JP6143042B2 - Ladder type polysilsesquioxane and method for producing the same - Google Patents
Ladder type polysilsesquioxane and method for producing the same Download PDFInfo
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- 229920000734 polysilsesquioxane polymer Polymers 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 19
- 238000005259 measurement Methods 0.000 description 13
- 125000000129 anionic group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001767 cationic compounds Chemical class 0.000 description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 229910001419 rubidium ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Description
本発明は、可溶性を示すアニオン性のラダー型ポリシルセスキオキサン及びその製造方法に関する。 The present invention relates to an anionic ladder-type polysilsesquioxane exhibiting solubility and a method for producing the same.
近年、有機成分と無機成分とを混合することにより、両成分の特徴を相乗的に高める有機−無機ハイブリッド材料が様々な分野で注目されている。その中でも、三官能性有機シランモノマー（シランカップリング剤）を用いて合成されるラダー型ポリシルセスキオキサン（ＰＳＱ）は、有機−無機ハイブリッド材料の中で注目されている材料の１つである。 In recent years, organic-inorganic hybrid materials that synergistically enhance the characteristics of both components by mixing organic and inorganic components have attracted attention in various fields. Among them, ladder type polysilsesquioxane (PSQ) synthesized using a trifunctional organosilane monomer (silane coupling agent) is one of the materials attracting attention among organic-inorganic hybrid materials. is there.
このラダー型ＰＳＱは、シロキサン結合が一次元方向に規則的につながったポリマーであり、主鎖構造が結合エネルギーの大きいＳｉ−Ｏ結合からなり、さらにラダー構造であるため、熱的、力学的及び化学的に安定した材料である。また、このＰＳＱは可溶性であるため、透明な溶液として利用することができる。 This ladder-type PSQ is a polymer in which siloxane bonds are regularly connected in a one-dimensional direction, the main chain structure is composed of Si—O bonds having a large bond energy, and is a ladder structure. It is a chemically stable material. Moreover, since this PSQ is soluble, it can be utilized as a transparent solution.
ラダー型ＰＳＱは、分子構造を制御することによって様々な用途に応用することができ、キラリティー誘起材料や化合物の吸着剤といった用途に用いることが期待されているが、カチオン性化合物の吸着剤として利用できるラダー型ＰＳＱについては報告されていない。 Ladder-type PSQ can be applied to various applications by controlling the molecular structure, and is expected to be used for applications such as chirality-inducing materials and compound adsorbents. There is no report on available ladder-type PSQ.
本発明は前述の問題点に鑑み、カチオン性化合物の吸着剤などに利用できるアニオン性のラダー型ポリシルセスキオキサン及びその製造方法を提供することを目的としている。 An object of the present invention is to provide an anionic ladder-type polysilsesquioxane that can be used as an adsorbent for a cationic compound and a method for producing the same, in view of the above-described problems.
本発明のラダー型ポリシルセスキオキサン及びその製造方法については、以下のとおりである。
（１）下記式（I）により表される単位の構造を有することを特徴とするラダー型ポリシルセスキオキサン。
The ladder-type polysilsesquioxane of the present invention and the production method thereof are as follows.
(1) A ladder-type polysilsesquioxane having a structure of a unit represented by the following formula (I).
（２）前記アルカリ金属イオンは、ナトリウムイオンであることを特徴とする前記（１）に記載のラダー型ポリシルセスキオキサン。 (2) The ladder-type polysilsesquioxane according to (1), wherein the alkali metal ion is a sodium ion.
（３）前記式（I）に表される単位の構造は、主鎖がねじれて形成されていることを特徴とする前記（１）又は（２）に記載のラダー型ポリシルセスキオキサン。 (3) The ladder type polysilsesquioxane according to (1) or (2), wherein the structure of the unit represented by the formula (I) is formed by twisting the main chain.
