JP2008019371A - Polyrotaxane and method for producing polyrotaxane - Google Patents
Polyrotaxane and method for producing polyrotaxane Download PDFInfo
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Abstract
【課題】効率良くポリロタキサンを製造する方法、および当該製造方法に伴う新規なポリロタキサンを提供する。
【解決手段】輪成分の開口部に軸分子が貫通し、軸分子の両末端にキャッピング剤によるブロック基を有してなるポリロタキサンを製造するにあたり、軸分子とキャッピング剤とを、両者が尿素結合により結合するように反応させる。具体的にはイソシアネート基とアミン基との組み合わせで、例えば、末端官能基がアミンである軸分子と、イソシアネート類であるキャッピング剤とを反応させる。
【選択図】なしA method for producing a polyrotaxane efficiently and a novel polyrotaxane associated with the production method are provided.
In producing a polyrotaxane in which a shaft molecule penetrates through an opening of a ring component and has a blocking group by a capping agent at both ends of the shaft molecule, the shaft molecule and the capping agent are bonded to each other by urea bonding. React to bind. Specifically, a combination of an isocyanate group and an amine group reacts, for example, an axial molecule whose terminal functional group is an amine with a capping agent that is an isocyanate.
[Selection figure] None
Description
本発明は、新規なポリロタキサンおよびその製造方法に関するものである。 The present invention relates to a novel polyrotaxane and a method for producing the same.
ポリロタキサンの効率的な製造方法の一例として、特許文献１に記載の方法が知られている。この製造方法では、軸分子として両末端がカルボキシル化されたポリエチレングリコールを用い、輪成分としてシクロデキストリンを用いて、擬ポリロタキサンを得た後、キャッピング剤としてアミン基または水酸基を有するものを用いてキャッピング反応を行い、ポリロタキサンを製造する。
従来のポリロタキサンの製造方法では、擬ポリロタキサンをキャッピングする際の反応が遅いため、輪成分であるシクロデキストリンが軸分子から遊離してしまい、その結果収率が著しく低下するなどの問題があった。特許文献１に記載の方法では、キャッピング反応時の温度を低くすることにより収率を上げているが、反応時間が長く、製造効率が悪かった。
In the conventional method for producing polyrotaxane, since the reaction when capping the pseudopolyrotaxane is slow, cyclodextrin as a ring component is liberated from the shaft molecule, and as a result, the yield is remarkably lowered. In the method described in
本発明は、このような実状に鑑みてなされたものであり、効率良くポリロタキサンを製造する方法、および当該製造方法に伴う新規なポリロタキサンを提供することを目的とする。 The present invention has been made in view of such a situation, and an object thereof is to provide a method for efficiently producing a polyrotaxane and a novel polyrotaxane associated with the production method.
上記目的を達成するために、第１に本発明は、輪成分の開口部に軸分子が貫通し、前記軸分子の両末端にブロック基を有してなるポリロタキサンであって、前記軸分子と前記ブロック基とが尿素結合により結合していることを特徴とするポリロタキサンを提供する（請求項１）。 In order to achieve the above object, first, the present invention provides a polyrotaxane in which an axial molecule penetrates through an opening of a ring component and has blocking groups at both ends of the axial molecule, A polyrotaxane is provided in which the blocking group is bonded with a urea bond (claim 1).
上記発明（請求項１）に係るポリロタキサンの製造においては、軸分子とブロック基との反応が、触媒等の試薬を必要とすることなく、効率良く進行するため、上記発明（請求項１）に係るポリロタキサンは、短時間に高収率で得られる。このポリロタキサンは新規なポリロタキサンである。 In the production of the polyrotaxane according to the above invention (Invention 1), the reaction between the shaft molecule and the blocking group proceeds efficiently without requiring a reagent such as a catalyst. Such polyrotaxane is obtained in a high yield in a short time. This polyrotaxane is a novel polyrotaxane.
上記発明（請求項１）においては、前記軸分子と前記ブロック基とが、イソシアネート基とアミン基との組み合わせの反応で結合していることが好ましい（請求項２）。 In the said invention (invention 1), it is preferable that the said axial molecule and the said block group are couple | bonded by reaction of the combination of an isocyanate group and an amine group (invention 2).
