CN103933870A - Composite film with poly-alkoxy functional layer - Google Patents
Composite film with poly-alkoxy functional layer Download PDFInfo
- Publication number
- CN103933870A CN103933870A CN201410192703.9A CN201410192703A CN103933870A CN 103933870 A CN103933870 A CN 103933870A CN 201410192703 A CN201410192703 A CN 201410192703A CN 103933870 A CN103933870 A CN 103933870A
- Authority
- CN
- China
- Prior art keywords
- poly
- functional layer
- alkoxyl
- composite film
- 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 with a poly-alkoxy functional layer, and belongs to the field of film material preparation. By the use of an interface polymerization method, a poly-alkoxy group is introduced into a composite film surface layer to prepare a composite film surface layer containing a hydrophilic alkoxy structure. The composite film with the poly-alkoxy functional layer is characterized in that one or a plurality of mixed aqueous solutions of water-soluble piperazine, m-phenylenediamine, p-phenylenediamine, polyvinyl alcohol, tetraethylenepentamine and polyethyleneimine and a poly-alkoxy derivative or a mixed organic solution subjected to interface polymerization and double-end active derivation generate condensation polymerization on the surface of a flat plate or hollow fiber ultra-filtration film; the hydrophilic alkoxy structure is introduced into the composite film surface to improve the hydrophilicity of the composite film surface and improve the pollution resistance capacity of the film material. The composite film can be applied to removal of organic or inorganic molecules dissolved in water.
Description
Technical field
The present invention relates to a kind of composite membrane with poly-alkoxyl functional layer, particularly a kind of macromolecule organic film for water treatment and chemical separation process.
Background technology
Method by interfacial polymerization applies one deck polyamide functional layer on the surface of micro-filtration support membrane, can obtain the less milipore filter in aperture, top layer or reverse osmosis membrane, is a kind of important composite membrane preparation method.Water-soluble monomer is coated to support membrane surface, after drying, makes to be dissolved in the monomer of organic solution and react with the diamine monomer applying, form fine and close functional layer on film surface, can be used for desalination and multiple water treatment field.
At present, the water-soluble monomer that interfacial polymerization adopts mostly is linear fatty amine, ester cyclammonium or aromatic amine, and the monomer that is dissolved in organic solution mostly is aroyl chloride.The composite membrane top layer hydrophily making is poor, easily pollutes, and is difficult to clean and recover after polluting, and has reduced service life, has improved cost.In membrane material, introducing hydrophilic radical, reduce surface water contact angle, can alleviate and prevent that film from polluting, is the main direction of studying of composite film material exploitation.In the hydrocarbyl chain of poly-alkoxyl derivatives, alternately there is oxygen element, increased the polarity of chain structure, improved the hydrophily of chain.The common derivative such as poly-ethoxy and propoxyl group is amphiphilic structure, can be used as nonionic surface active agent, thereby can improve the hydrophily on film surface to introducing poly-alkoxyl derivatives in composite membrane.For improving the reactivity of interfacial polymerization, the mixture of one or more in employing piperazine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), polyvinyl alcohol, tetraethylenepentamine and polymine is as water monomer, poly-alkoxyl derivatives and composition thereof is as oil phase monomer, generate hydrophily composite bed at support membrane surface aggregate, can improve film surface hydrophilic performance.Reduce by 10 ° to 15 ° through the comparable former support membrane of the standby composite membrane functional layer water contact angle of this legal system.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, prepare the hydrophilic composite film of a kind of top layer with poly-alkoxyl functional layer.Technical scheme of the present invention is summarized as follows:
A kind of composite membrane with poly-alkoxyl functional layer.
Composite membrane with poly-alkoxyl functional layer of the present invention, the preparation method of functional layer is the film that interfacial polymerization acquisition cross-linked structure occurs on support membrane surface by containing the poly-organic solution of alkoxyl derivatives and the aqueous solution of protonating agent.
Organic solution comprises one or more poly-alkoxyl derivatives (A), or itself and pyromellitic trimethylsilyl chloride or triisocyanate (B
1, B
2) in the solution of one or more mixing.The general structure of poly-alkoxyl derivatives is:
N is 1 to 25 integer
X is 1 to 5 integer
Wherein R
1and R
2be respectively the one in acid chloride group (COCl), NCO (NCO) or isothiocyanate group (NCS), R
1and R
2can be identical or different; R
3general formula is-C
mh
2m+1(m is 0 to 25 integer).
Triisocyanate (B
1, B
2) structural formula respectively:
The aqueous solution of protonating agent is one or more the aqueous solution of mixture comprising in piperazine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), polyvinyl alcohol, tetraethylenepentamine and polymine.