（４）２−シアノエチルトリエトキシシランを水酸化ナトリウム水溶液に混合して下記式（II）に表される構造の化合物を中間体として得る工程と、
下記式（II）に表される構造の化合物を加熱して縮合重合させ、陽イオン交換樹脂により下記式（III）に表される単位の構造の化合物を得る工程と、
下記式（III）に表される単位の構造の化合物に、メタノールまたはエタノールを含むアルカリ性溶液を混合し、カルボキシレート基と前記アルカリ性溶液中のアルカリ金属イオンとのイオン対を形成した固形物として下記式（VII）に表されるラダー型ポリシルセスキオキサンを抽出する工程と、
を有することを特徴とするラダー型ポリシルセスキオキサンの製造方法。
(4) mixing 2-cyanoethyltriethoxysilane with an aqueous sodium hydroxide solution to obtain a compound having a structure represented by the following formula (II) as an intermediate;
Heating and condensing a compound having a structure represented by the following formula (II) to obtain a compound having a unit structure represented by the following formula (III) by a cation exchange resin;
The compound of structural units represented by the following formula (III), following the mixed alkaline solution containing methanol or ethanol, solids to form an ion pair with the carboxylate groups and alkali metal ions of the alkaline solution Extracting the ladder-type polysilsesquioxane represented by the formula (VII) ;
A process for producing a ladder-type polysilsesquioxane, comprising:
本発明によれば、アニオン性を有するラダー型ＰＳＱにより、カチオン性化合物の吸着剤など、様々な分野に応用できる。 According to the present invention, the ladder type PSQ having an anionic property can be applied to various fields such as an adsorbent for a cationic compound.
本発明者は、アニオン性を有するラダー型ポリシルセスキオキサン（ＰＳＱ）を生成するため、鋭意に研究した結果、モノマーとして２−シアノエチルトリエトキシシランを用いてアルカリ性の条件下で重合反応させたところ、規則的な配列のラダー構造からなるアニオン性ラダー型ＰＳＱを得ることができることを見出した。 As a result of intensive research to produce an anionic ladder-type polysilsesquioxane (PSQ), the present inventor conducted a polymerization reaction under alkaline conditions using 2-cyanoethyltriethoxysilane as a monomer. However, it has been found that an anionic ladder type PSQ having a ladder structure with a regular arrangement can be obtained.
本発明に係るアニオン性ラダー型ＰＳＱは、主鎖がねじれた構造を形成し、複数のアニオン性ラダー型ＰＳＱが重なってヘキサゴナル積層構造を形成する。また、側鎖にはアニオン性のカルボキシレート基が形成されており、アルカリ金属イオンとイオン対を形成する。 The anionic ladder type PSQ according to the present invention forms a structure in which the main chain is twisted, and a plurality of anionic ladder type PSQs overlap to form a hexagonal laminated structure. In addition, an anionic carboxylate group is formed in the side chain and forms an ion pair with an alkali metal ion.
ここで、アルカリ金属イオンとは、ナトリウムイオン（Ｎａ+）、リチウムイオン（Ｌｉ+）、カリウムイオン（Ｋ+）、ルビジウムイオン（Ｒｂ+）、及びセシウムイオン（Ｃｓ+）のことを指し、この中でも、水酸化ナトリウムは入手が容易であることから、ナトリウムイオンであることが好ましい。 Here, the alkali metal ion means sodium ion (Na + ), lithium ion (Li + ), potassium ion (K + ), rubidium ion (Rb + ), and cesium ion (Cs + ). Especially, since sodium hydroxide is easy to acquire, it is preferable that it is a sodium ion.
次に、アニオン性ラダー型ＰＳＱの製造方法について説明する。
まず、水酸化ナトリウム水溶液に２−シアノエチルトリエトキシシランを混合比（重量比）が０．９：１〜３：１となるように混合して６時間〜２４時間攪拌することにより加水分解が起こり、次式（IV）に表される構造の化合物が得られる。
Next, the manufacturing method of anionic ladder type PSQ is demonstrated.
First, 2-cyanoethyltriethoxysilane is mixed with an aqueous sodium hydroxide solution so that the mixing ratio (weight ratio) is 0.9: 1 to 3: 1 and stirred for 6 to 24 hours to cause hydrolysis. Thus, a compound having a structure represented by the following formula (IV) is obtained.
