JPH0245534A - Linear phosphazene polymer containing viologen structure in side chain and production thereof - Google Patents
Linear phosphazene polymer containing viologen structure in side chain and production thereofInfo
- Publication number
- JPH0245534A JPH0245534A JP63196633A JP19663388A JPH0245534A JP H0245534 A JPH0245534 A JP H0245534A JP 63196633 A JP63196633 A JP 63196633A JP 19663388 A JP19663388 A JP 19663388A JP H0245534 A JPH0245534 A JP H0245534A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- polymer
- formulas
- tables
- formula
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 21
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 alkali metal salt Chemical class 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 3
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000000470 constituent Substances 0.000 abstract description 7
- 239000002798 polar solvent Substances 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NJRJILKFJZQFHG-UHFFFAOYSA-N 1-propyl-4-pyridin-4-ylpyridin-1-ium Chemical compound C1=C[N+](CCC)=CC=C1C1=CC=NC=C1 NJRJILKFJZQFHG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKFYEWXSRFQOKX-UHFFFAOYSA-N 1,4-dioxane;toluene Chemical compound C1COCCO1.CC1=CC=CC=C1 WKFYEWXSRFQOKX-UHFFFAOYSA-N 0.000 description 1
- NFEHEPZMNUSAIB-UHFFFAOYSA-N 1-hexyl-4-pyridin-4-ylpyridin-1-ium Chemical compound C1=C[N+](CCCCCC)=CC=C1C1=CC=NC=C1 NFEHEPZMNUSAIB-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- UQMQEGXOVRHYOV-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanol Chemical compound [Na].OCC(F)(F)F UQMQEGXOVRHYOV-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はビオロゲン構造を側鎖に含有する線状ホスファ
ゼンポリマーおよびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a linear phosphazene polymer containing a viologen structure in its side chain and a method for producing the same.
(従来の技術)
ビオロゲン誘導体は電解酸化還元反応によリー電子還元
を受は可逆的にラジカルツノチオンを生じ、それが着色
していることから、エレクトロクロミック表示素子とし
て注目されている。また多くの場合、光照射によっても
同様なラジカルカチオンを生じるのでフォトクロミック
材料としても有望視さバている7
従来からエレクトロクロミック材料としてタングステン
化合物の様な無機材料が検討されてきたが、色の鮮明さ
、多彩な色相の発現等の要求から、有機系の材料の探索
へと研究が移行した。(Prior Art) Viologen derivatives are attracting attention as electrochromic display elements because they undergo Lee electron reduction through electrolytic redox reaction and reversibly produce radical tsunotion, which is colored. Furthermore, in many cases, similar radical cations are generated by light irradiation, so they are considered promising as photochromic materials.7 Inorganic materials such as tungsten compounds have been considered as electrochromic materials, but Now, research has shifted to the search for organic materials due to the need to produce a wide variety of hues.
1、 1′−ジアルキル−4,4′−ジピリジンである
ビオロゲン化合物が、この要求を満たす1つの化合物と
して注目され、カソーデイック還元反応により、短い応
答時間で、可逆的に鮮明な色相を呈することがわかった
。Viologen compounds, which are 1, 1'-dialkyl-4,4'-dipyridines, have attracted attention as one compound that satisfies this requirement, and have been shown to reversibly exhibit clear hues in a short response time through cathodic reduction reactions. Understood.
しかし、この様な低分子肴のビオロゲン化合物では還元
反応で生ずる着色物質の電極面でのつきまわりが問題に
なり、それが繰り返し表示やメモリー寿命を短くする原
因となり実用化が妨げられている。However, with such low-molecular-weight viologen compounds, there is a problem in that the colored substances generated in the reduction reaction spread around the electrode surface, which causes repeated display and shortens memory life, hindering practical application.
そこでこれらの欠点を克服するため、ビオロゲン化合物
を高分子化する方法が検討されてき7”r−。In order to overcome these drawbacks, methods of polymerizing viologen compounds have been studied.
例えば、ポリマー主鎖にビオロゲン構造を含むものとし
て、モノメリックなビオロゲン化合物とビオロゲンポリ
マーを混合したもの(特開昭51−27884 )、ビ
オロゲンのジヒドロキシ誘導体トジイソシアネートを反
応させたウレタン結合のポリマー(%開昭57−113
23 )、アルキレン鎖で連なったビオロゲンポリマー
(特開昭59217791 )、およびp−ギシリレン
鎖で連なったビオロゲンポリマー(特開昭60−22’
1025)等がある。またビオロゲン構造をペンダント
に持つビオロゲンポリマーとしてはビオロゲン構造をベ
ンゼン核に結合させたスチレン誘導体とスチレン(!%
開昭56−26977 )、p−アミノスチレン(特開
昭57−11328 )またはN−ビニルピロリドン(
特開昭61−155411 )との共重合体、更にビオ
ロゲン構造を窒素原子に結合させて4級化した4−ビニ
ルピリジンとスチレンとの共重合体(特開昭58−13
6685 )等がある。Examples of polymers containing a viologen structure in the main chain include a mixture of a monomeric viologen compound and a viologen polymer (Japanese Patent Application Laid-open No. 51-27884), and a urethane-bonded polymer (% Kaisho 57-113
23), viologen polymers linked by alkylene chains (JP-A-59217791), and viologen polymers linked by p-gysilylene chains (JP-A-60-22').
1025) etc. In addition, as a viologen polymer having a pendant viologen structure, styrene derivatives with a viologen structure bonded to a benzene nucleus and styrene (!%
1982-26977), p-aminostyrene (Japanese Patent Publication No. 57-11328) or N-vinylpyrrolidone (
A copolymer of 4-vinylpyridine and styrene, which is quaternized by bonding a viologen structure to a nitrogen atom (Japanese Patent Application Laid-open No. 58-13)
6685) etc.
しかし、これC〕は何れも形成されたノイルムのガラス
転移温度が高いため、通常使用する条件下では柔軟性に
乏しく脆いだめ、電j面に密着させたりする加工面で扱
い灘い材料である。However, since the glass transition temperature of the formed film in both C] is high, it is inflexible and brittle under normal use conditions, making it difficult to handle when processing surfaces such as bonding it closely to the electrical surface. .
またこの様な材料では高分子鎖の熱運動性に乏l〜いた
め、低温に於て、可逆的な発色機能が期待できない。In addition, in such a material, the polymer chains have poor thermal mobility, so that a reversible coloring function cannot be expected at low temperatures.
これらの欠点を克服するため最近、線状のテトラヒドロ
フランポリマーの主鎖の1部にビオロゲン構造を含むゴ
ム状のボIJ ?−が開発され、ホトクロミズムやエレ
クトロクロミズムを示す材料であることが判り注目され
ている(特開昭61204224)。In order to overcome these drawbacks, rubber-like polymer IJ containing a viologen structure in a part of the main chain of a linear tetrahydrofuran polymer has recently been developed. - has been developed and has attracted attention as it has been found to be a material exhibiting photochromism and electrochromism (Japanese Patent Laid-Open No. 61204224).
