein, the development of aromatic polyamides reverse osmosis composite membrane has become entire membrane science skill The breach in art field and focus.But the low problem of reverse osmosis composite membrane water flux limits it extensively to a certain extent Using and development.In order to improve the water flux of composite membrane, there is a large amount of related work carrying out, mainly there are following three sides Face:
1, it designs, synthesize new membrane material and be used to prepare reverse osmosis composite membrane；
2, change filming technology appropriate；
3, by carrying out physics and chemical modification to composite membrane active layer material.
The chemical modification of active layer is most common way, main by introducing hydrophilic radical, such as sulfonic group and carboxylic Acidic group either introduces various polymer containing flexible main chain or big side group, for example, introducing in crosslinked polyamide system The polymer of polyvinyl alcohol, polyvinyl phenol and the hydroxyls such as polyethylene aniline (PAS) and its copolymer, amido hydrophilic radical, For example polyethylene aniline-polyvinyl alcohol hydrophilic copolymers (PmAS) are introduced in active layer, to improve water flux.But While improving the water flux of film, the sharp fall also retained along with salt, this is primarily due to polyethylene based polymers Flexible main chain introducing be unfavorable for salt retention raising.
CN201810378598.6 provides preparation method, reverse osmosis membrane and the reverse osmosis membrane system of a kind of high-flux reverse osmosis membrane Standby system, including following preparation step: quantitatively coating basement membrane liquid A on supporting layer, forms base membrane layer；It is quantitatively applied on base membrane layer Polymer fluid B is covered, with basement membrane layers of polymer, polymerization reaction occurs, forms composite layer, cleaning and oxidation processes are carried out to composite layer.It should Reverse osmosis membrane water flux is up to 47.31L/m2.h, salt rejection rate 93.4%.
CN201810506390.8 provides a kind of preparation method of high-flux composite reverse osmosis membrane, include the following steps: by Open support basement membrane is contacted with the aqueous phase solution of the compound containing two or more amidos；2) it will be soaked by aqueous phase solution The extra aqueous phase solution of open support membrane surface after profit removes；3) by step 2) treated open support basement membrane with contain There are two or more than two acid chloride group compound oil-phase solution contact；4) in the diaphragm backside coating by step 3) processing The aqueous solution of certain density high boiling hydrophilic organic molecule；5) complex reverse osmosis membrane is made in heat treatment.This is reverse osmosis Membrane flux is 20-28L/m2.h, salt rejection rate 97%-98%.
Prepared reverse osmosis membrane effect is general in the prior art.
Summary of the invention
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of sulfonation of amino-contained Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane.
The technical solution used in the present invention is as follows: a kind of sulfonation Cardo polyether sulfone polymer of amino-contained, chemical formula is such as Under:
The synthetic method of the sulfonation Cardo polyether sulfone polymer of above-mentioned amino-contained, synthetic route are as follows:
Detailed process is as follows: it is bis- that N- (2- amido) ethyl -3,3 '-being added in the dry reaction vessel equipped with water segregator (4- hydroxy phenyl) phthalimidine, sulfonation dichloro diphenyl sulfone, anhydrous K2CO3, toluene and N-Methyl pyrrolidone, be vigorously stirred It is warming up to 140-150 DEG C, toluene band is evaporated off toluene, is then slowly warming up to 160-180 DEG C after water 6 hours, and the reaction was continued extremely obtains To colorless transparent viscous liquid, it is cooled to room temperature and is diluted with suitable NMP, solution is filtered to remove a large amount of inorganic salts, side Filtrate is poured slowly into ethanol solution by stirring side, obtains white polymer and dissolves polymer again with NMP, so after dry It being precipitated in alcohol solvent afterwards, crystallization of the dissolution and precipitation is multiple repeatedly, and Soxhlet extraction finally is carried out to polymer with ethyl alcohol and is purified, 80 DEG C Lower vacuum drying.
The reverse osmosis composite membrane of the sulfonation Cardo polyether sulfone polymer preparation of above-mentioned amino-contained.
The reverse osmosis composite membrane is the sulfonation Cardo polyether sulfone polymer and isophthalic two of amino-contained described in claim 1 Amine mixing carries out interfacial polymerization with trimesoyl chloride and is prepared.
