Cross-linked gas permeable membrane of a cured perfluorinated urethane polymer, and optical gas sensors fabricated therewith

• US 5,453,248 A
• Filed: 08/12/1992
• Issued: 09/26/1995
• Est. Priority Date: 03/09/1992
• Status: Expired due to Term

• Current Assignee: Optical Sensors Incorporated
• Original Assignee: Optical Sensors Incorporated
• Inventors: Olstein, Alan
• Primary Examiner(s): Snay, Jeffrey R.
• Application Number:
  US07/911,175
• Time in Patent Office: 1,140 Days
• Field of Search: 528/65, 528/70, 528/75, 522/96, 522/97, 422/82.06, 422/82.07, 422/82.08, 422/82.09, 422/82.11, 436/166, 436/169, 436/136, 436/138, 436/133, 427/165, 250/458.1
• US Class Current: 422/82.07
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2845 Monohydroxy epoxy compounds
• CPC Class Codes: C08G 18/3215 containing aromatic groups or benzoquinone groups
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C08G 18/50 having heteroatoms other than oxygen
• CPC Class Codes: C08G 18/5015 having fluorine atoms
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: G01N 2021/772 Tip coated light guide
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B

Abstract

An optical sensor is provided for measuring dissolved gases such as O₂ or CO₂ in a fluid sample. The sensor is formulated so as to contain a gas permeable membrane of a cured perfluorinated urethane polymer and, incorporated therein, a gas-sensitive indicator component. Methods for making and using the membrane and sensor are provided as well.

Claims

1. A cross-linked gas permeable membrane useful in optical gas sensors for measuring O₂ or CO₂ in a fluid, comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises a perfluorinated urethane polymer precursor cross-linked with a cross-linking agent, and further wherein the precursor has the structural formula ##STR5## wherein Ar is a monocyclic aromatic moiety and X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof.

2. The membrane of claim 1, wherein the cross-linking agent is water.

3. The membrane of claim 1, wherein the polymeric matrix comprises approximately 95 wt. % to 99.5 wt. % perfluorinated polyurethane polymer precursor and approximately 0.5 wt. % to 5 wt. % cross-linking agent.

4. The membrane of claim 1, wherein the gas-sensitive indicator is selected from the group consisting of fluorescein, carboxyfluorescein, seminaphthorhodafluor, seminaphthofluorescein, naphthofluorescein, hydroxypyrene trisulfonic acid and dichlorofluorescein.

5. The membrane of claim 1, wherein the cross-linking agent is a diol.

6. The membrane of claim 5, wherein the diol is selected from the group consisting of bisphenol A and hexafluorobisphenol A.

7. The membrane of claim 1, wherein the gas-sensitive indicator is selected from the group consisting of complexes of ruthenium (II), osmium (II), iridium (III), rhodium, rhenium, and chromium (III) with one of 2,2'"'"'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl(1,10-phenanthroline), 4,7-dimethyl-1,10-phenanthroline, 4,7-disulfonated-diphenyl-1,10-phenanthroline, 2,2'"'"'-bi-2-thiazoline, 2,2'"'"'-bithiazole, 5-bromo-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline, complexes of VO (II), Cu (II), platinum (II), and zinc (II) with one of porphin etioporphorin tetraphenylporphyrin, mesoporphyrin IX dimethylester, protoporphyrin IX dimethylester and octaethylporphyrin, and combinations thereof.

8. The membrane of claim 7, wherein the gas-sensitive indicator is physically entrapped within the polymer matrix.

9. The membrane of claim 7, wherein the gas-sensitive indicator is covalently bound to the polymer matrix.

10. A cross-linked gas permeable membrane useful in optical gas sensors for measuring O₂ or CO₂ in a fluid, comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises a perfluorinated urethane polymer precursor having the structural formula ##STR6## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with a photoinitiator in the presence of radiation.

11. The membrane of claim 10, wherein the gas-sensitive indicator is selected from the group consisting of complexes of ruthenium (II), osmium (II), iridium (III), rhodium, rhenium, and chromium (III) with one of 2,2'"'"'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl(1,10-phenanthroline), 4,7-dimethyl-1,10-phenanthroline, 4,7-disulfonated-diphenyl-1,10-phenanthroline, 2,2'"'"'-bi-2-thiazoline, 2,2'"'"'-bithiazole, 5-bromo-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline, complexes of VO (II), Cu (II), platinum (II), and zinc (II) with one of porphin etioporphorin tetraphenylporphyrin, mesoporphyrin IX dimethylester, protoporphyrin IX dimethylester and octaethylporphyrin, and combinations thereof.