上記発明（請求項１，２）においては、前記輪成分がシクロデキストリンまたはシクロデキストリン誘導体であることが好ましい（請求項３）。
In the said invention (
第２に本発明は、輪成分の開口部に軸分子が貫通し、前記軸分子の両末端にキャッピング剤によるブロック基を有してなるポリロタキサンの製造方法であって、前記軸分子と前記キャッピング剤とを、両者が尿素結合により結合するように反応させることを特徴とするポリロタキサンの製造方法を提供する（請求項４）。 Second, the present invention relates to a method for producing a polyrotaxane having a shaft molecule penetrating through an opening of a ring component and having blocking groups formed by a capping agent at both ends of the shaft molecule, the shaft molecule and the capping The present invention provides a method for producing a polyrotaxane, characterized in that an agent is reacted with each other so that they are bonded by a urea bond (Claim 4).
上記発明（請求項４）によれば、触媒等の試薬を必要とすることなく、軸分子とブロック基との反応が効率良く進行するため、短時間に高収率でポリロタキサンを製造することができる。 According to the above invention (invention 4), since the reaction between the axial molecule and the blocking group proceeds efficiently without the need for a reagent such as a catalyst, a polyrotaxane can be produced in a high yield in a short time. it can.
上記発明（請求項４）においては、前記軸分子と前記キャッピング剤とを、イソシアネート基とアミン基との組み合わせで反応させることが好ましい（請求項５）。例えば、両末端にアミン基を有する軸分子と、イソシアネート基を有するキャッピング剤とを反応させるか、両末端にイソシアネート基を有する軸分子と、アミン基を有するキャッピング剤とを反応させることが好ましい。 In the said invention (invention 4), it is preferable to make the said axial molecule and the said capping agent react with the combination of an isocyanate group and an amine group (invention 5). For example, it is preferable to react an axial molecule having an amine group at both ends with a capping agent having an isocyanate group, or to react an axial molecule having an isocyanate group at both ends with a capping agent having an amine group.
上記発明（請求項４，５）においては、前記軸分子と前記キャッピング剤との反応における溶媒として、水を使用することが好ましい（請求項６）。
In the said invention (
一般的に、輪成分の開口部に軸分子を貫通させる擬ポリロタキサンの製造工程では、溶媒として水を使用するため、軸分子とキャッピング剤との反応でも溶媒として水を使用すると、擬ポリロタキサンの合成およびポリロタキサンの合成をワンポットで行うことができる。したがって、上記発明（請求項６）によれば、ポリロタキサンを極めて効率良く製造することができる。 Generally, in the production process of a pseudopolyrotaxane in which a shaft molecule penetrates through an opening of a ring component, water is used as a solvent. Therefore, when water is used as a solvent in the reaction between a shaft molecule and a capping agent, the synthesis of pseudopolyrotaxane is performed. And polyrotaxane can be synthesized in one pot. Therefore, according to the said invention (invention 6), a polyrotaxane can be manufactured very efficiently.
上記発明（請求項４〜６）においては、前記輪成分がシクロデキストリンまたはシクロデキストリン誘導体であることが好ましい（請求項７）。 In the said invention (inventions 4-6), it is preferable that the said ring component is a cyclodextrin or a cyclodextrin derivative (invention 7).
本発明によれば、触媒等の他の試薬を使用することなく、短時間に高収率でポリロタキサンを製造することができる。得られるポリロタキサンは、新規なポリロタキサンである。 According to the present invention, a polyrotaxane can be produced in a high yield in a short time without using another reagent such as a catalyst. The obtained polyrotaxane is a novel polyrotaxane.
以下、本発明の実施形態について説明する。
本実施形態では、輪成分の開口部に軸分子を貫通させて（軸分子を輪成分で包接させて）擬ポリロタキサンを製造し、次いで、得られた擬ポリロタキサンの軸分子とキャッピング剤とを、両者が尿素結合により結合するように反応させて、軸分子の両末端にブロック基を付加し、ポリロタキサンを得る。
Hereinafter, embodiments of the present invention will be described.
In the present embodiment, a pseudo-polyrotaxane is produced by penetrating a shaft molecule through an opening of a ring component (including inclusion of a shaft molecule with a ring component), and then the obtained pseudo-polyrotaxane is made of a shaft molecule and a capping agent. , Both are reacted so as to be bonded by a urea bond, and a blocking group is added to both ends of the axial molecule to obtain a polyrotaxane.
尿素結合は、通常、イソシアネート基とアミン基との反応による結合であるため、軸分子としては、末端にイソシアネート基またはアミン基を有するものを使用することが好ましい。 Since the urea bond is usually a bond formed by a reaction between an isocyanate group and an amine group, it is preferable to use an axial molecule having an isocyanate group or an amine group at the terminal.