Beneficial effects of the present invention are as follows: the present invention has synthesized the sulfonation of amino-contained water-soluble, with stiff backbone Polyether sulfone (SPES-NH2) high molecular material, and boundary is carried out with trimesoyl chloride (TMC) with it and m-phenylene diamine (MPD) (MPDA) mixing Face polymerization prepares reverse osmosis composite membrane.It is formed on polysulfone porous counterdie surface by the interface polymerization reaction of amine and polynary acyl chlorides Sulfonated polyether sulfone-polyamide composite layer of crosslinking improves water flux so that the sulfonic group of strongly hydrophilic is introduced active layer. Moreover, introducing in polyamide cross-linking system has rigidity fragrance main for the polymer of many flexible fatty main chains The SPES-NH of chain2Will not salt cutoff performance on composite membrane generate apparent influence.Simultaneously as active layer material and support All contain similar polyether sulfone structure in layer material, there is therebetween stronger interaction force, therefore make membrane module in reality Secondary pollution problem when border is run is improved.
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 Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to These attached drawings obtain other attached drawings and still fall within scope of the invention.
The chemical formula of the sulfonation Cardo polyether sulfone polymer of Fig. 1 amino-contained；
Fig. 2 is monomer PPH-NH2Infrared spectrum；
Fig. 3 is monomer PPH-NH2Nuclear magnetic resonance spectroscopy；
Fig. 4 is polymer SPES-NH2's1H NMR spectra；
Fig. 5 is polymer SPES-NH2FT-IR spectrogram；
Fig. 6 is polymer SPES-NH2TGA curve.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing Step ground detailed description.
The synthesis of the sulfonation Cardo polyether sulfone polymer of 1 amino-contained of embodiment:
Bis- (4- hydroxy phenyl) phthalimidine (PPH-NH of 1.N- (2- amido) ethyl -3,3 ' -2) synthesis:
Monomer PPH-NH2It synthesizes according to the following steps: in a 1000ml equipped with mechanical stirring, condenser pipe and nitrogen inlet Flask with three necks,round bottom in, sequentially add the ethylenediamine of phenolphthalein (PPH) and 200ml of 50.9 grams (0.16mol), solution shows Darkviolet.Reaction 24 hours is vigorously stirred at 120 DEG C, color becomes faint yellow.Most of unreacted ethylenediamine is distilled off Afterwards, it is cooled to room temperature, is while stirring poured slowly into solution in the ice water mixed liquor of 1000ml hydrochloric acid acidification, it is heavy to generate white It forms sediment.White solid is obtained by filtration, and is repeatedly washed with ice water.White solid is dissolved in hot water, filter, liquid cooling to be filtered but after, Under agitation, neutral generation white precipitate, filtering, ice water washing, crude product slowly are neutralized to 10% KOH solution It is recrystallized with the mixed solvent of second alcohol and water, white crystal is obtained, in 80℃Lower vacuum drying is for 24 hours.Yield: 80%.1H NMR (DMSO-d6) δ (ppm): 1.87~1.91 (2H, m, CH2).FTIR(KBr):1639cm-1(νC=O).Elemental Analysis (%) for C22H20N2O3(molecular weight,360.2)calculated:C,73.32；H,5.59；N, 7.77；Found:C,73.45；H,5.56；N,7.60.
Fig. 2 and 3 is monomer PPH-NH respectively2Infrared spectrum and nuclear magnetic resonance spectroscopy.From infrared spectroscopy, nuclear magnetic resonance wave It composes and Elemental analysis data may determine that, products therefrom PPH-NH2。
2. the preparation of sulfonation dichloro diphenyl sulfone (SDCDPS)
[1] sulfonation dichloro diphenyl sulfone (SDCDPS) synthesis reference literature report method (1.M.J.Sumner, W.L.Harrison,R.M.Weyers,Y.S.Kim,J.E.McGrath,J.S.Riffle,A.Brink,M.H.Brink, J.Membr.Sci.283(2006)393；2.F.Wang,M.Hickner,Y.S.Kim,T.A.Zawodzinski, J.E.McGrath,Direct polymerization of sulfonated poly(arylene ether sulfone) random(statistical)copolymers:candidates for new proton exchange membranes, J.membr.Sci.197(2002)231-242.).Yield:75%.1H NMR(DMSO-d6,ppm):δ8.36(s,1H), 7.87~7.91 (d, 1H), 7.68~7.71 (d, 1H) .Elemental analysis (%) for C12H6Cl2Na2O8S3 (molecular weight,491.25)calculated:C,29.34；H,1.23；Cl,14.43；Na,9.36；S,19.58； Found:C,28.78；H,1.30；Cl,14.03；Na,9.66；S,18.98.
