Thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11458440-B2
Application number	US-202016882752-A
Country	US
Kind code	B2
Filing date	May 26, 2020
Priority date	Aug 28, 2019
Publication date	Oct 4, 2022
Grant date	Oct 4, 2022

Abstract

A thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects and a preparation method thereof are disclosed. The preparation method includes: dissolving a highly water-stable metal organic framework CuBTTri in an n-hexane solution containing trimesoyl chloride by ultrasonic wave, immersing a polyethersulfone ultrafiltration membrane in an aqueous solution of m-phenylene diamine and taking out, and then immersing the ultrafiltration membrane in the trimesoyl chloride-n-hexane solution containing the aforementioned metal organic framework for reaction and modification, so as to obtain the thin-film composite polyamide reverse osmosis membrane. The resulting composite reverse osmosis membrane integrated with the anti-bacterial metal organic framework CuBTTri has a high reverse osmosis membrane permeability and possesses greatly improved and persistent anti-bacterial and anti-biofouling properties. The preparation method is simple and conducive to promotion, and has mild conditions.

First claim

What is claimed is:

1. A thin-film composite polyamide reverse osmosis membrane with anti-bacterial and anti-biofouling effects, comprising a substrate and a thin film, wherein the substrate is an ultrafiltration membrane, and the thin film is formed by loading an aromatic polyamide film containing a CuBTTri uniformly on a surface of the substrate,
wherein the CuBTTri has a molecular formula of H3[(Cu 4 C1) 3 -(BTTri) 8 ] and a structural formula of a backbone of the CuBTTri comprises Cu 2 + and an organic ligand H 3 BTTri, the H 3 BTTri is 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene, and the H 3 BTTri has a structural formula of

2. The thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 1 , wherein
the ultrafiltration membrane comprises at least one membrane selected from the group consisting of a polyacrylonitrile membrane, a polysulfone membrane, and a polyethersulfone membrane, and
the ultrafiltration membrane has a molecular weight cutoff of 10-20 kDa.

3. A method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 1 , comprising the steps of:
i) synthesizing the CuBTTri, comprising the steps in order of:
a) dissolving CuC1 2 .2H 2 O in a first organic solvent to obtain a copper chloride solution having a mass concentration of 3.8%-5.7%;
b) dissolving the H 3 BTTri in a second organic solvent to obtain a first solution, and adding HC1 dropwise to the first solution to acidify to pH 3.0-4.5, to obtain a triazole solution having a mass concentration of 0.5%-1%;
c) mixing the copper chloride solution prepared in step a) and the triazole solution prepared in step b) in a volume ratio of 1:(2-3) at 70-100° C. to react for 48-96 h to obtain a resultant; and
d) centrifuging the resultant obtained in step c) at 7500-8500 rpm for 5-10 min to obtain a purple precipitate, and vacuum drying the purple precipitate for 12-24 h to obtain the CuBTTri;

ii) preparing an aqueous solution of m-phenylene diamine having a mass concentration of 1.5%-2.5%;
iii) ultrasonic dispersing the CuBTTri obtained in step i) in a trimesoyl chloride-n-hexane solution having a mass concentration of 0.1%-0.15%, to obtain an n-hexane solution of CuBTTri having a mass concentration of 0.05%-0.2%;
iv) first immersing the ultrafiltration membrane in the aqueous solution of m-phenylene diamine obtained in step ii) to react for 1-2 min and taking out the ultrafiltration membrane, and removing the aqueous solution of m-phenylene diamine on a surface of the ultrafiltration membrane; and then immersing the ultrafiltration membrane in the n-hexane solution of CuBTTri obtained in step iii) to react for 30-60 s to form the thin film on the surface of the ultrafiltration membrane, and removing unreacted trimesoyl chloride on the surface of the ultrafiltration membrane to obtain the thin-film composite polyamide reverse osmosis membrane; and
v) heat-treating the thin-film composite polyamide reverse osmosis membrane obtained in step iv) at 50-80° C., and then immersing the thin-film composite polyamide reverse osmosis membrane in deionized water at 4° C.

4. The method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 3 , wherein the first organic solvent and the second organic solvent in step i) are identical solvents selected from the group consisting of N,N-dimethylformamide, tetrahydrofuran and N-methyl pyrrolidone.

5. The method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 3 , wherein an immersion manner of immersing the ultrafiltration membrane in step iv) is a full immersion and the surface of the ultrafiltration membrane is oriented upward.

6. The method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 3 , wherein the ultrafiltration membrane comprises at least one of a polyacrylonitrile membrane, a polysulfone membrane and a polyethersulfone membrane, and the ultrafiltration membrane has a molecular weight cutoff of 10-20 kDa.

7. The method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 6 , wherein the first organic solvent and the second organic solvent in step i) are identical solvents or each solvent is selected from the group consisting of N,N-dimethylformamide, tetrahydrofuran and N-methyl pyrrolidone.

8. The method for preparing the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 6 , wherein an immersion manner of immersing the ultrafiltration membrane in step iv) is a full immersion and the surface of the ultrafiltration membrane is oriented upward.

9. A method of using the thin-film composite polyamide reverse osmosis membrane with the anti-bacterial and anti-biofouling effects of claim 1 , comprising using the thin-film composite polyamide reverse osmosis membrane in water treatment.

10. The method of claim 9 , wherein bacteria die when in contact with the thin-film composite polyamide reverse osmosis membrane, a surface of the thin-film composite polyamide reverse osmosis membrane is uniformly loaded with the aromatic polyamide film containing the CuBTTri to achieve sterilization or bacterial growth inhibition.

11. The method of claim 9 , wherein the ultrafiltration membrane comprises at least one of a polyacrylonitrile membrane, a polysulfone membrane and a polyethersulfone membrane, and the ultrafiltration membrane has a molecular weight cutoff of 10-20 kDa.

12. The method of claim 11 , wherein bacteria die when in contact with the thin-film composite polyamide reverse osmosis membrane, a surface of the thin-film composite polyamide reverse osmosis membrane is uniformly loaded with the aromatic polyamide film containing the CuBTTri to achieve sterilization or bacterial growth inhibition.

Assignees

• Univ Tongji
• Univ Tianjin Polytechnic

Inventors

• Wang Zhiwei
• Wen Yue
• Zhang Hongwei
• Wang Jie
• Chen Yingqing
• Wu Zhichao

Classifications

• C07F1/08

  Copper compounds · CPC title

• B01D67/0006

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title

• B01D69/02

  characterised by their properties · CPC title

• B01D2323/30

  Cross-linking · CPC title

• B01D71/56

  Polyamides, e.g. polyester-amides · CPC title