JPH04168188A - Polymer temperature indicating material - Google Patents
Polymer temperature indicating materialInfo
- Publication number
- JPH04168188A JPH04168188A JP29354690A JP29354690A JPH04168188A JP H04168188 A JPH04168188 A JP H04168188A JP 29354690 A JP29354690 A JP 29354690A JP 29354690 A JP29354690 A JP 29354690A JP H04168188 A JPH04168188 A JP H04168188A
- Authority
- JP
- Japan
- Prior art keywords
- poly
- temperature
- alkylthiophene
- indicating material
- present
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title abstract description 26
- 229920000642 polymer Polymers 0.000 title description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 229920002848 poly(3-alkoxythiophenes) Polymers 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000004898 kneading Methods 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- -1 n-nonyl Chemical group 0.000 description 42
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- RFKWIEFTBMACPZ-UHFFFAOYSA-N 3-dodecylthiophene Chemical compound CCCCCCCCCCCCC=1C=CSC=1 RFKWIEFTBMACPZ-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZFHKVJTYIPMHEY-UHFFFAOYSA-N 2-pyridin-2-ylpyridine hydrochloride Chemical compound Cl.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 ZFHKVJTYIPMHEY-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- NJPMFDNZCLKTHE-UHFFFAOYSA-N 2-dodecylthiophene Chemical compound CCCCCCCCCCCCC1=CC=CS1 NJPMFDNZCLKTHE-UHFFFAOYSA-N 0.000 description 1
- GIFWAJGKWIDXMY-UHFFFAOYSA-N 2-octylthiophene Chemical compound CCCCCCCCC1=CC=CS1 GIFWAJGKWIDXMY-UHFFFAOYSA-N 0.000 description 1
- PIQKSZYJGUXAQF-UHFFFAOYSA-N 3-pentylthiophene Chemical compound CCCCCC=1C=CSC=1 PIQKSZYJGUXAQF-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、アルキル基の異なる２種類以上のポリ（３−
アルキルチオフェン）から構成される高分子示温材料に
関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides two or more types of poly(3-
This invention relates to a polymeric temperature-indicating material composed of (alkylthiophene).
〈従来の技術〉
従来の示温材料は金属錯塩結晶、液晶、あるいは電子供
与性呈色性有機化合物とフェノール性水酸基との呈色反
応などある温度のみで色変化を起こすため、連続的な温
度変化を観測するためには変色温度の異なる複数の材料
を使用しなけらばならなかった。<Conventional technology> Conventional temperature-indicating materials change color only at a certain temperature, such as metal complex crystals, liquid crystals, or color reactions between electron-donating color-forming organic compounds and phenolic hydroxyl groups. In order to observe this, it was necessary to use multiple materials with different color change temperatures.
また、変色温度を自由に選ぶことは困難で、その物質自
体の性質に依存していた。即ち、必要とする変色温度を
持った物質を求める場合、これまでに合成された物質よ
り選択するか、あるいは、これから合成されるのを使用
する以外に方法が無いのが実状であった。Furthermore, it was difficult to freely select the color change temperature, which depended on the properties of the substance itself. That is, in order to find a substance with the required color change temperature, the only way to find it is to select it from the substances that have been synthesized up to now, or to use one that will be synthesized in the future.
更に、これら材料は示温材料として使用するのに当たっ
て、何らかの支持体に担持させたり、ガラス管等に封入
する必要がある等の問題点を有している。Furthermore, when these materials are used as temperature-indicating materials, they have problems such as the need to support them on some kind of support or to encapsulate them in glass tubes or the like.
上記の問題点は、これらの材料を示温材料として利用す
る上で大きな制約となっており、用途開発の大きな障害
となっていた。The above-mentioned problems have been a major constraint on the use of these materials as temperature-indicating materials, and have been a major hindrance to the development of applications.
