CA2284300A1 - Phosphorescent oxygen sensors - Google Patents
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- CA2284300A1 CA2284300A1 CA002284300A CA2284300A CA2284300A1 CA 2284300 A1 CA2284300 A1 CA 2284300A1 CA 002284300 A CA002284300 A CA 002284300A CA 2284300 A CA2284300 A CA 2284300A CA 2284300 A1 CA2284300 A1 CA 2284300A1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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Abstract
A polymer material comprising a backbone containing nitrogen and one or more of sulfur and phosphorous, and at least one side chain, wherein either said at least one side chain or said backbone includes a phosphorescent dye agent.
Description
REFERENCE TO CO-PENDING APPLICATIONS
This is a continuation-in-part of U.S. provisional application serial number 60/060,084 filed on September 26, 1997, the subject matter of which is also incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. FIELD OF THE INVENTION
The present invention relates to novel polymers, to polymers for use as pressure sensors, more particularly phosphorescent oxygen sensors and more particularly to compositions for forming coatings therefor.
This is a continuation-in-part of U.S. provisional application serial number 60/060,084 filed on September 26, 1997, the subject matter of which is also incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. FIELD OF THE INVENTION
The present invention relates to novel polymers, to polymers for use as pressure sensors, more particularly phosphorescent oxygen sensors and more particularly to compositions for forming coatings therefor.
2. DESCRIPTION OF THE RELATED ART
The field of luminescent barometry has developed as a result of continuing difficulties encountered with other mechanical means to measure pressure distributions over aerodynamic surfaces. The theories of luminescent barometry are described in detail in U.S. Patent 5,359,887 and U.S. Patent 5,151,603, the subject matter of each of which is incorporated herein by reference. Luminescent barometry is based on the phenomenon that some phosphorescent materials emit light at a unique wavelength and which is 'quenched' by the presence of particular molecules such as oxygen. This quenching effect can be quantified so that the phosphorescent material, provided in an oxygen permeable matrix, can be used to measure, for example, the partial pressure of oxygen passing over aerodynamic surfaces.
As a consequence of their considerable fabrication advantages, the use of polymeric materials for the construction of sensing devices using this quenching effect is an area of intense current interest. Luminescent sensors based on composites comprising transition metal phosphorescent dyes immobilized in polymer matrices have attracted attention as oxygen sensors for both biomedical and barometric applications. Conventional phosphorescent dyes such as Pt (platinum) octaethylporphyrin (OEP) derivatives or Ru"
(ruthenium) bipyridyl (bipy) or phananthroline (Phen) derivatives with oxygen quenchable excited states have been dispersed in a silicone (otherwise known as polysiloxane) based polymer matrices due to their high gas permeability.
However, these conventional silicone-based polymer systems require cross-linking and tend to be incompatible with the dyes and can lead to undesirable local dye concentrations and thus reduced sensitivity. Most PtOEP based systems in cross-linked silicone polymer matrices also have non-linear dependence on air pressure thereby making measurements less accurate.
Furthermore, conventional polysiloxane coatings tend to continue cross-linking as I 5 their temperature rises which causes irreversible changes in their phosphorescent properties as a result, making their data subj ect to error and generally unsuitable for measurements taken in fluctuating temperature conditions.
It is therefore an object of the present invention to provide a novel composition for use as pressure sensors.
It is a further object of the present invention to provide a novel composition for use as phosphorescent sensors.
It is a further object of the present invention to provide a novel composition for use as phosphorescent oxygen sensors.
It is a further object of the present invention to provide a novel polymer which provides improved distribution of dye there through.
It is a further object of the present invention to provide a novel polymer with a backbone containing nitrogen and one or more of sulfur and phosphorous which provides improved distribution of dye there through.
SUMMARY OF THE INVENTION
Briefly stated, the invention involves a polymer material comprising a backbone containing nitrogen and one or more of sulfur and phosphorous, the polymer material further comprising at least one side chain, wherein either the at least one side chain or the backbone includes a phosphorescent dye agent.
Preferably, the backbone includes both sulfur and phosphorus having side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted CZ_ZO linear or branched alkyl group, a substituted or unsubstituted CZ_ZO linear or branched alkenyl group, a substituted or unsubstituted CZ_~o linear or branched alkynyl group, a substituted or unsubstituted C~_~o aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent. More particularly, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group including the dye agent.
In another aspect, the invention involves a pressure sensor comprising a substrate having a surface, a polymer material as defined herein above and applied to the surface to
The field of luminescent barometry has developed as a result of continuing difficulties encountered with other mechanical means to measure pressure distributions over aerodynamic surfaces. The theories of luminescent barometry are described in detail in U.S. Patent 5,359,887 and U.S. Patent 5,151,603, the subject matter of each of which is incorporated herein by reference. Luminescent barometry is based on the phenomenon that some phosphorescent materials emit light at a unique wavelength and which is 'quenched' by the presence of particular molecules such as oxygen. This quenching effect can be quantified so that the phosphorescent material, provided in an oxygen permeable matrix, can be used to measure, for example, the partial pressure of oxygen passing over aerodynamic surfaces.
As a consequence of their considerable fabrication advantages, the use of polymeric materials for the construction of sensing devices using this quenching effect is an area of intense current interest. Luminescent sensors based on composites comprising transition metal phosphorescent dyes immobilized in polymer matrices have attracted attention as oxygen sensors for both biomedical and barometric applications. Conventional phosphorescent dyes such as Pt (platinum) octaethylporphyrin (OEP) derivatives or Ru"
(ruthenium) bipyridyl (bipy) or phananthroline (Phen) derivatives with oxygen quenchable excited states have been dispersed in a silicone (otherwise known as polysiloxane) based polymer matrices due to their high gas permeability.
However, these conventional silicone-based polymer systems require cross-linking and tend to be incompatible with the dyes and can lead to undesirable local dye concentrations and thus reduced sensitivity. Most PtOEP based systems in cross-linked silicone polymer matrices also have non-linear dependence on air pressure thereby making measurements less accurate.
Furthermore, conventional polysiloxane coatings tend to continue cross-linking as I 5 their temperature rises which causes irreversible changes in their phosphorescent properties as a result, making their data subj ect to error and generally unsuitable for measurements taken in fluctuating temperature conditions.
It is therefore an object of the present invention to provide a novel composition for use as pressure sensors.
It is a further object of the present invention to provide a novel composition for use as phosphorescent sensors.
It is a further object of the present invention to provide a novel composition for use as phosphorescent oxygen sensors.
It is a further object of the present invention to provide a novel polymer which provides improved distribution of dye there through.
It is a further object of the present invention to provide a novel polymer with a backbone containing nitrogen and one or more of sulfur and phosphorous which provides improved distribution of dye there through.
SUMMARY OF THE INVENTION
Briefly stated, the invention involves a polymer material comprising a backbone containing nitrogen and one or more of sulfur and phosphorous, the polymer material further comprising at least one side chain, wherein either the at least one side chain or the backbone includes a phosphorescent dye agent.
Preferably, the backbone includes both sulfur and phosphorus having side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted CZ_ZO linear or branched alkyl group, a substituted or unsubstituted CZ_ZO linear or branched alkenyl group, a substituted or unsubstituted CZ_~o linear or branched alkynyl group, a substituted or unsubstituted C~_~o aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent. More particularly, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group including the dye agent.
In another aspect, the invention involves a pressure sensor comprising a substrate having a surface, a polymer material as defined herein above and applied to the surface to
3 form a coating.
In still another of its aspects, the invention provides a polymer material formed from a phosphorescent dye agent contained in a polymer material of formula A, wherein:
E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
RI to R6 are the same or different and are selected from the group comprising , oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group, and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
Preferably E 1 is in the form of sulfur VI, while E2 and E3 are each phosphorus. Each of R2 to R6 includes an oxygen or a nitrogen substituent. More particularly, each of R3 to R6 includes an aryloxy group or an alkamine group, and each is selected from the group consisting ofNHBu", OBu", OC6H~, OC6H,~CF3-m, OCHZCH=CHz and OC6H4CF3-p, and the group including the dye agent.
More preferably, R2 is a halogen, and more particularly R2 and R3 to RS are the same and R6 is the group including the dye agent. Still more particularly, R2 and R3 to RS are each NHBu" and the group including the dye agent includes a ruthenium substituent. Still more particularly, the group including the dye agent is Ru(4,7-diphenylphen)3.
In one embodiment, the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C3_zo cYcloalkyl group, a substituted C6_zo
In still another of its aspects, the invention provides a polymer material formed from a phosphorescent dye agent contained in a polymer material of formula A, wherein:
E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
RI to R6 are the same or different and are selected from the group comprising , oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group, and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
Preferably E 1 is in the form of sulfur VI, while E2 and E3 are each phosphorus. Each of R2 to R6 includes an oxygen or a nitrogen substituent. More particularly, each of R3 to R6 includes an aryloxy group or an alkamine group, and each is selected from the group consisting ofNHBu", OBu", OC6H~, OC6H,~CF3-m, OCHZCH=CHz and OC6H4CF3-p, and the group including the dye agent.
More preferably, R2 is a halogen, and more particularly R2 and R3 to RS are the same and R6 is the group including the dye agent. Still more particularly, R2 and R3 to RS are each NHBu" and the group including the dye agent includes a ruthenium substituent. Still more particularly, the group including the dye agent is Ru(4,7-diphenylphen)3.
In one embodiment, the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C3_zo cYcloalkyl group, a substituted C6_zo
4 aryl group and a substituted or unsubstituted C6_zo aralkyl group.
In still another of its aspects, the invention provides a polymer material of the formula B wherein:
EI, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
RI to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted C,_zo linear or branched alkenyl group, a substituted or unsubstituted C,_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group; and wherein at least one of RI to R6 is a group including a phosphorescent dye agent.
IS
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted Cz_,o linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group.
In still another of its aspects, the invention provides a method of forming a copolymer material of the formula B, comprising the steps of:
providing a first polymer block of the formula A, wherein:
In still another of its aspects, the invention provides a polymer material of the formula B wherein:
EI, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
RI to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted C,_zo linear or branched alkenyl group, a substituted or unsubstituted C,_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group; and wherein at least one of RI to R6 is a group including a phosphorescent dye agent.
IS
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted Cz_,o linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group.