かかる軸分子としては、例えば、末端官能基がアミンまたはイソシアネートであるポリテトラヒドロフラン、ポリエチレングリコール、ポリプロピレングリコール、ポリイソプレン、ポリイソブチレン、ポリブタジエン、ポリアクリル酸エステル、ポリジメチルシロキサン、ポリエチレン、ポリプロピレンの他、末端にアミン基またはイソシアネート基が導入された炭素数６〜１８のアルカン等が挙げられる。これらの中でも、水中での包接錯体形成能の観点から、末端官能基がアミンであるポリテトラヒドロフラン、ポリエチレングリコール、ポリプロピレングリコール；末端にアミン基が導入された炭素数６〜１８のアルカンなどを使用することが好ましい。 Such axial molecules include, for example, polytetrahydrofuran, polyethylene glycol, polypropylene glycol, polyisoprene, polyisobutylene, polybutadiene, polyacrylic acid ester, polydimethylsiloxane, polyethylene, and polypropylene whose terminal functional group is an amine or isocyanate. And an alkane having 6 to 18 carbon atoms into which an amine group or an isocyanate group is introduced. Among these, from the viewpoint of the ability to form an inclusion complex in water, polytetrahydrofuran, polyethylene glycol, polypropylene glycol whose terminal functional group is an amine; an alkane having 6 to 18 carbon atoms in which an amine group is introduced at the terminal is used. It is preferable to do.
軸分子の平均分子量は、特に限定されず、ポリロタキサンの使用目的に応じて適宜選択すればよいが、通常は数平均分子量（Ｍｎ）が１００〜５０００００であり、好ましくは５００〜１０００００であり、特に好ましくは１０００〜５００００である。 The average molecular weight of the axial molecule is not particularly limited, and may be appropriately selected according to the intended use of the polyrotaxane. Usually, the number average molecular weight (Mn) is 100 to 500,000, preferably 500 to 100,000. Preferably it is 1000-50000.
上記軸分子は、市販のものを使用することもできるし、従来公知の方法、例えば、Nature, 356, 325-327 (1992)に記載の方法などによって合成することもできる。具体的には、例えば、末端官能基をアミノ基とする場合には、ポリテトラヒドロフラン、ポリエチレングリコール等の軸分子の末端のヒドロキシル基をトシルクロライドによりトシル化し、その後フタルイミドカリウムによりフタルイミド化し、最後にヒドラジンを用いて還元を行い、軸分子の末端をアミノ基とする。 Commercially available shaft molecules can be used, and can be synthesized by a conventionally known method such as the method described in Nature, 356, 325-327 (1992). Specifically, for example, when the terminal functional group is an amino group, the hydroxyl group at the end of an axial molecule such as polytetrahydrofuran or polyethylene glycol is tosylated with tosyl chloride, then phthalimided with potassium phthalimide, and finally hydrazine To reduce the end of the shaft molecule to an amino group.
輪成分としては、特に限定されないが、α−シクロデキストリン、β−シクロデキストリン、γ−シクロデキストリン等のシクロデキストリンまたはシクロデキストリン誘導体が好ましい。 The ring component is not particularly limited, but cyclodextrins or cyclodextrin derivatives such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable.
シクロデキストリン誘導体としては、例えば、アルキル基、アセチル基、トリチル基、トシル基、トリメチルシラン基、フェニル基、ハロゲン基等の置換基が導入されたシクロデキストリンなどが挙げられる。上記置換基は、ポリロタキサンの使用目的に応じて適宜選択すればよいが、キャッピング剤との反応性の低い置換基、例えばアルキル基等を選択すると、後述するブロック基の付加工程（キャッピング工程）において、反応系を低温にする必要がなくなる。 Examples of cyclodextrin derivatives include cyclodextrins into which substituents such as alkyl groups, acetyl groups, trityl groups, tosyl groups, trimethylsilane groups, phenyl groups, and halogen groups are introduced. The substituent may be appropriately selected according to the purpose of use of the polyrotaxane, but when a substituent having low reactivity with the capping agent, such as an alkyl group, is selected, in a block group addition step (capping step) described later. This eliminates the need to lower the temperature of the reaction system.
