PH12017000259A1 - Color-reversible thermochromic compounds for moisture sensing compositions and thermochromic paint compositions - Google Patents
Color-reversible thermochromic compounds for moisture sensing compositions and thermochromic paint compositions Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000003973 paint Substances 0.000 title claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- 230000008859 change Effects 0.000 claims abstract description 25
- 238000009472 formulation Methods 0.000 claims abstract description 16
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 150000002891 organic anions Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 4
- 235000003704 aspartic acid Nutrition 0.000 description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- -1 copper nitrate Chemical class 0.000 description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000010981 turquoise Substances 0.000 description 3
- GUPMWVRHEBLNMF-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;copper Chemical compound [Cu].OC(=O)[C@@H](N)CC(O)=O GUPMWVRHEBLNMF-DKWTVANSSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229940006116 lithium hydroxide Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 229940093932 potassium hydroxide Drugs 0.000 description 2
- 229940083608 sodium hydroxide Drugs 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- HQCJJFPJPCUTEY-UHFFFAOYSA-N 1-[1-adamantyl(aziridin-1-yl)phosphoryl]aziridine Chemical compound C1CN1P(C12CC3CC(CC(C3)C1)C2)(=O)N1CC1 HQCJJFPJPCUTEY-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000004695 complexes Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
A thermochromic compound is comprised of a polymeric complex of copper and a linear diacid. The thermochromic compound undergoes a color change from a hydrated color state to a dehydrated color state upon removal of moisture at an elevated temperature, and undergoes a color change from the dehydrated color state to the hydrated color state upon adsorption of moisture at a reduced temperature. The thermochromic compound can be embedded in a matrix formulation of a moisture sensing composition, or dispersed in a liquid paint formulation of a thermochromic paint composition. To form the thermochromic compound, copper is reacted with a linear diacid in the presence of a basic salt to result in the polymeric complex.
Description
method of forming a color-reversible thermochromic compound.
According to this invention, the method comprises reacting copper with a linear dicarboxylic acid in the 3 nresence of a basic salt to form a polvmeric complex of copper and the linear dicarboxylic acid.
Tn one embodiment, the basic salt is a hydroxide salt selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide.
In one embodiment, the thermochromic compound is formed at an interface of two aqueous layers during the reaction.
In one embodiment, the reaction occurs at a temperature not greater than room temperature.
In one embodiment, the reaction mixture is allowed to stand for a period ranging from 1 to 2 weeks after adding the linear diacidslowly to copper in the presence of the basic salt.
The thermochromic compound of the present invention comprises a polymeric complex of copper and a linear dicarboxylic acid. The thermochromic compound 1s reversibly thermochromic, that is, it canundergoacolor change from a hydrated color state to a dehydrated color state uponremoval of moisture at anelevated temperature,
and can undergo a color change from the dehydrated color state to the hydrated color state upon adoccorption cof moisture at a reduced temperature lower thantheelevated temperature. In one embodiment, the elevated tfemperatiire ranges from 100°C £0 120°C. Several copper compounds, examples of which include copper carbonate, copper sulfate, and a complex of copper and oxalic acid, are known to possess thermochromic properties. These compounds, however, have limited applications because they undergo color change only at high temperatures.
In addition, the color changes these compounds undergo are irreversible. Another copper compound, i.e., copper nitrate, undergoes a color transition upon moisture removal above 100°C. Upon dehydration above 100°C, however, it melts while undergoing color change. When subsequently cooled down, it solidifies while undergoing another color change, but not to its original color prior to dehydration.
The thermochromic compound of the present invention does not have the disadvantages of the aforementioned copper compounds. It is a polymer that is stable at high temperatures due toameltingpoint above 300°C. Solvents and other triggering components are not required for thermochromism to take effect. In its solid state, the thermochromic compound changes color at around 100°C (i.e., color change to a dehydrated color state at an elevated temperature) upon removal of moisture, and reverts back to its original color upon cooling and rehydration (i.e. color change back to a hydrated color state at a reduced temperature lower than the elevated temperature) . The thermochromic compound is a nanafihril powder. which can be easily processed into powders, dispersions, films, and compressed flat pellets.