In still another of its aspects, the invention provides a method of forming a copolymer material of the formula B, comprising the steps of:
providing a first polymer block of the formula A, wherein:
5 E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R 1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_,o linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo ~'Yl group, a substituted or unsubstituted C3_,o cycloalkyl group; and wherein at least one of Rl to R6 is a group including a phosphorescent dye agent.
carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein to form a copolymer material of formula B
wherein:
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C,_,o linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
In yet another of its aspects, the present invention provides a coating composition comprising a polymer material, the polymer having a backbone and at least one side group with a phosphorescent dye agent as a member of the backbone or the side group, the polymer being capable of being applied as a coating. Preferably, the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
R 1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_,o linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo ~'Yl group, a substituted or unsubstituted C3_,o cycloalkyl group; and wherein at least one of Rl to R6 is a group including a phosphorescent dye agent.
carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein to form a copolymer material of formula B
wherein:
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C,_,o linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
In yet another of its aspects, the present invention provides a coating composition comprising a polymer material, the polymer having a backbone and at least one side group with a phosphorescent dye agent as a member of the backbone or the side group, the polymer being capable of being applied as a coating. Preferably, the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
6 In yet another of its aspects the present invention provides a polymer material formed from a polymer material having a backbone containing nitrogen and one or more of sulfur and phosphorous, the polymer material including at least one side group including a silicone group.
Preferably, the backbone contains sulfur and phosphorous, the polymer material is stable and the sulfur is in the form of sulfur VI. More preferably, the polymer material includes a number of silicone side groups. Still more preferably, each of the silicone side groups has a trimethylsilyl constituent. Still more preferably, each phosphorous in the backbone has a side group including silicone. Still more preferably, each side group on each phosphorus in the backbone includes a trimethylsilyl group.
In yet another of its aspects, the present invention provides a polymer material of formula A as defined herein above wherein at least one of Rl to R6 includes siloxane.
In yet another of its aspects, the present invention provides a method of forming a pressure sensor, comprising the steps of forming a stable polymer having a backbone containing nitrogen and one or more of sulfur and phosphorus, and with a plurality of side groups, and providing a silicone constituent on at least one of the side groups. Preferably, at least one silicone constituent is provided on a plurality of the side groups. More preferably, the backbone includes sulfur and phosphorous and each side group on the phosphorus includes a silicone constituent. Still more preferably, the sulfur has one side group including oxygen and a second side group including a silicone constituent.
In yet another aspect of the present invention, there is provided a polymer material having a backbone containing nitrogen and one or more of sulfur and phosphorous, and at least one silicone-bearing side group. Preferably, the polymer material has a glass transition temperature ranging from -20 ° C to 0 ° C.
Preferably, the backbone contains sulfur and phosphorous, the polymer material is stable and the sulfur is in the form of sulfur VI. More preferably, the polymer material includes a number of silicone side groups. Still more preferably, each of the silicone side groups has a trimethylsilyl constituent. Still more preferably, each phosphorous in the backbone has a side group including silicone. Still more preferably, each side group on each phosphorus in the backbone includes a trimethylsilyl group.
In yet another of its aspects, the present invention provides a polymer material of formula A as defined herein above wherein at least one of Rl to R6 includes siloxane.
In yet another of its aspects, the present invention provides a method of forming a pressure sensor, comprising the steps of forming a stable polymer having a backbone containing nitrogen and one or more of sulfur and phosphorus, and with a plurality of side groups, and providing a silicone constituent on at least one of the side groups. Preferably, at least one silicone constituent is provided on a plurality of the side groups. More preferably, the backbone includes sulfur and phosphorous and each side group on the phosphorus includes a silicone constituent. Still more preferably, the sulfur has one side group including oxygen and a second side group including a silicone constituent.
In yet another aspect of the present invention, there is provided a polymer material having a backbone containing nitrogen and one or more of sulfur and phosphorous, and at least one silicone-bearing side group. Preferably, the polymer material has a glass transition temperature ranging from -20 ° C to 0 ° C.
7 In yet another aspect of the present invention, there is provided a pressure sensor comprising a stable polymer material as defined above and a phosphorescent dye agent.
Preferably, the polymer and dye agent are in the form of a coating. More preferably, the pressure sensor is operatively characterized by a Stern V olmer plot having a linearity ranging from 0.980 to 1Ø More preferably, the sensor exhibits a Stern Volmer plot having a linearity ranging from 0.985 to 0.995, still more preferably 0.990 to 0.995.
Preferably, pressure sensor is operatively characterized by a Stern Volmerplot having the above ranges of linearity over a range of pressures, namely from about 0.1 to 75 psi, more preferably 0.1 to 50 psi, still more preferably 0.2 to 40 psi.
BRIEF DESCRIPTION OF THE DRAWINGS
Several preferred embodiments of the present invention will be provided, by way of example only, with reference to the appended drawings, wherein:
Figures A and B are schematic diagrams of polymerizations;
Figure 1 is a plot of a luminescence intensity ratio versus pressure ratio for one exemplified coating of the present invention;
Figure 2 is a PSP image of a wing model coated with the coating of figure l;
and Figure 3 is a comparison of pressure distribution measurements.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Briefly stated, the invention involves a polymer material comprising a backbone
Preferably, the polymer and dye agent are in the form of a coating. More preferably, the pressure sensor is operatively characterized by a Stern V olmer plot having a linearity ranging from 0.980 to 1Ø More preferably, the sensor exhibits a Stern Volmer plot having a linearity ranging from 0.985 to 0.995, still more preferably 0.990 to 0.995.
Preferably, pressure sensor is operatively characterized by a Stern Volmerplot having the above ranges of linearity over a range of pressures, namely from about 0.1 to 75 psi, more preferably 0.1 to 50 psi, still more preferably 0.2 to 40 psi.
BRIEF DESCRIPTION OF THE DRAWINGS
Several preferred embodiments of the present invention will be provided, by way of example only, with reference to the appended drawings, wherein:
Figures A and B are schematic diagrams of polymerizations;
Figure 1 is a plot of a luminescence intensity ratio versus pressure ratio for one exemplified coating of the present invention;
Figure 2 is a PSP image of a wing model coated with the coating of figure l;
and Figure 3 is a comparison of pressure distribution measurements.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Briefly stated, the invention involves a polymer material comprising a backbone
8 containing nitrogen and one or more of sulfur and phosphorous, the polymer material further comprising at least one side chain, wherein either the at least one side chain or the backbone includes a phosphorescent dye agent.
Preferably, the backbone has sulfur and phosphorous, which have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C~_ZO linear or branched alkyl group, a substituted or unsubstituted CZ_ZO linear or branched alkenyl group, a substituted or unsubstituted CZ_ZO linear or branched alkynyl group, a substituted or unsubstituted C~_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent. More particularly, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group bearing the dye agent, as shown, for example, at 2a.
In another aspect, the invention involves a phosphorescent oxygen sensor comprising a substrate having a surface, a polymer material as defined above and applied to the surface to form a coating.
In still another of its aspects, the invention provides a polymer material formed from a phosphorescent dye agent contained in a polymer material of formula A, wherein:
El, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising
Preferably, the backbone has sulfur and phosphorous, which have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C~_ZO linear or branched alkyl group, a substituted or unsubstituted CZ_ZO linear or branched alkenyl group, a substituted or unsubstituted CZ_ZO linear or branched alkynyl group, a substituted or unsubstituted C~_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent. More particularly, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group bearing the dye agent, as shown, for example, at 2a.
In another aspect, the invention involves a phosphorescent oxygen sensor comprising a substrate having a surface, a polymer material as defined above and applied to the surface to form a coating.
In still another of its aspects, the invention provides a polymer material formed from a phosphorescent dye agent contained in a polymer material of formula A, wherein:
El, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising
9 oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group, and wherein at least one of Rl to R6 is a group including a phosphorescent dye agent.
More particularly, the polymer material has a plurality of side chains, at least one of the side chains including the phosphorescent dye agent. Still more preferably, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group including the dye agent. In one embodiment, at least one of the side groups on the phosphorous bears the dye agent and the other side groups of the phosphorous are the same as the second side group on the sulfur.
1 S Preferably, the group including the dye agent includes a ruthenium substituent, more particularly a ruthenium phenanthroline complex.
The polymer material A is useful as an ingredient in phosphorescent oxygen sensors and coatings therefor. The polymer material A is polar, owing to the presence of electron rich sites in its backbone. The constituents of the polymer material A should be selected having regard to the oxygen environment in which the sensing is to take place and in particular the expected temperature ranges in which the sensor so formed is to be expected to be operable and this may be measured by the Glass Transition Temperature (T~), and which may be considered as the boundary of the temperatures substantially above which there is sufficient permeability for gases such as oxygen.
Preferably, the sulfur and phosphorus have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_,o linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C3_zo cycloalkyl group, a substituted C6_zo aryl group and a substituted or unsubstituted C6_zo aralkyl group.
More preferably, El is in the form of sulfur VI and R1 is oxygen, while each of E2 and E3 are phosphorus, providing a repeating PN segment in the backbone along with a relatively small terminating S=O segment. The S=O segment contributes an asymmetry to the backbone to discourage crystallization, which is sensitive to the regularity of the polymer chain. Moreover, the S=O segment contributes to an amorphous structure which is a contributing factor to the gas permeability of resulting polymers.
More preferably, each of R2 to R6 includes an oxygen or a nitrogen substituent and each of R2 to R6 may be provided in the form of an aryloxy group, an alkoxy group, arylamine group or an alkamine group and may include therein a phenyl group.
In this case, the aryloxy and the arylamine tend to increase T~ due to the fact that these groups tend to be relatively more rigid. In contrast, the alkoxy and alkamine groups tend to be more flexible, contributing to a lower T~ and higher permeability. In each of the oxy and amine groups, polarity is increased by the presence of oxygen and nitrogen substitutents.
These oxy and amine groups can be selected with increased polarity by providing for increasing numbers of polar substituents such as oxygen and nitrogen.
If desired, the permeability, T~ and polarity can be tailored by the selection, or for that matter, a mixture of groups along the polymer depending on the contribution of each group.
In some cases, the choice of the R groups may also influence the polarity of the polymer and thus the interactions between the polymer and the dye agent, leading in some cases to relatively uneven distribution and in other cases to relatively even distribution. However, the resulting composition, when used as a phosphorescent sensor, requires no cross-linking and therefore should be a desirable advance, in either case.
The polymers should also be formed so that they are stable for their intended use. In this case, the term stable polymer is intended to mean one which is stable in its intended environment, that is for a given period of time, and when subject to certain conditions, such as hydrolysis. For example, it is contemplated that some examples of such polymers, although stable in the short term may in fact be biodegradable, therefore with a planned breakdown beyond its intended useful life. Furthermore, the polymers should also have photo stability, that is be stable within reasonable tolerances to photo irradiation for the purposes of exiting the phosphorescent dye agent. In addition, the polymers should, to some degree depending on their intended life span, be resistant to attack by singlet oxygen, for example, a byproduct of the quenching process.
In a preferred embodiment, E 1 is in the form of sulfur and E2, E3 are each phosphorus. In a still further preferred embodiment, each of R2 to RS are an arylamine group and R6 is a ruthenium phenanthroline complex, such as Ru(4,7-diphenylphen)3.
Synthesis of an exemplified version of this further preferred version of the polymer material A is shown by the structures 1 to 3 and involves the thermal ring-opening polymerization of the cyclic monomer 1 followed by treatment of the halogenated polymer material 2 with an excess of n-butylamine and is further described below.