A kind of composite membrane with poly-alkoxyl functional layer is specific as follows:
Organic phase monomer gathers alkoxyl derivatives
By one or several protonating agent of a certain amount of list, and a certain amount of additive is dissolved in deionized water, is mixed with the aqueous solution of suitable concn, is coated on support membrane surface, dries.By one or more poly-alkoxyl derivatives (A) or with pyromellitic trimethylsilyl chloride or triisocyanate (B
1, B
2) in one or more mix, be mixed with certain density organic solution, be coated on above-mentioned surface of drying, under room temperature, react after certain hour and wash away excessive monomer and accessory substance by deionized water.
Organic solvent described in preparation method comprises the organic solvent of one or more mixing in n-hexane, cyclohexane, ether, ethyl acetate, toluene and dimethylbenzene.
Support membrane material comprises the micro-filtration membrane of one or more mixed materials in polysulfones, polyether sulfone, polyethers ether copper, polyacrylonitrile, polyimides, polyvinyl chloride, polypropylene, polytetrafluoroethylene (PTFE) or Kynoar.
Prepare the water treatment composite membrane of top layer containing hydrophilic radical with the organic solution of gathering alkoxyl derivatives or the preparation of its mixture 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 piperazine is dissolved in 500ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), add 6g triethylamine, be coated on polysulfones flat plate ultrafiltration support membrane surface, dry.By 2g compound (1) (n=1, x=0, m=0) be dissolved in and in 100ml cyclohexane, be mixed with the solution that concentration is 2% (w/v), be coated on above-mentioned surface of drying, under room temperature, leave standstill 30 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 2
6g m-phenylene diamine (MPD) is dissolved in 200ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), Polyethersulfone Hollow Fiber Plasma micro-filtration membrane be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By 5g compound (2) (n=1, x=0, m=1) and 1g pyromellitic trimethylsilyl chloride be dissolved in and in 100ml n-hexane, be mixed with the solution that concentration is 6% (w/v), the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, in 40 DEG C of reactions 30 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in deionized water stand-by.
Embodiment 3
9g p-phenylenediamine (PPD) is dissolved in 300ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), add 6g triethylamine, be coated on polyvinyl chloride ultrafiltration support membrane surface, dry.By 4g compound (3) (n=1, x=0, and 2g compound (4) (n=3 m=2), x=0, m=1) be dissolved in 100ml n-hexane and be mixed with the solution that concentration is 6% (w/v), be coated on above-mentioned surface of drying, in 30 DEG C of reactions 20 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 4
2g piperazine is dissolved in 100ml deionized water, is mixed with the aqueous solution that concentration is 2% (w/v), add 1g triethylamine, polysulfone hollow fibre micro-filtration membrane be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By 2g compound (1) (n=1, x=0, m=0) and 2g pyromellitic trimethylsilyl chloride be dissolved in and in 100ml n-hexane, be mixed with the solution that concentration is 4% (w/v), the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, normal-temperature reaction 20 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 5
1g tetraethylenepentamine and 1g piperazine are dissolved in 100ml deionized water, be mixed with the aqueous solution that concentration is 2% (w/v), add 1g triethylamine, suppressed aqueous phase solution is coated on to polytetrafluoroethylene (PTFE) ultrafiltration doughnut support membrane inner chamber by circulating pump, logical nitrogen is removed unnecessary water.By 0.05g compound (5) (n=1, x=0, m=0) and 0.1g pyromellitic trimethylsilyl chloride be dissolved in and in 100ml n-hexane, be mixed with the solution that concentration is 0.15% (w/v), by circulating pump, fuel tank is coated on to above-mentioned hollow fiber cavity of drying again, under 35 DEG C of conditions, react 10 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 6
3g polymine and 3g m-phenylene diamine (MPD) are dissolved in 100ml deionized water, are mixed with the aqueous solution that concentration is 6% (w/v), add 6g triethylamine, polyvinylidene fluoride hollow fiber micro-filtration membrane be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By 3g compound (6) (n=3, x=0, m=1) and 1g B
1be dissolved in 100ml cyclohexane, be mixed with the solution that concentration is 4% (w/v), the hollow-fibre membrane of above-mentioned processing be impregnated in to wherein 2 minutes, under room temperature, react 10 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 7
3g polyvinyl alcohol is dissolved in 100ml deionized water, is mixed with the aqueous solution that concentration is 3% (w/v), add 3g triethylamine, polyvinyl chloride micro-filtration membrane be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By 1g compound (7) (n=23, x=4, m=0) and 3g pyromellitic trimethylsilyl chloride be dissolved in 100ml cyclohexane, be mixed with the solution that concentration is 4% (w/v), the micro-filtration membrane of above-mentioned processing be impregnated in to wherein 2 minutes, at 70 DEG C, react 10 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
Embodiment 8
1.5g polyvinyl alcohol is dissolved in 100ml deionized water, is mixed with the aqueous solution that concentration is 1.5% (w/v), add 3g triethylamine, polyimides micro-filtration membrane be impregnated in this aqueous solution to 10 minutes, taking-up is dried.By 0.1g compound (8) (n=1, x=0, m=0) and 0.3g pyromellitic trimethylsilyl chloride be dissolved in 100ml cyclohexane, be mixed with the solution that concentration is 0.4% (w/v), the micro-filtration membrane of above-mentioned processing be impregnated in to wherein 2 minutes, under room temperature, react 10 minutes, wash away excessive monomer and accessory substance by deionized water, be soaked in isopropyl alcohol stand-by.