擬ポリロタキサンの製造は、末端に官能基を有する軸分子および輪成分を溶媒中、通常は水中に存在させた状態にして（例えば、輪成分の水溶液に軸分子を添加して）、その溶液を撹拌することによって行うことができる。加えて、撹拌後にその溶液を静置することが収率を向上させることができるので好ましい。好ましい静置期間としては、輪成分としてα−シクロデキストリンおよびγ−シクロデキストリンを用いる場合には、１日程度、β−シクロデキストリンを用いる場合には、３〜７日程度である。 Pseudopolyrotaxane is prepared by placing a shaft molecule having a functional group at the end and a ring component in a solvent, usually in water (for example, adding a shaft molecule to an aqueous solution of the ring component) This can be done by stirring. In addition, it is preferable to stand the solution after stirring because the yield can be improved. A preferable standing period is about 1 day when α-cyclodextrin and γ-cyclodextrin are used as the ring component, and about 3 to 7 days when β-cyclodextrin is used.
撹拌方法については特に制限はなく、常温または適当に制御された温度で、機械的撹拌処理、超音波処理などの方法で撹拌することができ、特に、超音波処理で撹拌することが好ましい。撹拌時間は、数分〜１時間の条件で行うことが好ましい。超音波の照射条件については特に制限はないが、周波数２０〜４０ｋＨｚで行うことが好ましい。 There is no restriction | limiting in particular about the stirring method, It can stir by methods, such as a mechanical stirring process and an ultrasonic treatment, at normal temperature or the temperature controlled appropriately, It is preferable to specifically stir by ultrasonic treatment. The stirring time is preferably performed under conditions of several minutes to 1 hour. Although there is no restriction | limiting in particular about the irradiation conditions of an ultrasonic wave, It is preferable to carry out with a frequency of 20-40 kHz.
キャッピング剤としては、軸分子として末端官能基がアミンのものを選択した場合には、イソシアネート基を有するキャッピング剤、軸分子として末端官能基がイソシアネートのものを選択した場合には、アミン基を有するキャッピング剤を使用する。 As a capping agent, when the terminal functional group is an amine having an amine group as the axial molecule, the capping agent has an isocyanate group, and when the axial molecule has an end functional group having an isocyanate, the amine group has an amine group. Use a capping agent.
イソシアネート基を有するキャッピング剤としては、軸分子を貫通したシクロデキストリンの遊離を防ぐため嵩高い分子が好ましく、例えば、３，５−ジメチルフェニルイソシアネート、４−トリチルフェニルイソシアネート等のモノイソシアネート類などが挙げられる。 The capping agent having an isocyanate group is preferably a bulky molecule in order to prevent the liberation of cyclodextrin penetrating the axial molecule, and examples thereof include monoisocyanates such as 3,5-dimethylphenyl isocyanate and 4-tritylphenyl isocyanate. It is done.
アミン基を有するキャッピング剤としては、例えば、３，５−ジメチルアニリン、４−トリチルアニリン等が挙げられる。 Examples of the capping agent having an amine group include 3,5-dimethylaniline and 4-tritylaniline.
上記で得られた擬ポリロタキサンと上記キャッピング剤とを混合することによって、擬ポリロタキサンの軸分子とキャッピング剤とを反応させ、尿素結合により軸分子の両末端にブロック基を付加（キャッピング）して、ポリロタキサンを得る。 By mixing the pseudopolyrotaxane obtained above and the above capping agent, the axial molecule of the pseudopolyrotaxane reacts with the capping agent, and a blocking group is added (capped) to both ends of the axial molecule by urea bonding, A polyrotaxane is obtained.
このとき、触媒等の他の試薬を使用しなくても、また加熱しなくても、反応は効率良く短時間で進行する。そして、得られるポリロタキサンの収率も高い。 At this time, the reaction proceeds efficiently and in a short time without using other reagents such as a catalyst or heating. And the yield of the obtained polyrotaxane is also high.
キャッピング剤の使用量は、軸分子の末端官能基に対して、モル基準で等量〜３０倍量であることが好ましく、特に２倍〜１０倍量であることが好ましい。 The amount of capping agent used is preferably equivalent to 30 times, more preferably 2 to 10 times the molar amount of the terminal functional group of the axial molecule.