しかし、このテトラヒドロフランポリマーの様な親水性
の強いポリマーをエレクトロクロミンク材料として使用
すると、水やアルコールの様な電解質を溶解するのに都
合の良い極性の強い溶媒には溶解してしまったり、電極
反応の際にポリマーの著しい劣化をきたす等欠小が多く
、表示素子として期待できないと言われている(Pol
ymer25.1302〜6 (1984) 〕。However, when a highly hydrophilic polymer like this tetrahydrofuran polymer is used as an electrochromic material, it may dissolve in highly polar solvents such as water or alcohol, which are convenient for dissolving electrolytes, or it may dissolve in electrodes. It is said that there are many defects such as significant deterioration of the polymer during the reaction, and that it cannot be expected to be used as a display element (Pol.
ymer25.1302-6 (1984)].
このように、従来のビオロゲンポリマーは種々の欠点を
有し1、実用性に乏1−.かった。As described above, conventional viologen polymers have various drawbacks1 and lack practicality1-. won.
(発明が解決しようとする課題)
本発明は、ゴム状弾性を示し5、低温でも使用でき、極
性溶媒に対して溶解性が小さく、メらに繰返し使用に対
して劣化の少ないといり点で、上記のような従来のビオ
ロゲンポ11−7.−の欠点が克服されたビオロゲン構
造を側鎖に含有する新規な線状ホスファゼンポリマーお
よびその製造方法を提供することを目的とするものであ
る。(Problems to be Solved by the Invention) The present invention exhibits rubber-like elasticity5, can be used at low temperatures, has low solubility in polar solvents, and has minimal deterioration even after repeated use. , conventional viologenpo 11-7. It is an object of the present invention to provide a novel linear phosphazene polymer containing a viologen structure in its side chain, which overcomes the drawbacks of - and a method for producing the same.
(課題を解決するための手段)
この様な目的のために、本発明者等は鋭意検討を重ねた
結果、
一般式(A)
α
f)二へ
〇
一般式(B)
P二N
β
および一般式(C)
β
−P=N
β
(pは2〜10の整数、R1は炭素数2〜10のアルキ
ル基、XlおよびX2は)・ロゲンである)で表わされ
るビオロゲン構造を有する基、そしてβは一般式−CH
2−R2(R2け炭素数1〜Sのフルオロアルキル基で
ある)で表わされる炭素数2〜5のフルオロアルキル基
である〕を主たる構成単位としてなり、置換基αが0.
04〜12モル係そ1.て置換基βが88〜99.96
モル係の割合で買換基αと置換基βが存在し、上記各構
成単位が頭尾結合でランダムに重合した構成を有し1分
子中に構成単位(A)まだは(B)が平均組成として少
なくとも1つ含まれている重合度5〜150 (lのビ
オロゲン構造を側鎖に含有する線状ホスファゼンポリマ
および一般式(A)
−P=N
〇
一般式(B)
P =N
!
一般式(C)
β
P=N−
β
一般式(D)
一般式(E)
β
−P=N−
および一般式(F)
γ
−P=N−
0X0
(pは2〜10の整数、R2は炭素数2〜10のアルギ
ル基、XlおよびX2はハロゲンである)で表わされる
ビオロゲン構造を有する基、βは一般式CH2−R2(
R2は炭素数1〜4のフルオロアルキル塾である)で表
わされる炭素数2〜5のフル素数1〜5のアルキル基、
Xlはハロゲン、pは2〜10の整数である)で表わさ
れる第四級アンモニウム塩残基である〕を主たる構成単
位としてなり、置換基αが004〜12モル%、置換基
βが83〜9996モル係そして置換基rがOより犬で
5モル%以下の割合で置換基α、置換基βおよび置換基
γが存在し、上記各構成単位が頭尾結合でランダムに重
合した構成を有し1分子中に構成単位穴、(Dまたほの
)が平均組成として少なくとも1つ含まれている重合度
5〜1500のビオロゲン構造を側鎖に含有する線状ホ
スファゼンポリマーがこの目的を満足させることを見出
し、本発明を完成させた。(Means for Solving the Problems) For this purpose, the inventors of the present invention have made extensive studies and found that the general formula (A) α f) 2 General formula (B) P2N β and A group having a viologen structure represented by the general formula (C) β -P=N β (p is an integer of 2 to 10, R1 is an alkyl group having 2 to 10 carbon atoms, Xl and X2 are ), and β has the general formula -CH
2-R2 (a fluoroalkyl group having 2 to 5 carbon atoms represented by R2 is a fluoroalkyl group having 1 to S carbon atoms) as the main structural unit, and the substituent α is 0.
04-12 moles 1. and the substituent β is 88 to 99.96
The substitution group α and the substituent β are present in a molar ratio, and the above-mentioned constituent units are randomly polymerized with head-to-tail bonds, and the constituent units (A) and (B) are on average in one molecule. A linear phosphazene polymer containing at least one viologen structure in its side chain with a degree of polymerization of 5 to 150 (L) and general formula (A) -P=N 〇 General formula (B) P=N! General Formula (C) β P=N- β General formula (D) General formula (E) β -P=N- and General formula (F) γ -P=N- 0X0 (p is an integer from 2 to 10, R2 is A group having a viologen structure represented by an argyl group having 2 to 10 carbon atoms, Xl and X2 are halogens, β is a group having a general formula CH2-R2 (
R2 is a fluoroalkyl group having 1 to 4 carbon atoms;
Xl is a halogen, p is an integer of 2 to 10)] as the main structural unit, the substituent α is 004 to 12 mol%, and the substituent β is 83 to 12 mol% 9996 molar ratio and substituent r is less than 5 mol% of O, and substituent α, substituent β, and substituent γ are present, and each of the above structural units has a structure in which the above-mentioned structural units are randomly polymerized with a head-to-tail bond. A linear phosphazene polymer containing a viologen structure in its side chain with a degree of polymerization of 5 to 1,500 and containing at least one structural unit hole (D or hole) in one molecule as an average composition satisfies this purpose. They discovered this and completed the present invention.
上記2群のポリマーは、新規物質であり、その意図され
る用途は共通I−7ており、かつその構成も側鎖に第四
級アンモニウム塩残基を有するか否かの点においてのみ
相違するだけである。上記2群のポリマーを構成する構
成単位の存在割合は確率的考察によれば下記のとおりで
ある。The above two groups of polymers are new substances and have the same intended use as I-7, and their structures differ only in whether or not they have quaternary ammonium salt residues in their side chains. Only. According to probabilistic considerations, the abundance ratios of the structural units constituting the above two groups of polymers are as follows.
すなわち一般式(A)で表わされる構成単位が1.44
4モル%以下一般式(B)で表わされる構成単位が0.