。
Claims (4)
1. with a composite membrane for poly-alkoxyl functional layer, it is characterized in that structure of composite membrane comprises high polymer micro-filtration basement membrane and compound its surperficial high polymer functional layer; High polymer micro-filtration basement membrane is the micro-filtration membrane of one or more mixed materials in polysulfones, polyether sulfone, polyethers ether copper, polyacrylonitrile, polyimides, polyvinyl chloride, polypropylene, polytetrafluoroethylene (PTFE) or Kynoar; High polymer functional layer is prepared in membrane surface polymerization by containing the poly-organic solution of alkoxyl derivatives and the aqueous solution of protonating agent.
2. according to a kind of composite membrane with poly-alkoxyl functional layer described in claims 1, it is characterized in that the organic solution that contains poly-alkoxyl derivatives comprises poly-alkoxyl derivatives, pyromellitic trimethylsilyl chloride and triisocyanate (B
1and B
2) in the organic solution of one or more mixed preparing.The general structure of poly-alkoxyl derivatives is (A):
N is 1 to 25 integer
X is 0 to 5 integer
Wherein R
1and R
2be respectively acid chloride group (
), one in NCO (NCO) or isothiocyanate group (NCS), R
1and R
2can be identical or different; R
3general formula is-C
mh
2m+1, m is 0 to 25 integer; Triisocyanate (B
1, B
2) structural formula respectively:
。
3. according to a kind of composite membrane with poly-alkoxyl functional layer described in claims 1, it is characterized in that the aqueous solution of protonating agent comprises the aqueous solution of one or more mixing in piperazine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), polyvinyl alcohol, tetraethylenepentamine and polymine.
4. according to a kind of composite membrane with poly-alkoxyl functional layer described in claims 1, the solvent that it is characterized in that preparing organic solution comprises one or more the mixture in n-hexane, cyclohexane, ether, ethyl acetate, toluene and dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410192703.9A CN103933870A (en) | 2014-05-07 | 2014-05-07 | Composite film with poly-alkoxy functional layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410192703.9A CN103933870A (en) | 2014-05-07 | 2014-05-07 | Composite film with poly-alkoxy functional layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103933870A true CN103933870A (en) | 2014-07-23 |
Family
ID=51181903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410192703.9A Pending CN103933870A (en) | 2014-05-07 | 2014-05-07 | Composite film with poly-alkoxy functional layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103933870A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295667A (en) * | 2017-01-13 | 2018-07-20 | 宁波大学 | A kind of positive osmosis composite membrane and preparation method thereof based on large aperture basement membrane |
| CN112604678A (en) * | 2020-12-17 | 2021-04-06 | 中国科学院过程工程研究所 | Photocatalytic composite particle and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0873780A1 (en) * | 1997-04-24 | 1998-10-28 | Eastman Kodak Company | Novel separative membrane and method for using this membrane |
| JP2001079374A (en) * | 1999-09-17 | 2001-03-27 | Saehan Ind Inc | Polyamide reverse osmosis combined membrane and its production |
| DE10207411A1 (en) * | 2002-02-21 | 2003-09-04 | Daimler Chrysler Ag | Preparation of composite membranes from branched polyalkoxysilane, useful in production of polymer electrolyte membrane fuel cells, comprises mixing branched polyalkoxysilane and organic proton conductor |
| US20100152077A1 (en) * | 2008-12-17 | 2010-06-17 | Cerion Technology Inc. | Process for Solvent Shifting a Nanoparticle Dispersion |
| CN102258949A (en) * | 2011-06-10 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for adjusting interfacial structure of polyamide reverse osmosis compound membrane |
| WO2013006288A1 (en) * | 2011-07-01 | 2013-01-10 | International Business Machines Corporation | Thin film composite membranes embedded with molecular cage compounds |
| KR101317640B1 (en) * | 2010-12-16 | 2013-10-15 | 웅진케미칼 주식회사 | Forward osmosis membrane for removing salt from sea water and manufacturing method threrof |
-
2014