The polymer material 3 is a hydrolytically stable amorphous elastomeric material and possesses a Tg of-17 °C giving it both relatively high free volume and gas permeability. The polymer material may also be formed as a relatively high quality film coating with dimensional stability without the need for cross-linking.
The intensity characteristics of a phosphorescent material can be modeled by the Stern-Volmer equation which can be expressed as follows:
Ii.oo/I= A + B(P/P,.oo)~ where I,.oo/I= Luminescence Intensity Ratio ( the 'LIR') I - luminescence intensity, I,,oo = luminescence intensity at 1.00 atmosphere. (used as a reference;
P - air pressure in atmospheres;
A - Coefficient for vacuum condition;
B - Coefficient corresponding to gradient of curve, or rate of change of the Luminescence Intensity Ratio;
Compositions containing the polymer material 3 together with phosphorescent dye agents may show reasonably well-defined Stern-Volmer behaviour and significantly improved sensitivity.
Preferably, the dye agent includes a platinum or a ruthenium substituent. More preferably, the dye agent is selected from the group consisting of Pt octaethylpophyrin, Ru"
bipyridyl and Ru'~ phenanthroline derivatives, though other known organic and inorganic dye agents are contemplated.
Compositions made according to the present invention have been shown to be usable on substrates such as stainless steel and alumina, though other substrates such as glass, plastics and metals are also contemplated.
In another aspect of the present invention, there is provided a copolymer material of the formula B wherein:
E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_,o linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group.
The copolymer material of the formula B may be formed by first providing a first polymer block of the formula A; and then carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein.
Conveniently, the second polymer block can be formed by a ring opening polymerization of a heterocyclic group in the presence of the first polymer block, wherein the heterocyclic group is selected from the group comprising a substituted C3_zo cycloalkyl group, a substituted C6_zo aryl group and a substituted or unsubstituted C6_zo aralkyl group. More preferably, the heterocyclic group is an unsaturated C3_5 cyclic group with the oxygen or nitrogen substituent therein. Still more preferably, the unsaturated heterocyclic group is tetrahydrofuran, ethylene oxide or propylene oxide.
More preferably, E1 is in the form of sulfur VI, while E2 and E3 are each phosphorus and R7 is an electron rich site such as sulfur, oxygen, nitrogen or any one of groups 15 or 16 in the periodic table and provides the electron rich site by virtue of their lone pair of unpaired electrons. The electron rich site is thus able to form a stable electron bond with the electron deficient sulfur and thereby initiate the ring opening polymerization in the presence of the first polymer block.
Preferably, the sulfur in the first polymer block is in a stable form, preferably a hydrolytically stable form, more preferably in the form of sulfur VI in view of the fact that sulfur in other forms such as sulfur IV may be unstable in some cases, such as for example polythiophosphazene. Further examples of unstable sulfur IV polymers may be found in I.
Manners (COORDINATION CHEMISTRY REVIEWS, 137, 1994, 109-129), the subject matter of which is incorporated herein by reference.
The copolymer material made according to the present invention provides improved integrity and one example of the copolymer material is shown at 4. While the polymer material 3 may provide the coating with a generally tacky consistency, the copolymer material 4 may be used to form a layer of material capable of withstanding its own weight. In other words, the copolymer material is envisaged in uses beyond mere coatings but perhaps in the formation or fabrication of devices with an inherent phosphorescent oxygen sensing capability.
It is also contemplated herein to form a polysiloxane polymer with a phosphorescent dye agent as described herein as a member of the polymer matrix.
A sample formed from polymer material 3 or copolymer material 4 with a T~ of -°C will typically allow the sample to be used in environments whose temperatures will substantially exceed -17 °C, that is where the sample will allow for the permeation of oxygen and hence allow for the subsequent quenching of luminescence.
The present invention provides a coating which, in some cases, may provide superior characteristics over those currently available. Like their polysiloxane counterparts, the present coatings based on the polymer material A or the copolymer material B
present phosphorescent properties that change with temperature. However, due to the lack of cross-linking in the matrix, the repeatability of the data presented by coatings based on the polymer material 3 or the copolymer material 4 can be substantially improved over their polysiloxane counterparts.
The present coatings form improved films with relatively faster drying times and without supplemental curing which is necessary for polysiloxane polymers. The present coatings have improved mechanical integrity and are believed to have substantially no long term flow (creep) on the surface.
Tables 1 to 4 are provided to illustrate a selection of possible groups for R1 to R6 in the polymer material of the formula A . These tables are obtained from several published papers, namely I. Manners (COORDINATION CHEMISTRY REVIEWS, 137, 1994, 109-129), the subject matter of which is incorporated herein by reference, and Y.
Ni et al (MACROMOLECULES 1992, 27, 7119), the subject matter of which is also incorporated herein by reference. It is worth noting that a number of R groups have T~ in the region of -18°C to 25°C and these may be considered desirable R groups for some applications.
Further details of the formation of copolymer material 4 can be seen in figure A and is believed to be representative of one method of forming in general the copolymer materials of formula B. In this case, the sulfur VI canon from poly(thionylphosphazene) attacks an oxygen site on a THF molecule to form an oxonium ion. Further reaction ofthis oxonium ion with more monomer generates a poly(THF) block.
In yet another of its aspects, the present invention provides a coating composition comprising a polymer material, the polymer having a backbone and at least one side group with a phosphorescent dye agent as a member of the backbone or the side group, the polymer being capable of being applied as a coating. Preferably, the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
In yet another of its aspects, the present invention provides a phosphorescent dye agent, comprising a phenanthroline complex which is reactive to form a polymer with the dye agent as a constituent thereof. Preferably, the complex is a ruthenium phenanthroline complex.
In still another of its aspects, the present invention provides a polymer material comprising the phosphorescent dye agent as a constituent thereof or as a substituent therein.
In still another of its aspects, the present invention provides a method of forming a phosphorescent dye agent, comprising the steps o~
providing a phenanthroline complex with a dye agent as a constituent thereof;
and forming a reactive site on the complex which is reactive to form a polymer.
Preferably, the complex is a ruthenium phenanthroline complex.
In yet another of its aspects, the present invention provides a method of forming a phosphorescent polymer material, comprising the steps of:
providing a phenanthroline complex with a dye agent as a constituent thereof;
forming a reactive site on the complex; and reacting the complex with a monomer to form a polymer.
Thus, the materials as described above provide for the use of poly(thionylphosphazenes) as shown at 3 which contain the phosphorescent dye agent as a constituent part of the polymer structure. The materials described herein provide increased loading of the dye agent which allows higher intrinsic intensity of phosphorescence making observation of light emission from the coatings easier. The materials herein also provide improved compatibility between the dye agent and the polymer matrix which may, in some cases, lead to more predictable Stern-Volmer behaviour. It is believed that the dye agent loading may also raise the potential use of thinner films which would thus allow more rapid response, which in turn may permit measurements in such applications as fluctuating pressure systems.
The dye bound polymer may be formed, for example, by providing a dye agent with at least one functional group, such as an amino group, which is a candidate for reaction with one or more side groups on halogenated polymer 2 to substitute at least one halogen with the functionalized dye agent, followed by treatment of the halogenated polymer with an excess of an amino group such as, for example, n-butylamine, as is described below, to form the polymer 2a. The polymer 2a may then be present in a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein, such as tetrahydrofuran or the others named above.
In yet another of its aspects the present invention provides a polymer material formed from a polymer material having a backbone containing nitrogen and one or more of nitrogen and phosphorous, the polymer material including at least one side group having a silicone constituent.
Preferably, the backbone has sulfur and phosphorous, the polymer is stable, more preferably hydrolitically stable, still more preferably with its sulfur in the form of sulfur VI.
More preferably, the polymer material includes a number of silicone side groups. Still more preferably, each of the silicone side groups has a trimethylsilyl constituent.
Still more preferably, each phosphorous in the backbone has a side group including silicone. Still more preferably, each side group on each phosphorus in the backbone includes a trimethylsilyl group.
In yet another of its aspects, the present invention provides a polymer material of formula A wherein E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus and any one or more of R1 to R6 includes a siloxane group.
In still another of its aspects, the present invention involves a copolymer material of formula B wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo ~'Yl group, a substituted or unsubstituted C3_zo cYcloalkyl group; and wherein at least one of R1 to R6 is a group including a siloxane group;
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C,_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted CZ_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
In yet another of its aspects, the present invention provides a method of forming a pressure sensor, comprising the steps of forming a stable polymer having a backbone containing nitrogen and one or more of sulfur and phosphorus, and with a plurality of side groups, and providing a silicone constituent on at least one of the side groups. Preferably, the backbone has sulfur and phosphorous, and at least one silicone constituent is provided on a plurality of the side groups. More preferably, each side group on the phosphorus includes a silicone constituent. Still more preferably, the sulfur has one side group including oxygen and a second side group including a silicone constituent.
In yet another aspect of the present invention, there is provided a polymer material having a backbone containing nitrogen and one or more of nitrogen and phosphorous, and at least one silicone including side group. Preferably, the polymer material has a backbone including sulfur and phosphorous and has a glass transition temperature ranging from -20 °C
to 0°C.
In yet another aspect of the present invention, there is provided a pressure sensor comprising a stable polymer material as defined above and a phosphorescent dye agent.
Preferably, the polymer and dye agent are in the form of a coating. More preferably, the pressure sensor is operatively characterized by a Stern Volmer plot having ranging from 0.980 to 1Ø More preferably, the sensor exhibits a Stern Volmer plot having a linearity ranging from 0.985 to 0.995, still more preferably 0.990 to 0.995. Still more preferably, the pressure sensors herein can in some cases be operatively characterized by a Stern Volmer plot having the above ranges of linearity over a range of pressures, namely from about 0.1 to 75 psi, more preferably 0.1 to 50 psi, still more preferably 0.2 to 40 psi.
Pressure sensors made according to the present invention can, in some cases, also be operatively characterized by a Stern Volmer plot having a slope ranging from 0.1 to 1.0, more preferably 0.2 to 0.9, more preferably 0.4 to 0.7 still more preferably 0.49 to 0.6 (for example ranging from 0.17 - 0.18, for one example of PTP(aminopropyltrisiloxane), and ranging from 0.49 to 0.60 for examples of the copolymer of Poly(THF) and PTP(aminopropyltrisiloxane)).
A polymer with at least one silicone-bearing side group may be formed, for example, by reacting the halogenated polymer 2 with a silicone-bearing side group having at least one functional group, such as an amino group, the latter to react with at least one of the halogen side groups on the polymer 2 to yield a polymer such as that shown at 5.
The co-polymer 4 may also include at least one silicon-bearing side group and this copolymer may be formed by subjecting the halogenated polymer 2 to a ring-opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein, such as tetrahydrofuran or the others named above, and thereafter subjecting the resulting halogenated copolymer to an excess of a silicone group having at least one functional site, such as an amino group, leading to a co-polymer such as that shown at 7.
