CN103406027A - Hydrophilic composite film containing ether groups in surface layer - Google Patents
Hydrophilic composite film containing ether groups in surface layer Download PDFInfo
- Publication number
- CN103406027A CN103406027A CN2013102405065A CN201310240506A CN103406027A CN 103406027 A CN103406027 A CN 103406027A CN 2013102405065 A CN2013102405065 A CN 2013102405065A CN 201310240506 A CN201310240506 A CN 201310240506A CN 103406027 A CN103406027 A CN 103406027A
- Authority
- CN
- China
- Prior art keywords
- film
- composite film
- hydrophilic
- top layer
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a composite film containing polyether groups in a surface layer and a preparation method thereof, belonging to the technical field of preparation of film materials. According to the preparation method disclosed by the invention, an interfacial polymerization method is utilized, the polyether groups with good hydrophilicity are introduced into the surface layer of the composite film so as to prepare the surface layer containing the hydrophilic polyether groups of the composite film. The preparation method is characterized by coating a water solution of water-soluble linear diamine on the surface layer of a flat plate or a hollow fiber ultrafiltration film, air-drying, further coating an organic solvent solution containing acyl chloride or isocyanate groups, further performing interfacial polymerization, and forming a skin layer containing the hydrophilic groups on a support body of the ultrafiltration film so that the surface chemical structure of the film has a hydrophilic chain structure, the hydrophobic property of a base film is improved and the anti-pollution capability of the film material is enhanced. The composite film can be applied to removing organic and inorganic molecules and particles dissolved in water.
Description
Technical field
The present invention relates to hydrophilic composite film of a kind of top layer ether-containing group and preparation method thereof, particularly a kind of organic film of macromolecule for water treatment and chemical separation process.
Background technology
Method by interfacial polymerization applies one deck polyamide film on the surface of micro-filtration basement membrane, can obtain the less milipore filter in aperture, top layer and reverse osmosis membrane, is a kind of important composite membrane preparation method.Water monomer piperazine or diamine monomer are coated to membrane surface, after drying, will be dissolved in the oil phase monomer pyromellitic trimethylsilyl chloride of cyclohexane and monomer that the film surface has applied reacts, on the film surface, form the dense film of one deck, can be used for desalination and multiple water treatment field.
At present, the water diamine monomer that interfacial polymerization adopts mostly is linear fatty amine, ester cyclammonium or aromatic amine, and the oil phase monomer is the aroyl chloride with phenyl ring.Prepared composite membrane top layer hydrophily is poor, therefore easily pollutes.After Organic Pollution, be difficult to clean and recover, thereby reducing the life-span, improved use cost.For preventing and reducing film and pollute, in membrane material, introduce hydrophilic radical, reduce the surface water contact angle, be the main direction of studying of this class composite membrane exploitation.The oligomer of ethylene glycol (polyethylene glycol, polyethers) is very hydrophilic structure, is commonly used for the fields such as surfactant, to introducing the polyethylene glycol unit of suitable length in composite membrane, can improve the hydrophily on film surface.For improving the reactivity of interfacial polymerization, adopt the amino polyethylene glycol of end as the water monomer, in the high polymer cross-linked network on top layer, introduce hydrophilic radical, thereby improve the surface hydrophilic performance.Through the comparable basement membrane of the standby composite membrane functional layer water contact angle of this legal system, reduce by 10 ° to 15 °.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, prepare the hydrophilic composite film of a kind of top layer ether-containing group.
Technical scheme of the present invention is summarized as follows:
Hydrophilic composite film of a kind of top layer ether-containing group and preparation method thereof.
The hydrophilic composite film its preparation method of top layer of the present invention ether-containing group is interfacial polymerization.The monomer be soluble in the aqueous phase is the linear polyethylene glycol of double-end amino (I), and its general structure is:
(I) n is 1 to 25 integer
The amino polyethylene glycol n of end in general formula value is 1-25, and corresponding material is the end aminodiglycol, holds amino triethylene glycol, the amino tetraethylene glycol of end, amino penta ethylene glycol of end etc. until hold amino cetomacrogol 1000.