12. The membrane of claim 11, wherein the gas-sensitive indicator is physically entrapped within the polymer matrix.

13. The membrane of claim 11, wherein the gas-sensitive indicator is covalently bound to the polymer matrix.

14. A cross-linked gas permeable membrane useful in optical gas sensors for measuring O₂ or CO₂ in a fluid, comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises an epoxy-terminated precursor having the structural formula ##STR7## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with a photoinitiator in the presence of radiation.

15. The membrane of claim 14, wherein the gas-sensitive indicator is selected from the group consisting of fluorescein, carboxyfluorescein, seminaphthorhodafluor, seminaphthofluorescein, naphthofluorescein, hydroxypyrene trisulfonic acid and dichlorofluorescein.

16. The membrane of claim 15, wherein the gas-sensitive indicator is physically entrapped within the polymer matrix.

17. The membrane of claim 15, wherein the gas-sensitive indicator is covalently bound to the polymer matrix.

21. The optical sensor of claim 14, wherein the sensor is a CO₂ sensor and the gas-sensitive indicator is selected from the group consisting of fluorescein, carboxyfluorescein, seminaphthorhodafluor, seminaphthofluorescein, naphthofluorescein, hydroxypyrene trisulfonic acid and dichlorofluorescein.

18. An optical gas sensor for measuring O₂ or CO₂ in a fluid, comprising:

an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from the distal end portion, and wherein the distal end portion has in optical communication therewith a gas sensor means comprising

a cross-linked gas permeable membrane comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises a perfluorinated urethane polymer precursor cross-linked with a cross-linking agent, and further wherein the precursor has the structural formula ##STR8## wherein Ar is a monocyclic aromatic moiety and X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof.

19. The optical sensor of claim 18, wherein the cross-linking agent is water.

20. The optical sensor of claim 18, wherein the sensor is an O₂ sensor and the gas-sensitive indicator is selected from the group consisting of complexes of ruthenium (II), osmium (II), iridium (III), rhodium, rhenium, and chromium (III) with one of 2,2'"'"'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl(1,10-phenanthroline), 4,7-dimethyl-1,10-phenanthroline, 4,7-disulfonated-diphenyl-1,10-phenanthroline, 2,2'"'"'-bi-2-thiazoline, 2,2'"'"'-bithiazole, 5-bromo-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline, complexes of VO (II), Cu (II), platinum (II), and zinc (II) with one of porphin etioporphorin tetraphenylporphyrin, mesoporphyrin IX dimethylester, protoporphyrin IX dimethylester and octaethylporphyrin, and combinations thereof.

22. The optical sensor of claim 18, wherein the cross-linking agent is a diol.

23. The optical sensor of claim 22, wherein the diol is selected from the group consisting of bisphenol A or hexafluorobisphenol A.

24. An optical gas sensor for measuring O₂ or CO₂ in a fluid, comprising:

an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from the distal end portion, and wherein the distal end portion has in optical communication therewith a gas sensor means comprising

a cross-linked gas permeable membrane comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises a perfluorinated urethane polymer precursor having the structural formula ##STR9## wherein Ar is a monocyclic aromatic moiety and X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with a photoinitiator in the presence of radiation.

25. The optical sensor of claim 24, wherein the sensor is an O₂ sensor and the gas-sensitive indicator is selected from the group consisting of complexes of ruthenium (II), osmium (II), iridium (III), rhodium, rhenium, and chromium (III) with one of 2,2'"'"'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl(1,10-phenanthroline), 4,7-dimethyl-1,10-phenanthroline, 4,7-disulfonated-diphenyl-1,10-phenanthroline, 2,2'"'"'-bi-2-thiazoline, 2,2'"'"'-bithiazole, 5-bromo-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline, complexes of VO (II), Cu (II), platinum (II), and zinc (II) with one of porphin etioporphorin tetraphenylporphyrin, mesoporphyrin IX dimethylester, protoporphyrin IX dimethylester and octaethylporphyrin, and combinations thereof.

26. The optical sensor of claim 24, wherein the sensor is a CO₂ sensor and the gas-sensitive indicator is selected from the group consisting of fluorescein, carboxyfluorescein, seminaphthorhodafluor, seminaphthofluorescein, naphthofluorescein, hydroxypyrene trisulfonic acid and dichlorofluorescein.

27. An optical gas sensor for measuring O₂ or CO₂ in a fluid, comprising:

an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from the distal end portion, and wherein the distal end portion has in optical communication therewith a gas sensor means comprising

a cross-linked gas permeable membrane comprising a polymeric matrix of a cured perfluorinated urethane polymer, the matrix having a gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises an epoxy-terminated precursor having the structural formula ##STR10## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with photoinitiator in the presence of radiation.