なお、水酸化ナトリウム水溶液の代わりに、他のアルカリ性水溶液を用いてもよい。水酸化ナトリウム水溶液の代わりに水酸化リチウム水溶液を用いる場合には、ナトリウムイオンの代わりにリチウムイオンの塩が得られる。また、水酸化ナトリウム水溶液の代わりに水酸化カリウム水溶液を用いる場合には、ナトリウムイオンの代わりにカリウムイオンの塩が得られる。また、水酸化ナトリウム水溶液の代わりに水酸化ルビジウム水溶液を用いる場合には、ナトリウムイオンの代わりにルビジウムイオンの塩が得られる。また、水酸化ナトリウム水溶液の代わりに水酸化セシウム水溶液を用いる場合には、ナトリウムイオンの代わりにセシウムイオンの塩が得られる。 In addition, you may use another alkaline aqueous solution instead of sodium hydroxide aqueous solution. When a lithium hydroxide aqueous solution is used instead of the sodium hydroxide aqueous solution, a lithium ion salt is obtained instead of the sodium ion. Moreover, when using potassium hydroxide aqueous solution instead of sodium hydroxide aqueous solution, the salt of potassium ion is obtained instead of sodium ion. When a rubidium hydroxide aqueous solution is used instead of the sodium hydroxide aqueous solution, a salt of rubidium ion can be obtained instead of sodium ion. When a cesium hydroxide aqueous solution is used instead of the sodium hydroxide aqueous solution, a cesium ion salt can be obtained instead of the sodium ion.
次に、式（IV）に表される構造の化合物を開放系で５０〜７０℃で加熱することで溶媒を蒸発させて縮合重合させる。一般的にモノマーから縮合重合によりＰＳＱを得る場合、不規則な３次元ネットワーク構造を形成し、不溶性の材料となりやすい。これに対して本実施形態では、式（IV）に表される構造の化合物が酸とアルカリとからなる塩を形成しているため、この構造により３次元的な重合を抑制し、可溶性の規則的な配列のラダー構造が得られる。 Next, the compound having the structure represented by the formula (IV) is heated at 50 to 70 ° C. in an open system to evaporate the solvent and undergo condensation polymerization. In general, when PSQ is obtained from a monomer by condensation polymerization, an irregular three-dimensional network structure is formed, which tends to be an insoluble material. On the other hand, in the present embodiment, since the compound having the structure represented by the formula (IV) forms a salt composed of an acid and an alkali, this structure suppresses three-dimensional polymerization, and the solubility rule. A typical ladder structure is obtained.
次に、陽イオン交換樹脂を用いてナトリウムイオンと水素イオンとを交換させると、次式（V）に表される構造のポリマーが得られる。ここで陽イオン交換樹脂としては、交換基としてスルホン酸基を有するもの、カルボキシル基を有するものなどが挙げられる。具体的には、生成した粉末状の粗生成物を陽イオン交換樹脂が入っている水に加えて室温で１〜３時間撹拌することによって、式（V）に表される構造のポリマーが得られる。 Next, when sodium ions and hydrogen ions are exchanged using a cation exchange resin, a polymer having a structure represented by the following formula (V) is obtained. Here, examples of the cation exchange resin include those having a sulfonic acid group as an exchange group and those having a carboxyl group. Specifically, the resulting powdery crude product is added to water containing a cation exchange resin and stirred at room temperature for 1 to 3 hours to obtain a polymer having a structure represented by the formula (V). It is done.
