阅读说明：本技术 一种氟化聚酰胺纳滤膜及其制备方法 (A kind of fluorination polyamide nanofiltration membrane and preparation method thereof ) 是由 邢卫红 钱杨伟 吴宏描 孙世鹏 于 2019-09-12 设计创作，主要内容包括：本发明涉及一种氟化聚酰胺纳滤膜及其制备方法。氟化聚酰胺纳滤膜是指由含氟聚乙烯亚胺为交联剂制备得到的一种分离膜,其制备步骤如下：将一种超滤基膜固定于界面聚合的装置中,加入含氟聚乙烯亚胺的水相溶液浸渍,去除表面多余水后,与多元酰氯或多元异氰酸酯单体的有机相溶液接触进行界面聚合反应,聚合反应后再进行热处理,最后用去离子水清洗得到所述氟化聚酰胺纳滤膜。该膜材料具有一二价离子分离功能,且抗污染性能好,适用于水质软化、废水处理等领域。(The present invention relates to a kind of fluorination polyamide nanofiltration membranes and preparation method thereof.Fluorination polyamide nanofiltration membrane refers to a kind of seperation film being prepared by fluorine-containing polyethyleneimine for crosslinking agent, its preparation step is as follows: a kind of ultrafiltration membranes are fixed in the device of interfacial polymerization, the aqueous phase solution dipping of fluorine-containing polyethyleneimine is added, after removing excess surface water, it is contacted with the organic phase solution of polynary acyl chlorides or multicomponent isocyanate monomer and carries out interface polymerization reaction, it is heat-treated again after polymerization reaction, is finally cleaned to obtain the fluorination polyamide nanofiltration membrane with deionized water.The membrane material has a divalent ion separation function, and antifouling property is good, is suitable for the fields such as water demineralization, wastewater treatment.)

1. a kind of preparation method of novel fluorination polyamide nanofiltration membrane, which comprises the following steps: by a kind of ultrafiltration base Film is fixed in interfacial polymerization device, and the aqueous phase solution dipping of fluorine-containing polyethyleneimine is added, after removing excess surface water, is added Interface polymerization reaction is carried out containing the organic phase solution of polynary acyl chlorides or multicomponent isocyanate monomer, then is heat-treated, is finally used Deionized water cleans to obtain the fluorination compound nanometer filtering membrane of polyamide.

2. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that a kind of ultrafiltration Basement membrane is flat plate ultrafiltration membrane or hollow fiber ultrafiltration membrane.

3. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that a kind of ultrafiltration Basal lamina material is polysulfones, polyether sulfone, one of polyacrylonitrile, nylon66 fiber, Kynoar, polytetrafluoroethylene (PTFE), polylactic acid.

4. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that described one kind is super The molecular cut off for filtering basement membrane is 4000~80000Da.

5. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that related polynary acyl Chlorine includes that the concentration of binary or ternary acyl chlorides or multicomponent isocyanate in organic phase is 0.01 ~ 5.0 wt%, the organic phase Solvent is hexane, heptane, octane, nonane, decane, benzene, toluene, dimethylbenzene, methanol, ethyl alcohol, methylene chloride, in ethyl acetate It is one or more of.

6. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that the aqueous phase solution In fluorine-containing polyethyleneimine amine concentration be 0.01 ~ 5.0 wt%, add carbonate in aqueous phase solution, metal hydroxides does alkali, adds Dosage concentration is 0 ~ 1 wt%.

7. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that aqueous phase solution dipping Afterwards, the minimizing technology of extra moisture film include drain, scraper strikes off, inert gas purge；It is anti-that organic phase solution interfacial polymerization is added It is 5 seconds ~ 10 minutes between seasonable, after interface polymerization reaction, is heat-treated, 50-80 DEG C of temperature range, handles the time 1-15 minutes.

8. the preparation method of novel fluorination polyamide nanofiltration membrane as described in claim 1, which is characterized in that fluorine-containing polyethyleneimine The general structure of amine are as follows:

Wherein dotted line represents N atom connection branch or hydrogen, Z be sulfonyl () or acyl group ()；R is perfluoroalkyl, General formula C_nF_2n+1, n 1-18.

Technical field

The present invention relates to new material and technical field of membrane separation, in particular to a kind of novel fluorination polyamide nanofiltration membrane and its Preparation method.

Background technique

Nanofiltration is a kind of novel membrane separation technique risen the eighties, and operating pressure is lower, and separation accuracy is between super Between filtering and being reverse osmosis, there is more application in fields such as water demineralization, wastewater treatment, pharmaceutical industry and food service industrys (J.E. Cadotte et al,Acs Symposium, 1981,1, 305-326;W.J. Lau, A.F. Ismail, Desalination, 2009,245 , 321-348;K. Nath, H.K. Dave, T.M. Patel, Trends Food Sci. Technol, ,2018, 73,12-24;S.P. Sun, T.A. Hatton, T.S. Chung, Environ Sci Technol ,2011,45 4003-4009.)。

Organic nanofiltration membrane with good application prospect because of the low and preferable designability of preparation cost, receive by the machine of common are Filter filter membrane have polyamide-based, polysulfones, cellulose acetate etc., often by interfacial polymerization, phase inversion, surface cladding process, The preparation of the methods of surface grafting method.Wherein interfacial polymerization is using technology the most mature, it utilizes polyamine, alcohol or phenols It is reacted at immiscible two-phase interface with polynary acyl chlorides and to form polymer foil and reach specific separating property, business polyamides Amine composite membrane is exactly to prepare gained in this way.However, the commercial generally existing fouling membrane of organic nanofiltration membrane (A.S. Al- Amoudi, Desalination, 2010,259 1-10.), solvent resistant, poor resistance to acid and alkali the problems such as, greatly reduce organic The separating property of nanofiltration membrane influences its service life.