The linear dicarboxylic acid used in the thermochromic compound of this invention has two carboxylic acid groups and a flexible linker between the two carboxylic acid groups. The flexible linker can be a linear substituted hydrocarbon having CH: groups ranging in number from 1l to 10. Examples of dicarboxylic acids with this type of flexible linker are succinic acid (HOOCC2H4COOH}, glutaric acid (HOOCC3HeCOCOH), and : adipic acid (HOOCC3H3COOH) . The flexible linker can also be a substituted hydrocarbon having at least one functional group attached thereto. Suitable examples of the functional group include -NHZ, -CnH2nCHs, where n ranges from 0 to 10, and -S03. Examples of dicarboxylic acids with this type of flexible linker are aspartic acid {HOOCCH,CH (NH>) COOH) , and glutamic acid (HOQC (CH») 2CH (NH2) COOH) . The flexible linker can also be an unsaturated hydrocarbon having l to 10 double bonds.
Examples of dicarboxylicacidswiththistypeof flexible linker are fumaric acid and maleic acid, both of which have one double bond. Fumaric acid and maleic acid are
10 So isomers with the same formula (HOOC (CH) COOH), but tne double bond in fumaricacidis inthe trans configuration, while the double bond in maleic acid is in the cis configuration.
The rarner in tha thermachromics comnoynind of this invention has a 2* charge. The source of the copper 2° ion can be an inorganic salt of copper, such as copper (II) sulfate, copper (II) nitrate, or copper (II) carbonate. Copper salts with organic anions, such as copper (II) acetate, can also be used.
The thermochromic compound of the present invention is formed by reacting copper with a linear dicarboxylic acid in the presence of a basic salt to form a polymeric complex of copper and the linear diacid. In one embodiment, the basic salt is a hydroxide salt, examples of which include sodiumhydroxide, potassiumhydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide. In the method of this invention, reaction occurs through a bilayer mechanism. A solution of the linear dicarboxylic acid and the basic salt in an ethanol/water solvent 1s added slowly to an agueous solution of the copper ion. This leads to the formation of a two-layer reaction mixture. The top layer is the linear dicarboxylic acid in ethanol /water solution, and the bottom layer 1s the copper solution. The thermochromic compound is formed at the interface of these two layers during the reaction. In the method of this invention, the reaction occurs at a temperature - not greater than room temperature. After the lincar dicarboxylic acid solution has been added to the copper solution, the reaction mixture is allowed to stand for
Aa nerind ranging from 1 tn 2 weeks, dnring which fime the thermochromic compound continues to be formed at the aforementioned interface via molecular self-assembly.
Example 1
The reaction between copper and adipic acid (HOOCC4HgCOOH) is described in this example. Copper (II) : nitrate (1.5 mmol) is first dissolved in water (2.0 ml) ina test tube. To another container, asolutionof adipic acid (1.0 mmol) in an ethanol /water mixture (5.0ml/1.0 ml) 1s deprotonated by adding NaOH (2 mmol, 80 mg). The diacid solution is then drawn using a pipette and added drop wise to the copper solution, generating two immiscible layers. The mixture is allowed to react at 5°C (inside a refrigerator) without stirring. The "formation of a homogeneous blue solid material is observed withinminutes. After two weeks, theblue solid material is collected, rinsed several times with deionized water, and then isolated via centrifugation at 3200 RPM for 5 minutes. The resulting precipitate is then freeze-dried overnight to obtain a blue powder.
The synthesized product is found tobe insoluble inwater and common organic solvents, such as triethylamine,
toluene, dichloromethane, Z2-propanol, ethyl acetate, chloroform, ethanol, and dimethylformamide, both at room temperature and high-temperature conditions. This indicates that the synthesized Cu-adipate complex is s nolumerics in nature The synthesized Cu-adipate polymeric complex hasameltingpoint greater than300°C, measured using a Mel-Temp Apparatus, confirming the stability of the reaction product. The melting point differs from known copper (II) complexes, which usually melt below 200°C, indicating that a new complex is formed.
Fourier transform infrared spectroscopy confirms the presence of the carboxylic acid functional group.