Being dissolved in the monomer of organic solvent in mutually is isophthalic three formyl chlorides (II) or triisocyanate (III
1, III
2), its structural formula is respectively:
The preparation method of the hydrophilic composite film of a kind of top layer ether-containing group is specific as follows:
Method one:
The linear polyethylene glycol of water monomer double-end amino (I), organic phase monomer isophthalic three formyl chlorides (II)
The linear polyethylene glycol of a certain amount of double-end amino (I) is dissolved in deionized water, is mixed with the aqueous solution of suitable concn, add a certain amount of triethylamine, be coated on membrane surface, dry.Isophthalic three formyl chlorides (II) are mixed with to certain density organic solution, are coated on above-mentioned surface of drying, under room temperature, after the reaction certain hour, film is placed in to deionized water and removes excessive monomer and accessory substance.
Reaction expression is:
Method two:
The linear polyethylene glycol of water monomer double-end amino (I), organic phase monomer triisocyanate (III
1Or III
2)
The linear polyethylene glycol of a certain amount of double-end amino (I) is dissolved in deionized water, is mixed with the aqueous solution of suitable concn, be coated on membrane surface, dry.By triisocyanate (III
1Or III
2) be mixed with certain density organic solution, be coated on above-mentioned surface of drying, at a certain temperature, after the reaction certain hour, film is placed in to deionized water and removes excessive monomer and accessory substance.
Reaction expression is:
The described organic solvent of preparation method one and method two is a kind of in n-hexane, cyclohexane, ether.
Basement membrane is micro-filtering flat plate film or the micro-filtration hollow-fibre membrane of a kind of material in polysulfones, polyether sulfone, polyvinyl chloride, polypropylene, polytetrafluoroethylene (PTFE) or Kynoar.
Using and hold amino polyethylene glycol as the water monomer, to prepare the water treatment composite membrane of top layer ether-containing group by interfacial polymerization, be conducive to improve the hydrophily on composite membrane top layer, reduce the service life that film pollutes, improves film.
Preparation Example
Embodiment 1
15g double-end amino diethylene glycol (DEG) is dissolved in the 50ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), add the 6g triethylamine, be coated on the polysulphone flat ultrafiltration membrane membrane surface, dry.5g isophthalic three formyl chlorides (II) are dissolved in the 10ml cyclohexane and are mixed with the solution that concentration is 5% (w/v), be coated on above-mentioned surface of drying, under room temperature standing 30 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Embodiment 2
6g double-end amino diethylene glycol (DEG) is dissolved in the 20ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), Polyethersulfone Hollow Fiber Plasma micro-filtration membrane outer surface be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By equal triisocyanate toluene (III
1) 2g is dissolved in the 10ml n-hexane and is mixed with the solution that concentration is 2% (w/v), and the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, is placed under 40 ℃ reaction 30 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Embodiment 3
9g double-end amino diethylene glycol (DEG) is dissolved in the 30ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), add the 6g triethylamine, be coated on the Pvc Ultrafiltration Membrane membrane surface, dry.By triphenylmethane triisocyanate (III
2) 7g is dissolved in the 10ml n-hexane and is mixed with the solution that concentration is 7% (w/v), is coated on above-mentioned surface of drying, and is placed at 30 ℃ of temperature reaction 20 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Embodiment 4
4.5g double-end amino triethylene glycol is dissolved in the 10ml deionized water, is mixed with the aqueous solution that concentration is 4.5% (w/v), add the 6g triethylamine, polypropylene hollow fiber micro-filtration membrane outer surface be impregnated in this aqueous solution to 10 minutes, taking-up is dried.5g isophthalic three formyl chlorides (II) are dissolved in the 10ml cyclohexane to be mixed with concentration be that concentration is the solution of 5% (w/v), the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, under room temperature, reaction is 20 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Embodiment 5
4.5g double-end amino triethylene glycol is dissolved in the 10ml deionized water, is mixed with the aqueous solution that concentration is 4.5% (w/v), add the 6g triethylamine, be coated on polytetrafluoroethylene (PTFE) milipore filter membrane surface, dry.By triphenylmethane triisocyanate (III
2) 2g is dissolved in the 10ml n-hexane that to be mixed with concentration be that concentration is the solution of 2% (w/v), is coated on above-mentioned surface of drying, under 35 ℃, react and after 10 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Embodiment 6
6g amino-end peg 200 is dissolved in the 10ml deionized water, is mixed with the aqueous solution that concentration is 6% (w/v), add the 6g triethylamine, polyvinylidene fluoride hollow fiber micro-filtration membrane outer surface be impregnated in this aqueous solution to 10 minutes, taking-up is dried.5g isophthalic three formyl chlorides (II) are dissolved in the 10ml cyclohexane to be mixed with concentration be that concentration is the solution of 5% (w/v), the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, under room temperature, reaction is 10 minutes, film is placed in to deionized water and removes excessive monomer and accessory substance.