08〜21.12モル%、一般式(C)で表わされる構
成単位が68.89〜9992モル係、一般式(D)で
表わされる構成単位が1.2モル%以下、−般式(E)
で表わされる構成単位が950モル係以下、そして一般
式(F)で表わされる構成単位が0.255モル%以下
ある。第1群のポリマーにおいては、構成単位(D)、
(E)およびCF)は存在しない。That is, the structural unit represented by general formula (A) is 1.44
4 mol% or less of the structural unit represented by the general formula (B) is 0.
08 to 21.12 mol%, the structural unit represented by the general formula (C) is 68.89 to 9992 mol%, the structural unit represented by the general formula (D) is 1.2 mol% or less, - the general formula (E )
The structural unit represented by formula (F) is 950 mol % or less, and the structural unit represented by general formula (F) is 0.255 mol % or less. In the first group of polymers, the structural unit (D),
(E) and CF) are not present.
上記の第1群のビオロゲン構造を側鎖に含有する線状ホ
スファゼンポリマーは例えば次の様な経路で合成される
。The linear phosphazene polymer containing the viologen structure of the first group in its side chain is synthesized, for example, by the following route.
1)環状ホスホニトリルクロリドの開環重合で得られた
数平均分子量300.000以下の線状ホスホニトリル
ジクロリドポリマーを、第三アミン(例工ばトリエチル
アミン、ピリジン等)の塩酸捕捉剤の存在下、2.2.
2− ) IJフルオロエタノール、2.2.3.3.
4.4.4−ヘプタフルオロ−1−ブタノール 2.2
.3.3.4.4.5.5−オクタフルオロ−1−ペン
タノール、2.2.3.3.3−ペンタフルオロ−1−
プロパツール、2.2.3゜3−テトラフルオロ−1−
プロパツール等の一般式(I)HO−CI−■2−R2
(R2は炭素数1〜4のフルオロアルキル基である)の
炭素数2〜5のフルオロアルコールと一般式(TI)
(式中、pは2〜IOの整数、XlおよびX2は)・ロ
ゲン、R1は炭素数2〜10のアルキル基である)で表
わされるビオロゲン構造を有するアルコールとを反応さ
せる方法。1) A linear phosphonitrile dichloride polymer having a number average molecular weight of 300.000 or less obtained by ring-opening polymerization of cyclic phosphonitrile chloride in the presence of a hydrochloric acid scavenger of a tertiary amine (eg triethylamine, pyridine, etc.) 2.2.
2-) IJ fluoroethanol, 2.2.3.3.
4.4.4-Heptafluoro-1-butanol 2.2
.. 3.3.4.4.5.5-octafluoro-1-pentanol, 2.2.3.3.3-pentafluoro-1-
Proper tool, 2.2.3゜3-tetrafluoro-1-
General formula (I) HO-CI-■2-R2 of propa tools, etc.
(R2 is a fluoroalkyl group having 1 to 4 carbon atoms) and a fluoroalcohol having 2 to 5 carbon atoms and the general formula (TI) (wherein p is an integer of 2 to IO, Xl and X2 are), rogene, R1 is an alkyl group having 2 to 10 carbon atoms).
ここにおいて、反応温度は好ましくは50〜200C1
さらに好ましくは80〜150Cであり、反応時間は好
ましくは5〜100時間、さらに好ましくは10〜50
時間である。溶媒はトルエン ジオキサン、テトラヒド
ロフラン、アセトン、クロロベンゼン等が好ましい。反
応後は溶媒除去後少量の上記溶媒に再溶解し、その溶液
を水酸化ナトリウム等のアルカリ水溶液で数回処理し、
精製する。Here, the reaction temperature is preferably 50 to 200 C1
More preferably, the temperature is 80 to 150C, and the reaction time is preferably 5 to 100 hours, even more preferably 10 to 50 hours.
It's time. Preferred solvents include toluene dioxane, tetrahydrofuran, acetone, and chlorobenzene. After the reaction, the solvent is removed and redissolved in a small amount of the above solvent, and the solution is treated several times with an alkaline aqueous solution such as sodium hydroxide.
refine.
2)上記線状ホスホニトリルジクロリドポリマーと、該
ポリマー中の塩素に対するモル比が088〜0.999
6の上記炭素数2〜5のフルオロアルコールのアルカリ
金属塩を先ず反応させ、しかる後前記一般式(If)で
表わされるビオロゲン構造を有するアルコールを第三ア
ミンの存在下に反応させる方法。2) The molar ratio of the linear phosphonitrile dichloride polymer to chlorine in the polymer is 088 to 0.999.
A method of first reacting an alkali metal salt of the above-mentioned fluoroalcohol having 2 to 5 carbon atoms, and then reacting an alcohol having a viologen structure represented by the general formula (If) in the presence of a tertiary amine.
この場合、それぞれの段階における反応温度、反応時間
および溶媒、塩酸捕捉剤、精製方法等は上記1)の場合
と同様である。In this case, the reaction temperature, reaction time, solvent, hydrochloric acid scavenger, purification method, etc. in each step are the same as in 1) above.
前記第2群のビオロゲン構造を側鎖に含有するM状ホス
ファゼンポリマーは例えば次の様な経路で合成される。The M-type phosphazene polymer containing the second group of viologen structures in its side chain can be synthesized, for example, by the following route.
3)線状ホスホニトリルジクロリドポリマーに上記炭素
数2〜5のフルオロアルコールド一般式(式中、X2は
ハロゲン、R1は炭素数2〜10のアルキル基である)
で表わされる化合物および一般式(IV)
X−【CH2楯 OH
(IV)
(式中、pは2〜10の整数、Xlはハロゲンである)
で表わされる例えば、エチレンブロムヒドリン、3−7
”コモ−1−プロパツール、8−プロモー1−オクタツ
ール等のハロゲン化アルコールを用い、塩酸捕捉剤とし
ての第三アミンに炭素数1〜5のアルギル基を有するト
リアルキルアミンまたはピリジンを用いる方法。3) The above-mentioned fluoroalcoholde having 2 to 5 carbon atoms is added to the linear phosphonitrile dichloride polymer according to the general formula (wherein, X2 is a halogen and R1 is an alkyl group having 2 to 10 carbon atoms).
Compounds represented by and general formula (IV)
For example, ethylene bromohydrin, 3-7
``A method using a halogenated alcohol such as como-1-propatool, 8-promo-1-octatool, etc., and using a trialkylamine or pyridine having an argyl group having 1 to 5 carbon atoms as a tertiary amine as a hydrochloric acid scavenger. .
この場合、反応温度、反応時間、溶媒、精製方法等は前
記1)の場合と同様である。In this case, the reaction temperature, reaction time, solvent, purification method, etc. are the same as in the case of 1) above.