Thus, the polymer of formula 5 incorporates silicones as side groups and thus should, in some cases, make such polymers more permeable to oxygen while the backbone allows for film formation without the need for cross-linking. The combination of the non-cross-linking capability provided in this case by the sulfur, nitrogen and/or phosphorous, and the improved permeability provided by one or more side groups should, in some cases, provide improved sensitivity as well as more predictable and linear Stern-Volmer behaviour.
Copolymers and blends with organic monomers (such as THF as shown above) should in some cases also provide additional improvements and performance.
Thus, the polymer materials disclosed herein and the polymer materials formed with these polymer materials and a dye agent may be useful in a number of environments, including that ofpressure sensors, particularly phosphorescent sensors when used with phosphorescent dye agents, in a number of different oxygen environments, such as in the atmosphere, in other oxygen-containing fluid environments, such as in gases and liquids containing oxygen, with particular applications including that of measuring the efficiency of aeronautic and aquatic I 5 planforms (such as air craft fuselages and boat hulls), the measurement of the presence of (and possibly the content of) oxygen in ground water and the like.
While discussions herein are focused on polymers having nitrogen and both sulfur and phosphorous in the backbone, there are contemplated other polymers which do not necessarily have both sulfur and phosphorous. For example, other polymers may just have repeating S-N-S-N or P-N-P-N backbones, or of other irregularly or regularly repeating combinations of N, S and/or P.
Embodiments of the present invention will be described with reference to the following examples which are presented for illustrative purposes only and are not intended to limit the scope of the invention.
EXAMPLE: SYNTHESIS OF A DYE-BOUND POLYMER
5-amino-1,10-phenanthroline:
To a solution of 5-nitro-1,10 phenanthroline (1.00g) in ethanol (40 ml) with Pd/C
(0.40 g) were added sodium borohydride (2.00 g) in several portions over 2 hours. The resulting solution was kept stirring for 12 hours under N,. The solution was filtered and the filtrate was concentrated. Then ether was added to the filtrate to crystallize the product (0.33 g, yield: 38%).
4-aminomethyl-1,10-phenanthroline:
This synthesis was accomplished in 3 steps from 4-methyl-1,10-phenanthroline.
1,10-phenanthroline-4-carboaldehyde: Se02 ( 1.22 g, 99%) was dissolved in 20 ml refluxing dioxane/water (v/v, 94:4). 4-methyl-1,10-phenanthroline (1.00 g) in 80 ml dioxane/water (v/v, 94:4) was added drop wise over 1 hour. Refluxing was continued for 2 hours under N2.
The resulting solution was filtered through celite when hot. The product (1.00 g, containing selenium residues) crystallized as yellow solids and were used without further purification.
1,10-phenanthroline-4-carboaldoxime: A solution of the 1,10-phenanthroline-4-carboaldehyde product (1.00 g), hydroxyamine hydrochloride (2.00 g) and pyridine (4 ml) in ethanol (60 ml) was heated under reflux for 12 hours under N2. The resulting grey solids were separated from the ethanol solution. The grey solids were recrystallized in hot ethanol.
The product was dried in vacuo (0.65 g, yield: 61 %).
4-aminomethyl-1,10-phenanthroline: A suspension solution of 1,10-phenanthroline-4-carboaldoxime (0.5 g) in 100 ml ethanol containing 2% perchloric acid was hydrogenated at atmospheric pressure, over 10% Pd/C ( 150 mg) for 12 hours and then was refluxed for 2 hours. The solution was filtered and the filtrate was concentrated. Ether was added to the filtrate to crystallize the product (0.44 g, 97%).
Synthesis of Ru Dyes Functionalized with Amino Groups Cis-Dichlorobis (4,7-diphenyl-1,10-phenanthroline)ruthenium: Ruthenium trichloride (2.0 g), 4,7-diphenyl-1,10-phenanthroline (5.8 g), lithium chloride (2.2 g) were heated at reflux in 30 ml of DMF for 3 hours. The solution was then added with 80 ml of acetone and stored at 0°C overnight. Purple solids were collected by suction filtration and washed by water. The crude products were stirred in the cold acetone for 3 hours and filtered. The product suspended in water (100 ml) was heated under reflux for 2 hours and treated with lithium chloride (5.0 g). The purple solids precipitated from the cold solution and were filtered and dried in vacuo (2.5 g).
Ru[4,7-diphenyl-1,10-phenanthroline)2(L)][C104]z (L=5-amino-1,10-phenanthroline or 4-I 5 aminomethyl-1,10-phenanthroline):
Ru(4,7-diphenyl-1,10-phenanthroline),C1, (200 mg) and 60 mg of L were heated under reflux in 200 ml ethanol/water (v/v 70:30) for 18 hours under N,. The resulting solution was treated with LiCIOa (4.0 g). Red orange solids were collected by filtration and washed by water, hexane and ether (200 g, yield: 90%).
Synthesis of Dye Bound Polymer:
A CHZC12 solution of Ru[4,7-diphenyl-1,10-phenanthroline)2(L)]z (L=5-amino-1,10-phenanthroline or 4-aminomethyl-1,10-phenanthroline) (1.0 mg) was added to poly(pentachlorothionylphosphazene) (200 mg) in CH,C12 solution while being stirred at room temperature. After 4 hours, the mixture was cooled to 0°C and excess n-BuNHz (10 equiv.) was added into the mixture and was stirred for overnight. After this reaction finished, the polymer was precipitated in water (three times) and then precipitated in water methanol (three times). Characterization was achieved by 1 H NMR and 31 P NMR. Films were spray coated from organic solvents such as CH,CI, or 1,2-dichloroethane.
ANALYSIS
Samples were placed in a pressure chamber which was equipped with a viewing window to permit in-situ pressure measurements. The pressure chamber was equipped with an adjustable pressure supply of compressed air. All the measurements were made at room temperature (22 ~ 1 °C).
An imaging system was used to detect changes in luminescence intensity as a function of pressures. A 75 Watt tungsten Halogen lamp was used as a light source with a 40 nm band pass filter centred at 450 nm to obtain the blue light. A cut-off filter, corresponding to OG
590 nm for the Ruthenium dye-bound polymer, was placed in front of a liquid nitrogen cooled CCD detector (MODEL LN/CCD, PRINCETON INSTRUMENTS, INC.) with 578 x 384 pixels in a cell size of 13.25 X 8.83 mm'-. Luminescent light from the sample surface was collected with a camera lens (NIKON, SSmm,1:1.2) and imaged onto the CCD
detector. The pressure of the sample chamber was measured by a pressure gauge (MODEL FA233, WALLACE AND TIERNAN) with an accuracy of ~ 0.1 psi. The results are shown in figure 1, as a plot of a luminescence intensity ratio versus pressure ratio, showing a substantially linear relationship therebetween.
A scale wing model was also coated with the dye-bound polymer as discussed herein above and was positioned in a 5X5 foot wind tunnel and subjected to wind speeds of Mach 0.8. Two images were taken in order to calculate the pressure distribution over the model surface. One image (hereinafter referred to as the 'wind-on' image) was taken when the wind speed was Mach 0.8 where the pressure distribution on the model is unknown.
The other image (hereinafter referred to as the 'wind-off image) was taken when the wind was off so that the pressure distribution on the model was a constant of 1 atm. The wind-off image was divided by the wind-on image and the resulting image was shown in figure 2, which presents a complete static pressure mapping. Figure 2 also demonstrates, for example, the transition from relatively low pressure present at the leading edge of the wing (as shown by the dark colour) to a relatively high pressure at the trailing edge of the wing, as would be expected.
Figure 3 is a comparison of pressure distribution measurements on a wing model at Mach 0.8.
The solid circles are pressure tap measurements and the solid line is a pressure sensitive paint measurement.
EXAMPLE: SYNTHESIS OF POLYMER WITH SILOXANE SIDE GROUP
(3-aminopropyl)-heptamethyltrisiloxane.
In a 250 mL round bottom flask was placed freshly distilled (N-trimethylsilyl)allylamine ( 10 g, 0.07 mol) (which was prepared via the literature procedure of Bachrach and co-workers in Bachrach, A., Zilkha, A. Eur. Polym. J. 1984, 20, 493. Also see Speir, J.
L. Adv.
Organomet. Chem. 1979, 17, 407.) was mixed with freshly distilled 1,1,1,3,3,5,5-heptamethyltrisiloxane ( 17.2 g, 0.07 mol). To this was added THF 0100 mL) and chloroplatinic acid hexahydrate (0.5 mol. %). The reaction mixture was refluxed for 12 hours or until no Si-H stretching peak in the infrared spectrum at 2145 cm' could be detected. The reaction mixture was then cooled to room temperature, and a large excess of 95% ethanol (~SOmL) was added. The reaction mixture was then refluxed for 12 hours to remove the N-trimethylsilyl protecting group. The product was isolated by vacuum distillation and purified by vacuum fractional distillation from Ba0 [bp 45 ~C
(0.05 mmHg)]. (18 g, 83 %). 'H NMR (CDCl3) 8(ppm): 2.65 (1H, m, CHZCHZCHZ), 1.46 (2H, m, CHZCHzCH2), 0.52 (2H, m, CHZCHZCHZ), 0.13 (9H, s, Si(CH3)3), 0.11 (6H, s, Si(CH3)z), 0.05 (6H, s, Si(CH3)Z). '3C NMR (CDZCIZ) S(ppm): 45.85 (H2NCH2CHZCH2-), 28.01 (HZNCHZCHZCHZ-), 15.80 (HZNCHZCH2CHz-), 2.32, 1.78, 0.65 (Si(CH3)).
Poly(aminopropyl-heptamethyltrisiloxane)thionylphosphazene The cyclic thionylphosphaaene (2.0 g) was heated in an evacuated sealed Pyrex tube at 165 ~C for 4 h. The tube contents were then dissolved in ca. (ie.
approximately) 40 ml of CHZCIz and the solution was concentrated to ca 10 ml and was then added dropwise to 200 ml of stirred hexanes via cannula. The colorless, moisture sensitive, elastomeric polymer was dissolved in 100 ml of CHZClzand (3-aminopropyl)-heptamethyltrisiloxane was added dropwise to the polymer solution which was cooled to 0 ~C. White precipitation formed immediately after the addition. The solution was concentrated to ca. 20 ml and filtered through a filter frit. the precipitation was carried out by first redissolving the dried crude product in ca. 10 ml of THF then precipitating into water three times followed by precipitating from CHZCIz into hexanes three times. Final product was dried from CHZC12 under high vacuum for 24 hours at ambient temperature (84 %). 3'P NMR (CHZCIz) 8(ppm):
1.45, 0.94. 'H NMR (CDC13) 8(ppm): 2.85 (m, br, propyl), 1.48 (m, br, propyl), 0.63 (m, br, propyl), 0.12(s, br, Si(CH3)), 0.04 (s, br, Si(CH3)). '3C NMR (CDZCl2) 8(ppm): 44.76 (propyl), 26.17 (propyl), 16.15 (propyl), 2.02, 1.62, 0.67 (Si(CH3)). 29Si NMR
(CHZCIz) 8(ppm): 9.22, -0.80, -18.70. GPC measurement: Mw = 1.44 x 105, PDI = 1.8.
