WO2001034682A1 - Detecteurs d'oxygene phosphorescents - Google Patents

Detecteurs d'oxygene phosphorescents Download PDF

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Publication number
WO2001034682A1
WO2001034682A1 PCT/CA1999/001036 CA9901036W WO0134682A1 WO 2001034682 A1 WO2001034682 A1 WO 2001034682A1 CA 9901036 W CA9901036 W CA 9901036W WO 0134682 A1 WO0134682 A1 WO 0134682A1
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group
substituted
unsubstituted
polymer material
linear
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PCT/CA1999/001036
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English (en)
Inventor
Ian Manners
Xijia Gu
Mitchell A. Winnik
Ralph Ruffolo
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Ian Manners
Xijia Gu
Winnik Mitchell A
Ralph Ruffolo
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Application filed by Ian Manners, Xijia Gu, Winnik Mitchell A, Ralph Ruffolo filed Critical Ian Manners
Priority to PCT/CA1999/001036 priority Critical patent/WO2001034682A1/fr
Priority to AU10229/00A priority patent/AU1022900A/en
Publication of WO2001034682A1 publication Critical patent/WO2001034682A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G79/025—Polyphosphazenes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/76—Chemiluminescence; Bioluminescence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/152—Side-groups comprising metal complexes
    • C08G2261/1526—Side-groups comprising metal complexes of Os, Ir, Pt, Ru, Rh or Pd
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/524—Luminescence phosphorescent
    • C08G2261/5242—Luminescence phosphorescent electrophosphorescent