擬ポリロタキサンとキャッピング剤とを反応させるには、当該擬ポリロタキサンとキャッピング剤との混合物を撹拌するだけでよく、溶媒中で攪拌して行ってもよいし、固相で攪拌して行ってもよい。なお、溶媒中での攪拌は、撹拌子、撹拌翼等を用いた機械的撹拌処理で十分足りる。また、固相での撹拌には、乳鉢、ボールミル、ミキサー等を用いるとよい。 In order to react the pseudopolyrotaxane and the capping agent, it is only necessary to stir the mixture of the pseudopolyrotaxane and the capping agent. The pseudopolyrotaxane and the capping agent may be stirred in a solvent or in a solid phase. . For stirring in the solvent, mechanical stirring treatment using a stirring bar, a stirring blade or the like is sufficient. Moreover, it is good to use a mortar, a ball mill, a mixer etc. for the stirring in a solid phase.
溶媒としては、ジメチルホルムアミド、テトラヒドロフラン、クロロホルム、アセトン等の有機溶媒の他、水をも使用することができる。通常、試薬としてイソシアネートを使用する場合には、イソシアネートとの反応を防止するために水を溶媒として選択することはないが、本方法では溶媒として水の使用が可能である。一般的に、擬ポリロタキサンの製造は、水を溶媒として行うため、ここで溶媒として水を使用すると、擬ポリロタキサンの合成およびポリロタキサンの合成をワンポットで行うことができ、したがって、ポリロタキサンを極めて効率良く製造することができる。 As the solvent, water can be used in addition to organic solvents such as dimethylformamide, tetrahydrofuran, chloroform, and acetone. Usually, when isocyanate is used as a reagent, water is not selected as a solvent in order to prevent reaction with isocyanate, but in this method, water can be used as a solvent. In general, since pseudo-polyrotaxane is produced using water as a solvent, if water is used as the solvent, the synthesis of the pseudo-polyrotaxane and the polyrotaxane can be carried out in one pot. Therefore, the polyrotaxane can be produced very efficiently. can do.
溶媒の温度は、輪成分としてキャッピング剤との反応性が高いもの、例えばイソシアネート基と反応し易い水酸基を有するシクロデキストリン等を用いた場合、その反応を防止するために、−１０〜５℃とすることが好ましい。一方、輪成分としてキャッピング剤との反応性が低いもの、例えば水酸基がアルキル基等に置換されたシクロデキストリン等を用いた場合、溶媒の温度は特に限定されず、常温または適当に制御された温度とすればよい。 The temperature of the solvent is −10 to 5 ° C. in order to prevent the reaction when a high reactivity with the capping agent as a ring component, for example, cyclodextrin having a hydroxyl group that easily reacts with an isocyanate group is used. It is preferable to do. On the other hand, when a ring component having low reactivity with the capping agent, for example, cyclodextrin in which the hydroxyl group is substituted with an alkyl group or the like, the temperature of the solvent is not particularly limited, and is normal temperature or an appropriately controlled temperature. And it is sufficient.
反応時間は、０．１〜５時間程度、特に０．５〜３時間であることが好ましい。このように、本方法によれば、短時間で、しかも高収率でポリロタキサンを製造することができる。なお、精製は常法によって行えばよい。 The reaction time is preferably about 0.1 to 5 hours, particularly 0.5 to 3 hours. Thus, according to this method, a polyrotaxane can be produced in a short time and in a high yield. The purification may be performed by a conventional method.
以上の方法によって得られるポリロタキサンは、輪成分の開口部に軸分子が貫通し、軸分子とブロック基とが尿素結合により結合してなるものである。このようなポリロタキサンは、従来にはない新規なポリロタキサンである。 The polyrotaxane obtained by the above method is one in which a shaft molecule penetrates through the opening of the ring component and the shaft molecule and the blocking group are bonded by a urea bond. Such a polyrotaxane is a novel polyrotaxane that has not existed before.
以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.
〔実施例１〕
輪成分であるα−シクロデキストリン（ナカライテスク社製）１．５ｇをイオン交換水１０ｍｌに溶解させた水溶液に、軸分子として末端官能基アミンのポリテトラヒドロフラン（Ａｌｄｒｉｃｈ社製，Polytetrahydrofuran bis (3-aminopropyl) terminated，Ｍｎ：１１００）５０ｍｇを加え、超音波（周波数：３５ｋＨｚ）を２０分間照射し、室温で一晩静置した。そして、析出した固体を回収し、乾燥させて擬ポリロタキサンを得た。
[Example 1]
Polytetrahydrofuran bis (3-aminopropyl, polytetrahydrofuran bis (3-aminopropyl), a terminal functional amine as an axial molecule, in an aqueous solution obtained by dissolving 1.5 g of α-cyclodextrin (manufactured by Nacalai Tesque) as a ring component in 10 ml of ion-exchanged water. ) terminated, Mn: 1100) 50 mg was added, ultrasonic waves (frequency: 35 kHz) were irradiated for 20 minutes, and the mixture was allowed to stand overnight at room temperature. The precipitated solid was collected and dried to obtain a pseudopolyrotaxane.
