EP1889049A2 - Thermochrome und thermofluoreszierende pigmente: intensivierung von farbe und fluoreszenz mit zusätzen - Google Patents

Thermochrome und thermofluoreszierende pigmente: intensivierung von farbe und fluoreszenz mit zusätzen

Info

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.)
Withdrawn
Application number
EP06770799A
Other languages
English (en)
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
Original Assignee
Rhode Island Board of Education
Priority date (The priority date 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 date listed.)
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/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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.

Landscapes

  • 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)
EP06770799A 2005-05-25 2006-05-22 Thermochrome und thermofluoreszierende pigmente: intensivierung von farbe und fluoreszenz mit zusätzen Withdrawn EP1889049A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68460305P 2005-05-25 2005-05-25
PCT/US2006/019676 WO2006127569A2 (en) 2005-05-25 2006-05-22 Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additives

Publications (1)

Publication Number Publication Date
EP1889049A2 true EP1889049A2 (de) 2008-02-20

Family

ID=37452679

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06770799A Withdrawn EP1889049A2 (de) 2005-05-25 2006-05-22 Thermochrome und thermofluoreszierende pigmente: intensivierung von farbe und fluoreszenz mit zusätzen

Country Status (2)

Country Link
EP (1) EP1889049A2 (de)
WO (1) WO2006127569A2 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG176983A1 (en) 2009-07-08 2012-02-28 Dermira Canada Inc Tofa analogs useful in treating dermatological disorders or conditions
CN103575421B (zh) * 2012-08-09 2016-05-04 中山市云创知识产权服务有限公司 发光二极管芯片的温度测量方法及使用的热敏高分子材料
EP2843128A1 (de) * 2013-09-03 2015-03-04 Teijin Aramid B.V. Synthetische Faser geeignet erfasst zu werden
US10184840B2 (en) 2015-01-07 2019-01-22 The Boeing Company Portable device for quantifying thermochromatic coating signatures
US10352777B2 (en) * 2015-01-07 2019-07-16 The Boeing Company Systems and methods for monitoring temperatures of batteries
CN105111415B (zh) * 2015-09-15 2017-05-03 天津理工大学 一种侧链含萘基团的聚噻吩衍生物及其制备方法和应用
EP3470195B1 (de) 2017-10-12 2026-04-29 The Procter & Gamble Company Blasgeformter artikel mit visuellen effekten, vorformling, verfahren
US11046473B2 (en) 2018-07-17 2021-06-29 The Procter And Gamble Company Blow molded article with visual effects
US11724847B2 (en) 2018-10-19 2023-08-15 The Procter & Gamble Company Blow molded article with debossing
EP3953130B1 (de) 2019-04-11 2024-08-14 The Procter & Gamble Company Blasgeformter artikel mit visuellen effekten
WO2021142194A1 (en) 2020-01-08 2021-07-15 The Procter & Gamble Company Blow molded multilayer article with color gradient

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
US6706218B2 (en) * 2000-01-11 2004-03-16 The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations Thermochromic polymers for rapid visual assessment of temperature

Non-Patent Citations (1)

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Title
See references of WO2006127569A3 *

Also Published As

Publication number Publication date
WO2006127569A2 (en) 2006-11-30
WO2006127569A3 (en) 2007-11-08

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