〈発明が解決しようとする課題〉
本発明は、上述したような問題点を解消するためになさ
れたもので、全く新しいタイプの示温材料を提供しよう
とするものである。即ち、本発明の目的は、複数の異種
の材料を選択使用することなく単一の材料で変色温度が
室温付近から高温度域までの実用上必要な広域温度範囲
の示温か可能で、かつ連続的な温度変化を観測できる示
温材料を提供することにある。又本発明の他の目的は、
それ自体でフィルム化等の加工が容易にできる高分子示
温材料を提供することにある。<Problems to be Solved by the Invention> The present invention has been made to solve the above-mentioned problems, and aims to provide a completely new type of temperature-indicating material. That is, the object of the present invention is to be able to display a discoloration temperature over a wide range of temperatures that is practically necessary from around room temperature to a high temperature range using a single material without selecting and using a plurality of different materials, and to continuously display the temperature. The object of the present invention is to provide a temperature-indicating material that allows observation of temperature changes. Another object of the present invention is to
The object of the present invention is to provide a polymer temperature-indicating material that can be easily processed into a film by itself.
く課題を解決するための手段〉
本発明者は、炭素数４以上のアルキル基を有するポリ（
３−アルキルチオフェン）についてサーモクロミズムへ
の用途展開を検討した結果、アルキル基の異なる２種類
以上のポリマー同士をブレッドすることで、−ある特定
の温度範囲で徐々に変色してい（新たな高分子示温材料
が得られることを見いだし本発明を完成した。Means for Solving the Problems> The present inventor has discovered that poly(
As a result of considering the application of 3-alkylthiophene) to thermochromism, we found that by blending two or more types of polymers with different alkyl groups, the color gradually changes in a certain temperature range (new polymer They discovered that a temperature-indicating material could be obtained and completed the present invention.
即ち、本発明は下記一般式（１）
（式中、Ｒは炭素数４以上のアルキル基、ｎ＝５〜４０
０を示す）で表わされ、かつ、該アルキル基が異なる少
くとも２種類のポリ（３−アルキルチオフェン）から構
成されることを特徴とする。That is, the present invention relates to the following general formula (1) (wherein, R is an alkyl group having 4 or more carbon atoms, n = 5 to 40
0), and the alkyl group is composed of at least two different types of poly(3-alkylthiophene).
本発明で使用する上記一般式（Ｉ）のポリ（３−アルキ
ルチオフェン）は、３−アルキルチオフェンの化学的酸
化重合、或いは電気化学的酸化重合、または２．５−ジ
ハロゲン化−３−アルキルチオフェンの金属または有機
金属錯体による脱ハロゲン化等の方法によって得ること
ができる。The poly(3-alkylthiophene) of the general formula (I) used in the present invention can be produced by chemical oxidative polymerization of 3-alkylthiophene, electrochemical oxidative polymerization, or 2,5-dihalogenated-3-alkylthiophene. It can be obtained by a method such as dehalogenation using a metal or an organometallic complex.
本発明でいう３−アルキルチオフェンの炭素数４以上の
アルキル基としては、例えばｎ−ブチル、ｎ−ペンチル
、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−ノニル、ｎ−デシ
ル、ｎ−ウンデシル、ｎ−ドデシル、ｎ−ヘキサデシル
、ｎ−エイコシル、ｎ−ドコシル等が挙げられ、必要と
する変色開始温度、終了温度および変色温度範囲によっ
て適宜これらのアルキル基を選択すればよい。また、脱
ハロゲン化のためのハロゲンとしては、塩素、臭素、ヨ
ウ素が挙げられる。Examples of the alkyl group having 4 or more carbon atoms in 3-alkylthiophene in the present invention include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-nonyl, n-decyl, n-undecyl, n- Examples include dodecyl, n-hexadecyl, n-eicosyl, n-docosyl, etc., and these alkyl groups may be appropriately selected depending on the required discoloration start temperature, end temperature, and discoloration temperature range. Furthermore, halogens for dehalogenation include chlorine, bromine, and iodine.