なお、本発明のポリマーは、平均組成として考えたとき
に1分子中に少なくとも1個のビオロゲン構造を有する
基を含有している。ただし、ビオロゲン構造を有する基
の含1が少なすぎると、エレクトロクロミックまたはフ
ォトクロミック特性を示さなくなり、またこれらの含量
が多すぎると、上記特性の耐久性が低下しポリマーのガ
ラス転移温度が上昇するために、使用温度に於てゴム弾
性を示さなくなり有用性が減少するので、ビオロゲン構
造を有する基の割合は0.04〜12モル係の範囲、好
まI〜りけ01〜5モル係の範囲である。The polymer of the present invention contains at least one group having a viologen structure in one molecule when considered as an average composition. However, if the content of the group having a viologen structure is too small, electrochromic or photochromic properties will not be exhibited, and if the content is too large, the durability of the above properties will decrease and the glass transition temperature of the polymer will increase. In addition, since it exhibits no rubber elasticity at the temperature of use and its usefulness is reduced, the proportion of groups having a viologen structure is in the range of 0.04 to 12 moles, preferably in the range of I to 0.1 to 5 moles. be.
また第2群のビオロゲン構造を側鎖に含有する線状ホス
ファゼンポリマー、すなわち方法3)で得られたポリマ
ーの場合、第四級アンモニウム塩残基の割合が高くなる
とポリマーのガラス転移温度が高くなり好ましくないの
で、第四級アンモニウム塩残基の割合は5モル%以下、
好ましくは2モル%以下である。この様に、方法3)で
得られるポリマーはエレクトロクロミズムやフォトクロ
ミズムに対して効果がなく、フルオロアルキル基に比べ
てポリマーのガラス転移温度を高くする作用のある第四
級アンモニウム塩残基を含む点において不利であるが、
一方、方法1)および2)を実施する際の原料である一
般式(II)で表わされるビオロゲン構造を有するアル
コールの合成ならびに精製の工程が省略でき一般式(1
)の化合物と一般式(1’V)の・・ロゲン化アルコー
ルとから直接目的重合体を得ることかできるので製造工
程が簡略化され製造コストが低下する点で大きな利益が
ある。In addition, in the case of linear phosphazene polymers containing the second group of viologen structures in their side chains, that is, polymers obtained by method 3), the glass transition temperature of the polymer increases as the proportion of quaternary ammonium salt residues increases. Since this is not preferable, the proportion of quaternary ammonium salt residues is 5 mol% or less,
Preferably it is 2 mol% or less. In this way, the polymer obtained by method 3) has no effect on electrochromism or photochromism, and contains quaternary ammonium salt residues that have the effect of raising the glass transition temperature of the polymer compared to fluoroalkyl groups. Although it is disadvantageous in
On the other hand, it is possible to omit the synthesis and purification steps of the alcohol having a viologen structure represented by general formula (II), which is a raw material when carrying out methods 1) and 2), and the general formula (1)
Since the desired polymer can be directly obtained from the compound of formula (1'V) and the logenated alcohol of general formula (1'V), there is a great advantage in that the manufacturing process is simplified and the manufacturing cost is reduced.
本発明のポリマーの重合度Vi5〜1500であるが、
好まり、 <は10〜1500である。The degree of polymerization Vi of the polymer of the present invention is from 5 to 1500,
Preferably, < is 10-1500.
(発明の効果)
本発明の線状ホスファゼンポリマーは主鎖ではなく側鎖
にビオロゲン構造を含むので、ガラス転移温度が低く低
温でも使用できるゴム状弾性体であり、水、アルコール
等の極性溶媒中で使用しても溶解したり劣化することが
少なく、長時間に亘って使用し得る有用なゴム状機能性
材料である。(Effects of the Invention) Since the linear phosphazene polymer of the present invention contains a viologen structure in the side chain rather than the main chain, it is a rubber-like elastic body with a low glass transition temperature and can be used even at low temperatures. It is a useful rubber-like functional material that hardly dissolves or deteriorates even when used in the environment, and can be used for a long time.
(実施例)
以下に代表的なビオロゲン構造含有中間体の合成例とそ
れらの線状ホスファゼンボリマーノ側鎖への導入方法の
実施例を示すが、本発明に係るビオロゲン構造を含有す
る線状ホスファゼンポリマーはこの様な製造法によって
得られたもののみに限定されるものではない。(Example) Examples of synthesis of typical viologen structure-containing intermediates and examples of methods for introducing them into the linear phosphazene borimano side chain are shown below. Polymers are not limited to those obtained by such manufacturing methods.
参考例1
l−n−プロピル−4,4′−ビピリジニウムモノプロ
ミドの合成
窒素ガス雰囲気下、攪拌器およびリフラックスクーラー
をつけたフラスコに4.4′−ビピリジル10y−1n
−プロピルプロミド71およびアセトニ) IJル20
0耐加え、48時間攪拌還流を続けた。Reference Example 1 Synthesis of l-n-propyl-4,4'-bipyridinium monopromide 4,4'-bipyridyl 10y-1n was placed in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere.
-propyl bromide 71 and acetoni) IJ Le 20
The mixture was added for 30 minutes, and stirring and refluxing was continued for 48 hours.
反応後室温に放置して生成した少量の黄色沈澱を口割し
、その口銭を完全に蒸発させて得た凌色沈澱を少量のエ
ーテルで洗浄した。残った固体をアセトニトリル溶液か
ら再結晶して吸湿性の強い黄色結晶(1−n−プロピル
−4,4′−ビピリジニウムモノプロミド)を111(
収率65 % ) TGた。After the reaction, a small amount of yellow precipitate formed by standing at room temperature was split into portions, and the portion was completely evaporated to obtain a pale colored precipitate, which was washed with a small amount of ether. The remaining solid was recrystallized from an acetonitrile solution to give highly hygroscopic yellow crystals (1-n-propyl-4,4'-bipyridinium monopromide) as 111 (
Yield: 65%) TG.
参考例2
1−n〜プロピル、1’−(2−ヒドロキシ)エチル−
4,4′−ビビリジニウムジプロミドの合成
窒素ガス雰囲気下、攪拌器およびリフラックスクーラー
をつけだフラスコに参考例1と同様にして合成した1−
n−プロピル−4,4′−ビピリジニウムモノプロミド
14.97、エチレンブロムヒドリン8.41およびア
セトニトリル200d加え、48時間攪拌、還流を続け
た。Reference example 2 1-n~propyl, 1'-(2-hydroxy)ethyl-
Synthesis of 4,4'-biviridinium dipromide 1- was synthesized in the same manner as in Reference Example 1 in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere.
14.97 d of n-propyl-4,4'-bipyridinium monopromide, 8.41 d of ethylene bromohydrin and 200 d of acetonitrile were added, and stirring and refluxing were continued for 48 hours.
生成した黄色結晶を口割し、少量のアセトニトリルで洗
浄して目的とする1−n−プロピル、1′(2−ヒドロ
キシ)エチル−4,4′−ビビリンニウムジブロミドを
1335c(収率57係)得た。The yellow crystals formed were split and washed with a small amount of acetonitrile to obtain the desired 1-n-propyl, 1'(2-hydroxy)ethyl-4,4'-bivillinium dibromide, 1335c (yield: 57%). )Obtained.