28. The optical sensor of claim 27, wherein the sensor is an O₂ sensor and the gas-sensitive indicator is selected from the group consisting of complexes of ruthenium (II), osmium (II), iridium (III), rhodium, rhenium, and chromium (III) with one of 2,2'"'"'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl(1,10-phenanthroline), 4,7-dimethyl-1,10-phenanthroline, 4,7-disulfonated-diphenyl-1,10-phenanthroline, 2,2'"'"'-bi-2-thiazoline, 2,2'"'"'-bithiazole, 5-bromo-1,10-phenanthroline, and 5-chloro-1,10-phenanthroline, complexes of VO (II), Cu (II), platinum (II), and zinc (II) with porphin etioporphorin tetraphenylporphyrin, mesoporphyrin IX dimethylester, protoporphyrin IX dimethylester and octaethylporphyrin, and combinations thereof.

29. The optical sensor of claim 27, wherein the sensor is a CO₂ sensor and the gas-sensitive indicator is selected from the group consisting of fluorescein, carboxyfluorescein, seminaphthorhodafluor, seminaphthofluorescein, naphthofluorescein, hydroxypyrene trisulfonic acid and dichlorofluorescein.

30. A method for making an optical gas sensor for measuring O₂ or CO₂ in a fluid, comprising the steps of:

(a) providing an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from said distal end portion;

(b) coating said distal end portion with a solution containing a photocurable polymeric precursor, which precursor has the structural formula ##STR11## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and a gas-sensitive indicator component; and

(c) effecting cross-linking of the precursor by irradiating the distal end portion through the optical waveguide using radiation of a wavelength effective to cure the precursor.

31. A method for making an optical sensor for measuring O₂ or CO₂ in a fluid, comprising the steps of:

(a) providing an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from said distal end portion;

(b) coating said distal end portion with a solution containing a perfluorinated urethane polymer precursor and a gas-sensitive indicator component, to provide a precursor-coated tip; and

(c) effecting cross-linking of said precursor, thereby providing at the distal end portion a gas sensor means comprising a cross-linked gas permeable membrane of a cured perfluorinated urethane polymer, the membrane having said gas-sensitive indicator component incorporated therein, wherein the cured perfluorinated urethane polymer comprises said perfluorinated urethane polymer precursor cross-linked with a cross-linking agent, and further wherein the precursor has the structural formula ##STR12## wherein Ar is a monocyclic aromatic moiety and X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof.

32. The method of claim 31, wherein cross-linking is carried out by contacting the precursor-coated tip with a cross-linking agent.

33. A method for making an optical gas sensor for measuring O₂ or CO₂ in a fluid, comprising the steps of:

(a) providing an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from said distal end portion;

(b) coating said distal end portion with a solution containing a photocurable polymeric precursor, which precursor having the structural formula ##STR13## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and a gas-sensitive indicator component; and

(c) effecting cross-linking of the precursor by irradiating the distal end portion through the optical waveguide using radiation of a wavelength effective to cure the precursor.

34. A method for making an optical sensor for measuring O₂ or CO₂ in a fluid, comprising the steps of:

(a) providing an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from said distal end portion;

(b) coating said distal end portion with a solution containing a perfluorinated urethane polymer precursor and a gas-sensitive indicator component, to provide a precursor-coated tip; and

(c) effecting cross-linking of said precursor, thereby providing at the distal end portion a gas sensor means comprising a cross-linked gas permeable membrane of a cured perfluorinated urethane polymer, the membrane having said gas-sensitive indicator component incorporated therein, wherein said perfluorinated urethane polymer precursor has the structural formula ##STR14## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with a photoinitiator in the presence of radiation.

35. The method of claim 34, wherein cross-linking is carried out by irradiating the distal end portion of the optical waveguide.

36. The method of claim 34, wherein the irradiating is effected through the optical waveguide.

37. A method for making an optical sensor for measuring O₂ or CO₂ in a fluid, comprising the steps of:

(a) providing an optical waveguide having a distal end portion for monitoring a gas component within a fluid, and a proximal end portion for communication with means for receiving a signal from said distal end portion;

(b) coating said distal end portion with a solution containing a perfluorinated urethane polymer precursor and a gas-sensitive indicator component, to provide a precursor-coated tip; and

(c) effecting cross-linking of said precursor, thereby providing at the distal end portion a gas sensor means comprising a cross-linked gas permeable membrane of a cured perfluorinated urethane polymer, the membrane having said gas-sensitive indicator component incorporated therein, wherein the precursor is an epoxy-terminated precursor having the structural formula ##STR15## wherein Ar is a monocyclic aromatic moiety, X is a perfluorinated polyether linkage containing approximately 2 to 100 recurring perfluorinated mer units having the structure --CF₂ O), --CF₂ CF₂ O), or combinations thereof, and n is an integer in the range of 0 to 6 inclusive, and further wherein the precursor is cured with a photoinitiator in the presence of radiation.

38. The method of claim 37, wherein cross-linking is carried out by irradiating the distal end portion of the optical waveguide.

39. The method of claim 37, wherein the irradiating is effected through the optical waveguide.