Energy-dispersive X-ray spectroscopy data confirm the presence copper. Thermogravimetric data show a ratio of 1:1 between copper and the diacid. X-ray diffraction data confirm the crystalline property of the complex, and the absence of copper oxides. The complex prepared at a low temperature exists as homogenous nanofibers with an average width of 104 (£24) nm and length of 1844 (£716) nm. Transmission electron microscopy (TEM) data of the complex prepared at low temperature show the diameter dimension at 149.98 (£62.85) nm and length of 452.11 (+167) nm and high aspect ratio of 75:226.
The complex exhibits a NYPD blue color (i.e., a hydrated color state) at room temperature but changes color tooldgoldyellow (i.e., adehydrated color state) upon dehydration at around 100°C. The complex reverts
. to its light blue color {(i.e., the hydrated color state) sconce rehydrated at room temperature.
Example 2
Example 2 differs from Example 1 in that the reaction
S was conducted at room temperature. The complex nrenared at room temperature has a rod-like structure with loose thin fiber-like structures (139.0 (£39) nm in width; 796 (£75) nm in length).
Example 3
Example 3 differs from Example 1 in that succinic acid (HOOCC:H4COOH) instead of adipic acid is used to react with copper. The resulting thermochromic compound of Example 3 differs structurally from the resulting thermochromic compound of Example 1. Uniform small and thick fiber-like nanorods are observed for the
Cu-adipate complex from Example 1, whereas longer, thinner and linear nanofibers are observed for the
Cu-succinate complex from Example 3. A transmission electron microscopy image of the Cu-succinate complex reveals that the complex exists as nanofibrils with average diameters of 97.01 (242.34) nm, average lengths of 2958.89 (+931.67) nm and an aspect ratio of 49:1479.
Generally, when the reaction is conducted at colder conditions, the nanofibers grow gradually, allowing slow formationof straight chainswith longer and thinner strands.
The copper~succinate complex isbrightblueincolor.
In particular, 1t has a turquoise 3 shade (i.e., a hydrated color state) 2t room Lenperature, changes into a sea green color (i.e., a dehydrated color state) upon dehvdration at 100°C, and then reverts back to the turguoise 3 color once in contact with moisture at room temperature.
Example 4
Example 4 differs from Example 1 in that aspartic acid (HOOCCH2CH (NH.) COOH) instead of adipic acid is used to react with copper. The flexible linker of aspartic acid contains an -NHz functional group. The resulting thermochromic compound has anAir Force Blue color (i.e., a hydrated color state) at room temperature, but changes color toviridian green (i.e., adehydrated color state) 5 upon heating at 235°C. However, when the compound is heated in the presence of a moisture absorber, the complex changed from Air Force blue color to viridian green at above 100°C, and changes to a cadet blue 5 color upon rehydration at room temperature. :
Example 5
Example 5 differs from Example 1 in that fumaric acid (HOOC (CH) COOH) instead of adipic acid is used to react with copper. The flexible linker of fumaricacidcontains a double bond in the trans configuration. The resulting
Cu-fumarate complex exists as pointedslender crystals.
It exhibits a cadet blue 4 color (i.e., a hydrated color state) until temperatures above 250°C. When it is heated in the presence of a moisture absorber, the complex changes froma cadet blue 4d color sca ctraw yellow ecolor (i.e., a dehydrated color state) upon dehydration, and then reverts to the cadet blue 4 color when exposed to mnisture at room temperature
Example 6
Example 6 differs from Example 1 in that maleic acid (HOOC (CH) 2CO0H) instead of adipic acid is used to react with copper. The flexible linker of maleic acid contains a double bond in the cis configuration. Maleic acid is an isomer of fumaric acid. The resulting Cu-maleate complex appears as nanorods, with formation of crystal clusters. It exhibits an ocean blue color (i.e., a hydrated color state) at room temperature, turns a turquoise 3 color (i.e., a dehydrated color state) upon dehydration at around 100°C, and then reverts to the turquoise 3 color upon rehydration,
The thermochromic compound of the present invention can be embedded in a matrix formulation to produce a moisture sensing composition. The matrix formulation can be silica gel in bead form or powder form. One method of preparing the moisture sensing composition involves preparing a solution of sodium silicate and the thermochromic compound, followed by acidifying the solutiontoformsilicicacid. Silicicacidreadily loses water to formsilica gel. As the silicic acid turns into silica gel, the thermochromic compound is embedded into }
EE RRR RRR
16 : the gel by gelatinous precipitation.