実施例1
窒素ガス雰囲気下、攪拌器およびリフラックスクーラー
をつけたフラスコに参考例2で合成した1−n−プロピ
ル、1’−(2−ヒドロキシ)エチル−4,4’−ビビ
リジニウムジプロミド2.0%、トリフロロエタノール
11.07、)IJエチルアミン201jおよびジオキ
サン20.dを加え、それに線状ジクロロホスファゼン
ポリマー(数平均分子量52.000 ) 6デを含む
トルエン溶液20m/を室温、攪拌下、1時間かかって
滴下した。その後26時間攪拌、還流を続けた。反応後
溶媒を蒸発させ残留した固体を少量のアセトンに溶解し
、その溶液を水酸化ナトリウム水溶液中に注いで精製し
、得られた固体を再びアセトンに溶解して次に純水中に
注いで精製することを2回繰り返したところ4.2?の
赤紫色のゴム状弾性のポリマーが回収された。Example 1 1-n-propyl, 1'-(2-hydroxy)ethyl-4,4'-biviridinium dipropylene synthesized in Reference Example 2 in a flask equipped with a stirrer and a reflux cooler under a nitrogen gas atmosphere. 2.0% trifluoroethanol, 11.07% trifluoroethanol, ) IJ ethylamine 201j and dioxane 20. d was added thereto, and 20 mL of a toluene solution containing linear dichlorophosphazene polymer (number average molecular weight 52.000) 6D was added dropwise thereto over 1 hour at room temperature with stirring. Thereafter, stirring and refluxing were continued for 26 hours. After the reaction, the solvent was evaporated, the remaining solid was dissolved in a small amount of acetone, the solution was poured into an aqueous sodium hydroxide solution for purification, the obtained solid was dissolved again in acetone, and then poured into pure water. After repeating the refining process twice, it turned out to be 4.2? A reddish-purple, rubbery, elastic polymer was recovered.
このポリマーはクロロホルム、アセトン、メチルエチル
ケトン、エタノール、テトラヒドロフラン、ジオキサン
等に易溶、ガラス転移温度−37Cで数平均分子量は2
6.000であった。このポリマーのIRおよびH−N
MRスペクトルを第1図および第2図に示す。This polymer is easily soluble in chloroform, acetone, methyl ethyl ketone, ethanol, tetrahydrofuran, dioxane, etc., has a glass transition temperature of -37C, and a number average molecular weight of 2.
It was 6.000. IR and H-N of this polymer
The MR spectra are shown in FIGS. 1 and 2.
IRスペクトルに於ては、トリフロロエトキシ置換ホス
ファゼンポリマーの吸収の他に、ピリジニウムイオン環
の伸縮振動に基づく特徴的な吸収が1645Cr11’
に現われた。In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the pyridinium ion ring is found in 1645Cr11'.
appeared in
第2図に示す’H−NMRスペクトルの各ピークの帰属
は次の通りである。The assignment of each peak in the 'H-NMR spectrum shown in FIG. 2 is as follows.
[有]
■
OCH□CF3
@−N=P
尚、’H−NMRスペクトルに於て、各ピークの強度比
から組成を求めると■/のキ1./65(モル1モル)
であった。[Yes] ■ OCH□CF3 @-N=P In addition, in the 'H-NMR spectrum, when the composition is determined from the intensity ratio of each peak, ■ / Ki 1. /65 (1 mole)
Met.
上記結果から得られたポリマー中の各構成単位の割合を
求めると下記のとおりである。The proportions of each structural unit in the polymer obtained from the above results are as follows.
一般式(A)の構成単位(以下単に(A)等と略記する
)002モル%; (B) 2.98モル係;(C)9
7.00モル%
実施例2
実施例1に於て、1−n−プロピル、1’−(2−ヒド
ロキシ)エチル−4,4′−ビピリジニウムジブロミド
の使用量を5.01にする以外は実施例1と全く同様に
して実験を行なったところ3.g5r−の赤紫色のゴム
状ポリマーが得られた。そのものの溶解性は実施例1で
得られたポリマーのそれと同様であった。但し、ガラス
転移温度は一22c、数平均分子量は22,000であ
った。Constituent unit of general formula (A) (hereinafter simply abbreviated as (A) etc.) 002 mol%; (B) 2.98 mol%; (C) 9
7.00 mol% Example 2 Same as Example 1 except that the amount of 1-n-propyl, 1'-(2-hydroxy)ethyl-4,4'-bipyridinium dibromide was changed to 5.01. An experiment was conducted in exactly the same manner as in Example 1.3. A reddish-purple rubbery polymer of g5r- was obtained. Its solubility was similar to that of the polymer obtained in Example 1. However, the glass transition temperature was -22c and the number average molecular weight was 22,000.
このポリマーのIRおよびH−NMRスペクトルを第3
図および第4図に示す。The IR and H-NMR spectra of this polymer were
As shown in FIG.
’H−NMRスペク゛トルで現われた各ピークの強度比
から組成を求めると、実施例1に示した構造式のおよび
■の割合は■/■キ1/28(モル1モル)であった。When the composition was determined from the intensity ratio of each peak appearing in the 'H-NMR spectrum, the ratio of and in the structural formula shown in Example 1 was 1/28 (1 mole).
上記の結果から、各構成単位の割合を求めると下記のと
おりである。From the above results, the proportions of each structural unit are determined as follows.
(A)0.12モル係; (B) 6.66モル係;
(C) 93.22モル%
実施例3
窒素ガス雰囲気下、攪拌器およびリフラックスクーラー
なつけたフラスコにジオキサン10m1および線状ジク
ロロホスファゼンポリマー(数平均、分子、f1185
,000 ) 354を含むトルエン溶液10 rRl
を加え、それにトリフロロエタノールナトリウム塩のテ
トラヒドロフラン溶液(4モル//)11.6mlを室
温、攪拌下、1時間かかって滴下し、その後26時間攪
拌、還流を続けた。内容物を室温にしてから、それにト
リエチルアミン5rILtおよび1n−プロピル、1’
−(2−ヒドロキシ)エチル、4..4’−ビビリジニ
ウムジプロミドl?を加えると系は直ちに濃青色になっ
た。(A) 0.12 molar ratio; (B) 6.66 molar ratio;
(C) 93.22 mol% Example 3 Under a nitrogen gas atmosphere, 10 ml of dioxane and a linear dichlorophosphazene polymer (number average, molecular, f1185
,000) 10 rRl of toluene solution containing 354
was added thereto, and 11.6 ml of a tetrahydrofuran solution (4 mol//) of trifluoroethanol sodium salt was added dropwise thereto at room temperature with stirring over 1 hour, followed by continued stirring and reflux for 26 hours. After the contents were brought to room temperature, triethylamine 5rILt and 1n-propyl, 1'
-(2-hydroxy)ethyl, 4. .. 4'-Biviridinium dipromide l? When added, the system immediately turned dark blue.
