EP1889049A2 - Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additives - Google Patents

Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additives

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Publication number
EP1889049A2
EP1889049A2 EP06770799A EP06770799A EP1889049A2 EP 1889049 A2 EP1889049 A2 EP 1889049A2 EP 06770799 A EP06770799 A EP 06770799A EP 06770799 A EP06770799 A EP 06770799A EP 1889049 A2 EP1889049 A2 EP 1889049A2
Authority
EP
European Patent Office
Prior art keywords
substituted
unsubstituted
radical
thermochromic
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06770799A
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German (de)
French (fr)
Inventor
Brett Lucht
William B. Euler
Yu Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhode Island Board of Education
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Rhode Island Board of Education
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Filing date
Publication date
Application filed by Rhode Island Board of Education filed Critical Rhode Island Board of Education
Publication of EP1889049A2 publication Critical patent/EP1889049A2/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • thermochromic indicator materials comprised of polythiophenes.
  • Polythiophenes are known for their electrically conductive properties.
  • One technique used to study polythiophenes is to analyze associated color changes when the temperature of the polythiophene is varied. Color changes provide insight into the electro-conductive properties of the polymer.
  • the useful life of many products can become compromised if exposed to temperatures above a pre-determined temperature.
  • Controlling the predetermined temperature, raising or lowering, is important for wide applicability for various applications.
  • the present invention addresses this need.
  • the invention comprises a temperature sensitive polymer that visually changes color at a proscribed temperature within the range of between about -30 to 150 0 C.
  • the temperature of the color change (hereinafter referred to as the thermochromic transition) can be adjusted by synthetically modifying the thermochromic polymer.
  • the thermochromic transition temperature can be further modified via the incorporation of various small molecule additives including the monomer from which the polymer was prepared and structurally related compounds.
  • the thermochromic polymer/small molecule additive composites can be dispersed in commercial plastics (polyurethane, polystyrene, polyethylene, etc.) at low concentrations and retain the controlled reversibility.
  • the temperature sensitive polymer /additive composites can also be used as a pigment for inks.
  • the thermochromic polymers are generally of the structure:
  • Ri-R ⁇ a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted aryl radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical
  • n is between 1 and 1000
  • m is between 0 and 1000
  • 1 is between 1 and 1000.
  • the invention is directed to a method of adding monomer, or other small molecules, to substituted polythiophenes to modify or enhance the thermochromic and thermoflourescent properties of the materials allowing one to determine the genuineness of an article.
  • the monomer, or other small molecule comprised of a compound having the following structures: R-Ar-R' , R-X, or linear alkane
  • X a halogen (F, Cl, Br, or I).
  • thermochromic/thermoflourescent transition temperature centered at 65 0 C is light red/orange in color below the thermochromic/thermoflourescent transition temperature with very weak fluorescence and a bright yellow color with a strong emission of yellow/orange light.
  • Addition of octadecylthiophene lowers the transition temperature to 52 0 C, darkens the low temperature color to red/purple but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
  • Fig. 1 are plots of Polymer A DSC versus heat flow:
  • Fig. 2 are photographs of poly(3-(oligoethylene oxide)-4-methylthiophene with Poly(ethyleneglycol) dimethyl ether.
  • thermochromic transitions For regiorandom polymers longer substituents such as n- hexadecyl have lower temperature thermochromic transitions (81 0 C) than shorter chain substituents such as n-octyl (130 0 C).
  • the regioregular polymers have higher thermochromic transitions than the regiorandom polymers but the same inverse correlation with chainlength is observed.
  • the n-hexadecyl and n-octyl have thermochromic transition centered around 125 and 175 0 C.
  • the thermochromic transition temperatures are dependent upon the molecular weight of the polymer. Lower molecular weight polymers have lower thermochromic transition temperatures while higher molecular weight polymers have higher thermochromic transition temperatures.
  • thermochromic transition and the color of the thermochromic material can be further modified by the incorporation of various small molecule additives.