3. the synthesis of polymer: polymer is synthesized by PPH-NH2With the contracting of sulfonation dichloro diphenyl sulfone (SDCDPS) What poly- reaction was realized, synthesis step is as follows: dry mechanical stirring, water segregator, condenser pipe and import and export of nitrogen being housed at one In the 100ml flask with three necks,round bottom of pipe, SDCDPS (4.9125 grams, 0.01mol), PPH-NH are sequentially added2(3.6041g, 0.01mol), anhydrous K2CO3The N-Methyl pyrrolidone (NMP) of (3.04g, 0.022mol), 10ml toluene and 12ml.Acutely stir It mixes and is warming up to 145 DEG C, toluene band is evaporated off toluene, is then slowly warming up to 170 DEG C, the reaction was continued 8 hours, obtains after water 6 hours Colorless transparent viscous liquid is cooled to room temperature and is diluted with suitable NMP, and solution is filtered to remove a large amount of inorganic salts.While stirring It mixes side filtrate is poured slowly into ethanol solution, obtains white polymer.After drying, polymer is dissolved again with NMP, then It being precipitated in alcohol solvent, crystallization of the dissolution and precipitation is multiple repeatedly, Soxhlet extraction finally is carried out 48 hours to polymer with ethyl alcohol, 80 DEG C Lower vacuum drying 12 hours.Yield: 93%.FTIR (KBr): 1672cm-1(νC=O), 3360~3450cm-1(νN-H),1249cm-1 (νO=S=O).
Chemical formula is as follows:
Fig. 4 and Fig. 5 is polymer SPES-NH respectively2's1H NMR and FT-IR spectrum.It can see from Fig. 5, 1249cm-1,1026cm-1,690cm-1It is the characteristic absorption peak of sulfonic acid group (O=S=O)；The absorption peak of typical phthalimide There are three, respectively appear in 1705cm-1(νsym), C=O 1659cm-1(νasym) and 1368cm C=O-1(νC-Nimide).Poly- It closes and occurs SDCDPS and PPH-NH in the infrared spectroscopy of object simultaneously2Partial Feature absorption peak, illustrate that two kinds of monomers have been sent out Raw polymerization reaction generates expected polymer SPES-NH2。
4. polymer (SPES-NH2) dissolubility: SPES-NH2It can be good at being dissolved in the non-matter such as NMP, DMSO, DMAC In sub- polar solvent, but alcohols and halogenated hydrocarbon solvent are not dissolved in.Simultaneously as introducing the sulfonic acid group of strongly hydrophilic, make Polymer shows biggish solubility in water, and this point be exactly carry out that interfacial polymerization prepares reverse osmosis composite membrane must Want condition.
5. polymer (SPES-NH2) hot property: as shown in fig. 6, the thermal weight loss process of polymer and general sulfonation are poly- It is similar to close object, mainly divides three phases:
1) the first zero-g period was between 100 DEG C~200 DEG C, mainly caused by the evaporation of hydrone.Due to polymerization Contain the sodium group of a large amount of strongly hydrophilics in object, easily by some relatively weak active force water suctions, when slightly heated When, this partial moisture is easy to lose, and causes the weightlessness of first stage.
2) thermal weight loss of second stage about starts to occur at 290 DEG C, and the weightlessness in this stage is mainly due to sodium sulfonate Pyrolytic.The weightlessness in two above stage is the essential characteristic of sulfonated polymer thermogravimetric curve, that is to say, that Ji Husuo There is the thermal weight loss process of sulfonated polymer that will have more dehydration and sulfonic acid group two stages of decomposition than non-sulfonated polymer.
3) weightlessness of phase III begins at approximately 420 DEG C, aliphatic alkyl segment and main chain mainly in polymer Degradation.
The preparation of 2 reverse osmosis composite membrane of embodiment:
The preparation of reverse osmosis composite membrane includes two parts: the preparation of counterdie and active layer.Open support as counterdie Layer material is polysulfones (PSF), it preparation method biliographic data (A.L.Ahmad, B.S.Ooi, J.P.Choudhury, Preparation and characterization of co-polyamide thin film composite membrane from piperazine and 3,5-diaminobenzoic acid,Desalination 158(2003)101-108.)
The active layer for closing film can be prepared by the interfacial polymerization method on counterdie, and steps are as follows for specific experiment:
1) aqueous phase solution (A liquid): including the SPES-NH of 1% (w/v) concentration in aqueous solution2And MPDA, triethylamine (TEA) With dodecyl sodium sulfate (DDS), and with camphorsulfonic acid adjust solution pH value, filter it is spare.
2) organic phase solution (B liquid): B liquid is certain density TMC cyclohexane solution, is filtered spare.
3) interfacial polymerization: A liquid is poured on counterdie, after horizontal immersion 2 hours, goes remaining solution, room temperature on counterdie Lower placement, until the liquid that nothing obviously flows on counterdie.Then upper B liquid is crosslinked by acyl chlorides and amido, when standing one section Between after, outwell remaining solution.