更に24時間攪拌、還流を続けた後内容物について実施
例1と同様の後処理を施したところ、実施例1で得られ
たポリマーと同様の溶解性のガラス転移温度−42C1
数平均分子i33,000の赤紫色ポリマーがz、5y
1j%られた。After further stirring and refluxing for 24 hours, the contents were subjected to the same post-treatment as in Example 1, and the result was a glass transition temperature of -42C1 with the same solubility as the polymer obtained in Example 1.
A reddish-purple polymer with a number average molecular i of 33,000 is z, 5y
1j% was lost.
’H−NMItスペクトルで現われた各ピークの強度比
から組成を求めると、実施例1に示した構造式のおよび
0の割合は■10キ]/93(モル1モル)であった。When the composition was determined from the intensity ratio of each peak appearing in the 'H-NMIt spectrum, the ratio of and 0 in the structural formula shown in Example 1 was 1/93 (1 mol).
上記の結果から各構成単位の割合を求めると下記のとお
りである。The proportions of each constituent unit are determined from the above results as follows.
(A)0.01モル%; (B) 2.11モル係;
(C) 97.88モル%
実施例4
窒素ガス雰囲気下、攪拌器およびリフラックスクーラー
をつけたフラスコにエチレンブロムヒドリン0.777
、)リフコロエタノール5.6?1参考例1で合成した
1−n−プロピル−4,47−ビピリジニウムモノプロ
ミド2.8り、トリエチルアミン10.81Llおよび
ジオキサン1011Ll加え、それ(線状ジクロロホス
ファゼンポリマー(数平均分子量52,000 ) 3
)を含むトルエン溶液1011Llを室温、攪拌下、
1時間かかつて滴下した。(A) 0.01 mol%; (B) 2.11 mol%;
(C) 97.88 mol% Example 4 Under a nitrogen gas atmosphere, 0.777% of ethylene bromohydrin was added to a flask equipped with a stirrer and a reflux cooler.
,) 5.6?1 liters of 1-n-propyl-4,47-bipyridinium monopromide synthesized in Reference Example 1, 10.81 Ll of triethylamine and 1011 Ll of dioxane were added to it (linear dichlorophosphazene). Polymer (number average molecular weight 52,000) 3
) at room temperature with stirring.
It was dripping for about an hour or so.
その後、攪拌下、26時間還流を続けた。反応終了後、
内容物について実施例1と同様の後処理をしたところ、
実施例■で得られたポリマーと同様の溶解性を示すガラ
ス転移温度−18C1数平均分子+J]8.000の濃
赤褐色のコ゛ム状ポリマーが2.9?得られた。Thereafter, reflux was continued for 26 hours while stirring. After the reaction is complete,
When the contents were post-treated in the same manner as in Example 1,
A dark reddish-brown comb-shaped polymer with a glass transition temperature of -18C1 number average molecule +J]8.000 exhibiting a solubility similar to that of the polymer obtained in Example (2) has a glass transition temperature of 2.9? Obtained.
このポリマーのIRおよび”H−NMRスペクトルを第
5図および第6図に示す。The IR and H-NMR spectra of this polymer are shown in FIGS. 5 and 6.
IRスペクトルに於ては、トリフロロエトキシ置換ホス
ファゼンポリマーの吸収の他に、ピリジニウムイオン環
の伸縮振動に基づく特徴的な吸収が1645crn”に
現われた。尚、第四アンモニウムイオンの特性吸収(1
400crr1−1付近)はフロロエトキシホスファゼ
ンポリマーの強い吸収と重なり確認できなかった。In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the pyridinium ion ring appeared at 1645 crn.
400 crr1-1) could not be confirmed due to the strong absorption of the fluoroethoxyphosphazene polymer.
第6図に示す’H−NMRスペクトルの各ピークの帰属
は次の通りである。The assignment of each peak in the 'H-NMR spectrum shown in FIG. 6 is as follows.
0C112CF3
0−N=P
尚、’H−NMRスペクトルで現われた各ピークの強度
比から上記構造式の割合は■:[F]:Oキ3: 18
0 : 1と計算された。0C112CF3 0-N=P Furthermore, from the intensity ratio of each peak appearing in the 'H-NMR spectrum, the ratio of the above structural formula is ■: [F]: Oki 3: 18
It was calculated as 0:1.
上記の結果から各構成単位の割合を求めると下記のとお
りである。The proportions of each constituent unit are determined from the above results as follows.
(A)0.03モル係;(B)3.19モル%;(C)
95.7Qモル係;の)0.02モル係: (E) 1
. o 6モル%; (Fl O,(11モル係以下
実施例5
参考例1に於て、n−プロピルプロミドの代りに、それ
と等モルの1−ブロモへブタンを使用する以外は参考例
1と同様の方法で1−n−へフチルー4.4′−ビピリ
ジニウムモノプロミドを合成した。続いて参考例2に於
て、1−n−プロピル−4,4’−ビピリジニウムモノ
7′ロミドの代りに上記で合成したモノプロミドを、ま
た、エチレンブロムヒドリンの代りに6−ブロモ−1−
ヘキサノールをそれぞれ使用する以外は参考例2と同様
の方法で1−n−ヘプチル、1’−(6−ヒドロキシ)
へキシル−4,4′−ビピリジニウムジプロミドを合成
した。(A) 0.03 mol%; (B) 3.19 mol%; (C)
0.02 mole ratio: (E) 1
.. o 6 mol %; 1-n-hephthyl-4,4'-bipyridinium monopromide was synthesized in the same manner as in Reference Example 2. Instead of the monopromide synthesized above, and instead of ethylene bromohydrin, 6-bromo-1-
1-n-heptyl, 1'-(6-hydroxy) in the same manner as in Reference Example 2 except that hexanol was used, respectively.
Hexyl-4,4'-bipyridinium dipromide was synthesized.
次に実施例1に於て1−n−プロピル、1′(2−ヒド
ロキシ)エチル−4,4′−ビビリジニウムジブロミド
2.01の代りに、上記参考例2の方法に従って合成し
た1−n−ヘプチル、1’−(6−ヒドロキシ)へキシ
ル−4,4′−ビピリシニウムジブロミド2.6?使用
する以外は実施例1と全く同様の実験を行なったところ
、4.21の赤紫色のゴム状ポリマーが得られた。その
ものの溶解性は実施例1で得られたポリマーのそれと同
様であった。Next, in Example 1, 1-n-propyl, 1'(2-hydroxy)ethyl-4,4'-biviridinium dibromide 2.01 was replaced with 1 synthesized according to the method of Reference Example 2 above. -n-heptyl, 1'-(6-hydroxy)hexyl-4,4'-bipyricinium dibromide 2.6? An experiment was carried out in exactly the same manner as in Example 1, except that 4.21 reddish-purple rubbery polymers were obtained. Its solubility was similar to that of the polymer obtained in Example 1.