The thermochromic compound of the present invention can also be dispersed in a liquid paint formulation to produce a thermochromic paint composition. The basic components of anv paint composition are a pigment. and a binder. The pigment provides the color of the paint composition, and the binder holds the pigment to a surface where the paint composition is applied. The thermochromic compound of the present invention can serve as the pigment of the thermochromic paint composition. One method of preparing the thermochromic paint composition involves dispersing the thermochromic compound of the present invention in a liquid mixture comprised of a solvent having the binder dissolved or dispersed therein. The solvent can be water or an organic solvent.
While the invention has been described in connection with what are considered the exemplary embodiments, it is understood that this invention is not limited to the disclosed embodiments but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation so as to encompass all such modifications and equivalent arrangements.
1 : NI 20 uN Co
COLOR-REVERSIBLE THERMOCHROMIC COMPOUNDS FOR MOISTURE 6 “ }
SENSING COMPOSITIONS AND THERMOCHROMIC PAINT %
COMPOSITIONS Sy
S Field of the invention
The present invention relates to thermochrofiic compounds and thermochromic compositions. In particular, the present invention relates to a thermochromic compound comprising a polymeric complex of copper and a linear diacid, a thermochromic moisture-sensing composition having the thermochromic compound embedded therein, and a thermochromic paint composition having the thermochromic compound dispersed therein.
I5
Some transition metal complexes, as well as some organic compounds, are known to possess thermochromism, i.e., they change color due to a change in temperature.
The origin of the thermochromic effect is a molecular rearrangement caused by the temperature change. The rearrangement may be a change in geometry, such as that observed in bis (diethylammonium) tetrachlorocuprate, which changes color due to a change from a square planar geometry to a distorted tetrahedral geometry. The rearrangement mayalsobe achange incoordinationnumber, such as that observed in bis (diethylammonium)
’ tetrachloronickelate (II), which changes color due to a change from 2 coordination number of =ix, to 2 coordination number of four. Other rearrangement mechanisms are possible, such as a change in the lattice structure. or achanage inthenatureof the ligands bonded to the transition metal. Compounds with thermochromic properties have useful applications as temperature sensors and moisture sensors.
It is possible to synthesize transition metal polymeric complexes by combining the transition metal ion with an organic diacid. For example, in the article “Amino Acid Based Metal-Organic Nanofibers” published in the Journal of the American Chemical Society in
December 2009, the authors reported the synthesis of i5 a copper-aspartic acid complex. Aspartic acid is an aliphatic diacid with the formula HOOCCH2>CH (NH2) COOH.
The copper-aspartic acid complex is a blue polymeric nanofiber. Most studies on metal-organic diacid complexes, however, use rigid, conjugateddiacids, such as terephthalic acid. Few studies describe the use of flexible organic linkers. In addition, many studies focus on obtaining metal-organic diacid complexes with large crystal structures. Few studies describe attempts tosynthesize crystalswithdimensions in the nanoscale.
Such nanomaterials would have properties not present in bulk crystals, which broaden their potential applications.
Copper compounds are generally colored, and some : exhibit thermechremic properties. Examples of these compounds are disclosed in the article “Thermochromism of Inorganic Compounds” published in Chemical Reviews in December 1968. Basic copper carbonate 1s known to change color fromgreen to black at 320°C, copper sulfate is known to change color fromgreen to brownish at 265°C, and copper nitrate is known to change color from blue to brown-black at 250°C. The color changes, however, are irreversible. The same article also describes a copper complex with oxalic acid (HOOCCOOH), which undergoes an irreversible color change from light blue to black at 355°C. Since these copper complexes undergo color change at temperatures greater than 250°C, they become unsuitable in applications where temperatures are below 250°C. Moreover, their irreversible color changes limit their practical use, since they cannot be recycled.
Thermochromic moisture-sensing compositions, e.g. silica gel moisture sensors, are self-indicatingsilica gels prepared by adding a moisture sensitive indicator to the basic silica gel. The indicator changes color as it adsorbs moisture, giving a visual indication as to the capacity of thesilicagel toadsorbmoremoisture.