Claims (5)
1. the hydrophilic composite film of a top layer ether-containing group, is characterized in that composite membrane by high polymer micro-filtration basement membrane and be coated on its lip-deep hydrophilic crosslinked polyamide composite bed forming.
2. according to the hydrophilic composite film of a kind of top layer ether-containing group of claim 1, it is characterized in that hydrophilic crosslinked polyamide composite bed by water-soluble diamine monomer and be dissolved in the monomer of organic solvent by membrane surface generation interfacial polymerization, preparing, water-soluble diamine monomer used is the linear polyethylene glycol of double-end amino (I), and its general structure is:
It is used that to be dissolved in the monomer of organic solvent in mutually be isophthalic three formyl chlorides (II) or triisocyanate (III
1, III
2), its structural formula is respectively:
3. according to the hydrophilic composite film of a kind of top layer ether-containing group of claim 1 or 2, it is characterized in that described organic solvent is a kind of in n-hexane, cyclohexane, ether.
4. according to the hydrophilic composite film of a kind of top layer ether-containing group of claim 1 or 2, it is characterized in that high polymer micro-filtration basement membrane is a kind of micro-filtering flat plate film prepared or the micro-filtration hollow-fibre membrane in polysulfones, polyether sulfone, polyvinyl chloride, polypropylene, polytetrafluoroethylene (PTFE) or Kynoar.
5. according to claim 1 or to the hydrophilic composite film of a kind of top layer ether-containing group of 4 any one, it is characterized in that the linear Aqueous Solutions of Polyethylene Glycol of double-end amino is coated on membrane surface, after drying, apply the organic solution of pyromellitic trimethylsilyl chloride, interfacial polymerization occurs in (method two) under normal temperature (method one) or heating condition, formation has ultrafiltration, nanofiltration or De Mo top layer, reverse osmosis membrane aperture, and its reaction expression is:
Method one:
Method two:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102405065A CN103406027A (en) | 2013-06-18 | 2013-06-18 | Hydrophilic composite film containing ether groups in surface layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102405065A CN103406027A (en) | 2013-06-18 | 2013-06-18 | Hydrophilic composite film containing ether groups in surface layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103406027A true CN103406027A (en) | 2013-11-27 |
Family
ID=49599096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102405065A Pending CN103406027A (en) | 2013-06-18 | 2013-06-18 | Hydrophilic composite film containing ether groups in surface layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103406027A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289117A (en) * | 2014-10-29 | 2015-01-21 | 天津工业大学 | Taurine modified hydrophilic complex film |
| CN104383822A (en) * | 2014-11-28 | 2015-03-04 | 天津工业大学 | Polyvinyl chloride hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN104587845A (en) * | 2015-01-26 | 2015-05-06 | 天津工业大学 | Composite membrane with hydrophilic separation layer |
| CN107469639A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | Composite nanometer filtering film and preparation method thereof |
| CN109265731A (en) * | 2018-08-28 | 2019-01-25 | 宁波联城住工科技有限公司 | Waterproof ventilated membrane and preparation method thereof |
| CN109337110A (en) * | 2018-08-28 | 2019-02-15 | 宁波联城住工科技有限公司 | Waterproof ventilated membrane and preparation method thereof |
| CN111330459A (en) * | 2020-03-25 | 2020-06-26 | 湖南沁森高科新材料有限公司 | Preparation method of high-flux composite reverse osmosis membrane and prepared reverse osmosis membrane |
| CN111420566A (en) * | 2020-03-03 | 2020-07-17 | 浙江工业大学 | Preparation method of fluorinated organic nanoparticle-containing polyamide solvent-resistant nanofiltration membrane |
| CN111437735A (en) * | 2020-04-02 | 2020-07-24 | 山东魔方新能源科技有限公司 | Water transmission film |
-
2013
- 2013-06-18 CN CN2013102405065A patent/CN103406027A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289117A (en) * | 2014-10-29 | 2015-01-21 | 天津工业大学 | Taurine modified hydrophilic complex film |