但し、ガラス転移温度は一30′c、数平均分子量は3
0,000であった。However, the glass transition temperature is -30'c and the number average molecular weight is 3.
It was 0,000.
このポリマーのIRおよび H−NMRスペクトルを第
7図および第8図にそれぞれ示す。The IR and 1 H-NMR spectra of this polymer are shown in Figures 7 and 8, respectively.
IRスペクトルに於ては、トリフロロエトキシ置換ホス
ファゼンポリマーの吸収の他K、ピリジニウムイオン環
の伸縮振動に基づく特徴的な吸収が1645crn’に
現われた。In the IR spectrum, in addition to the absorption of the trifluoroethoxy-substituted phosphazene polymer, a characteristic absorption based on the stretching vibration of the K and pyridinium ion rings appeared at 1645 crn'.
第8図に示す11I −NMRスペクトルの各ピークは
次の様に帰属した。Each peak in the 11I-NMR spectrum shown in FIG. 8 was assigned as follows.
[有]
■
0CH2CF3
■ −N=P−
尚、’H−NMRスペクトルに於て、各ピークの強度比
から組成を求めると■10キ1/32(モル1モル)で
あった。[Yes] (1) 0CH2CF3 (1) -N=P- In addition, in the 'H-NMR spectrum, the composition was determined from the intensity ratio of each peak, and it was found to be (1) 10 x 1/32 (1 mol).
上記の結果から各構成単位の割合を求めると下記のとお
りであった。The proportions of each structural unit were calculated from the above results and were as follows.
(A)0.09モル係; (B) 5.88モル係;(
C594,03モル係参考例3
実施例5で合成したビオロゲン構造を側鎖に含む線状ホ
スファイ/ポリマーのエレクトロクロミック表示素子と
しての使用例を第9図を用いて説明すると、セルlを形
成するに際し、上記ポリマーをアセトンに溶解し、その
溶液をガラス基板2と電極部3とからなる透明ガラス電
極(I TOガラス)4の電極部3上に塗布して溶媒を
蒸発させ、膜状エレクトロクロミック(EC)材料層5
で核!極部3を被覆することにより、表示電極6を形成
する。この表示電極6と対向電極7との間にスペーサー
8を挿入して設けた空間に過塩素酸リチウムのメタノー
ル溶液を満して溶液層9を形成した。このようにして形
成したセル1に表示電極6を陰極として115Vの電圧
を印加したところ、印加前の赤紫色が青緑色に変化した
。この青緑色の状態で逆電圧を印加すると、元の赤紫色
に戻った。(A) 0.09 molar ratio; (B) 5.88 molar ratio; (
C594,03 molar reference example 3 An example of the use of the linear phosphite/polymer containing the viologen structure in the side chain synthesized in Example 5 as an electrochromic display element will be explained with reference to FIG. 9. Cell 1 is formed. At this time, the above polymer is dissolved in acetone, and the solution is applied onto the electrode section 3 of a transparent glass electrode (ITO glass) 4 consisting of a glass substrate 2 and an electrode section 3, and the solvent is evaporated to form a film-like electrochromic. (EC) material layer 5
And nuclear! By covering the pole portion 3, a display electrode 6 is formed. A spacer 8 was inserted between the display electrode 6 and the counter electrode 7, and a space therebetween was filled with a methanol solution of lithium perchlorate to form a solution layer 9. When a voltage of 115 V was applied to the cell 1 thus formed using the display electrode 6 as a cathode, the reddish-purple color before application changed to blue-green. When a reverse voltage was applied in this bluish-green state, it returned to its original reddish-purple color.
この操作を10,000回繰り返l−たが、表示電極(
iは可逆的に変色し、電極部3および膜状EC材料層5
に変化は認められず、また色相にも変化は認められなか
った。This operation was repeated 10,000 times, but the display electrode (
i reversibly changes color, and the electrode part 3 and the film-like EC material layer 5
No change was observed in the color, and no change in hue was observed.
第1図および第2図は実施例1で得られたポリマーのI
nスペクトルおよび’H−NMRスペクトル、第3図お
よび第4図は実施例2で得られたポリマーのInスペク
トルおよび’H−NMRスペクトル、第5図および第6
図は実施例4でj4られたポリマー7)Inスペクトル
およUIII−NMRスペクトル、第7図および第8図
は実施例5で浸ら妊たポリマーのInスペクトルおよび
’H−NMRスペクトル、第9図は本発明のポリマーを
エレクトロクロミック表示素子として用いたセルの一実
施例における横断面図を示す。Figures 1 and 2 show the I of the polymer obtained in Example 1.
The n spectrum and 'H-NMR spectrum, Figures 3 and 4 are the In spectrum and 'H-NMR spectrum of the polymer obtained in Example 2, Figures 5 and 6.
Figures 7) In spectrum and UIII-NMR spectrum of the polymer soaked in Example 4, Figures 7 and 8 show In spectrum and 'H-NMR spectrum of the polymer soaked in Example 5, Figure 9. 1 shows a cross-sectional view of an example of a cell using the polymer of the present invention as an electrochromic display element.
Claims (8)
キル基、X_1およびX_2はハロゲンである)で表わ
されるビオロゲン構造を有する基、そしてβは一般式−
CH_2−R_2(R_2は炭素数1〜4のフルオロア
ルキル基である)で表わされる炭素数2〜5のフルオロ
アルキル基である〕を主たる構成単位としてなり、置換
基αが0.04〜12モル%そして置換基βが88〜9
9.96モル%の割合で置換基αと置換基βが存在し、
上記各構成単位が頭尾結合でランダムに重合した構成を
有し1分子中に構成単位(A)または(B)が平均組成
として少なくとも1つ含まれている重合度5〜1500
のビオロゲン構造を側鎖に含有する線状ホスファゼンポ
リマー。(1) General formula (A) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, General formula (B) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, and General formula (C) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [Here, α is a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (p is an integer of 2 to 10, R_1 is an alkyl group having 2 to 10 carbon atoms, X_1 and X_2 are halogens) a group having the structure, and β is the general formula −
CH_2-R_2 (R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) is a fluoroalkyl group having 2 to 5 carbon atoms] as the main structural unit, and the substituent α is 0.04 to 12 mol. % and substituent β is 88-9
Substituent α and substituent β are present in a ratio of 9.96 mol%,
The above structural units have a structure in which they are randomly polymerized with head-to-tail bonds, and each molecule contains at least one structural unit (A) or (B) as an average composition.The degree of polymerization is 5 to 1500.
A linear phosphazene polymer containing a viologen structure in its side chain.
がn−C_3H_7である請求項1記載のポリマー。(2) R_2 is a trifluoromethyl group, p is 2, R_1
The polymer of claim 1, wherein n-C_3H_7.