Commercial self-indicating silica gels contain thermochromic cobalt chloride (CoCl:) or ammonium tetrachlorocobaltate (II) (NH4)2CoCls. Both compounds are blue when dehydrated, and pink when hydrated. Cobalt
COMP LEXes, NCWavar, are known to have toxic offecto on health and the environment. The European Union has ‘classified the blue to pink self-indicating silica gel asatoxirmaterial since 2000. Non-toxic. thermochromic organic dyes or iron salts may be used as alternatives tothe blue to pink self-indicating silica gel. For these substances to be reused, however, they must be regenerated by exposure to high temperatures. Since 10- active components of these substances are destroyed at high temperatures, the substances become unusable after repeated use. Thus, there is a need for a non-toxic, thermally stable, color-reversible thermochromic compound for moisture sensing applications.
U.S. Patent No. 4,424,990 discloses a thermochromic composition comprised of basic copper carbonate and a sulfur-containing organic acid having a general formula
S[(CH2)aCOOH] 2, where n ranges from 1 to 10. The complex changes color at temperatures in the range of 165°C to 240°C. The patent also claims a thermochromic liquid paint formulation where the thermochromic composition - is dispersed. Finally, it claims a coupling on which the thermochromic liquid paint formulation is applied.
The thermochromic liquid paint formulation would not be effective at temperatures below 165°C.
U.S. Patent No. 3,816,335 discloses a polymeric thermochromic material where HgI, and a thermochromic inorganic compound, such as CoCl: 6H:0, NiSO4 7H:O, are anifecrmly dispersed inte a polymer matrix prior to cross-linking of the polymer matrix. The thermochromic material was simply dispersed in the polymer matrix and is not polvmeric by itself.
An object of this invention 1s to provide a color-reversible thermochromic compound suitable for °° moisture sensing compositions and thermochromic paint compositions.
The thermochromic compound of this invention comprises a polymeric complex of copper and a linear dicarboxylic acid. The thermochromic compound 1s capable of undergoing a color change from a hydrated color state to a dehydrated color state upon removal of moisture at an elevated temperature. It is also capable of undergoing a color change from the dehydrated color state to the hydrated color state upon adsorption of moisture at a reduced temperature lower than the elevated temperature.
In one embodiment, the elevated temperature ranges from 100°C to 120°C.
In one embodiment, the linear dicarboxylic acid has carboxylic acid groups and a flexible linker in between the carboxylic acid groups.
In one embodiment, the flexible linker is a linear saturated hydrocarbon having CH: groups ranging in number from 1 tc 10.
In one embodiment, the flexible linker 1s a substituted hydrocarbon having at least one functional aroup attached thereto. The functional aroupmav be ~NH», -CnH2nCH3, where n ranges from 0 to 10, or -SOs.
In one embodiment, the flexible linker 1s an unsaturated hydrocarbon having 1 to 10 double bonds.
In one embodiment, the copper has a 2' charge.
In one embodiment, the copper has an anion selected from nitrate, sulfate, carbonate, and acetate.
According to another aspect of this invention, a moisture sensing composition comprises a matrix formulation having the thermochromic compound of this i5 invention embedded therein.
In one embodiment, thematrix formulation isasilica gel, which may be in the form of beads or powders.
According to yet another aspect of this invention, a thermochromic paint composition comprises a liquid paint formulation having the thermochromic compound of this invention dispersed therein. The thermochromic compound can serve as a pigment of the thermochromic paint composition.
In one embodiment, the liquid paint formulation comprises a solvent, e.g. water or an organic solvent, having binders dissolved or dispersed therein.