Poly[(aminopropyl-heptamethyltrisiloxane)thionylphosphazene]-b-poly(tetrahydrofuran) The cyclic thionylphosphazene (2.0 g) was heated in an evacuated sealed Pyrex tube at 165 ~C for 4 h. The tube contents were then dissolved in ca. 40 ml of CHZC12 and the solution was concentrated to ca 10 ml and was then added dropwise to 200 ml of stirred hexanes via cannula. The colorless, moisture sensitive, elastomeric polymer was dissolved in 100 ml of THF and the solution then stored in the refrigerator at -14 ~C
for 48 h. A
significant solution viscosity increase was noticed. (3-aminopropyl)-heptamethyltrisiloxane was added dropwise to the polymer solution which was cooled to 0 oC. White precipitation formed immediately after the addition. The solution was concentrated to ca. 20 ml and filtered through a filter frit. The precipitation was carried out by first redissolving the dried crude product in ca. 10 ml of THF then precipitating into water three times followed by precipitating from CHzCl2 into hexanes three times. Final product was dried from CHzCIz under high vacuum for 24 hours at ambient temperature. Yield of 5, a colorless film forming material (79 %). 3'P NMR (CHZC12) 8(ppm): 1.39, 0.94. 'H NMR (CDCl3) 8(ppm):
3.45 (s, br, poly-THF), 3.01 (m, br, propyl), 1.65 (s, br, poly-THF), 1.37 (m, br, propyl), 0.94 (m, br, propyl), 0.15 (s, br, Si(CH3)), 0.05 (s, br, Si(CH3)). '3C NMR (CDZC12) 8(ppm): 71.33 (poly-THF), 45.16 (propyl), 27.43 (poly-THF), 26.51 (propyl), 16.44 (propyl), 2.40, 1.57, 1.07 (Si(CH3)). GPC measurment: Mw = 2.93 x 105, PDI = 1.8.
ANALYSIS
Samples utilizing the siloxane-bound polymers were placed in a pressure chamber which was equipped with a viewing window to permit in-situ pressure measurements. The pressure chamber was equipped with an adj ustable pressure supply of compressed air. All the measurements were made at room temperature (22 ~ 1 °C).
An imaging system was used to detect changes in luminescence intensity as a function of pressures. A 75 Watt tungsten Halogen lamp was used as a light source with a 40 nm band pass filter centred at 450 nm to obtain the blue light. A cut-off filter, corresponding to OG
590 nm for the Ruthenium dye-bound polymer, was placed in front of a liquid nitrogen cooled CCD detector (MODEL LN/CCD, PRINCETON INSTRUMENTS, INC.) with 578 x 384 pixels in a cell size of 13.25 X 8.83 mm'. Luminescent light from the sample surface was collected with a camera lens (NIKON, SSmm, 1:1.2) and imaged onto the CCD
detector. The pressure of the sample chamber was measured by a pressure gauge (MODEL FA233, WALLACE AND TIERNAN) with an accuracy of ~ 0.1 psi.
Testing of several samples in this manner yielded standard Stern Volmer plots with slopes ranging from 0.17 - 0.18, and for the copolymer of Poly(THF) and PTP(aminopropyltrisiloxane) ranging from 0.49 to 0.60, with a linearity ranging from 0.990 to 1Ø
More particularly, the polymer material has a plurality of side chains, at least one of the side chains including the phosphorescent dye agent. Still more preferably, the sulfur has a first side group including oxygen and a second side group, the phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBu" or a group including the dye agent. In one embodiment, at least one of the side groups on the phosphorous bears the dye agent and the other side groups of the phosphorous are the same as the second side group on the sulfur.
1 S Preferably, the group including the dye agent includes a ruthenium substituent, more particularly a ruthenium phenanthroline complex.
The polymer material A is useful as an ingredient in phosphorescent oxygen sensors and coatings therefor. The polymer material A is polar, owing to the presence of electron rich sites in its backbone. The constituents of the polymer material A should be selected having regard to the oxygen environment in which the sensing is to take place and in particular the expected temperature ranges in which the sensor so formed is to be expected to be operable and this may be measured by the Glass Transition Temperature (T~), and which may be considered as the boundary of the temperatures substantially above which there is sufficient permeability for gases such as oxygen.
Preferably, the sulfur and phosphorus have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_,o linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
Preferably, the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C3_zo cycloalkyl group, a substituted C6_zo aryl group and a substituted or unsubstituted C6_zo aralkyl group.
More preferably, El is in the form of sulfur VI and R1 is oxygen, while each of E2 and E3 are phosphorus, providing a repeating PN segment in the backbone along with a relatively small terminating S=O segment. The S=O segment contributes an asymmetry to the backbone to discourage crystallization, which is sensitive to the regularity of the polymer chain. Moreover, the S=O segment contributes to an amorphous structure which is a contributing factor to the gas permeability of resulting polymers.
More preferably, each of R2 to R6 includes an oxygen or a nitrogen substituent and each of R2 to R6 may be provided in the form of an aryloxy group, an alkoxy group, arylamine group or an alkamine group and may include therein a phenyl group.
In this case, the aryloxy and the arylamine tend to increase T~ due to the fact that these groups tend to be relatively more rigid. In contrast, the alkoxy and alkamine groups tend to be more flexible, contributing to a lower T~ and higher permeability. In each of the oxy and amine groups, polarity is increased by the presence of oxygen and nitrogen substitutents.
These oxy and amine groups can be selected with increased polarity by providing for increasing numbers of polar substituents such as oxygen and nitrogen.
If desired, the permeability, T~ and polarity can be tailored by the selection, or for that matter, a mixture of groups along the polymer depending on the contribution of each group.
In some cases, the choice of the R groups may also influence the polarity of the polymer and thus the interactions between the polymer and the dye agent, leading in some cases to relatively uneven distribution and in other cases to relatively even distribution. However, the resulting composition, when used as a phosphorescent sensor, requires no cross-linking and therefore should be a desirable advance, in either case.
The polymers should also be formed so that they are stable for their intended use. In this case, the term stable polymer is intended to mean one which is stable in its intended environment, that is for a given period of time, and when subject to certain conditions, such as hydrolysis. For example, it is contemplated that some examples of such polymers, although stable in the short term may in fact be biodegradable, therefore with a planned breakdown beyond its intended useful life. Furthermore, the polymers should also have photo stability, that is be stable within reasonable tolerances to photo irradiation for the purposes of exiting the phosphorescent dye agent. In addition, the polymers should, to some degree depending on their intended life span, be resistant to attack by singlet oxygen, for example, a byproduct of the quenching process.
In a preferred embodiment, E 1 is in the form of sulfur and E2, E3 are each phosphorus. In a still further preferred embodiment, each of R2 to RS are an arylamine group and R6 is a ruthenium phenanthroline complex, such as Ru(4,7-diphenylphen)3.
Synthesis of an exemplified version of this further preferred version of the polymer material A is shown by the structures 1 to 3 and involves the thermal ring-opening polymerization of the cyclic monomer 1 followed by treatment of the halogenated polymer material 2 with an excess of n-butylamine and is further described below.
The polymer material 3 is a hydrolytically stable amorphous elastomeric material and possesses a Tg of-17 °C giving it both relatively high free volume and gas permeability. The polymer material may also be formed as a relatively high quality film coating with dimensional stability without the need for cross-linking.
The intensity characteristics of a phosphorescent material can be modeled by the Stern-Volmer equation which can be expressed as follows:
Ii.oo/I= A + B(P/P,.oo)~ where I,.oo/I= Luminescence Intensity Ratio ( the 'LIR') I - luminescence intensity, I,,oo = luminescence intensity at 1.00 atmosphere. (used as a reference;
P - air pressure in atmospheres;
A - Coefficient for vacuum condition;
B - Coefficient corresponding to gradient of curve, or rate of change of the Luminescence Intensity Ratio;
Compositions containing the polymer material 3 together with phosphorescent dye agents may show reasonably well-defined Stern-Volmer behaviour and significantly improved sensitivity.
Preferably, the dye agent includes a platinum or a ruthenium substituent. More preferably, the dye agent is selected from the group consisting of Pt octaethylpophyrin, Ru"
bipyridyl and Ru'~ phenanthroline derivatives, though other known organic and inorganic dye agents are contemplated.
Compositions made according to the present invention have been shown to be usable on substrates such as stainless steel and alumina, though other substrates such as glass, plastics and metals are also contemplated.
In another aspect of the present invention, there is provided a copolymer material of the formula B wherein:
E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_,o linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted C,_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cYcloalkyl group.
The copolymer material of the formula B may be formed by first providing a first polymer block of the formula A; and then carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein.
Conveniently, the second polymer block can be formed by a ring opening polymerization of a heterocyclic group in the presence of the first polymer block, wherein the heterocyclic group is selected from the group comprising a substituted C3_zo cycloalkyl group, a substituted C6_zo aryl group and a substituted or unsubstituted C6_zo aralkyl group. More preferably, the heterocyclic group is an unsaturated C3_5 cyclic group with the oxygen or nitrogen substituent therein. Still more preferably, the unsaturated heterocyclic group is tetrahydrofuran, ethylene oxide or propylene oxide.
More preferably, E1 is in the form of sulfur VI, while E2 and E3 are each phosphorus and R7 is an electron rich site such as sulfur, oxygen, nitrogen or any one of groups 15 or 16 in the periodic table and provides the electron rich site by virtue of their lone pair of unpaired electrons. The electron rich site is thus able to form a stable electron bond with the electron deficient sulfur and thereby initiate the ring opening polymerization in the presence of the first polymer block.
Preferably, the sulfur in the first polymer block is in a stable form, preferably a hydrolytically stable form, more preferably in the form of sulfur VI in view of the fact that sulfur in other forms such as sulfur IV may be unstable in some cases, such as for example polythiophosphazene. Further examples of unstable sulfur IV polymers may be found in I.
Manners (COORDINATION CHEMISTRY REVIEWS, 137, 1994, 109-129), the subject matter of which is incorporated herein by reference.
The copolymer material made according to the present invention provides improved integrity and one example of the copolymer material is shown at 4. While the polymer material 3 may provide the coating with a generally tacky consistency, the copolymer material 4 may be used to form a layer of material capable of withstanding its own weight. In other words, the copolymer material is envisaged in uses beyond mere coatings but perhaps in the formation or fabrication of devices with an inherent phosphorescent oxygen sensing capability.
It is also contemplated herein to form a polysiloxane polymer with a phosphorescent dye agent as described herein as a member of the polymer matrix.
