EP1889049A2 - Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additives - Google Patents
Thermochromic and thermoflourescent pigments: enhancing color and flourescence with additivesInfo
- 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- Withdrawn
Links
- 239000000654 additive Substances 0.000 title claims abstract description 18
- 239000000049 pigment Substances 0.000 title claims description 9
- 230000002708 enhancing effect Effects 0.000 title description 2
- -1 alkyl radical Chemical class 0.000 claims abstract description 105
- 230000007704 transition Effects 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000003384 small molecules Chemical class 0.000 claims abstract description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000005840 aryl radicals Chemical class 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008859 change Effects 0.000 claims abstract description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229930192474 thiophene Natural products 0.000 claims abstract description 4
- 239000004305 biphenyl Substances 0.000 claims abstract description 3
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 3
- 230000002441 reversible effect Effects 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract 6
- 238000001816 cooling Methods 0.000 claims abstract 2
- 230000002427 irreversible effect Effects 0.000 claims abstract 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004606 Fillers/Extenders Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920001290 polyvinyl ester Polymers 0.000 claims description 3
- 229920001289 polyvinyl ether Polymers 0.000 claims description 3
- 229920001291 polyvinyl halide Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 3
- 150000001408 amides Chemical class 0.000 claims 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 125000004001 thioalkyl group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 28
- 239000002131 composite material Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229920000123 polythiophene Polymers 0.000 description 12
- ARFJPHXJBIEWSZ-UHFFFAOYSA-N 3-octadecylthiophene Chemical compound CCCCCCCCCCCCCCCCCCC=1C=CSC=1 ARFJPHXJBIEWSZ-UHFFFAOYSA-N 0.000 description 11
- 239000000976 ink Substances 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ASWOZWYFBVLCMR-UHFFFAOYSA-N 1,4-dihexoxybenzene Chemical compound CCCCCCOC1=CC=C(OCCCCCC)C=C1 ASWOZWYFBVLCMR-UHFFFAOYSA-N 0.000 description 1
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- BPNQMPWZDNUCPT-UHFFFAOYSA-N 2-octadecylthiophene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CS1 BPNQMPWZDNUCPT-UHFFFAOYSA-N 0.000 description 1
- 229920003332 Epotuf® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920006063 Lamide® Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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)
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).
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 |
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| WO (1) | WO2006127569A2 (en) |
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| EP2641906B1 (en) | 2009-07-08 | 2015-04-22 | Dermira (Canada), Inc. | Tofa analogs useful in treating dermatological disorders or conditions |
| CN103575421B (en) * | 2012-08-09 | 2016-05-04 | 中山市云创知识产权服务有限公司 | The thermometry of light-emitting diode chip for backlight unit and the thermo-sensitive high molecule material of use |
| EP2843128A1 (en) * | 2013-09-03 | 2015-03-04 | Teijin Aramid B.V. | Synthetic tracking fiber |
| US10352777B2 (en) * | 2015-01-07 | 2019-07-16 | The Boeing Company | Systems and methods for monitoring temperatures of batteries |
| US10184840B2 (en) | 2015-01-07 | 2019-01-22 | The Boeing Company | Portable device for quantifying thermochromatic coating signatures |
| CN105111415B (en) * | 2015-09-15 | 2017-05-03 | 天津理工大学 | Polythiophene derivative with side chain containing naphthalene groups and preparing method and application of polythiophene derivative |
| EP3470195A1 (en) | 2017-10-12 | 2019-04-17 | The Procter & Gamble Company | Blow molded article with visual effects |
| US11046473B2 (en) | 2018-07-17 | 2021-06-29 | The Procter And Gamble Company | Blow molded article with visual effects |
| WO2020081114A1 (en) | 2018-10-19 | 2020-04-23 | The Procter & Gamble Company | Blow molded article with debossing |
| MX2021012431A (en) | 2019-04-11 | 2021-11-12 | Procter & Gamble | Blow molded article with visual effects. |
| WO2021142194A1 (en) | 2020-01-08 | 2021-07-15 | The Procter & Gamble Company | Blow molded multilayer article with color gradient |
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| 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 |
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