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the backbone includes both sulfur and phosphorus having side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2.20 linear or branched alkenyl group, a substituted or unsubstituted C 2.20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . : cycloalkyl group.
  • the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent.
  • 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.
  • the invention in another aspect, involves a pressure sensor comprising a substrate having a surface, a polymer material as defined herein above and applied to the surface to form a coating.
  • 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;
  • Rl to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C 2.20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group, and wherein at least one of Rl to R6 is a group including a phosphorescent dye agent.
  • R2 is a halogen, and more particularly R2 and R3 to R5 are the same and R6 is the group including the dye agent. Still more particularly, R2 and R3 to R5 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 .
  • the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C 3 . 20 cycloalkyl group, a substituted C 6.20 aryl group and a substituted or unsubstituted C 6 . 20 aralkyl group.
  • the invention provides a polymer material of the formula B wherein:
  • El . E2 and E3 are the same or are different and are selected from sulfur or phosphorus;
  • Rl to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2.2U linear or branched alkynyl group, a substituted or unsubstituted C 6.20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group; and wherein at least one of Rl 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 C-, .2 briefly linear or branched alkyl group, a substituted or unsubstituted C 2.20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 2U aryl group, a substituted or unsubstituted C 3 ., 0 cycloalkyl group.
  • the invention provides a method of forming a copolymer material of the formula B, comprising the steps of:
  • 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 C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group; and wherein at least one of Rl 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 C, . , 0 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group.
  • the present invention provides a coating composition
  • 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.
  • the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
  • 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.
  • the backbone contains sulfur and phosphorous
  • the polymer material is stable and the sulfur is in the form of sulfur VI.
  • 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.
  • the present invention provides a polymer material of formula A as defined herein above wherein at least one of Rl to R6 includes siloxane.
  • 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.
  • a silicone constituent is provided on a plurality of the side groups.
  • the backbone includes sulfur and phosphorous and each side group on the phosphorus includes a silicone constituent.
  • the sulfur has one side group including oxygen and a second side group including a silicone constituent.
  • a polymer material having a backbone containing nitrogen and one or more of sulfur and phosphorous, and at least one silicone-bearing side group.
  • the polymer material has a glass transition temperature ranging from -20°C to 0°C.
  • a pressure sensor comprising a stable polymer material as defined above and a phosphorescent dye agent
  • 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 a linearity ranging from 0.980 to 1.0. 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.
  • pressure sensor is 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.
  • FIGS 1, 2 and 3 are schematic diagrams of polymerizations
  • Figure 4 is a plot of a luminescence intensity ratio versus pressure ratio for one exemplified coating of the present invention
  • Figure 5 is a PSP image of a wing model coated with the coating of figure 4.
  • Figure 6 is a comparison of pressure distribution measurements.
  • 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.
  • 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 2.20 linear or branched alkyl group, a substituted or unsubstituted C,. 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 2U aryl group, a substituted or unsubstituted C 3.20 cycloalkyl group.
  • side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C 2.20 linear or branched alkyl group, a substituted or unsubstituted C,. 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group,
  • the polymer has a plurality of side chains at least one of the side chains including the phosphorescent dye agent.
  • 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.
  • 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.
  • 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;
  • Rl to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2.20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group, and wherein at least one of Rl to R6 is a group including a phosphorescent dye agent.
  • the polymer material has a plurality of side chains, at least one of the side chains including the phosphorescent dye agent.
  • 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.
  • 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.
  • 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.
  • T Glass Transition Temperature
  • the sulfur and phosphorus have side groups selected from the group consisting of oxygen, a halogen, methyl, a substituted or unsubstituted C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2.20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group.
  • the group including the dye agent includes a heterocyclic group selected from the group comprising a substituted C 3 . 20 cycloalkyl group, a substituted C 6 . 20 aryl group and a substituted or unsubstituted C 6 . 20 aralkyl group.
  • 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.
  • the aryloxy and the arylamine tend to increase T G due to the fact that these groups tend to be relatively more rigid.
  • the alkoxy and alkamine groups tend to be more flexible, contributing to a lower T Cl and higher permeability.
  • 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.
  • the permeability, T G 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • El is in the form of sulfur and E2, E3 are each phosphorus, ln a still further preferred embodiment, each of R2 to R5 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:
  • I, , K luminescence intensity at 1 .00 atmosphere, (used as a reference;
  • compositions containing the polymer material 3 together with phosphorescent dye agents may show reasonably well-defined Stern-Volmer behaviour and significantly improved sensitivity.
  • 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.
  • Rl to R6 are the same or different and are selected from the group comprising oxygen, a halogen, hydrogen, methyl a substituted or unsubstituted C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 _ : ⁇ linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group; and wherein at least one of Rl 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 C ⁇ >.-. ( , linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3.20 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.
  • 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 C 3.20 cycloalkyl group, a substituted C 6 . 20 aryl group and a substituted or unsubstituted C 6.20 aralkyl group. More preferably, the heterocyclic group is an unsaturated C 3.5 cyclic group with the oxygen or nitrogen substituent therein. Still more preferably, the unsaturated heterocyclic group is tetrahydrofuran. ethylene oxide or propylene oxide.
  • El is in the form of sulfur VI
  • E2 and E3 are each phosphorus
  • 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.
  • 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.
  • 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.
  • 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 G of -17 °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.
  • the present coatings based on the polymer material A or the copolymer material B present phosphorescent properties that change with temperature.
  • 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 5 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 Rl to R6 in 0 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 G in the region of 5 -18 °C to 25 °C and these may be considered desirable R groups for some applications.
  • copolymer material 4 Further details of the formation of copolymer material 4 can be seen in figure 4 and is believed to be representative of one method of forming in general the copolymer materials of formula B.
  • the sulfur VI cation from poly(thionylphosphazene) attacks an oxygen site on a THF molecule to form an oxonium ion. Further reaction of this oxonium ion with more monomer generates a poly(THF) block.
  • the present invention provides a coating composition
  • 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.
  • the polymer material is in a solvent mixture and the solvent mixture is homogeneous.
  • 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.
  • the complex is a ruthenium phenanthroline complex.
  • the present invention provides a polymer material comprising the phosphorescent dye agent as a constituent thereof or as a substituent therein.
  • the present invention provides a method of forming a phosphorescent dye agent, comprising the steps of:
  • the complex is a ruthenium phenanthroline complex.
  • the present invention provides a method of forming a phosphorescent polymer material, comprising the steps of:
  • 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 functional ized 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.
  • 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.
  • 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.
  • 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.
  • the present invention provides a polymer material of formula A wherein El . E2 and E3 are the same or are different and are selected from sulfur or phosphorus and any one or more of Rl to R6 includes a siloxane group.
  • the present invention involves a copolymer material of formula B wherein:
  • El. 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 C 2 . 20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group; and wherein at least one of Rl 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 .20 linear or branched alkyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkenyl group, a substituted or unsubstituted C 2 . 20 linear or branched alkynyl group, a substituted or unsubstituted C 6 . 20 aryl group, a substituted or unsubstituted C 3 . 20 cycloalkyl group.
  • 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.
  • 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.
  • the sulfur has one side group including oxygen and a second side group including a silicone constituent.
  • a polymer material having a backbone containing nitrogen and one or more of nitrogen and phosphorous, and at least one silicone including side group.
  • the polymer material has a backbone including sulfur and phosphorous and has a glass transition temperature ranging from -20°C to O°C.
  • a pressure sensor comprising a stable polymer material as defined above and a phosphorescent dye agent.
  • the polymer and dye agent are in the form of a coating.
  • the pressure sensor is operatively characterized by a Stern Volmer plot having ranging from 0.980 to 1.0. 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.
  • 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 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(aminopropyl
  • 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.
  • 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
  • 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 of pressure 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 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.
  • 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.
  • 1.10-phenanthroline-4-carboaldehyde SeO 2 (1.22 g, 99%) was dissolved in 20 ml refluxing dioxane/water (v/v, 94:4). 4-methyl-l ,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 N 2 . 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 l,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 N 2 . 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-l ,10-phenanthroline A suspension solution of l ,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%).
  • Cis-Dichlorobis (4,7-diphenyl-l ,10-phenanthroline)ruthenium Ruthenium trichloride (2.0 g), 4,7-diphenyl-l ,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 Cl 2 200 mg
  • 60 mg of L were heated under reflux in 200 ml ethanol/water (v/v 70:30) for 18 hours underN 2 .
  • the resulting solution was treated with LiClO 4 (4.0 g). Red orange solids were collected by filtration and washed by water, hexane and ether (200 g, yield: 90%).
  • 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.
  • CCD detector MODEL LN/CCD, PRINCETON INSTRUMENTS, INC.
  • Luminescent light from the sample surface was collected with a camera lens (NIKON, 55mm, 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
  • 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
  • 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. (ie. approximately) 40 ml
  • 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 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 3 .
  • Luminescent light from the sample surface was collected with a camera lens (NIKON, 55mm, 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.