  • the best small molecule additives are structurally related to the monomer, such as 3-alkylthiophene, from which the polymer was prepared.
  • the invention includes the use of polythiophene/small molecule additive composite as a neat mixture or admixed with paints including polyurethanes, polysiloxanes, polyacrylates, and other related polymer-based paints and coatings with about 0.5 % polythiophene/small molecule additive composite with retention of the thermochromic behavior.
  • thermochromic polymer-based pigments can be incorporated via injection molding or extrusion into many commercially important plastics such as poly (ethylene terephthalate) (PET), polysytrene, polyethylene (HDPE and LDPE), other polyolefins, polydienes, polycarbonates, poly acrylics, poly acrylic acids, poly aery lamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, poly(vinyl nitrile)s poly vinyl esters, polyesters, polysulfones, poly sulfonamides, poly amides, polyimines, polyimides, carbohydrates, and polymer mixtures and copolymers.
  • PET ethylene terephthalate
  • HDPE and LDPE high density polyethylene
  • other polyolefins polydienes
  • polycarbonates poly acrylics, poly acrylic acids, poly aery lamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, poly
  • polythiophene/small molecule additive composite exhibiting controlled thermochromic transitions are dispersed in commercially available printable ink formulations, e.g. oil with resins, pigment extenders and other additives, to form thermal indicator ink systems.
  • the polythiophenes are present in the thermal indicator ink in an amount of 1.0-25% by weight based on the total weight of the thermal indicator ink, preferably 7.0 to 14% weight.
  • the ink can be printed using conventional methods such as ink-jet and letter press.
  • Examples of ink formulations that polythiophene can be dispersed in can include combinations of resins such as cellulose, nitrocellulose with co-binders including polyamides, polyester amides, alkyd, epoxy acrylates, amine acrylates, polyurethanes, and polyvinyl butyral (UNI-REZ, UNI-JET, BECKOSOL,
  • suitable oils such as napthenic petroleum oils and vegetable oils, e.g. soy bean oil
  • suitable pigment extenders and additives that can include organic acids and esters of organic acids such as malic acid and organic solvents such as 1,5-pentanediol, diethylene glycol, along with other alcohols and related compounds (VERTEC, SYLFAT, UNI-KYD, and ICM, DY-SOLVE lines of additives.).
  • the thermal indicator ink is printed on at least a portion of a suitable substrate, e.g. a portion of paper, plastic, or ceramic food/beverage containers, a portion of packaging materials for foods and goods, labels, a portion of labels, stickers, etc., using conventional printing methods.
  • a suitable substrate e.g. a portion of paper, plastic, or ceramic food/beverage containers, a portion of packaging materials for foods and goods, labels, a portion of labels, stickers, etc.
  • the polythiophenes dispersed in the ink system can be in particulate form and have diameters in the range of between about 0.01 - 0.1 microns thereby rendering the system suitable for fine printing.
  • the thermal indicator material is applied to an article, e.g., a portion of paper, plastic or ceramic food/beverage containers, as a coating on an area of the article, or the entire article, which will be visible during the expected use of the article.
  • the coating can be applied by any technique known in the art, such as by brush, roller, spraying, etc. Accordingly, the coatings typically have a thickness of 0.1 to 1000 microns.
  • the thermal indicator material can also be absorbed on a surface or both absorbed and adsorbed on a surface.
  • Suitable carrier mediums to be admixed with the polythiophene/small molecule additive composite exhibiting controlled reversible thermochromic transitions can include polyurethanes; elastomers including polysiloxanes and polydienes; polyacrylates, poly (ethylene terephthalate)s (PET), polysytrenes, polyolefins including polyethylenes (HDPE and LDPE) and polypropylene, polycarbonates, polyacrylics, poly aery lie acids, polyacrylamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, polyvinyl nitrile)s polyvinyl esters, polyesters, polysofones, poly sulfonamides, polyamides, polyimines, polyimides, and carbohydrates.