得られた擬ポリロタキサン３３０ｍｇをジメチルホルムアミド溶媒に分散させ、キャッピング剤として３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）３５ｍｇを添加し、０℃で１時間撹拌し反応させた。得られた反応溶液をジエチルエーテルに注ぎ再沈澱させ、沈殿物を回収し、水およびメタノールで洗浄した後、乾燥させてポリロタキサンを得た（収量：７７ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図１に示す。 330 mg of the obtained pseudopolyrotaxane was dispersed in a dimethylformamide solvent, 35 mg of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) was added as a capping agent, and the mixture was stirred and reacted at 0 ° C. for 1 hour. The obtained reaction solution was poured into diethyl ether and reprecipitated, and the precipitate was collected, washed with water and methanol, and then dried to obtain a polyrotaxane (yield: 77 mg). A 1 H-NMR chart of the obtained polyrotaxane is shown in FIG.
〔実施例２〕
キャッピング工程の溶媒として、ジメチルホルムアミドの替わりにテトラヒドロフランを使用する以外、実施例１と同様にしてポリロタキサンを製造した（収量：１１５ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図２に示す。
[Example 2]
A polyrotaxane was produced in the same manner as in Example 1 except that tetrahydrofuran was used instead of dimethylformamide as a solvent for the capping step (yield: 115 mg). A 1 H-NMR chart of the obtained polyrotaxane is shown in FIG.
〔実施例３〕
実施例１と同様にして輪成分と軸分子とを反応させ、反応溶液を一晩静置した後、その反応溶液（水溶液）中に、キャッピング剤としての３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）３５ｍｇを添加した。その後は実施例１と同様にしてポリロタキサンを製造した（ワンポット合成；収量：１３０ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図３に示す。
Example 3
The ring component and the shaft molecule were reacted in the same manner as in Example 1 and the reaction solution was allowed to stand overnight, and then 3,5-dimethylphenyl isocyanate (Aldrich) as a capping agent was added to the reaction solution (aqueous solution). 35 mg) was added. Thereafter, polyrotaxane was produced in the same manner as in Example 1 (one-pot synthesis; yield: 130 mg). A 1 H-NMR chart of the obtained polyrotaxane is shown in FIG.
〔実施例４〕
トリチルアニリン（Ａｌｄｒｉｃｈ社製）をトルエン中でＨＣｌガスおよびトリホスゲンと反応させることにより、４−トリチルフェニルイソシアネートを得た。キャッピング剤として、３，５−ジメチルフェニルイソシアネートの替わりに上記４−トリチルフェニルイソシアネートを使用する以外、実施例３と同様にしてポリロタキサンを製造した（収量：６８ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図４に示す。
Example 4
4-Tritylphenyl isocyanate was obtained by reacting trityl aniline (manufactured by Aldrich) with HCl gas and triphosgene in toluene. A polyrotaxane was produced in the same manner as in Example 3 except that 4-tritylphenyl isocyanate was used instead of 3,5-dimethylphenyl isocyanate as a capping agent (yield: 68 mg). FIG. 4 shows a 1 H-NMR chart of the obtained polyrotaxane.
〔実施例５〕
α−シクロデキストリン（ナカライテスク社製）を、ジメチルホルムアルデヒド中、水素化ナトリウムおよびヨウ化メチルと反応させることにより、メチル化α−シクロデキストリンを得た。
Example 5
α-cyclodextrin (manufactured by Nacalai Tesque) was reacted with sodium hydride and methyl iodide in dimethylformaldehyde to obtain methylated α-cyclodextrin.
得られたメチル化α−シクロデキストリン（輪成分）０．８ｇをイオン交換水２ｍｌに溶解させた水溶液に、軸分子として末端官能基アミンのポリテトラヒドロフラン（Ａｌｄｒｉｃｈ社製，Polytetrahydrofuran bis (3-aminopropyl) terminated，Ｍｎ：１１００）２４ｍｇを加え、超音波（周波数：３５ｋＨｚ）を２０分間照射し、室温で一晩静置した。 Polytetrahydrofuran bis (3-aminopropyl), a polytetrahydrofuran bis (3-aminopropyl) of a terminal functional amine as an axial molecule, in an aqueous solution obtained by dissolving 0.8 g of the obtained methylated α-cyclodextrin (ring component) in 2 ml of ion-exchanged water. 24 mg of terminated, Mn: 1100) was added, ultrasonic waves (frequency: 35 kHz) were irradiated for 20 minutes, and the mixture was allowed to stand overnight at room temperature.