次に、式（V）に表されるポリマーに水酸化ナトリウムのメタノール溶液を混合すると、イオン化して次式（VI）に表されるカルボキシレート基を有するラダー構造のＰＳＱが得られる。なお、メタノール溶液の代わりにエタノール溶液を用いてもよい。また、式（V）に表されるポリマーと、水酸化ナトリウムとの混合比（モル比）が１：１となるように混合し、水酸化ナトリウム溶液の濃度は、０．１〜１重量％とする。 Next, when a methanol solution of sodium hydroxide is mixed with the polymer represented by the formula (V), PSQ having a ladder structure having a carboxylate group represented by the following formula (VI) is obtained by ionization. An ethanol solution may be used instead of the methanol solution. Further, the polymer represented by the formula (V) and sodium hydroxide were mixed so that the mixing ratio (molar ratio) was 1: 1, and the concentration of the sodium hydroxide solution was 0.1 to 1% by weight. And
なお、アルカリ金属イオンを他のイオンにする場合は、水酸化ナトリウムの代わりにそのイオンを有するアルカリ性物質を用いる。具体的には、リチウムイオンのラダー型ＰＳＱを得る場合には、水酸化ナトリウムの代わりに水酸化リチウムを用いる。また、カリウムイオンのラダー型ＰＳＱを得る場合には、水酸化ナトリウムの代わりに水酸化カリウムを用いる。また、ルビジウムイオンのラダー型ＰＳＱを得る場合には、水酸化ナトリウムの代わりに水酸化ルビジウムを用いる。また、セシウムイオンのラダー型ＰＳＱを得る場合には、水酸化ナトリウムの代わりに水酸化セシウムを用いる。 When the alkali metal ion is changed to another ion, an alkaline substance having the ion is used instead of sodium hydroxide. Specifically, lithium hydroxide is used instead of sodium hydroxide to obtain a lithium ion ladder type PSQ. In addition, when obtaining a ladder-type PSQ of potassium ions, potassium hydroxide is used instead of sodium hydroxide. Further, when obtaining rubidium ion ladder type PSQ, rubidium hydroxide is used instead of sodium hydroxide. Moreover, when obtaining ladder type PSQ of cesium ions, cesium hydroxide is used instead of sodium hydroxide.
以上のような製造手順により得られるアニオン性のラダー型ＰＳＱは、図１に示すように、主鎖が右または左回りにねじれて形成されており、その結果、図２に示すようなヘキサゴナル積層構造を形成する。このとき、ラダー型ＰＳＱの主鎖部分の両端は、Ｓｉ−ＯＨ結合が形成されている。また、分子量は、以上のような条件下で縮合重合させると、８０００〜１６０００の範囲内であると考えられる。 As shown in FIG. 1, the anionic ladder-type PSQ obtained by the manufacturing procedure as described above is formed by twisting the main chain clockwise or counterclockwise. As a result, the hexagonal laminate as shown in FIG. Form a structure. At this time, Si—OH bonds are formed at both ends of the main chain portion of the ladder-type PSQ. Further, the molecular weight is considered to be in the range of 8000 to 16000 when subjected to condensation polymerization under the above conditions.
このように本発明のラダー型ＰＳＱは、官能基としてアニオン性のカルボキシレート基を有し、さらに可溶性であることから、カチオン性化合物の吸着剤として利用することができる。例えば、セシウムイオンなどの陽イオンを含む化合物から選択的に陽イオンを除去することも可能である。また、陽性の発光性物質を吸着し、円偏光発光材料などへ応用することも可能である。 Thus, the ladder-type PSQ of the present invention has an anionic carboxylate group as a functional group and is further soluble, so that it can be used as an adsorbent for a cationic compound. For example, it is possible to selectively remove cations from a compound containing cations such as cesium ions. It is also possible to adsorb positive luminescent substances and apply them to circularly polarized light emitting materials.
次に、本発明の実施例について説明する。なお、この実験における条件等は、本発明の実施可能性等を確認するために採用した例であり、本発明は、これらの例に限定されるものではない。 Next, examples of the present invention will be described. The conditions and the like in this experiment are examples adopted for confirming the feasibility of the present invention, and the present invention is not limited to these examples.
