Lead ion sensors, methods of making and uses thereof

Patent metadata

Field	Value
Publication number	US-9952173-B2
Application number	US-201315021917-A
Country	US
Kind code	B2
Filing date	Sep 30, 2013
Priority date	Sep 30, 2013
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

Copolymers including at least one optionally substituted 2-hydroxy-5-sulfonic aniline as a first constituent unit and at least one optionally substituted phenylenediamine as a second constituent unit are disclosed. Compositions containing the copolymers, and methods of making the copolymers are also disclosed. The compositions can also contain for example an ethylene-vinyl acetate copolymer (EVA) and/or electrical conducting additives. The compositions can, for example, be used for detecting lead ions in a sample.

First claim

What is claimed is:

1. A copolymer comprising at least one optionally substituted 2-hydroxy-5-sulfonic aniline as a first constituent unit and at least one optionally substituted phenylenediamine as a second constituent unit, wherein the first constituent unit is present in the copolymer in an amount of about 5% to about 10% by mole and the second constituent unit is present in the copolymer in an amount of about 90% to about 95% by mole, and wherein particles of the copolymer have an average diameter of about 2000 nm.

2. The copolymer of claim 1 , wherein the first constituent unit is represented by Formula I:

wherein R 1 is hydrogen or an electron-donating group, and R 2 is hydrogen or an electron-donating group.

3. The copolymer of claim 2 , wherein R 1 is —CH 3 , —NH 2 , —NHC(O)OCH 2 CH 3 , or hydrogen.

4. The copolymer of claim 2 , wherein the electron-donating group is C 1-6 alkyl, C 1-6 alkoxy, —OH, an amino group, C 1-6 hydroxyalkyl, C 1-6 alkylthio, or a carbamate.

5. The copolymer of claim 1 , wherein the second constituent unit is represented by Formula II:

wherein Z 1 , Z 2 , and Z 3 are each independently hydrogen or an electron-donating group.

6. The copolymer of claim 5 , wherein Z 1 is hydrogen, —NH 2 , —CH 3 , —OH, —OCH 3 , or —CH 2 OH.

7. The copolymer of claim 5 , wherein Z 2 is hydrogen, —OCH 3 , or —SCH 3 .

8. The copolymer of claim 5 , wherein Z 3 is hydrogen, —OCH 3 , or —CH 3 .

9. The copolymer of claim 1 , wherein the second constituent unit is represented by Formula III, Formula IV, or Formula V:

wherein G 1 and G 2 are each independently hydrogen or an electron-donating group.

10. The copolymer of claim 9 , wherein G 1 and G 2 are each independently hydrogen or methoxy.

11. The copolymer of claim 1 , wherein the copolymer has a molar ratio of the first constituent unit to the second constituent unit of about 5:95.

12. A polymeric membrane for ion sensitive measurement comprising an ethylene-vinyl acetate copolymer (EVA) and one or more ionophores that are selective toward lead ions, wherein the one or more ionophores include particles of a copolymer having at least one optionally substituted 2-hydroxy-5-sulfonic aniline as a first constituent unit and at least one optionally substituted phenylenediamine as a second constituent unit, wherein the first constituent unit is present in the copolymer in an amount of about 5% to about 10% by mole and the second constituent unit is present in the copolymer in an amount of about 90% to about 95% by mole, and wherein the particles of the copolymer have an average diameter of about 2000 nm.

13. The polymeric membrane of claim 12 , wherein the first constituent unit is represented by Formula I:

wherein R 1 is hydrogen or an electron-donating group, and R 2 is hydrogen or an electron-donating group.

14. The polymeric membrane of claim 13 , wherein R 1 is —CH 3 , —NH 2 , —NHC(O)OCH 2 CH 3 , or hydrogen.

15. The polymeric membrane of claim 13 , wherein the electron-donating group is C 1-6 alkyl, C 1-6 alkoxy, —OH, an amino group, C 1-6 hydroxyalkyl, C 1-6 alkylthio, or a carbamate.