本発明でいう３−アルキルチオフェンの化学的酸化重合
は、重合触媒として例えば塩化アルミニウム、塩化第二
鉄、塩化モリブデン、塩化タングステン、塩化スズ、塩
化アンチモン、五フッ化ヒ素等のルイス酸として知られ
ている化合物を用いて行うことができる。The chemical oxidative polymerization of 3-alkylthiophene in the present invention is carried out using known Lewis acids such as aluminum chloride, ferric chloride, molybdenum chloride, tungsten chloride, tin chloride, antimony chloride, and arsenic pentafluoride as polymerization catalysts. It can be carried out using a compound that is
これらの重合触媒を、前記３−アルキルチオフェンに添
加することにより室温で容易にポリ（３−アルキルチオ
フェン）を合成することができる。By adding these polymerization catalysts to the 3-alkylthiophene, poly(3-alkylthiophene) can be easily synthesized at room temperature.
また、３−アルキルチオフェンの電気化学的酸化重合は
、アセトニトリル、ベンゾ巨トリル、炭酸プロピレン等
の溶媒中で、支持塩として例えばテトラ−ｎ−プチルア
ンモニウムテトラフルオロボレイト、テトラエチルアン
モニウムテトラフルオロボレイト、過塩素酸テトラ−ｎ
−ブチルアンモニウム、過塩素酸テトラエチルアンモニ
ウム、塩化テトラ−ｎ−ブチルアンモニウム、塩化テト
ラエチルアンモニウム等を用いて、定電圧、定電位、或
いは定電流電解重合で行われる。この時用いられる電極
は導体であれば特に制限はなく、白金板やニッケル板等
の金属、炭素電極、ネサガラスやＩＴＯガラス等のガラ
ス電極などが使用される。Further, electrochemical oxidative polymerization of 3-alkylthiophene can be carried out in a solvent such as acetonitrile, benzomegatrile, propylene carbonate, etc., using supporting salts such as tetra-n-butylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, or tetraethylammonium tetrafluoroborate. Tetra-n perchlorate
The polymerization is carried out by constant voltage, constant potential, or constant current electrolytic polymerization using -butylammonium, tetraethylammonium perchlorate, tetra-n-butylammonium chloride, tetraethylammonium chloride, etc. The electrode used at this time is not particularly limited as long as it is a conductor, and metals such as platinum plates and nickel plates, carbon electrodes, glass electrodes such as Nesa glass and ITO glass, etc. are used.
一方、本発明でいう脱ハロゲン化の方法のうち、２．５
−ジハロゲン化−３−アルキルチオフェンを直接重合す
る方法の場合に用いられる重合触媒としては、臭化ビス
（２，２’−ビピリジン）ニッケル、塩化ビス（２，２
’−ビピリジン）ニッケル、ビス（１゜５−シクロオク
タジエン）ニッケル等ニッケルの０価或いは２価の錯体
があげられる。On the other hand, among the dehalogenation methods referred to in the present invention, 2.5
- Polymerization catalysts used in the method of directly polymerizing dihalogenated-3-alkylthiophene include bis(2,2'-bipyridine)nickel bromide, bis(2,2'-bipyridine) chloride,
Zero-valent or divalent complexes of nickel such as '-bipyridine) nickel and bis(1°5-cyclooctadiene) nickel can be mentioned.
また、２．５−ジハロゲン化−３−アルキルチオフェン
をジグリニャール化し重合する方法の場合に用いられる
触媒としては、臭化ビス（２，２’−ビピリジン）ニッ
ケル、塩化ビス（２，２’−ビピリジン）ニッケル、ビ
ス（１，５−シクロオクタジエン）ニッケル、塩化ニッ
ケル、塩化コバルト、塩化第二鉄、塩化ビス（２，２”
−ビピリジン）パラジウム、臭化ビス（トリフェニルホ
スフィン）ニッケル等遷移金属の塩や有機錯体があげら
れる。また、上記遷移金属塩や有機錯体の存在下で、ア
セトニトシル、ベンゾニトリル、炭酸プロピレン等の溶
媒中で、前記白金板等の電極を用いて２，５−ジハロゲ
ン化−３−アルキルチオフェンを電解重合することもで
きる。In addition, the catalysts used in the method of polymerizing 2,5-dihalogenated-3-alkylthiophene by digrignardization include bis(2,2'-bipyridine)nickel bromide and bis(2,2'-bipyridine) chloride. bipyridine) nickel, bis(1,5-cyclooctadiene)nickel, nickel chloride, cobalt chloride, ferric chloride, bis(2,2” chloride)
-bipyridine) palladium, bis(triphenylphosphine)nickel bromide, and other transition metal salts and organic complexes. Furthermore, in the presence of the above transition metal salt or organic complex, 2,5-dihalogenated-3-alkylthiophene is electrolytically polymerized in a solvent such as acetonityl, benzonitrile, or propylene carbonate using an electrode such as the platinum plate. You can also.