  • polyurethanes elastomers including polysiloxanes and polydienes
  • polyacrylates poly (ethylene terephthalate)s (PET), polysytrenes, polyo
  • addition of monomer (3-octadecylthiophene) to polymer results in a significant lowering of the thermochromic transition temperature, deepening of the color, and enhancement of the flourescence properties of poly(3-alkylthiophene)s.
  • the addition of other small molecules such as octadecylbenzene have a similar effect.
  • a sample of poly(3-octadecylthiophene) is light red in color at room temperature.
  • thermochromic/thermoflourescent transition occurs at 65 C.
  • thermochromic/thermoflourescent transition is lowered to 50 C.
  • the high temperature color is yellow in both cases.
  • monomer decreases the transition temperature by approximately 15 C.
  • the flourescence is modified.
  • thermochromic transition temperature a significant lowering of the thermochromic transition temperature and deepening of color.
  • 3-octadecylthiophene to poly(3-octadecylthioophene) (2: 1 monomer:polymer by weight
  • the color is changed from red/yellow to a deep purple at room temperature.
  • thermochromic/thermoflourescent transition occurs at 50 C.
  • thermochromic/thermoflourescent transition is lowered to 35 C.
  • the high temperature color is yellow in both cases.
  • the addition of monomer decreases the transition temperature by approximately 15 C.
  • the change in thermochromic transition is related to the change in melting transition as measured by Differential Scanning Calorimetry (DSC), as seen in Figure 1.
  • DSC Differential Scanning Calorimetry
  • oligo(ethyleneglycol)dimethyl ether with Mn 250 to poly(3-oligoethylene oxide)-4-methylthiophene)s significantly lowers the thermochromic temperature.
  • the thermochromic transition of the pure polymer occurs at 65 0 C.
  • oligo(ethylene glycol)dimethyl ether the transition temperature is lowered to 5 0 C, as seen in Figure 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)

Abstract

A thermal indicator material and method of producing a material capable of a thermochromic transition upon undergoing a temperature change. The material comprises a plurality of compounds having the following structure: (I) wherein R1-R6 = a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted aryl radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical n is between 1 and 1000, m is between 0 and 1000, and 1 is between 1 and 1000; with added small molecules, the small molecule additive having the following structure: R-Ar-R' , R-X, linaer alkane, or oligoethylene oxide small molecules with molecular weight less than 1,000 AMU wherein R-R' = a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical and Ar = a substituted or unsubstituted aromatic or heteroaromatic radical including but not limited to benzene, thiophene, naphthalene, flourene, anthracene, pyridine, indine, biphenyl, phenanthrene, and furan X = a halogen (F, Cl, Br, or I). The thermochromic transition of the material is reversible. The thermochromic transition is a two step transition, such that when the samples are heated above the thermochromic transition temperature followed by a rapid cooling to a temperature below the thermochromic transition temperature in a time of less than about 5 seconds, a new low temperature color is generated which then has an irreversible thermochromic transition.

Description

THERMOCHROMIC AND THERMOFLOURESCENT PIGMENTS: ENHANCING COLOR AND FLOURESCENCE WITH ADDITIVES
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation application of Provisional Patent Application 60/684,442 filed with the United States Patent and Trademark Office on May 25, 2005.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to thermochromic indicator materials comprised of polythiophenes.
2. Description of Relevant Art
Polythiophenes are known for their electrically conductive properties. One technique used to study polythiophenes is to analyze associated color changes when the temperature of the polythiophene is varied. Color changes provide insight into the electro-conductive properties of the polymer. There are numerous patent and literature citations which describe this work.
In many instances it is clearly desirable to know when an object or article reaches or has exceeded a specific temperature simply by viewing the object and noting that at least a portion of the object has exhibited a color change. Viewing includes visual observation by an individual or detection of color change by a sensor, which sensor would output a signal to be detected in any suitable manner.