その反応溶液（水溶液）中に、キャッピング剤としての３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）３２ｍｇを添加し、０℃で１時間反応させた。得られた反応溶液をジエチルエーテルに注ぎ再沈澱させ、沈殿物を回収した。それを分取ゲルパーミエーションクロマトグラフィー（展開溶媒：ＣＨＣｌ３）にかけて高分子量体（Ｍｗ：１３０００，Ｍｗ／Ｍｎ：１．５）を回収し、乾燥させてポリロタキサンを得た（収量：８５ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図５に示す。 To the reaction solution (aqueous solution), 32 mg of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) as a capping agent was added and reacted at 0 ° C. for 1 hour. The obtained reaction solution was poured into diethyl ether and reprecipitated to collect the precipitate. It was subjected to preparative gel permeation chromatography (developing solvent: CHCl 3 ) to recover a high molecular weight product (Mw: 13000, Mw / Mn: 1.5) and dried to obtain a polyrotaxane (yield: 85 mg). FIG. 5 shows a 1 H-NMR chart of the obtained polyrotaxane.
〔実施例６〕
実施例５と同様にして輪成分と軸分子とを反応させ、反応溶液を一晩静置した。そして、析出した固体を回収し、乾燥させた後、その固体を乳鉢に入れ、さらにキャッピング剤としての３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）３２ｍｇを添加し、３０分間乳棒を使用して混合し反応させた。得られた反応物をジエチルエーテルで洗浄した後、固体を回収して乾燥させた。それを分取ゲルパーミエーションクロマトグラフィー（展開溶媒：ＣＨＣｌ３）にかけて高分子量体（Ｍｗ：１３０００，Ｍｗ／Ｍｎ：１．６）を回収し、乾燥させてポリロタキサンを得た（収量：５０ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図６に示す。
Example 6
The ring component and the shaft molecule were reacted in the same manner as in Example 5, and the reaction solution was allowed to stand overnight. Then, after the precipitated solid is collected and dried, the solid is placed in a mortar, and 32 mg of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) as a capping agent is added, and a pestle is used for 30 minutes. Mix and react. The obtained reaction product was washed with diethyl ether, and the solid was collected and dried. It was subjected to preparative gel permeation chromatography (developing solvent: CHCl 3 ) to recover a high molecular weight product (Mw: 13000, Mw / Mn: 1.6) and dried to obtain a polyrotaxane (yield: 50 mg). FIG. 6 shows a 1 H-NMR chart of the obtained polyrotaxane.
〔実施例７〕
ポリテトラヒドロフラン（Ａｌｄｒｉｃｈ社製，Polytetrahydrofuran，Ｍｎ：２９００）をクロロホルムに溶解させ、トシルクロライドを添加し、触媒にピリジンを用いて一晩撹拌を行った。その後、希塩酸による分液洗浄、そして減圧乾燥を行い、得られた液体をジエチルエーテルに注ぎ、再沈澱を行った。析出した固体を回収し乾燥させ、トシル化ポリテトラヒドロフランを得た。
Example 7
Polytetrahydrofuran (manufactured by Aldrich, Polytetrahydrofuran, Mn: 2900) was dissolved in chloroform, tosyl chloride was added, and the mixture was stirred overnight using pyridine as a catalyst. Thereafter, liquid separation washing with dilute hydrochloric acid and drying under reduced pressure were performed, and the obtained liquid was poured into diethyl ether for reprecipitation. The precipitated solid was collected and dried to obtain tosylated polytetrahydrofuran.
次に、得られたトシル化ポリテトラヒドロフランをジメチルホルムアミドに溶解させ、フタルイミドカリウムを添加し、５時間沸点還流を行った。反応溶液を濾過した濾液をジエチルエーテルに注ぎ再沈澱を行い、析出した固体を回収し乾燥させることでフタルイミド化ポリテトラヒドロフランを得た。 Next, the tosylated polytetrahydrofuran obtained was dissolved in dimethylformamide, potassium phthalimide was added, and boiling point reflux was performed for 5 hours. The filtrate obtained by filtering the reaction solution was poured into diethyl ether for reprecipitation, and the precipitated solid was collected and dried to obtain phthalimidized polytetrahydrofuran.