得られた本発明のポリ（３−アルキルチオフェン）は、
示温材料として用いる限りにおいて、前記いずれの合成
方法をとっても何ら問題ないが、量産性や経済性、取扱
い性などから考えれば、化学的酸化重合法が最も好まし
い。The obtained poly(3-alkylthiophene) of the present invention is
As long as it is used as a temperature-indicating material, there is no problem with any of the synthesis methods described above, but the chemical oxidative polymerization method is the most preferred from the viewpoint of mass production, economy, and handling.
こうして得られた本発明のポリ（３−アルキルチオフェ
ン）を使って、本発明のアルキル基の異なる少なくとも
２種類のポリ（３−アルキルチオフェン）を構成する方
法としては、溶液状態で混合する方法、固体粉末を溶融
混練する方法、又はそれぞれのポリ（３−アルキルチオ
フェン）単体フィルムを層状に積層する方法などがある
。本発明の高分子示温材料は変色開始温度より低温側で
は赤色を呈しており、変色領域で橙色、変色終了温度以
上で黄色を呈する。これにより、連続的に温度変化を観
測することができる。Methods for constructing at least two types of poly(3-alkylthiophene) having different alkyl groups of the present invention using the poly(3-alkylthiophene) of the present invention obtained in this way include a method of mixing in a solution state; Examples include a method of melt-kneading solid powders, and a method of laminating individual poly(3-alkylthiophene) films in layers. The polymer temperature-indicating material of the present invention exhibits a red color at a temperature lower than the discoloration start temperature, an orange color in the discoloration region, and a yellow color above the discoloration end temperature. This allows continuous observation of temperature changes.
また、本発明のポリ（３−アルキルチオフェン）の混合
ポリマー自体は溶媒に可溶でキャスト膜を形成すること
が可能であり、あるいは熱可塑性であるため溶融後成形
することもできる。更に、これらのキャスト′成形した
膜は光の透過性もあり、デイスプレィへの応用も可能で
ある。また、該混合ポリマーの溶液自体も温度変化によ
って同様の変色を示すため、溶液状態で使用することも
できる。Further, the mixed polymer of poly(3-alkylthiophene) of the present invention itself is soluble in a solvent and can form a cast film, or can be molded after melting because it is thermoplastic. Furthermore, these cast films are transparent to light and can be applied to displays. Further, since the mixed polymer solution itself exhibits a similar color change due to temperature changes, it can also be used in a solution state.
これらの特徴を合せ考えると、本発明の高分子示温材料
は工業材料その他の用途に応用する上で、きわめて優れ
た示温材料といえる。Considering these characteristics together, the polymer temperature-indicating material of the present invention can be said to be an extremely excellent temperature-indicating material for application to industrial materials and other uses.
〈実施例〉 以下に実施例によって本発明を詳細に示す。<Example> The present invention will be illustrated in detail by way of examples below.
〔ポリ（３−アルキルチオフェン）の合成〕下記に示す
５種類の３−アルキルチオフェン４．７ｇのそれぞれに
対して、クロロホルム３００ｄ中に無水塩化第二鉄２４
ｇを溶解した溶液を加えて室温で１０時間攪拌した。[Synthesis of poly(3-alkylthiophene)] For each of 4.7 g of the five types of 3-alkylthiophene shown below, 24 g of anhydrous ferric chloride was added in 300 d of chloroform.