Fluorine material has excellent thermal stability, chemical stability and low because of the special physics of fluorine atom and chemical property The characteristics such as surface energy, (X. Zhao, Y. Su, W. Chen, J. Peng, Z. in terms of special material and antipollution material Jiang, J. Membr. Sci., 2012,415,824-834.) there is more application.How fluoro-containing group to be introduced into and is received It is current problem to be solved to improve the antifouling property and service life of nanofiltration membrane in filter membrane.

Summary of the invention

The present invention provides a kind of fluorination polyamide nanofiltration membrane and preparation method thereof.The fluorination polyamide nanofiltration of this method preparation Film has excellent water demineralization, waste treatment capacity, and antifouling property is good.

The invention is realized by the following technical scheme:

A kind of preparation method of novel fluorination polyamide nanofiltration membrane, the specific steps of which are as follows: a kind of ultrafiltration membranes are fixed on boundary In the polyplant of face, be added fluorine-containing polyethyleneimine aqueous phase solution dipping, remove excess surface water after, be added polynary acyl chlorides or The organic phase solution of multicomponent isocyanate monomer carries out interface polymerization reaction, then is heat-treated, and is finally cleaned with deionized water Obtain the fluorination compound nanometer filtering membrane of polyamide.

A kind of ultrafiltration membranes are flat plate ultrafiltration membrane or hollow fiber ultrafiltration membrane.

A kind of ultrafiltration membranes material is polysulfones, polyether sulfone, polyacrylonitrile, nylon66 fiber, Kynoar, polytetrafluoroethyl-ne One of alkene, polylactic acid.

A kind of molecular cut off of ultrafiltration membranes is 4000~80000Da.

The concentration of related polynary acyl chlorides or multicomponent isocyanate in organic phase is the wt% of 0.01 wt% ~ 5.0, institute Stating organic phase solvent is hexane, heptane, octane, nonane, decane, benzene, toluene, dimethylbenzene, methanol, ethyl alcohol, methylene chloride, acetic acid One or more of ethyl ester.

The related fluorine-containing polyethyleneimine amine concentration of water phase is the wt% of 0.01 wt% ~ 5.0, adds carbonate in water phase, gold Belong to hydroxide and do alkali, additive amount concentration is the wt% of 0 wt% ~ 1.

The preparation method, which is characterized in that water phase dipping after, the minimizing technology of extra moisture film include drain, scraper It strikes off, inert gas purge.It is 5 seconds ~ 10 minutes that the organic phase interface polymerization reaction time, which is added, and interface polymerization reaction finishes Afterwards, it is heat-treated, 50-80 DEG C of temperature range, is handled time 1-15 minutes.

The general formula of the fluorine-containing polyethyleneimine:

Wherein dotted line represents N atom connection branch or hydrogen, Z be sulfonyl () or acyl group ()；R is perfluoroalkyl, General formula C_nF_2n+1, n 1-18.

The utility model has the advantages that

1) it by the control section to conditions such as monomer concentration, reaction time, realizes to the micro-structure of nanofiltration membrane and the tune of separating property Control；

2) preparation nanofiltration membrane has preferable separating property to a dianion；

3) its separating layer of nanofiltration membrane made from and ultrafiltration matrix are tightly combined, and have preferable mechanical property；

4) nanofiltration membrane made from has good anti-organic pollution ability.

Detailed description of the invention

Ultrafiltration membranes (a) described in Fig. 1 embodiment 3, the surface (b) of the novel fluorination polyamide nanofiltration membrane prepared and section (c) electron microscopic picture.

The IR Characterization map for being fluorinated polyamide nanofiltration membrane, polysulfones ultrafiltration membranes of preparation described in Fig. 2 embodiment 3, FPA For the fluorination polyamide nanofiltration membrane of the preparation, PSF is polysulfones ultrafiltration membranes.

Fluorination polyamide nanofiltration membrane (a), polysulfone ultrafiltration membrane (b) and the polyamide nanofiltration membrane of preparation described in Fig. 3 embodiment 3 (c) XPS characterization result comparison, PA is polyamide nanofiltration membrane.

Antipollution number of the fluorination polyamide nanofiltration membrane of preparation described in Fig. 4 embodiment 3 to humic acid and bovine serum albumin According to.

The alkaline resistance properties test of the fluorination polyamide nanofiltration membrane of preparation described in Fig. 5 embodiment 3.

Specific embodiment

Below in conjunction with specific embodiment, the present invention is described further, but the embodiment given is not constituted and wanted to right Ask the limitation of range.