A sample formed from polymer material 3 or copolymer material 4 with a T~ of -°C will typically allow the sample to be used in environments whose temperatures will substantially exceed -17 °C, that is where the sample will allow for the permeation of oxygen and hence allow for the subsequent quenching of luminescence.
The present invention provides a coating which, in some cases, may provide superior characteristics over those currently available. Like their polysiloxane counterparts, the present coatings based on the polymer material A or the copolymer material B
present phosphorescent properties that change with temperature. However, due to the lack of cross-linking in the matrix, the repeatability of the data presented by coatings based on the polymer material 3 or the copolymer material 4 can be substantially improved over their polysiloxane counterparts.
The present coatings form improved films with relatively faster drying times and without supplemental curing which is necessary for polysiloxane polymers. The present coatings have improved mechanical integrity and are believed to have substantially no long term flow (creep) on the surface.
Tables 1 to 4 are provided to illustrate a selection of possible groups for R1 to R6 in the polymer material of the formula A . These tables are obtained from several published papers, namely I. Manners (COORDINATION CHEMISTRY REVIEWS, 137, 1994, 109-129), the subject matter of which is incorporated herein by reference, and Y.
Ni et al (MACROMOLECULES 1992, 27, 7119), the subject matter of which is also incorporated herein by reference. It is worth noting that a number of R groups have T~ in the region of -18°C to 25°C and these may be considered desirable R groups for some applications.
Further details of the formation of copolymer material 4 can be seen in figure A and is believed to be representative of one method of forming in general the copolymer materials of formula B. In this case, the sulfur VI canon from poly(thionylphosphazene) attacks an oxygen site on a THF molecule to form an oxonium ion. Further reaction ofthis oxonium ion with more monomer generates a poly(THF) block.
In yet another of its aspects, the present invention provides a coating composition comprising a polymer material, the polymer having a backbone and at least one side group with a phosphorescent dye agent as a member of the backbone or the side group, the polymer being capable of being applied as a coating. Preferably, the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
In yet another of its aspects, the present invention provides a phosphorescent dye agent, comprising a phenanthroline complex which is reactive to form a polymer with the dye agent as a constituent thereof. Preferably, the complex is a ruthenium phenanthroline complex.
In still another of its aspects, the present invention provides a polymer material comprising the phosphorescent dye agent as a constituent thereof or as a substituent therein.
In still another of its aspects, the present invention provides a method of forming a phosphorescent dye agent, comprising the steps o~
providing a phenanthroline complex with a dye agent as a constituent thereof;
and forming a reactive site on the complex which is reactive to form a polymer.
Preferably, the complex is a ruthenium phenanthroline complex.
In yet another of its aspects, the present invention provides a method of forming a phosphorescent polymer material, comprising the steps of:
providing a phenanthroline complex with a dye agent as a constituent thereof;
forming a reactive site on the complex; and reacting the complex with a monomer to form a polymer.
Thus, the materials as described above provide for the use of poly(thionylphosphazenes) as shown at 3 which contain the phosphorescent dye agent as a constituent part of the polymer structure. The materials described herein provide increased loading of the dye agent which allows higher intrinsic intensity of phosphorescence making observation of light emission from the coatings easier. The materials herein also provide improved compatibility between the dye agent and the polymer matrix which may, in some cases, lead to more predictable Stern-Volmer behaviour. It is believed that the dye agent loading may also raise the potential use of thinner films which would thus allow more rapid response, which in turn may permit measurements in such applications as fluctuating pressure systems.
The dye bound polymer may be formed, for example, by providing a dye agent with at least one functional group, such as an amino group, which is a candidate for reaction with one or more side groups on halogenated polymer 2 to substitute at least one halogen with the functionalized dye agent, followed by treatment of the halogenated polymer with an excess of an amino group such as, for example, n-butylamine, as is described below, to form the polymer 2a. The polymer 2a may then be present in a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein, such as tetrahydrofuran or the others named above.
In yet another of its aspects the present invention provides a polymer material formed from a polymer material having a backbone containing nitrogen and one or more of nitrogen and phosphorous, the polymer material including at least one side group having a silicone constituent.
Preferably, the backbone has sulfur and phosphorous, the polymer is stable, more preferably hydrolitically stable, still more preferably with its sulfur in the form of sulfur VI.
More preferably, the polymer material includes a number of silicone side groups. Still more preferably, each of the silicone side groups has a trimethylsilyl constituent.
Still more preferably, each phosphorous in the backbone has a side group including silicone. Still more preferably, each side group on each phosphorus in the backbone includes a trimethylsilyl group.
In yet another of its aspects, the present invention provides a polymer material of formula A wherein E 1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus and any one or more of R1 to R6 includes a siloxane group.
In still another of its aspects, the present invention involves a copolymer material of formula B wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted Cz_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted Cz_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo ~'Yl group, a substituted or unsubstituted C3_zo cYcloalkyl group; and wherein at least one of R1 to R6 is a group including a siloxane group;
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C,_zo linear or branched alkyl group, a substituted or unsubstituted Cz_zo linear or branched alkenyl group, a substituted or unsubstituted CZ_zo linear or branched alkynyl group, a substituted or unsubstituted C6_zo aryl group, a substituted or unsubstituted C3_zo cycloalkyl group.
In yet another of its aspects, the present invention provides a method of forming a pressure sensor, comprising the steps of forming a stable polymer having a backbone containing nitrogen and one or more of sulfur and phosphorus, and with a plurality of side groups, and providing a silicone constituent on at least one of the side groups. Preferably, the backbone has sulfur and phosphorous, and at least one silicone constituent is provided on a plurality of the side groups. More preferably, each side group on the phosphorus includes a silicone constituent. Still more preferably, the sulfur has one side group including oxygen and a second side group including a silicone constituent.
In yet another aspect of the present invention, there is provided a polymer material having a backbone containing nitrogen and one or more of nitrogen and phosphorous, and at least one silicone including side group. Preferably, the polymer material has a backbone including sulfur and phosphorous and has a glass transition temperature ranging from -20 °C
to 0°C.
In yet another aspect of the present invention, there is provided a pressure sensor comprising a stable polymer material as defined above and a phosphorescent dye agent.
Preferably, the polymer and dye agent are in the form of a coating. More preferably, the pressure sensor is operatively characterized by a Stern Volmer plot having ranging from 0.980 to 1Ø More preferably, the sensor exhibits a Stern Volmer plot having a linearity ranging from 0.985 to 0.995, still more preferably 0.990 to 0.995. Still more preferably, the pressure sensors herein can in some cases be operatively characterized by a Stern Volmer plot having the above ranges of linearity over a range of pressures, namely from about 0.1 to 75 psi, more preferably 0.1 to 50 psi, still more preferably 0.2 to 40 psi.
Pressure sensors made according to the present invention can, in some cases, also be operatively characterized by a Stern Volmer plot having a slope ranging from 0.1 to 1.0, more preferably 0.2 to 0.9, more preferably 0.4 to 0.7 still more preferably 0.49 to 0.6 (for example ranging from 0.17 - 0.18, for one example of PTP(aminopropyltrisiloxane), and ranging from 0.49 to 0.60 for examples of the copolymer of Poly(THF) and PTP(aminopropyltrisiloxane)).
A polymer with at least one silicone-bearing side group may be formed, for example, by reacting the halogenated polymer 2 with a silicone-bearing side group having at least one functional group, such as an amino group, the latter to react with at least one of the halogen side groups on the polymer 2 to yield a polymer such as that shown at 5.
The co-polymer 4 may also include at least one silicon-bearing side group and this copolymer may be formed by subjecting the halogenated polymer 2 to a ring-opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein, such as tetrahydrofuran or the others named above, and thereafter subjecting the resulting halogenated copolymer to an excess of a silicone group having at least one functional site, such as an amino group, leading to a co-polymer such as that shown at 7.
Thus, the polymer of formula 5 incorporates silicones as side groups and thus should, in some cases, make such polymers more permeable to oxygen while the backbone allows for film formation without the need for cross-linking. The combination of the non-cross-linking capability provided in this case by the sulfur, nitrogen and/or phosphorous, and the improved permeability provided by one or more side groups should, in some cases, provide improved sensitivity as well as more predictable and linear Stern-Volmer behaviour.
Copolymers and blends with organic monomers (such as THF as shown above) should in some cases also provide additional improvements and performance.
Thus, the polymer materials disclosed herein and the polymer materials formed with these polymer materials and a dye agent may be useful in a number of environments, including that ofpressure sensors, particularly phosphorescent sensors when used with phosphorescent dye agents, in a number of different oxygen environments, such as in the atmosphere, in other oxygen-containing fluid environments, such as in gases and liquids containing oxygen, with particular applications including that of measuring the efficiency of aeronautic and aquatic I 5 planforms (such as air craft fuselages and boat hulls), the measurement of the presence of (and possibly the content of) oxygen in ground water and the like.
While discussions herein are focused on polymers having nitrogen and both sulfur and phosphorous in the backbone, there are contemplated other polymers which do not necessarily have both sulfur and phosphorous. For example, other polymers may just have repeating S-N-S-N or P-N-P-N backbones, or of other irregularly or regularly repeating combinations of N, S and/or P.
Embodiments of the present invention will be described with reference to the following examples which are presented for illustrative purposes only and are not intended to limit the scope of the invention.
EXAMPLE: SYNTHESIS OF A DYE-BOUND POLYMER
5-amino-1,10-phenanthroline:
To a solution of 5-nitro-1,10 phenanthroline (1.00g) in ethanol (40 ml) with Pd/C
(0.40 g) were added sodium borohydride (2.00 g) in several portions over 2 hours. The resulting solution was kept stirring for 12 hours under N,. The solution was filtered and the filtrate was concentrated. Then ether was added to the filtrate to crystallize the product (0.33 g, yield: 38%).
4-aminomethyl-1,10-phenanthroline:
This synthesis was accomplished in 3 steps from 4-methyl-1,10-phenanthroline.
1,10-phenanthroline-4-carboaldehyde: Se02 ( 1.22 g, 99%) was dissolved in 20 ml refluxing dioxane/water (v/v, 94:4). 4-methyl-1,10-phenanthroline (1.00 g) in 80 ml dioxane/water (v/v, 94:4) was added drop wise over 1 hour. Refluxing was continued for 2 hours under N2.
The resulting solution was filtered through celite when hot. The product (1.00 g, containing selenium residues) crystallized as yellow solids and were used without further purification.
1,10-phenanthroline-4-carboaldoxime: A solution of the 1,10-phenanthroline-4-carboaldehyde product (1.00 g), hydroxyamine hydrochloride (2.00 g) and pyridine (4 ml) in ethanol (60 ml) was heated under reflux for 12 hours under N2. The resulting grey solids were separated from the ethanol solution. The grey solids were recrystallized in hot ethanol.
The product was dried in vacuo (0.65 g, yield: 61 %).