得られたフタルイミド化ポリテトラヒドロフランをエタノールに溶解させ、ヒドラジンを添加し、２０時間沸点還流を行った。反応溶液を濾過した濾液をジエチルエーテルに注ぎ再沈澱を行い、析出した固体を回収し、末端官能基アミンのポリテトラヒドロフラン（１Ｈ−ＮＭＲ測定によるＭｎ：７８００）を得た。 The obtained phthalimidized polytetrahydrofuran was dissolved in ethanol, hydrazine was added, and boiling point reflux was performed for 20 hours. The filtrate obtained by filtering the reaction solution was poured into diethyl ether for reprecipitation, and the precipitated solid was collected to obtain polytetrahydrofuran (Mn: 1800 by 1 H-NMR measurement) of a terminal functional group amine.
軸分子として、上記で得られた末端官能基アミンのポリテトラヒドロフランを使用する以外、実施例３と同様にしてポリロタキサンを製造した（収量：３７ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図７に示す。 A polyrotaxane was produced in the same manner as in Example 3 except that the terminal functional group amine polytetrahydrofuran obtained above was used as the axial molecule (yield: 37 mg). FIG. 7 shows a 1 H-NMR chart of the obtained polyrotaxane.
〔実施例８〕
軸分子として、末端官能基アミンのポリテトラヒドロフランの替わりに末端官能基アミンのポリエチレングリコール（Ａｌｄｒｉｃｈ社製，Polyethyleneglycol bis (3-aminopropyl) terminated，Ｍｎ：１５００）５０ｍｇを使用し、キャッピング剤としての３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）の添加量を５０ｍｇとする以外、実施例３と同様にしてポリロタキサンを製造した（収量：３５ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図８に示す。
Example 8
Instead of polytetrahydrofuran as a terminal functional amine, 50 mg of polyethylene glycol as a terminal functional amine (Aldrich, Polyethyleneglycol bis (3-aminopropyl) terminated, Mn: 1500) is used as an axial molecule, A polyrotaxane was produced in the same manner as in Example 3 except that the addition amount of 5-dimethylphenyl isocyanate (manufactured by Aldrich) was 50 mg (yield: 35 mg). FIG. 8 shows a 1 H-NMR chart of the obtained polyrotaxane.
〔実施例９〕
軸分子として、末端官能基アミンのポリテトラヒドロフランの替わりにジアミノドデカン１００ｍｇを使用し、キャッピング剤としての３，５−ジメチルフェニルイソシアネート（Ａｌｄｒｉｃｈ社製）の添加量を１００ｍｇとする以外、実施例３と同様にしてポリロタキサンを製造した（収量：２３４ｍｇ）。得られたポリロタキサンの１Ｈ−ＮＭＲチャートを図９に示す。
Example 9
Example 3 except that 100 mg of diaminododecane was used as the axial molecule instead of polytetrahydrofuran of the terminal functional amine, and the amount of 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) as a capping agent was 100 mg. In the same manner, polyrotaxane was produced (yield: 234 mg). The 1 H-NMR chart of the obtained polyrotaxane is shown in FIG.
本発明は、効率良くポリロタキサンを製造するのに有用である。また、本発明に係る新規ポリロタキサンは、ゲル材料、架橋材料、医療材料等に用いられる機能性材料として有用である。 The present invention is useful for efficiently producing a polyrotaxane. Moreover, the novel polyrotaxane according to the present invention is useful as a functional material used for gel materials, cross-linking materials, medical materials and the like.
Claims (7)
前記軸分子と前記ブロック基とが尿素結合により結合していることを特徴とするポリロタキサン。 A polyrotaxane in which an axial molecule penetrates through an opening of a ring component and has blocking groups at both ends of the axial molecule,
The polyrotaxane, wherein the axial molecule and the blocking group are bonded by a urea bond.
前記軸分子と前記キャッピング剤とを、両者が尿素結合により結合するように反応させることを特徴とするポリロタキサンの製造方法。 A method for producing a polyrotaxane in which a shaft molecule penetrates through an opening of a ring component and has a blocking group by a capping agent at both ends of the shaft molecule,
A method for producing a polyrotaxane, wherein the axial molecule and the capping agent are reacted so that they are bonded together by a urea bond.
The method for producing a polyrotaxane according to any one of claims 4 to 6, wherein the ring component is a cyclodextrin or a cyclodextrin derivative.
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