For example, the useful life of many products can become compromised if exposed to temperatures above a pre-determined temperature. Controlling the predetermined temperature, raising or lowering, is important for wide applicability for various applications. The present invention addresses this need.
SUMMARY OF THE INVENTION
Broadly, the invention comprises a temperature sensitive polymer that visually changes color at a proscribed temperature within the range of between about -30 to 1500C. The temperature of the color change (hereinafter referred to as the thermochromic transition) can be adjusted by synthetically modifying the thermochromic polymer. The thermochromic transition temperature can be further modified via the incorporation of various small molecule additives including the monomer from which the polymer was prepared and structurally related compounds. The thermochromic polymer/small molecule additive composites can be dispersed in commercial plastics (polyurethane, polystyrene, polyethylene, etc.) at low concentrations and retain the controlled reversibility. The temperature sensitive polymer /additive composites can also be used as a pigment for inks. The thermochromic polymers are generally of the structure:
wherein Ri-Rδ = a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted aryl radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical
n is between 1 and 1000, m is between 0 and 1000, and
1 is between 1 and 1000.
The invention is directed to a method of adding monomer, or other small molecules, to substituted polythiophenes to modify or enhance the thermochromic and thermoflourescent properties of the materials allowing one to determine the genuineness of an article. The monomer, or other small molecule, comprised of a compound having the following structures: R-Ar-R' , R-X, or linear alkane
Small molecules with molecular weight less than 1,000 AMU wherein R-R'
= a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical and Ar = a substituted or unsubstituted aromatic or heteroaromatic radical including but not limited to benzene, thiophene, naphthalene, flourene, anthracene, pyridine, indine, biphenyl, phenanthrene, and furan. X = a halogen (F, Cl, Br, or I).
Some examples are as follows. In each example a 2:1 ratio (wt) of small molecule to polymer was used. A poly(3octadecylthiophene) with a thermochromic/thermoflourescent transition temperature centered at 65 0C is light red/orange in color below the thermochromic/thermoflourescent transition temperature with very weak fluorescence and a bright yellow color with a strong emission of yellow/orange light. Addition of octadecylthiophene lowers the transition temperature to 52 0C, darkens the low temperature color to red/purple but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
Addition of octadecylbenzene lowers the transition temperature to 48 0C, darkens the low temperature color to red/purple but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
Addition of 1,4-dihexyloxybenzene lowers the transition temperature to 50
0C, darkens the low temperature color to red but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
Addition of octadecylbromide lowers the transition temperature to 50 0C, darkens the low temperature color to red but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
Addition of mineral oil lowers the transition temperature to 45 0C, darkens the low temperature color to red but does not significantly alter the low temperature fluorescence. Upon heating the composite changes color to yellow with a very strong yellow/orange emission.
These and other features and objectives of the present invention will now be described in greater detail with reference to the accompanying drawings, wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 are plots of Polymer A DSC versus heat flow: and
Fig. 2 are photographs of poly(3-(oligoethylene oxide)-4-methylthiophene with Poly(ethyleneglycol) dimethyl ether.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
The synthesis of cqmpound(s) I is known in the art In the synthesis of compound(s) I to exhibit the color change at the pre-determined temperature, e.g., for the series of poly(3-alkylthiophene)s, there is roughly an inverse correlation with the length of the n-alkane substituent and the temperature of the thermochromic transition for both the regiorandom (Ri=alkyl, Rt=alkyl, n«0.8, m∞0.2, 1=40-80, R2,R3,R5,Rό=H) and regioregular (Ri=alkyl, n= 40-80, m=0, poly(3-n-alkylthiophene)s. For regiorandom polymers longer substituents such as n- hexadecyl have lower temperature thermochromic transitions (81 0C) than shorter chain substituents such as n-octyl (130 0C). The regioregular polymers have higher thermochromic transitions than the regiorandom polymers but the same inverse correlation with chainlength is observed. The n-hexadecyl and n-octyl have thermochromic transition centered around 125 and 175 0C. The thermochromic transition temperatures are dependent upon the molecular weight of the polymer. Lower molecular weight polymers have lower thermochromic transition temperatures while higher molecular weight polymers have higher thermochromic transition temperatures. The temperature of the thermochromic transition and the color of the thermochromic material can be further modified by the incorporation of various small molecule additives. The best small molecule additives are structurally related to the monomer, such as 3-alkylthiophene, from which the polymer was prepared.