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Abstract

L'invention concerne une matière polymère comprenant un squelette renfermant du nitrogène, du soufre et/ou du phosphore, et au moins une chaîne latérale, ladite chaîne latérale ou ledit squelette contenant un agent de coloration phosphorescent.
PCT/CA1999/001036 1999-11-05 1999-11-05 Detecteurs d'oxygene phosphorescents WO2001034682A1 (fr)

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PCT/CA1999/001036 WO2001034682A1 (fr) 1999-11-05 1999-11-05 Detecteurs d'oxygene phosphorescents
AU10229/00A AU1022900A (en) 1999-11-05 1999-11-05 Phosphorescent oxygen sensors

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800722B2 (en) 2001-05-23 2004-10-05 Sri International Electroluminescent polymers and use thereof in light-emitting devices
CN106996840A (zh) * 2017-04-18 2017-08-01 合肥工业大学 一种基于超支化聚合物的力响应型荧光传感器及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111589429B (zh) * 2020-05-28 2021-11-02 南昌航空大学 一种邻菲罗啉聚合物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536480A2 (fr) * 1991-10-10 1993-04-14 BOC HEALTH CARE, Inc. Copolymères à base de polysiloxanes et de polyuréthanes contenant des colorants phosphorescents sensible à l'oxygène
CA2204319A1 (fr) * 1997-05-02 1998-11-02 Ian Manners Detecteurs phosphorescents pour l'oxygene
CA2227309A1 (fr) * 1998-01-16 1999-07-16 Ian Manners Detecteur phosphorescent d'oxygene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536480A2 (fr) * 1991-10-10 1993-04-14 BOC HEALTH CARE, Inc. Copolymères à base de polysiloxanes et de polyuréthanes contenant des colorants phosphorescents sensible à l'oxygène
CA2204319A1 (fr) * 1997-05-02 1998-11-02 Ian Manners Detecteurs phosphorescents pour l'oxygene
CA2227309A1 (fr) * 1998-01-16 1999-07-16 Ian Manners Detecteur phosphorescent d'oxygene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800722B2 (en) 2001-05-23 2004-10-05 Sri International Electroluminescent polymers and use thereof in light-emitting devices
US7098297B2 (en) 2001-05-23 2006-08-29 Sri International Electroluminescent polymers and use thereof in light-emitting devices
CN106996840A (zh) * 2017-04-18 2017-08-01 合肥工业大学 一种基于超支化聚合物的力响应型荧光传感器及其制备方法
CN106996840B (zh) * 2017-04-18 2019-04-05 合肥工业大学 一种基于超支化聚合物的力响应型荧光传感器及其制备方法

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