4-aminomethyl-1,10-phenanthroline: A suspension solution of 1,10-phenanthroline-4-carboaldoxime (0.5 g) in 100 ml ethanol containing 2% perchloric acid was hydrogenated at atmospheric pressure, over 10% Pd/C ( 150 mg) for 12 hours and then was refluxed for 2 hours. The solution was filtered and the filtrate was concentrated. Ether was added to the filtrate to crystallize the product (0.44 g, 97%).
Synthesis of Ru Dyes Functionalized with Amino Groups Cis-Dichlorobis (4,7-diphenyl-1,10-phenanthroline)ruthenium: Ruthenium trichloride (2.0 g), 4,7-diphenyl-1,10-phenanthroline (5.8 g), lithium chloride (2.2 g) were heated at reflux in 30 ml of DMF for 3 hours. The solution was then added with 80 ml of acetone and stored at 0°C overnight. Purple solids were collected by suction filtration and washed by water. The crude products were stirred in the cold acetone for 3 hours and filtered. The product suspended in water (100 ml) was heated under reflux for 2 hours and treated with lithium chloride (5.0 g). The purple solids precipitated from the cold solution and were filtered and dried in vacuo (2.5 g).
Ru[4,7-diphenyl-1,10-phenanthroline)2(L)][C104]z (L=5-amino-1,10-phenanthroline or 4-I 5 aminomethyl-1,10-phenanthroline):
Ru(4,7-diphenyl-1,10-phenanthroline),C1, (200 mg) and 60 mg of L were heated under reflux in 200 ml ethanol/water (v/v 70:30) for 18 hours under N,. The resulting solution was treated with LiCIOa (4.0 g). Red orange solids were collected by filtration and washed by water, hexane and ether (200 g, yield: 90%).
Synthesis of Dye Bound Polymer:
A CHZC12 solution of Ru[4,7-diphenyl-1,10-phenanthroline)2(L)]z (L=5-amino-1,10-phenanthroline or 4-aminomethyl-1,10-phenanthroline) (1.0 mg) was added to poly(pentachlorothionylphosphazene) (200 mg) in CH,C12 solution while being stirred at room temperature. After 4 hours, the mixture was cooled to 0°C and excess n-BuNHz (10 equiv.) was added into the mixture and was stirred for overnight. After this reaction finished, the polymer was precipitated in water (three times) and then precipitated in water methanol (three times). Characterization was achieved by 1 H NMR and 31 P NMR. Films were spray coated from organic solvents such as CH,CI, or 1,2-dichloroethane.
ANALYSIS
Samples were placed in a pressure chamber which was equipped with a viewing window to permit in-situ pressure measurements. The pressure chamber was equipped with an adjustable pressure supply of compressed air. All the measurements were made at room temperature (22 ~ 1 °C).
An imaging system was used to detect changes in luminescence intensity as a function of pressures. A 75 Watt tungsten Halogen lamp was used as a light source with a 40 nm band pass filter centred at 450 nm to obtain the blue light. A cut-off filter, corresponding to OG
590 nm for the Ruthenium dye-bound polymer, was placed in front of a liquid nitrogen cooled CCD detector (MODEL LN/CCD, PRINCETON INSTRUMENTS, INC.) with 578 x 384 pixels in a cell size of 13.25 X 8.83 mm'-. Luminescent light from the sample surface was collected with a camera lens (NIKON, SSmm,1:1.2) and imaged onto the CCD
detector. The pressure of the sample chamber was measured by a pressure gauge (MODEL FA233, WALLACE AND TIERNAN) with an accuracy of ~ 0.1 psi. The results are shown in figure 1, as a plot of a luminescence intensity ratio versus pressure ratio, showing a substantially linear relationship therebetween.
A scale wing model was also coated with the dye-bound polymer as discussed herein above and was positioned in a 5X5 foot wind tunnel and subjected to wind speeds of Mach 0.8. Two images were taken in order to calculate the pressure distribution over the model surface. One image (hereinafter referred to as the 'wind-on' image) was taken when the wind speed was Mach 0.8 where the pressure distribution on the model is unknown.
The other image (hereinafter referred to as the 'wind-off image) was taken when the wind was off so that the pressure distribution on the model was a constant of 1 atm. The wind-off image was divided by the wind-on image and the resulting image was shown in figure 2, which presents a complete static pressure mapping. Figure 2 also demonstrates, for example, the transition from relatively low pressure present at the leading edge of the wing (as shown by the dark colour) to a relatively high pressure at the trailing edge of the wing, as would be expected.
Figure 3 is a comparison of pressure distribution measurements on a wing model at Mach 0.8.
The solid circles are pressure tap measurements and the solid line is a pressure sensitive paint measurement.
EXAMPLE: SYNTHESIS OF POLYMER WITH SILOXANE SIDE GROUP
(3-aminopropyl)-heptamethyltrisiloxane.
In a 250 mL round bottom flask was placed freshly distilled (N-trimethylsilyl)allylamine ( 10 g, 0.07 mol) (which was prepared via the literature procedure of Bachrach and co-workers in Bachrach, A., Zilkha, A. Eur. Polym. J. 1984, 20, 493. Also see Speir, J.
L. Adv.
Organomet. Chem. 1979, 17, 407.) was mixed with freshly distilled 1,1,1,3,3,5,5-heptamethyltrisiloxane ( 17.2 g, 0.07 mol). To this was added THF 0100 mL) and chloroplatinic acid hexahydrate (0.5 mol. %). The reaction mixture was refluxed for 12 hours or until no Si-H stretching peak in the infrared spectrum at 2145 cm' could be detected. The reaction mixture was then cooled to room temperature, and a large excess of 95% ethanol (~SOmL) was added. The reaction mixture was then refluxed for 12 hours to remove the N-trimethylsilyl protecting group. The product was isolated by vacuum distillation and purified by vacuum fractional distillation from Ba0 [bp 45 ~C
(0.05 mmHg)]. (18 g, 83 %). 'H NMR (CDCl3) 8(ppm): 2.65 (1H, m, CHZCHZCHZ), 1.46 (2H, m, CHZCHzCH2), 0.52 (2H, m, CHZCHZCHZ), 0.13 (9H, s, Si(CH3)3), 0.11 (6H, s, Si(CH3)z), 0.05 (6H, s, Si(CH3)Z). '3C NMR (CDZCIZ) S(ppm): 45.85 (H2NCH2CHZCH2-), 28.01 (HZNCHZCHZCHZ-), 15.80 (HZNCHZCH2CHz-), 2.32, 1.78, 0.65 (Si(CH3)).
Poly(aminopropyl-heptamethyltrisiloxane)thionylphosphazene The cyclic thionylphosphaaene (2.0 g) was heated in an evacuated sealed Pyrex tube at 165 ~C for 4 h. The tube contents were then dissolved in ca. (ie.
approximately) 40 ml of CHZCIz and the solution was concentrated to ca 10 ml and was then added dropwise to 200 ml of stirred hexanes via cannula. The colorless, moisture sensitive, elastomeric polymer was dissolved in 100 ml of CHZClzand (3-aminopropyl)-heptamethyltrisiloxane was added dropwise to the polymer solution which was cooled to 0 ~C. White precipitation formed immediately after the addition. The solution was concentrated to ca. 20 ml and filtered through a filter frit. the precipitation was carried out by first redissolving the dried crude product in ca. 10 ml of THF then precipitating into water three times followed by precipitating from CHZCIz into hexanes three times. Final product was dried from CHZC12 under high vacuum for 24 hours at ambient temperature (84 %). 3'P NMR (CHZCIz) 8(ppm):
1.45, 0.94. 'H NMR (CDC13) 8(ppm): 2.85 (m, br, propyl), 1.48 (m, br, propyl), 0.63 (m, br, propyl), 0.12(s, br, Si(CH3)), 0.04 (s, br, Si(CH3)). '3C NMR (CDZCl2) 8(ppm): 44.76 (propyl), 26.17 (propyl), 16.15 (propyl), 2.02, 1.62, 0.67 (Si(CH3)). 29Si NMR
(CHZCIz) 8(ppm): 9.22, -0.80, -18.70. GPC measurement: Mw = 1.44 x 105, PDI = 1.8.
Poly[(aminopropyl-heptamethyltrisiloxane)thionylphosphazene]-b-poly(tetrahydrofuran) The cyclic thionylphosphazene (2.0 g) was heated in an evacuated sealed Pyrex tube at 165 ~C for 4 h. The tube contents were then dissolved in ca. 40 ml of CHZC12 and the solution was concentrated to ca 10 ml and was then added dropwise to 200 ml of stirred hexanes via cannula. The colorless, moisture sensitive, elastomeric polymer was dissolved in 100 ml of THF and the solution then stored in the refrigerator at -14 ~C
for 48 h. A
significant solution viscosity increase was noticed. (3-aminopropyl)-heptamethyltrisiloxane was added dropwise to the polymer solution which was cooled to 0 oC. White precipitation formed immediately after the addition. The solution was concentrated to ca. 20 ml and filtered through a filter frit. The precipitation was carried out by first redissolving the dried crude product in ca. 10 ml of THF then precipitating into water three times followed by precipitating from CHzCl2 into hexanes three times. Final product was dried from CHzCIz under high vacuum for 24 hours at ambient temperature. Yield of 5, a colorless film forming material (79 %). 3'P NMR (CHZC12) 8(ppm): 1.39, 0.94. 'H NMR (CDCl3) 8(ppm):
3.45 (s, br, poly-THF), 3.01 (m, br, propyl), 1.65 (s, br, poly-THF), 1.37 (m, br, propyl), 0.94 (m, br, propyl), 0.15 (s, br, Si(CH3)), 0.05 (s, br, Si(CH3)). '3C NMR (CDZC12) 8(ppm): 71.33 (poly-THF), 45.16 (propyl), 27.43 (poly-THF), 26.51 (propyl), 16.44 (propyl), 2.40, 1.57, 1.07 (Si(CH3)). GPC measurment: Mw = 2.93 x 105, PDI = 1.8.
ANALYSIS
Samples utilizing the siloxane-bound polymers were placed in a pressure chamber which was equipped with a viewing window to permit in-situ pressure measurements. The pressure chamber was equipped with an adj ustable pressure supply of compressed air. All the measurements were made at room temperature (22 ~ 1 °C).
An imaging system was used to detect changes in luminescence intensity as a function of pressures. A 75 Watt tungsten Halogen lamp was used as a light source with a 40 nm band pass filter centred at 450 nm to obtain the blue light. A cut-off filter, corresponding to OG
590 nm for the Ruthenium dye-bound polymer, was placed in front of a liquid nitrogen cooled CCD detector (MODEL LN/CCD, PRINCETON INSTRUMENTS, INC.) with 578 x 384 pixels in a cell size of 13.25 X 8.83 mm'. Luminescent light from the sample surface was collected with a camera lens (NIKON, SSmm, 1:1.2) and imaged onto the CCD
detector. The pressure of the sample chamber was measured by a pressure gauge (MODEL FA233, WALLACE AND TIERNAN) with an accuracy of ~ 0.1 psi.