まず、０．２１７ｇの２−シアノエチルトリエトキシシランを濃度が８％の水酸化ナトリウム水溶液５ｍＬに混合して１３時間攪拌し、式（IV）に表される化合物を生成した。この化合物は単離することが困難であるため、そのまま次の反応に用い、水溶液を開放系で５０〜６０℃で加熱し、溶媒を蒸発させて重縮合を進行させた。その後、生成した粉末状の粗生成物を約１００ｃｍ3のＨ+タイプの陽イオン交換樹脂が入っている１００ｍＬの水に加えて室温で３時間撹拌し、陽イオン交換樹脂をろ別した後、得られた水溶液をロータリーエバポレーターで２０ｍＬまで濃縮し、その後凍結乾燥することで１．７６５ｇの式（V）に表される構造の化合物（以下、ＰＳＱ−ＣＯＯＨ）を得た。そして、ＰＳＱ−ＣＯＯＨの一部を採取し、Ｓｈｉｍａｄｚｕ製のＦＴＩＲ-８４００ ｓｐｅｃｔｒｏｍｅｔｅｒによる赤外分光測定、及びＪＥＯＬ製のＥＣＸ-４００ ｓｐｅｃｔｒｏｍｅｔｅｒによる核磁気共鳴（ＮＭＲ）分光測定を行った。 First, 0.217 g of 2-cyanoethyltriethoxysilane was mixed with 5 mL of an aqueous 8% sodium hydroxide solution and stirred for 13 hours to produce a compound represented by the formula (IV). Since this compound is difficult to isolate, it was directly used in the next reaction, and the aqueous solution was heated in an open system at 50 to 60 ° C. to evaporate the solvent and proceed polycondensation. Thereafter, the resulting powdery crude product was added to 100 mL of water containing about 100 cm 3 of H + type cation exchange resin, stirred at room temperature for 3 hours, and the cation exchange resin was filtered off. The obtained aqueous solution was concentrated to 20 mL with a rotary evaporator, and then lyophilized to obtain 1.765 g of a compound represented by the formula (V) (hereinafter, PSQ-COOH). Then, a part of PSQ-COOH was sampled and subjected to infrared spectroscopic measurement using Shimadzu FTIR-8400 spectrometer and nuclear magnetic resonance (NMR) spectroscopic measurement using JEOL ECX-400 spectrometer.
図３は、本実施例により作製したＰＳＱ−ＣＯＯＨの赤外分光法による測定結果を示す図である。図３に示すように、カルボキシル基については１７１３ｃｍ-1付近に吸収ピークが確認され、Ｓｉ−Ｏ結合については、１０３４ｃｍ-1、１１２６ｃｍ-1付近に吸収ピークが確認された。 FIG. 3 is a diagram showing a measurement result of infrared spectroscopy of PSQ-COOH produced according to this example. As shown in FIG. 3, for the carboxyl group was confirmed absorption peak near 1713 cm -1, for the Si-O bond, 1034Cm -1, absorption peaks were confirmed near 1126cm -1.
図４〜図６は、本実施例により作製したＰＳＱ−ＣＯＯＨの核磁気共鳴（ＮＭＲ）分光法による測定結果を示す図である。図４〜図６に示すように、ａ，ｂの位置における（−ＣＨ2−）の存在が確認され、さらに、カルボキシル基を構成するＣ、及び主鎖部分のＳｉの存在も確認された。また、Ｔ2ピークが存在することから、ＰＳＱ−ＣＯＯＨの主鎖部分の両端はＳｉ−ＯＨ結合が存在していることも確認された。 4-6 is a figure which shows the measurement result by the nuclear magnetic resonance (NMR) spectroscopy of PSQ-COOH produced by the present Example. As shown in FIGS. 4 to 6, the presence of (—CH 2 —) at the positions a and b was confirmed, and the presence of C constituting the carboxyl group and Si in the main chain portion was also confirmed. Further, since the T 2 peak was present, it was also confirmed that Si—OH bonds were present at both ends of the main chain portion of PSQ—COOH.
次に、０．０２２８ｇの本実施例により作製したＰＳＱ−ＣＯＯＨに、０．００７２ｇの水酸化ナトリウムとメタノール溶液１．８ｍＬとを加えて１時間撹拌し、この懸濁液をガラス基板上に塗布して室温で放置して乾燥することで式（VI）に表される単位の構造の化合物（以下、ＰＳＱ−ＣＯＯ-Ｎａ+）を得た。そして、ＰＳＱ−ＣＯＯ-Ｎａ+の一部を採取し、Ｓｈｉｍａｄｚｕ製のＦＴＩＲ-８４００ ｓｐｅｃｔｒｏｍｅｔｅｒによる赤外分光測定、及びＸ'Ｐｅｒｔ Ｐｒｏ ｄｉｆｆｒａｃｔｏｍｅｔｅｒ （ＰＡＮａｌｙｔｉｃａｌ製）によるＸ線回折測定を行った。 Next, to 0.0228 g of PSQ-COOH prepared in this example, 0.0072 g of sodium hydroxide and 1.8 mL of methanol solution were added and stirred for 1 hour, and this suspension was applied onto a glass substrate. Then, the compound having a unit structure represented by the formula (VI) (hereinafter referred to as PSQ-COO − Na + ) was obtained by allowing to stand and drying at room temperature. Then, a part of PSQ-COO − Na + was collected and subjected to infrared spectroscopic measurement using FTIR-8400 spectrometer manufactured by Shimadzu and X-ray diffraction measurement using X′Pert Pro diffractometer (manufactured by PANallytical).