がn−C_7H_1_5である請求項1記載のポリマー
。(3) R_2 is trifluoromethyl group, p is 6, R_1
The polymer of claim 1, wherein n-C_7H_1_5.
( I )HO−CH_2−R_2(式中R_2は炭素数
1〜4のフルオロアルキル基である)で表わされるフル
オロアルコールと一般式(II) ▲数式、化学式、表等があります▼(II) (式中、pは2〜10の整数、X_1およびX_2はハ
ロゲン、R_1は炭素数2〜10のアルキル基である)
で表わされるビオロゲン構造を有するアルコールとを第
三アミンの存在下に反応させることを特徴とする請求項
1に記載のポリマーの製造方法。(4) A linear phosphonitrile dichloride polymer containing a fluoroalcohol represented by the general formula (I) HO-CH_2-R_2 (in the formula, R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) and the general formula (II) ▲Math. , chemical formulas, tables, etc.▼(II) (In the formula, p is an integer of 2 to 10, X_1 and X_2 are halogens, and R_1 is an alkyl group having 2 to 10 carbon atoms.)
The method for producing a polymer according to claim 1, characterized in that the alcohol having a viologen structure represented by: is reacted in the presence of a tertiary amine.
マー中の塩素に対するモル比が0.88〜0.9996
で一般式( I ′)MO−CH_2−R_2(式中、R
_2は炭素数1〜4のフルオロアルキル基、Mはアルカ
リ金属である)で表わされるフルオロアルコールのアル
カリ金属塩とを反応させ、次いで一般式(II) ▲数式、化学式、表等があります▼(II) (式中、pは2〜10の整数、X_1およびX_2はハ
ロゲン、R_1は炭素数2〜10のアルキル基である)
で表わされるビオロゲン構造を有するアルコールを第三
アミンの存在下に反応させることを特徴とする請求項1
に記載のポリマーの製造方法。(5) The molar ratio of the linear phosphonitrile dichloride polymer to chlorine in the polymer is 0.88 to 0.9996
with the general formula (I') MO-CH_2-R_2 (in the formula, R
(_2 is a fluoroalkyl group having 1 to 4 carbon atoms, M is an alkali metal) is reacted with an alkali metal salt of a fluoroalcohol represented by general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( II) (wherein p is an integer of 2 to 10, X_1 and X_2 are halogens, and R_1 is an alkyl group having 2 to 10 carbon atoms)
Claim 1 characterized in that an alcohol having a viologen structure represented by is reacted in the presence of a tertiary amine.
A method for producing the polymer described in .
キル基、X_1およびX_2はハロゲンである)で表わ
されるビオロゲン構造を有する基、βは一般式−CH_
2−R_2(R_2は炭素数1〜4のフルオロアルキル
基である)で表わされる炭素数2〜5のフルオロアルキ
ル基そしてγは一般式▲数式、化学式、表等があります
▼ (R_3)_3X^■_1または▲数式、化学式、表等
があります▼(R_3は炭素数1〜5のアルキル基、X
_1はハロゲン、pは2〜10の整数である)で表わさ
れる第四級アンモニウム塩残基である〕を主たる構成単
位としてなり、置換基αが0.04〜12モル%、置換
基βが83〜99.96モル%そして置換基γが0より
大で5モル%以下の割合で置換基α、置換基βおよび置
換基γが存在し、上記各構成単位が頭尾結合でランダム
に重合した構成を有し1分子中に構成単位(A)、(B
)または(D)が平均組成として少なくとも1つ含まれ
ている重合度5〜1500のビオロゲン構造を側鎖に含
有する線状ホスファゼンポリマー。(6) General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, General formula (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, General formula (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , General formula (D) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, General formula (E) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼, and General formula (F) ▲ Contains mathematical formulas, chemical formulas, tables, etc. 〔 Here, α is the viologen structure represented by the general formula ▲ Numerical formula, chemical formula, table, etc. The group β has the general formula -CH_
2-R_2 (R_2 is a fluoroalkyl group having 1 to 4 carbon atoms) and γ is a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (R_3)_3X^ ■_1 or ▲Mathematical formulas, chemical formulas, tables, etc.▼(R_3 is an alkyl group with 1 to 5 carbon atoms,
_1 is a halogen, p is an integer of 2 to 10) is a quaternary ammonium salt residue] as the main structural unit, the substituent α is 0.04 to 12 mol%, and the substituent β is Substituent α, substituent β, and substituent γ are present at a ratio of 83 to 99.96 mol% and substituent γ is greater than 0 and 5 mol% or less, and each of the above structural units is randomly polymerized with a head-to-tail bond. The structural units (A) and (B) are contained in one molecule.
) or (D) as an average composition, a linear phosphazene polymer containing a viologen structure in its side chain and having a degree of polymerization of 5 to 1500.
がn−C_3H_7そしてγが−CH_2CH_2N^
■(C_2H_5)_3X^■_1である請求項6に記
載のポリマー。(7) R_2 is trifluoromethyl group, p is 2, R_1
is n-C_3H_7 and γ is -CH_2CH_2N^
7. The polymer according to claim 6, which is ■(C_2H_5)_3X^■_1.
( I )HO−CH_2−R_2(式中、R_2は炭素
数1〜4のフルオロアルキル基である)で表わされるフ
ルオロアルコールと一般式(III) ▲数式、化学式、表等があります▼(III) (式中、X_2はハロゲン、R_1は炭素数2〜10の
アルキル基である)で表わされる化合物および一般式(
IV) ▲数式、化学式、表等があります▼(IV) (式中、pは2〜10の整数、X_1はハロゲンである
)で表わされるハロゲン化アルコールを第三アミンとし
て炭素数1〜5のアルキル基を有するトリアルキルアミ
ンまたはピリジンを用いて反応させることを特徴とする
請求項6に記載のポリマーの製造方法。(8) Linear phosphonitrile dichloride polymer, general formula (I) fluoroalcohol represented by HO-CH_2-R_2 (in the formula, R_2 is a fluoroalkyl group having 1 to 4 carbon atoms), and general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, X_2 is a halogen, R_1 is an alkyl group having 2 to 10 carbon atoms) and the general formula (
IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, p is an integer of 2 to 10, and X_1 is a halogen. 7. The method for producing a polymer according to claim 6, wherein the reaction is carried out using a trialkylamine or pyridine having an alkyl group.
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ID=16361008
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CN105237774A (en) * | 2015-10-08 | 2016-01-13 | 黑龙江大学 | Carbazolylpolyphosphazene-containing electrochromic material, and preparation method and application thereof |
-
1988
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---|---|---|---|---|
CN105237774A (en) * | 2015-10-08 | 2016-01-13 | 黑龙江大学 | Carbazolylpolyphosphazene-containing electrochromic material, and preparation method and application thereof |
CN105237774B (en) * | 2015-10-08 | 2018-01-23 | 黑龙江大学 | A kind of electrochromic material of carbazolyl-containing polyphosphazene and its preparation method and application |
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