A solution of g was added thereto, and the mixture was stirred at room temperature for 10 hours.
３−ｎ−ブチルチオフェン
３−ｎ−ペンチルチオフェン
３−ｎ−オクチルチオフェン
３−ｎ−ドデシルチオフェン
３−ｎ−トコシルチオフェン
上記反応生成物のそれぞれをメタノール１２中に加えて
よく攪拌した後、生成物を決別し、メタノール、希塩酸
、水、アンモニア水を含むメタノール、蒸留水の順に充
分洗浄し、減圧下８０°Ｃで１２時間乾燥し、上記モノ
マーに対応した５種類のポリ（３−アルキルチオフェン
）を合成した。3-n-butylthiophene 3-n-pentylthiophene 3-n-octylthiophene 3-n-dodecylthiophene 3-n-tocosylthiophene After adding each of the above reaction products to methanol 12 and stirring well, the product The materials were separated, thoroughly washed in the order of methanol, dilute hydrochloric acid, water, methanol containing aqueous ammonia, and distilled water, dried at 80°C under reduced pressure for 12 hours, and five types of poly(3-alkylthiophenes) corresponding to the above monomers were washed. ) was synthesized.
得られたポリ（３−アルキルチオフェン）を使用して下
記の実施例１〜９に示す本発明の高分子示温材料を作成
した。The obtained poly(3-alkylthiophene) was used to prepare polymeric temperature-indicating materials of the present invention shown in Examples 1 to 9 below.
実施例１
ポリ（３−ｎ−ペンチルチオフェン）１ｇとボ’Ｊ（３
−ｎ−ドデシルチオフェン）１ｇをクロロホルム２０ｄ
に溶解混合し、ガラス基板上にキャストしフィルムを得
た。Example 1 1 g of poly(3-n-pentylthiophene) and Bo'J (3
-n-dodecylthiophene) 1g in chloroform 20d
The solution was mixed and cast onto a glass substrate to obtain a film.
実施例２
ポ’Ｊ（３−ｎ−ペンチルチオフェン）１ｇとポリ （
３−ｎ−ドデシルチオフェン）０．５ｇをクロロホルム
２０１ｄに溶解混合し、ガラス基板上にキャストしフィ
ルムを得た。Example 2 1 g of po'J (3-n-pentylthiophene) and poly (
0.5 g of 3-n-dodecylthiophene) was dissolved and mixed in 201d of chloroform and cast onto a glass substrate to obtain a film.
実施例３
ポリ（３−ｎ−ペンチルチオフェン）０．５ｇとポリ（
３−ｎ−ドデシルチオフェン）１ｇをクロロホルム２０
ｄに溶解混合し、ガラス基板上にキャストしフィルムを
得た。Example 3 0.5 g of poly(3-n-pentylthiophene) and poly(3-n-pentylthiophene)
1 g of 3-n-dodecylthiophene) in chloroform 20
d was dissolved and mixed, and cast on a glass substrate to obtain a film.
実施例４
ポリ（３−ｎ−ペンチルチオフェン）１ｇとポリ（３−
ｎ−オクチルチオフェン）１ｇをクロロホルム２０ｄに
溶解混合し、ガラス基板上にキャストしフィルムを得た
。Example 4 1 g of poly(3-n-pentylthiophene) and poly(3-n-pentylthiophene)
1 g of n-octylthiophene was dissolved and mixed in 20 d of chloroform and cast onto a glass substrate to obtain a film.
実施例５
ポリ（３−ｎ−ペンチルチオフェン）１ｇとポ＋Ｊ（３
−、ｎ−トコシルチオフェン）１ｇをクロロホルム２０
ｄに溶解混合し、ガラス基板上にキャストしフィルムを
得た。Example 5 1 g of poly(3-n-pentylthiophene) and poly(3-n-pentylthiophene)
-, n-tocosylthiophene) 1g in chloroform 20
d was dissolved and mixed, and cast on a glass substrate to obtain a film.