図７は、本実施例により作製したＰＳＱ−ＣＯＯＨ及びＰＳＱ−ＣＯＯ-Ｎａ+の赤外分光法による測定結果を示す図である。図７に示すように、１４１２ｃｍ-1、１５６６ｃｍ-1付近に吸収ピークが確認され、カルボキシル基からカルボキシレート基に置換されていることが確認された。また、Ｓｉ−Ｏ結合もＰＳＱ−ＣＯＯＨの場合とほぼ同じ位置に吸収ピークが確認され、そのままＳｉ−Ｏ結合が存在していることが確認された。 FIG. 7 is a graph showing the measurement results of PSQ—COOH and PSQ—COO − Na + produced in this example by infrared spectroscopy. As shown in FIG. 7, absorption peaks were confirmed in the vicinity of 1412 cm −1 and 1566 cm −1 , and it was confirmed that the carboxyl group was substituted with a carboxylate group. In addition, the absorption peak of Si—O bond was confirmed at almost the same position as in the case of PSQ—COOH, and it was confirmed that the Si—O bond was present as it was.
図８は、本実施例により作製したＰＳＱ−ＣＯＯＨ及びＰＳＱ−ＣＯＯ-Ｎａ+のＸ線回折法による測定結果を示す図である。図８に示すように、（１００）面、（１１０）面及び（２００）面のピークが検出され、図９に示すように複数のＰＳＱ−ＣＯＯ-Ｎａ+がヘキサゴナル状に積層された構造であることが確認された。また、分子量は、29Ｓｉ−ＮＭＲ測定による末端定量法により約１０×１０3と算出された。 FIG. 8 is a diagram showing measurement results of PSQ—COOH and PSQ—COO − Na + produced by this example by the X-ray diffraction method. As shown in FIG. 8, peaks of (100) plane, (110) plane and (200) plane are detected, and as shown in FIG. 9, a plurality of PSQ-COO − Na + are stacked in a hexagonal shape. It was confirmed that there was. The molecular weight was calculated to be about 10 × 10 3 by terminal quantification by 29 Si-NMR measurement.
以上のように本実施例によれば、アニオン性のカルボキシレート基を有するラダー型ＰＳＱを作製することができる。これにより、カチオン性化合物の吸着剤や、円偏光発光材料などへ応用することも可能であるといえる。 As described above, according to this example, a ladder-type PSQ having an anionic carboxylate group can be produced. Thus, it can be applied to adsorbents of cationic compounds and circularly polarized light emitting materials.
Claims (4)
下記式（II）に表される構造の化合物を加熱して縮合重合させ、陽イオン交換樹脂により下記式（III）に表される単位の構造の化合物を得る工程と、
下記式（III）に表される単位の構造の化合物に、メタノールまたはエタノールを含むアルカリ性溶液を混合し、カルボキシレート基と前記アルカリ性溶液中のアルカリ金属イオンとのイオン対を形成した固形物として下記式（IV）に表されるラダー型ポリシルセスキオキサンを抽出する工程と、
を有することを特徴とするラダー型ポリシルセスキオキサンの製造方法。
Heating and condensing a compound having a structure represented by the following formula (II) to obtain a compound having a unit structure represented by the following formula (III) by a cation exchange resin;
The compound of structural units represented by the following formula (III), following the mixed alkaline solution containing methanol or ethanol, solids to form an ion pair with the carboxylate groups and alkali metal ions of the alkaline solution Extracting the ladder-type polysilsesquioxane represented by the formula (IV) ;
A process for producing a ladder-type polysilsesquioxane, comprising:
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