In one embodiment, the invention includes the use of polythiophene/small molecule additive composite as a neat mixture or admixed with paints including polyurethanes, polysiloxanes, polyacrylates, and other related polymer-based paints and coatings with about 0.5 % polythiophene/small molecule additive composite with retention of the thermochromic behavior. The thermochromic polymer-based pigments can be incorporated via injection molding or extrusion into many commercially important plastics such as poly (ethylene terephthalate) (PET), polysytrene, polyethylene (HDPE and LDPE), other polyolefins, polydienes, polycarbonates, poly acrylics, poly acrylic acids, poly aery lamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, poly(vinyl nitrile)s poly vinyl esters, polyesters, polysulfones, poly sulfonamides, poly amides, polyimines, polyimides, carbohydrates, and polymer mixtures and copolymers. The plastics retain a visually retrievable thermochromic response with pigment loadings of about 0.5 % polymer- based pigment. In yet another embodiment of the invention, polythiophene/small molecule additive composite exhibiting controlled thermochromic transitions are dispersed in commercially available printable ink formulations, e.g. oil with resins, pigment extenders and other additives, to form thermal indicator ink systems. The polythiophenes are present in the thermal indicator ink in an amount of 1.0-25% by weight based on the total weight of the thermal indicator ink, preferably 7.0 to 14% weight. The ink can be printed using conventional methods such as ink-jet and letter press. Examples of ink formulations that polythiophene can be dispersed in can include combinations of resins such as cellulose, nitrocellulose with co-binders including polyamides, polyester amides, alkyd, epoxy acrylates, amine acrylates, polyurethanes, and polyvinyl butyral (UNI-REZ, UNI-JET, BECKOSOL,
EPOTUF), suitable oils such as napthenic petroleum oils and vegetable oils, e.g. soy bean oil, and suitable pigment extenders and additives that can include organic acids and esters of organic acids such as malic acid and organic solvents such as 1,5-pentanediol, diethylene glycol, along with other alcohols and related compounds (VERTEC, SYLFAT, UNI-KYD, and ICM, DY-SOLVE lines of additives.).
In yet another embodiment the invention, the thermal indicator ink is printed on at least a portion of a suitable substrate, e.g. a portion of paper, plastic, or ceramic food/beverage containers, a portion of packaging materials for foods and goods, labels, a portion of labels, stickers, etc., using conventional printing methods. The polythiophenes dispersed in the ink system can be in particulate form and have diameters in the range of between about 0.01 - 0.1 microns thereby rendering the system suitable for fine printing.
In another embodiment of the invention, the thermal indicator material is applied to an article, e.g., a portion of paper, plastic or ceramic food/beverage containers, as a coating on an area of the article, or the entire article, which will be visible during the expected use of the article. The coating can be applied by any technique known in the art, such as by brush, roller, spraying, etc. Accordingly, the coatings typically have a thickness of 0.1 to 1000 microns. The thermal indicator material can also be absorbed on a surface or both absorbed and adsorbed on a surface.
Suitable carrier mediums to be admixed with the polythiophene/small molecule additive composite exhibiting controlled reversible thermochromic transitions can include polyurethanes; elastomers including polysiloxanes and polydienes; polyacrylates, poly (ethylene terephthalate)s (PET), polysytrenes, polyolefins including polyethylenes (HDPE and LDPE) and polypropylene, polycarbonates, polyacrylics, poly aery lie acids, polyacrylamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, polyvinyl nitrile)s polyvinyl esters, polyesters, polysofones, poly sulfonamides, polyamides, polyimines, polyimides, and carbohydrates.