4) post-process: being heat-treated 10 minutes at 70 DEG C keeps polymerization reaction more thorough.Then, composite membrane is spent respectively Ionized water and NaHSO3Solution cleaning, obtains reverse osmosis composite membrane after being heat-treated again, coats glycerol cryo-conservation.
Wherein, MPDA/SPES-NH2=2, TMC concentration 1%, (w/v), the interfacial polymerization time is 4 minutes, and polymer is glutinous Degree is 1.13dl/g.
The salt rejection rate of obtained composite membrane is 97.3%, water flux 51.2L/m2.h。
With the MPDA/TMC (R of interfacial polymerization preparationj=99.0%, Flux=37.4L/m2.h)(L.Li,S.Zhang, X.Zhang,G.Zheng,Polyamide thin film composite membranes prepared from 3,4′,5- biphenyl triacyl chloride,3,3′,5,5′-biphenyl tetraacyl chloride and m- Phenylenediamine, J.Membr.Sci.289 (2007) 258-267.]) performance of reverse osmosis composite membrane compares, although TMC/MPDA/SPES-NH2The salt rejection rate of composite membrane decreases, but water flux is but from original 37.4L/m2.h it is increased to 51.2L/m2.h。
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.

Claims (5)

1. a kind of sulfonation Cardo polyether sulfone polymer of amino-contained, it is characterised in that chemical formula is as follows:
2. the synthetic method of the sulfonation Cardo polyether sulfone polymer of amino-contained described in claim 1, it is characterised in that synthesis road Line is as follows:
3. the synthetic method of the sulfonation Cardo polyether sulfone polymer of amino-contained according to claim 2, it is characterised in that tool Body process is as follows: bis- (the 4- hydroxy benzenes of N- (2- amido) ethyl -3,3 '-being added in the dry reaction vessel equipped with water segregator Base) phthalimidine, sulfonation dichloro diphenyl sulfone, anhydrous K2CO3, toluene and N-Methyl pyrrolidone, be vigorously stirred and be warming up to 140- 150 DEG C, toluene band is evaporated off toluene, is then slowly warming up to 160-180 DEG C, it is colorless and transparent to obtaining that the reaction was continued after water 6 hours Viscous liquid is cooled to room temperature and is diluted with suitable NMP, and solution is filtered to remove a large amount of inorganic salts, while stirring will filter Liquid is poured slowly into ethanol solution, is obtained white polymer and is dissolved polymer again with NMP after dry, then molten in ethyl alcohol It is precipitated in agent, crystallization of the dissolution and precipitation is multiple repeatedly, finally carries out Soxhlet extraction to polymer with ethyl alcohol and purifies, is dried in vacuo at 80 DEG C.
4. reverse osmosis composite membrane prepared by the sulfonation Cardo polyether sulfone polymer of amino-contained described in claim 1.
5. reverse osmosis composite membrane prepared by the sulfonation Cardo polyether sulfone polymer of amino-contained according to claim 4, special Sign is: the reverse osmosis composite membrane is the sulfonation Cardo polyether sulfone polymer and m-phenylene diamine (MPD) of amino-contained described in claim 1 Mixing carries out interfacial polymerization with trimesoyl chloride and is prepared.
CN201910755001.XA 2019-08-15 2019-08-15 A kind of the sulfonation Cardo polyether sulfone polymer and synthetic method, reverse osmosis composite membrane of amino-contained Pending CN110527093A (en)

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CN111303427A (en) * 2020-05-14 2020-06-19 富海(东营)新材料科技有限公司 Industrial purification process of high-purity low-ash polysulfone resin
CN111359457A (en) * 2020-04-02 2020-07-03 南京清研高分子新材料有限公司 Sulfonated polyarylethersulfone nanofiltration membrane and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111359457A (en) * 2020-04-02 2020-07-03 南京清研高分子新材料有限公司 Sulfonated polyarylethersulfone nanofiltration membrane and preparation method thereof
CN111359457B (en) * 2020-04-02 2021-12-14 南京清研高分子新材料有限公司 Sulfonated polyarylethersulfone nanofiltration membrane and preparation method thereof
CN111303427A (en) * 2020-05-14 2020-06-19 富海(东营)新材料科技有限公司 Industrial purification process of high-purity low-ash polysulfone resin
CN111303427B (en) * 2020-05-14 2020-09-04 富海(东营)新材料科技有限公司 Industrial purification process of high-purity low-ash polysulfone resin

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