- 2014-05-07 CN CN201410192703.9A patent/CN103933870A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0873780A1 (en) * | 1997-04-24 | 1998-10-28 | Eastman Kodak Company | Novel separative membrane and method for using this membrane |
| JP2001079374A (en) * | 1999-09-17 | 2001-03-27 | Saehan Ind Inc | Polyamide reverse osmosis combined membrane and its production |
| DE10207411A1 (en) * | 2002-02-21 | 2003-09-04 | Daimler Chrysler Ag | Preparation of composite membranes from branched polyalkoxysilane, useful in production of polymer electrolyte membrane fuel cells, comprises mixing branched polyalkoxysilane and organic proton conductor |
| US20100152077A1 (en) * | 2008-12-17 | 2010-06-17 | Cerion Technology Inc. | Process for Solvent Shifting a Nanoparticle Dispersion |
| KR101317640B1 (en) * | 2010-12-16 | 2013-10-15 | 웅진케미칼 주식회사 | Forward osmosis membrane for removing salt from sea water and manufacturing method threrof |
| CN102258949A (en) * | 2011-06-10 | 2011-11-30 | 南京帝膜净水材料开发有限公司 | Method for adjusting interfacial structure of polyamide reverse osmosis compound membrane |
| WO2013006288A1 (en) * | 2011-07-01 | 2013-01-10 | International Business Machines Corporation | Thin film composite membranes embedded with molecular cage compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295667A (en) * | 2017-01-13 | 2018-07-20 | 宁波大学 | A kind of positive osmosis composite membrane and preparation method thereof based on large aperture basement membrane |
| CN112604678A (en) * | 2020-12-17 | 2021-04-06 | 中国科学院过程工程研究所 | Photocatalytic composite particle and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108435002B (en) | Preparation method of functionalized carbon quantum dot modified composite nanofiltration membrane | |
| Qiu et al. | Synthesis of high flux forward osmosis membranes by chemically crosslinked layer-by-layer polyelectrolytes | |
| CN103406027A (en) | Hydrophilic composite film containing ether groups in surface layer | |
| CN104209022A (en) | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof | |
| CN109351190B (en) | Cross-linked fluorine-containing polyamide composite solvent-resistant nanofiltration membrane, preparation method and application thereof | |
| CN104289117A (en) | Taurine modified hydrophilic complex film | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| KR102293090B1 (en) | Composite semipermeable membrane | |
| CN112473372A (en) | Conductive forward osmosis membrane and preparation method thereof | |
| CN105327627B (en) | A kind of block sulfonated polyether aromatic phosphine blending/polyamide of polysulfones is combined the preparation method of forward osmosis membrane | |
| CN105817146B (en) | A kind of CNT is modified the preparation method of NF membrane | |
| CN105268333A (en) | Preparation method of polyvinylidene fluoride/graphene oxide composite ultrafiltration membrane | |
| KR20140073300A (en) | Separation membrane, and water treatment device using said separation membrane | |
| WO2013151248A1 (en) | Silicone polymer asymmetric composite membrane and production method therefor | |
| KR20130131260A (en) | Reverse osmosis membrane having property of high initial flux | |
| CN104923086A (en) | Semi-aromatic polyamide compound reverse osmosis membrane and preparation method thereof | |
| CN101362055A (en) | Preparation method of positively charged hyperfiltration membrane and products thereof | |
| CN109224888A (en) | A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application | |
| CN101077798A (en) | Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof | |
| CN113842783B (en) | Acid-resistant high-flux polyarylether composite nanofiltration membrane, and preparation method and application thereof | |
| CN103933870A (en) | Composite film with poly-alkoxy functional layer | |
| RU2717512C2 (en) | Chlorine-resistant hydrophilic filtration membranes based on polyaniline | |
| KR20140005489A (en) | High flux reverse osmosis membrane comprising xanthene compound and manufacturing method thereof | |
| CN109865501B (en) | Preparation method of composite membrane for adsorbing and removing organic dye in water | |
| CN112058094A (en) | Loose nanofiltration membrane and preparation method thereof |
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: 20140723 |