The invention will further be described with reference to following non-limiting examples. Example I
In one example, addition of monomer (3-octadecylthiophene) to polymer (poly(3-octadecylthiophene, regiorandom, Mn = 6,600) results in a significant lowering of the thermochromic transition temperature, deepening of the color, and enhancement of the flourescence properties of poly(3-alkylthiophene)s. The addition of other small molecules such as octadecylbenzene have a similar effect. For example, a sample of poly(3-octadecylthiophene) is light red in color at room temperature. Upon addition of 3 -octadecylthiophene to poly(3- octadecylthioophene) (2:1 monomer :polymer by weight) the color is changed to a deep purple at room temperature. Furthermore in the pure polymer sample the thermochromic/thermoflourescent transition occurs at 65 C. Upon addition of 3- octadecylthiophene to poly (3 -octadecylthiophene) (2: 1) the thermochromic/thermoflourescent transition is lowered to 50 C. The high temperature color is yellow in both cases. The addition of monomer decreases the transition temperature by approximately 15 C. Finally, the flourescence is modified. Addition of 3-octadecylthiophene to poly(3-octadecylthiophene) increases the intensity of the flourescenece of the polymer/monomer composite above the thermochromic/thermoflourescence transition temperature by approximatly 3x when compared to the polymer alone. The addition of monomer (3-octadecylthiophene) or other small molecules such as octadecylbenzene to thermochromic/thermoflourescent polymer (poly(3-octadecylthiophene) results in an enhancement of the color and flourescenec changing properties. In another example, the addition of monomer (3-octadecylthiophene) to polymer (poly(3-octadecylthiophene, regioregular, Mn = 3,300) results in a significant lowering of the thermochromic transition temperature and deepening of color. Upon addition of 3-octadecylthiophene to poly(3-octadecylthioophene) (2: 1 monomer:polymer by weight) the color is changed from red/yellow to a deep purple at room temperature. Furthermore in the pure polymer sample the thermochromic/thermoflourescent transition occurs at 50 C. Upon addition of 3- octadecylthiophene to poly(3-octadecylthiophene) (2: 1) the thermochromic/thermoflourescent transition is lowered to 35 C. The high temperature color is yellow in both cases. The addition of monomer decreases the transition temperature by approximately 15 C. The change in thermochromic transition is related to the change in melting transition as measured by Differential Scanning Calorimetry (DSC), as seen in Figure 1. In another example, the addition of oligo(ethyleneglycol)dimethyl ether with Mn 250 to poly(3-oligoethylene oxide)-4-methylthiophene)s (Mn = 11,500) significantly lowers the thermochromic temperature. The thermochromic transition of the pure polymer occurs at 65 0C. Upon addition of oligo(ethylene glycol)dimethyl ether the transition temperature is lowered to 5 0C, as seen in Figure 2.
The foregoing description has been limited to a specific embodiment of the invention. It will be apparent, however, that variations and modifications can be made to the invention, with the attainment of some or all of the advantages of the invention. Therefore, it is the object of the appended claims to cover all such variations and modifications as come within the true spirit and scope of the invention.
Having described our invention, what we now claim is:

Claims

1 L A thermal indicator material capable of a thermochromic transition
2 upon undergoing a temperature change, said material comprising:
3 a plurality of compounds having the following structure:
4 wherein R1-R6 = a hydrogen, substituted or unsubstituted alkyl radical, substituted
5 or unsubstituted alkoxy radical, substituted or unsubstituted aryl radical, substituted
6 or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical,
7 substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical,
8 substituted or unsubstituted amine radical, substituted or unsubstituted amide
9 radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl 0 radical 1 n is between 1 and 1000, m is between 0 and 1000, and 1 is between 1 and 1000; 2 with added small molecules, the small molecule additive having the following 3 structure: 4 R-Ar-R' , R-X, linaer alkane, or oligoethylene oxide 5 small molecules with molecular weight less than 1,000 AMU 6 wherein R-R' = a hydrogen, substituted or unsubstituted alkyl radical, 7 substituted or unsubstituted alkoxy radical, substituted or unsubstituted thioalkyl 8 radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted 9 acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted 0 amine radical, substituted or unsubstituted amide radical, substituted or 1 unsubstituted heteroaryl or substituted or unsubstituted aryl radical and Ar = a 2 substituted or unsubstituted aromatic or heteroaromatic radical including but not 3 limited to benzene, thiophene, naphthalene, flourene, anthracene, pyridine, indine, 4 biphenyl, phenanthrene, and furan 5 X = a halogen (F, Cl, Br, or I).