16. The polymeric membrane of any one of claim 12 , wherein the second constituent unit is represented by Formula II

wherein Z 1 , Z 2 , and Z 3 are each independently hydrogen or an electron-donating group.

17. The polymeric membrane of claim 16 , wherein:
Z 1 is hydrogen, —NH 2 , —CH 3 , —OH, —OCH 3 , or —CH 2 OH; or
Z 2 is hydrogen, —OCH 3 , or —SCH 3 ; or
Z 3 is hydrogen, —OCH 3 , or —CH 3 .

18. The polymeric membrane of claim 12 , wherein the second constituent unit is represented by Formula III, Formula IV, or Formula V:

wherein G 1 and G 2 are each independently hydrogen or an electron-donating group.

19. The polymeric membrane of claim 18 , wherein G 1 and G 2 are each independently hydrogen or methoxy.

20. The polymeric membrane of claim 12 , wherein the polymeric membrane comprises the one or more ionophores in an amount of about 0.1% to about 10% by weight.

21. The polymeric membrane of claim 12 , wherein the polymeric membrane comprises the one or more ionophores in an amount of about 4.5% by weight.

22. The polymeric membrane of claim 12 , wherein the polymeric membrane comprises one or more ion exchangers.

23. The polymeric membrane of claim 22 , wherein the polymeric membrane comprises the one or more ion exchangers in an amount of about 0% to about 8% by weight.

24. The polymeric membrane of claim 22 , wherein the one or more ion exchangers are sodium tetraphenylborate (NaTPB), potassium tetraphenylborate (KTPB), potassium tetrakis(4-chlorophenyl)]borate (KTClPB), potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (KTFPB), sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB), or combinations thereof.

25. The polymeric membrane of claim 12 , wherein the polymeric membrane has an average thickness of about 30 μm to about 400 μm.

26. The polymeric membrane of claim 12 , wherein the polymeric membrane comprises one or more electrical conducting additives.

27. The polymeric membrane of claim 26 , wherein the one or more electrical conducting additives comprise a conducting polymer, metal nanoparticles, a graphene nanosheet, a carbon nanotube, carbon black, polyaniline nanosticks, or any combination thereof.

28. The polymeric membrane of claim 27 , wherein the conducting polymer comprises polyaniline, polypyrrole, polythiophene, polyacetylene, poly(3,4-ethylenedioxythiophene), poly(3-octylthiophene), or any combination thereof.

29. The polymeric membrane of claim 12 , wherein the polymeric membrane is substantially plasticizer free.

30. A sensor for measuring lead ions, the sensor comprising: a lead ion-selective electrode, wherein the lead ion-selective electrode comprises a polymer matrix and particles of a copolymer, wherein the copolymer comprises at least one optionally substituted 2-hydroxy-5-sulfonic aniline as a first constituent unit and at least one optionally substituted phenylenediamine as a second constituent unit, wherein the first constituent unit is present in the copolymer in an amount of about 5% to about 10% by mole and the second constituent unit is present in the copolymer in an amount of about 90% to about 95% by mole, and wherein the particles of the copolymer have an average diameter of about 2000 nm.

31. The sensor of claim 30 , wherein the sensor further comprises a reference electrode.

32. A method for detecting lead ions in a sample, the method comprising: providing a sample suspected of containing one or more lead ions;
contacting the sample with a sensor, wherein the sensor comprises a reference e

Assignees

• Univ Tongji

Inventors

• Huang Meirong
• Ding Yongbo
• Li Xingui

Classifications

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08L27/06

  Homopolymers or copolymers of vinyl chloride · CPC title

• C08J2327/06

  Homopolymers or copolymers of vinyl chloride · CPC title

• C08K3/0066

  Chemistry & Metallurgy · mapped topic

• C08L23/0853

  Ethylene vinyl acetate copolymers · CPC title