実施例６
ポリ（３−ｎ−へキシルチオフェン）１ｇとポリ（３−
ｎ−ドデシルチオフェン）１ｇをクロロホルム２０Ｍ１
に溶解混合し、ガラス基板上にキャストしフィルムを得
た。Example 6 1 g of poly(3-n-hexylthiophene) and poly(3-n-hexylthiophene)
n-dodecylthiophene) 1g in chloroform 20M1
The solution was mixed and cast onto a glass substrate to obtain a film.
実施例７
ポリ（３−ｎ−オクチルチオフェン）１ｇとボ’） （
３−ｎ−ドデシルチオフェン）１ｇをクロロホルム２０
ｄに溶解混合し、ガラス基板上にキャストしフィルムを
得た。Example 7 1 g of poly(3-n-octylthiophene) and
1 g of 3-n-dodecylthiophene) in chloroform 20
d was dissolved and mixed, and cast on a glass substrate to obtain a film.
実施例８
ポリ（３−ｎ−ブチルチオフェン）１ｇとポリ（３−ｎ
−ドデシルチオフェン）１ｇをクロロホルム２０１１１
に溶解混合し、ガラス基板上にキャストしフィルムを得
た。Example 8 1 g of poly(3-n-butylthiophene) and poly(3-n-butylthiophene)
-dodecylthiophene) 1g in chloroform 20111
The solution was mixed and cast onto a glass substrate to obtain a film.
実施例９
ポリ（３−ｎ−ブチルチオフェン）１ｇとポリ（３−ｎ
−ドデシルチオフェン）１ｇとポリ （３−ｎ−トコシ
ルチオフェン）１ｇをクロロボルム２０Ｍ１に溶解混合
し、ガラス基板上にキャストしフィルムを得た。Example 9 1 g of poly(3-n-butylthiophene) and poly(3-n-butylthiophene)
-dodecylthiophene) and 1 g of poly(3-n-tocosylthiophene) were dissolved and mixed in chloroborum 20M1, and the mixture was cast onto a glass substrate to obtain a film.
上記により得られたそれぞれのフィルムにつぃて、該フ
ィルムをヒータープレート上で１０°Ｃ／分の速度で昇
温および／又は降温して、該フィルムの変色温度を観察
し、本発明の高分子示温材料としての示温特性を評価し
、表−１の結果を得た。For each film obtained above, the temperature of the film was raised and/or lowered at a rate of 10°C/min on a heater plate, and the discoloration temperature of the film was observed. The temperature-indicating properties as a molecular temperature-indicating material were evaluated, and the results shown in Table 1 were obtained.
なお、表−１には、変色状態が左から右へ移行する昇温
の場合について示したもので、降温の場合は右から左へ
移行する。Note that Table 1 shows the case where the temperature increases, in which the discoloration state shifts from left to right, and the discoloration state shifts from right to left in the case of temperature decrease.
表−１の結果から、明らかなとおり、本発明の示温材料
は、変色温度領域が広く、かつ、置換アルキル基を適宜
選択することによって変色温度領域をコントロールでき
る点で優れた効果が得られることを確認した。As is clear from the results in Table 1, the temperature-indicating material of the present invention has a wide color change temperature range, and has excellent effects in that the color change temperature range can be controlled by appropriately selecting the substituted alkyl group. It was confirmed.
（発明の効果〉
本発明の高分子示温材料は、変色温度範囲を自由に制御
でき、かつ連続的に変色温度が観測でき、またフィルム
成形など加工性に優れているため各種工業における温度
検知、化学反応等における温度上昇下陳の監視、危険物
容器または貯蔵所における温度指示による災害防止、電
気回路及び電気機器の過負荷による発熱の早期発見用温
度標識、風呂の温度標識、表示装置、広告紙、教材、玩
具等が考えられ非常に有用である。(Effects of the Invention) The polymer temperature-indicating material of the present invention can freely control the discoloration temperature range and continuously observe the discoloration temperature, and has excellent processability such as film forming, so it can be used for temperature detection in various industries. Monitoring of temperature rises in chemical reactions, etc., disaster prevention by indicating temperature in hazardous materials containers or storage areas, temperature signs for early detection of heat generation due to overload of electrical circuits and electrical equipment, temperature signs for baths, display devices, advertisements. Paper, teaching materials, toys, etc. can be considered and are very useful.