Testing of several samples in this manner yielded standard Stern Volmer plots with slopes ranging from 0.17 - 0.18, and for the copolymer of Poly(THF) and PTP(aminopropyltrisiloxane) ranging from 0.49 to 0.60, with a linearity ranging from 0.990 to 1Ø
Claims (66)
1. A polymer material comprising a backbone containing nitrogen and one or more of sulfur and phosphorous, and at least one side chain, wherein either said at least one side chain or said backbone includes a phosphorescent dye agent.
2. A polymer material as defined in claim 1 wherein said sulfur and phosphorus have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group.
3. A polymer material as defined in claim 1 having a plurality of side chains at least one of said side chains including said phosphorescent dye agent.
4. A polymer material as defined in claim 3 wherein said sulfur has a first side group including oxygen.
5.A polymer material as defined in claim 4 wherein said sulfur has a second side group, said phosphorous has first and second side groups, the first and second side groups on phosphorus and the second side group on sulfur being either NHBun or a group including said dye agent.
6. A polymer material as defined in claim 5 wherein at least one of the side groups on said phosphorous includes said dye agent.
7. A polymer material as defined in claim 6 wherein one of the side groups on said phosphorous includes said dye agent and the other side groups of said phosphorous are the same as the second side group on said sulfur.
8. A polymer material as defined in claim 7 wherein said group including said dye agent includes a ruthenium substituent.
9. A polymer materials as defined in claim 8 wherein the group including said dye agent comprises a ruthenium phenanthroline complex.
10. A polymer material as defined in claim 8 wherein the group including said dye agent includes a heterocyclic group selected from the group comprising a substituted C3-20 cycloalkyl group, a substituted C6-20 aryl group and a substituted or unsubstituted C6-20 aralkyl group.
11. A phosphorescent oxygen sensor comprising a substrate having a surface, a polymer material as defined in claim 1 applied to said surface to form a coating.
12. A polymer material formed from a phosphorescent dye contained in a polymer material of formula A, wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group, and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group, and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
13. A polymer material as defined in claim 12 wherein E1 is in the form of sulfur VI.
14. A polymer material as defined in claim 13 wherein E2 and E3 are each phosphorus.
15. A polymer material as defined in claim 14 wherein each of R2 to R6 includes an oxygen or a nitrogen substituent.
16. A polymer material as defined in claim 15 wherein each of R3 to R6 includes an aryloxy group or an alkamine group.
17. A polymer material as defined in claim 16 wherein R3 to R6 are each selected from the group consisting of NHBu n, OBu n, OC6H4, OC6H4CF3-m, OCH2CH=CH2 and OC6H4CF3-p, and the group including said dye agent.
18. A polymer material as defined in claim 17 wherein R2 is a halogen.
19. A polymer material as defined in claim 18 wherein R2 and R3 to R5 are the same and R6 is the group including said dye agent.
20. A polymer material as defined in claim 19 wherein R2 and R3 to R5 are each NHBu n.
21. A polymer material as defined in claim 20 wherein said group including said dye agent includes a ruthenium substituent.
22. A polymer materials as defined in claim 21 wherein the group including said dye agent is Ru(4,7-diphenylphen)3
23. A polymer material as defined in claim 21 wherein the group including said dye agent includes a heterocyclic group selected from the group comprising a substituted C3-20 cycloalkyl group, a substituted C6-20 aryl group and a substituted or unsubstituted C6-20 aralkyl group.
24. A copolymer material of the formula B wherein E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group.
R1 to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group.
25. A copolymer material as defined in claim 24 wherein E1 is in the form of sulfur VI
and R1 is oxygen.
and R1 is oxygen.
26. A copolymer material as defined in claim 25 wherein E2 and E3 are each phosphorus.
27. A copolymer material as defined in claim 26 wherein R7 is oxygen, nitrogen or sulfur.
28. A copolymer material as defined in claim 27 wherein R3 to R6 are each selected from the group consisting of NHBu", OBu", OC6H4, OC6H4CF3-m, OCH2CH=CH2 and OC6H4CF3-p, and the group including said dye agent.
29. A copolymer material as defined in claim 28 wherein R2 is a halogen.
30. A copolymer material as defined in claim 29 wherein R2 and R3 to R5 are the same and R6 is the group including said dye agent.
31. A copolymer material as defined in claim 30 wherein R2 and R3 to R5 are each NHBu".
32. A copolymer material as defined in claim 31 wherein said group including said dye agent includes a ruthenium substituent.
33. A copolymer materials as defined in claim 32 wherein the group including said dye agent is Ru(4,7-diphenylphen)3
34. A copolymer material as defined in claim 32 wherein the group including said dye agent includes a heterocyclic group selected from the group comprising a substituted C3-20 cycloalkyl group, a substituted C6-20 aryl group and a substituted or unsubstituted C6-20 aralkyl group.
35. A method of forming a copolymer material of the formula B, comprising the steps of:
providing a first polymer block of the formula A, wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein to form a copolymer material of formula B wherein:
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group;
providing a first polymer block of the formula A, wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a phosphorescent dye agent.
carrying out a ring opening polymerization of an unsaturated heterocyclic group having at least one electron rich site therein to form a copolymer material of formula B wherein:
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group;
36. A method as defined in claim 35 wherein said ring opening polymerization step is carried out in the presence of said first polymer block.
37. A method as defined in claim 36 wherein said unsaturated heterocyclic group is in the form of an unsaturated C3-5 cyclic group with an oxygen or nitrogen substituent therein.
38. A method as defined in claim 37 wherein said unsaturated heterocyclic group is tetrahydrofuran, ethylene oxide or propylene oxide.
39. A phosphorescent dye agent, comprising a phenanthroline complex which is reactive to form a polymer with said dye agent as a constituent thereof.
40. A dye agent as defined in claim 39 wherein said complex is a ruthenium phenanthroline complex.
41. A polymer material comprising the phosphorescent dye agent of claim 39 as a constituent thereof.
42. A coating composition comprising a polymer having a backbone and at least one side group with a phosphorescent dye agent as a member of said backbone or said side group, said polymer being capable of being applied as a coating.
43. A coating composition as defined in claim 42 wherein said polymer material is in a solvent mixture.
44. A coating composition as defined in claim 43 wherein said solvent mixture is homogeneous.
45. A method of forming a phosphorescent dye agent, comprising the steps of:
providing a phenanthroline complex with a dye agent as a constituent thereof;
and forming a reactive site on said complex which is reactive to form a polymer.
providing a phenanthroline complex with a dye agent as a constituent thereof;
and forming a reactive site on said complex which is reactive to form a polymer.
46. A method as defined in claim 45 wherein said complex is a ruthenium phenanthroline complex.
47. A method of forming a phosphorescent polymer material, comprising the steps of:
providing a phenanthroline complex with a dye agent as a constituent thereof;
forming a reactive site on said complex; and reacting said complex with a monomer to form a polymer.
providing a phenanthroline complex with a dye agent as a constituent thereof;
forming a reactive site on said complex; and reacting said complex with a monomer to form a polymer.
48. A method as defined in claim 47 wherein said complex is a ruthenium phenanthroline complex.
49. A polymer material comprising a backbone containing nitrogen and one or more of sulfur and phosphorous, said polymer material including at least one side group having a silicone constituent.
50. A polymer material as defined in claim 49 wherein the sulfur is in the form of sulfur VI.
51. A polymer material as defined in claim 49 wherein said polymer material includes a number of silicone side groups.
52. A polymer material as defined in claim 50 wherein each of said silicone side groups has a trimethylsilyl constituent.
53. A polymer material as defined in claim 49 wherein each phosphorous in said backbone has a side group including silicone.
54. A polymer material as defined in claim 53 wherein each side group on each phosphorus in said backbone includes a trimethylsilyl group.
55. A polymer material of formula A wherein E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus and any one or more of R1 to R6 includes a siloxane group.
56. A copolymer material of formula B wherein:
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a siloxane group;
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group.
E1, E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
R1 to R6 are the same or different and is selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group; and wherein at least one of R1 to R6 is a group including a siloxane group;
R7 is selected from oxygen, nitrogen or from groups 15 and 16 of the periodic table of elements;
R8 is selected from the group comprising methylene, a substituted or unsubstituted C2-20 linear or branched alkyl group, a substituted or unsubstituted C2-20 linear or branched alkenyl group, a substituted or unsubstituted C2-20 linear or branched alkynyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted C3-20 cycloalkyl group.
57. A method of forming a pressure sensor, comprising the steps of forming a stable polymer having a backbone containing nitrogen and one or more of sulfur and phosphorus, and with a plurality of side groups, and providing a silicone constituent on at least one of the side groups.
58. A method as defined in claim 57 further comprising the step of providing at least one silicone constituent on a plurality of said side groups.
59. A method as defined in claim 58, wherein each side group on said phosphorus includes a silicone constituent.
60. A method as defined in claim 59 wherein said sulfur has one side group including oxygen and a second side group including a silicone constituent.
61. A polymer material having a backbone including nitrogen and one or more of sulfur and phosphorous, and at least one side group including silicone.
62. A polymer material as defined in claim 61 having a glass transition temperature ranging from -20°C to 0°C.
63. A pressure sensor comprising a stable polymer material as defined in claim 58 and a phosphorescent dye agent.
64. A pressure sensor as defined in claim 63 wherein the polymer and dye agent are in the form of a coating.
65. A pressure sensor as defined in claim 63 wherein said sensor is operatively characterized by a Stern Volmer plot having a linearity ranging from 0.985 to 0.995.
66. A pressure sensor as defined in claim 65 wherein said sensor is operatively characterized by a Stern Volmer plot having a linearity ranging from 0.990 to 0.995.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002284300A CA2284300A1 (en) | 1999-09-29 | 1999-09-29 | Phosphorescent oxygen sensors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002284300A CA2284300A1 (en) | 1999-09-29 | 1999-09-29 | Phosphorescent oxygen sensors |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2284300A1 true CA2284300A1 (en) | 2001-03-29 |
Family
ID=4164259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002284300A Abandoned CA2284300A1 (en) | 1999-09-29 | 1999-09-29 | Phosphorescent oxygen sensors |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2284300A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996840A (en) * | 2017-04-18 | 2017-08-01 | 合肥工业大学 | A kind of force-responsive type fluorescent optical sensor based on dissaving polymer and preparation method thereof |
-
1999
- 1999-09-29 CA CA002284300A patent/CA2284300A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106996840A (en) * | 2017-04-18 | 2017-08-01 | 合肥工业大学 | A kind of force-responsive type fluorescent optical sensor based on dissaving polymer and preparation method thereof |
| CN106996840B (en) * | 2017-04-18 | 2019-04-05 | 合肥工业大学 | A kind of force-responsive type fluorescent optical sensor and preparation method thereof based on dissaving polymer |
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