2. The material of claim 1 wherein the thermochromic transition is reversible.
3. The material of claim 1 wherein the thermochromic transition is a two step transition, such that when the samples are heated above the thermochromic transition temperature followed by a rapid cooling to a temperature below the thermochromic transition temperature in a time of less than about 5 seconds, a new low temperature color is generated which then has a irreversible thermochromic transition.
4. The material of claim 1 wherein the cooled compounds are admixed with a carrier medium.
5. The material of claim 4 wherein the cooled compounds are present in the thermal indicator material in an amount of about 0.05 to about 25.0% by weight based on the total weight of the thermal indicator material.
6. The material of claim 1 wherein R1 and R4 are C20-C50 alkyls or substituted alkyls, and R2, R3,R5 and R6 are H, n is 0.8, m is 0.2, and 1 is between 15 and 100.
7. The material of claim 1 wherein the pre-determined temperature is in the range of between about -30 to 1500C.
8. The material of claim 1 wherein R1 and R4 are -(CH2)21CH3, R2, R35R5 and R6 are H, n is 0.8, m is 0.2, and 1 is between 25 and 50.
9. The method of claim 8 wherein the pre-determined temperature is 60 0C and a first low temperature color is burgandy, a high temperature color is yellow and a second low temperature color is orange.
10. The material of claim 4 wherein the carrier medium is selected from the group consisting of polyurethanes; elastomers including polysiloxanes and polydienes; polyacrylates, poly(ethylene terephthalate)s (PET), polysytrenes, poly olefins including polyethylenes (HDPE and LDPE) and polypropylene, polycarbonates, polyacrylics, polyacrylic acids, polyacrylamides, polymethacrylics, polyvinyl ethers, polyvinyl halides, polyvinyl nitrile)s polyvinyl esters, polyesters, polysulfones, polysulfonamides, polyamides, polyimines, polyimides, and carbohydrates.
11. The material of claim 4 wherein the carrier medium is an ink formulation 12. The material of claim 11 wherein the ink formulation comprises oils, resins, pigment extenders and additives. 13. A method for producing a thermal indicator material which comprises: providing a plurality of compounds having the following structure:
wherein RrR6 = a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted aryl radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical n is between 1 and 1000, m is between 0 and 1000, and 1 is between 1 and 1000; with added small molecules, the small molecule additive has the following structure R-Ar-R' , R-X, linaer alkane, or oligoethylene oxide. Small molecules with molecular weight less than 1 ,000 AMU wherein R-R' = a hydrogen, substituted or unsubstituted alkyl radical, substituted or unsubstituted alkoxy radical, substituted or unsubstituted thioalkyl radical, substituted or unsubstituted trialkylsilyl radical, substituted or unsubstituted acyl radical, substituted or unsubstituted ester radical, substituted or unsubstituted amine radical, substituted or unsubstituted amide radical, substituted or unsubstituted heteroaryl or substituted or unsubstituted aryl radical and Ar = a substituted or unsubstituted aromatic or heteroaromatic radical including but not limited to benzene, thiophene, naphthalene, flourene, anthracene, pyridine, indine, biphenyl, phenanthrene, and furan. X = a halogen (F, Cl, Br, or I).
EP06770799A 2005-05-25 2006-05-22 Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additives Withdrawn EP1889049A2 (en)

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