Claims (1)
０を示す）で表わされ、かつ該アルキル基が異なる少く
とも２種類のポリ（３−アルキルチオフェン）から構成
されることを特徴とする高分子示温材料。[Claims] The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (I) (In the formula, R is an alkyl group having 4 or more carbon atoms, n = 5 to 40
0) and is composed of at least two types of poly(3-alkylthiophene) having different alkyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29354690A JP2844122B2 (en) | 1990-11-01 | 1990-11-01 | Polymer thermometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29354690A JP2844122B2 (en) | 1990-11-01 | 1990-11-01 | Polymer thermometer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04168188A true JPH04168188A (en) | 1992-06-16 |
| JP2844122B2 JP2844122B2 (en) | 1999-01-06 |
Family
ID=17796155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29354690A Expired - Fee Related JP2844122B2 (en) | 1990-11-01 | 1990-11-01 | Polymer thermometer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2844122B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2158764A1 (en) * | 1999-01-27 | 2001-09-01 | Fundacion Cidetec | Set of thermochromic varnishes consists of transparent varnish and solutions of alkyl thiophene derivatives for accurate rapid temperatures indication |
| 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 |
| WO2004003498A3 (en) * | 2002-06-28 | 2004-03-18 | Rhode Island Education | Thermochromic indicator materials with controlled reversibility |
| JP2008510853A (en) * | 2004-08-19 | 2008-04-10 | ザ ユニバーシティ オブ アクロン | Photonic crystal, conjugated polymer suitable for photonic crystal, and method for synthesizing conjugated polymer |
| JP2009520043A (en) * | 2005-11-24 | 2009-05-21 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing regioregular polymer |
| JP2009520044A (en) * | 2005-11-24 | 2009-05-21 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Regioregular polyselenophenes |
-
1990
- 1990-11-01 JP JP29354690A patent/JP2844122B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2158764A1 (en) * | 1999-01-27 | 2001-09-01 | Fundacion Cidetec | Set of thermochromic varnishes consists of transparent varnish and solutions of alkyl thiophene derivatives for accurate rapid temperatures indication |
| 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 |
| WO2004003498A3 (en) * | 2002-06-28 | 2004-03-18 | Rhode Island Education | Thermochromic indicator materials with controlled reversibility |
| EP1517943A2 (en) * | 2002-06-28 | 2005-03-30 | The Board of Governors for higher education, State of Rhode Island and providence plantations | Thermochromic indicator materials with controlled reversibility |
| EP1517943A4 (en) * | 2002-06-28 | 2006-05-03 | Rhode Island Education | Thermochromic indicator materials with controlled reversibility |
| US7517475B2 (en) | 2002-06-28 | 2009-04-14 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Thermochromic indicator materials with controlled reversibility |
| EP2258747A1 (en) * | 2002-06-28 | 2010-12-08 | The Board of Governors for Higher Education State of Rhode Island And Providence Plantations | Thermal indicator material and method for producing it |
| JP2008510853A (en) * | 2004-08-19 | 2008-04-10 | ザ ユニバーシティ オブ アクロン | Photonic crystal, conjugated polymer suitable for photonic crystal, and method for synthesizing conjugated polymer |
| JP2009520043A (en) * | 2005-11-24 | 2009-05-21 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing regioregular polymer |
| JP2009520044A (en) * | 2005-11-24 | 2009-05-21 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Regioregular polyselenophenes |
| KR101295985B1 (en) * | 2005-11-24 | 2013-08-13 | 메르크 파텐트 게엠베하 | Process of preparing regioregular polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2844122B2 (en) | 1999-01-06 |
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