Another object of this invention is to provide a
Claims (1)
- Coe Lo New oo Y, oUaN “ Claims: & :Oy .1. 2A thermochromic compound comprising a polymer Ca complex of copper and a linear dicarboxylic acid/ 42. The thermochromic compound accordinagtoclaiml,/which is capable of undergoing a color change from a hydrated color state to a dehydrated color state upon removal of moisture at an elevated temperature.3. The thermochromic compound according to claim 2, wherein the elevated temperature ranges from 100°C to 120°C.4. The thermochromic compoundaccordingtoclaim2, which is capable of undergoing a color change from the dehydrated color state to the hydrated color state upon adsorption of moisture at a reduced temperature lower than the elevated temperature.5. The thermochromic compound according to claim 1, wherein the lineardicarboxylicacidhas carboxylic acid groups and a flexible linker in between the carboxylic acid groups.6. The thermochromic compound according to claim 5, wherein the flexible linker is selected from:EERE. 18 os {a) a linear saturated hydrocarbon having CH: groups ranging in number from 1 to 10: (b}) a substituted hydrocarbon having at least one functional group attached thereto; and fc) an unsaturated hvdrocarbon having one to ten double bonds.7. The thermochromic compound according to claim 6, wherein the flexible linker is a substituted hydrocarbon, and the at least one functional group is selected from -NH2, -CnH2nCH3, where n ranges from 0 to 10, and -SOs.8. The thermochromic compound according to claim 1, wherein the copper has a 2% charge. i59. The thermochromic compound according to claim 8, ’ wherein the copper has an inorganic anion.10. The thermochromic compound according to claim 9, wherein the inorganic anion is selected from nitrate, sulfate, and carbonate.11. The thermochromic compound according to claim 8, wherein the copper has an organic anion.12. The thermochromic compound according te claim 11, wherein the organic anion is acetate.EEE —— RRR ERR ITE. . 19 .12. A moisture sensing composition comprising a matrix formulation having embedded therein a thermochromic compound according to any one of claims 1 to 12.14. The moisture sensing composition according to claim 13, wherein the matrix formulation is a silica gel.15. The moisture sensing composition according to claim 14, wherein the silica gel is in the form of beads.16. The moisture sensing composition according to claim 14, wherein the silica gel is in the form of powders. 3 17. A thermochromic paint composition comprising a liquid paint formulation having dispersed therein a thermochromic compound according to any one of claims 1 to 12. ' 20 18. The thermochromic paint composition according to claim 17, wherein the thermochromic compound serves as a pigment of the thermochromic paint composition.19. The thermochromic paint composition according to claiml7, whereinthe liguidpaint formulation comprises a solvent havingbindersdissolvedordispersedtherein.20. The thermochromic paint composition according to Clalin 15, wherein the scivent 1.35 selected from water and an organic solvent.21. A method nf forming a thermochromic compound according to claim 1, comprising reacting copper with a linear dicarboxylic acid in the presence cf a basic salt to forma polymeric complex of copper and the linear dicarboxylic acid.22. The method according to claim 21, wherein the basic salt is a hydroxide salt.23. The method according to claim 22, wherein the hydroxide salt is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, and cesium hydroxide.24. The method according to claim 21, wherein the linear dicarboxylic acid has carboxylic acid groups and a flexible linker in between the carboxylic acid groups.25. The method according to claim 21, wherein the copper has a 2* charge.26. The method according to claim 21, wherein the thermochromic compound is formed at an interface of two aqueous layers during the reaction.27. The method according to claim 21, wherein the reaction occurs at a temperature not greater than room temneratnre28. The method accerding to claim 21, wherein the reactionmixture is allowed to stand for aperiod ranging from 1 to 2 weeks after adding the linear dicarboxylic acid slowly to copper in the presence of the basic salt.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424990A (en) * | 1980-01-30 | 1984-01-10 | Raychem Corporation | Thermochromic compositions |
| RU2010128915A (en) * | 2007-12-14 | 2012-01-20 | Кимберли-Кларк Ворлдвайд, Инк. (Us) | HUMIDITY SENSORS |
-
2017
- 2017-09-11 PH PH12017000259A patent/PH12017000259A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424990A (en) * | 1980-01-30 | 1984-01-10 | Raychem Corporation | Thermochromic compositions |
| RU2010128915A (en) * | 2007-12-14 | 2012-01-20 | Кимберли-Кларк Ворлдвайд, Инк. (Us) | HUMIDITY SENSORS |
Non-Patent Citations (1)
| Title |
|---|
| AMINO ACID BASED METAL-ORGANIC NANOFIBERS" J. Am. Chem. Soc., 2009, 131, 18222-18223 (IMAZ ET.AL.) 13 October 2009 * |
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