| CN104383822A (en) * | 2014-11-28 | 2015-03-04 | 天津工业大学 | Polyvinyl chloride hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN104383822B (en) * | 2014-11-28 | 2019-10-11 | 天津工业大学 | Polyvinyl chloride hollow fiber composite nanometer filtering film and preparation method thereof |
| CN104587845A (en) * | 2015-01-26 | 2015-05-06 | 天津工业大学 | Composite membrane with hydrophilic separation layer |
| CN107469639A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | Composite nanometer filtering film and preparation method thereof |
| CN109265731A (en) * | 2018-08-28 | 2019-01-25 | 宁波联城住工科技有限公司 | Waterproof ventilated membrane and preparation method thereof |
| CN109337110A (en) * | 2018-08-28 | 2019-02-15 | 宁波联城住工科技有限公司 | Waterproof ventilated membrane and preparation method thereof |
| CN109337110B (en) * | 2018-08-28 | 2021-07-30 | 广东联城住工装备信息科技有限公司 | Waterproof breathable film and preparation method thereof |
| CN109265731B (en) * | 2018-08-28 | 2021-07-30 | 广东联城住工装备信息科技有限公司 | Waterproof breathable film and preparation method thereof |
| CN111420566A (en) * | 2020-03-03 | 2020-07-17 | 浙江工业大学 | Preparation method of fluorinated organic nanoparticle-containing polyamide solvent-resistant nanofiltration membrane |
| CN111330459A (en) * | 2020-03-25 | 2020-06-26 | 湖南沁森高科新材料有限公司 | Preparation method of high-flux composite reverse osmosis membrane and prepared reverse osmosis membrane |
| CN111437735A (en) * | 2020-04-02 | 2020-07-24 | 山东魔方新能源科技有限公司 | Water transmission film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103406027A (en) | Hydrophilic composite film containing ether groups in surface layer | |
| Sun et al. | Novel mussel-inspired zwitterionic hydrophilic polymer to boost membrane water-treatment performance | |
| Li et al. | Nanofibrous hydrogel composite membranes with ultrafast transport performance for molecular separation in organic solvents | |
| Xu et al. | Nanocomposite organic solvent nanofiltration membranes by a highly-efficient mussel-inspired co-deposition strategy | |
| Lv et al. | Nanofiltration membranes via co-deposition of polydopamine/polyethylenimine followed by cross-linking | |
| US10442709B2 (en) | Selectively permeable graphene oxide membrane | |
| CN1289173C (en) | Acid stable membranes for nanofiltration | |
| Li et al. | Bioinspired fabrication of composite nanofiltration membrane based on the formation of DA/PEI layer followed by cross-linking | |
| KR101677800B1 (en) | Polyamide water-treatment membranes having properies of high durability and manufacturing method thereof | |
| US10427109B2 (en) | Composite semipermeable membrane and production thereof | |
| CN104190265A (en) | Low-pressure high-flux chlorine-containing polymer nanofiltration membrane with stable separation layer and preparation method thereof | |
| Bandehali et al. | A new type of [PEI-glycidyl POSS] nanofiltration membrane with enhanced separation and antifouling performance | |
| CN104190272A (en) | Anti-pollution composite reverse osmosis membrane and preparation method thereof | |
| CN104289117A (en) | Taurine modified hydrophilic complex film | |
| CN105327627B (en) | A kind of block sulfonated polyether aromatic phosphine blending/polyamide of polysulfones is combined the preparation method of forward osmosis membrane | |
| CN103285741A (en) | Preparation method of solvent-resistant compound nanofiltration membrane | |
| Zhu et al. | Fabrication of thin film composite nanofiltration membranes by coating water soluble disulfonated poly (arylene ether sulfone) and in situ crosslinking | |
| CN105498547A (en) | Preparation method of low-voltage positive charge hollow fiber nanofiltration membrane | |
| WO2011136029A1 (en) | Semi-permeable composite membrane | |
| Liu et al. | From ultrafiltration to nanofiltration: Nanofiltration membrane fabricated by a combined process of chemical crosslinking and thermal annealing | |
| CN101362055A (en) | Preparation method of positively charged hyperfiltration membrane and products thereof | |
| Xu et al. | Fabrication of polyimide-based hollow fiber membrane by synergetic covalent-crosslinking strategy for organic solvent nanofiltration (OSN) application | |
| CN101912741A (en) | Polyamide composite reverse osmosis membrane containing nano materials | |
| CN105983348A (en) | Preparation method for polyesteramide composite nanofiltration membrane | |
| CN112742222A (en) | Preparation method of PVC aliphatic zwitterionic ion exchange membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131127 |