Name: a simple and efficient protocol for the catalytic insertion polymerization of functional norbornenes
Uploaded: 2017-02-27T13:00:00
Description: Watch this Scientific Journal Video about A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes at JoVE.com

The authors acknowledge funding from Fonds de Recherche du Qu&#233;bec - Nature et Technologies, from Conseil Recherches en Sciences Naturelles et G&#233;nie (program INNOV) and PrimaQu&#233;bec.

ポリ（5-ノルボルネン-2-カルボン酸）、PNBE（CO 2 H）の調製<ol><li> モノマーNBE（CO 2 H）の調製 <ol><li> （4.9 gであり、4.5×10 -2モル、0.02当量）、アクリル酸（AA）（327 gであり、4.5モル、2当量）及びヒドロキノンを秤量し、コンデンサーを備えた丸底2リットルフラスコに追加しおよび磁気攪拌棒。シリコーン油浴を用いて150℃でフラスコを加熱します。 </li><...

<ol>
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ここで提案する方法はシンプル、かつスケールアップが容易に受け入れられます。受け取った全ての化学物質は、精製することなく使用することができます。下位尺度（ 例えばスケール≤1グラム）で反応を行うことは、通常の取り扱いおよび収集の間の材料の避けられない損失による低い収率をもたらすことに注意してください。 触媒は、カチオン化剤と商用の...

ノルボルネン、NBE（ジシクロペンタジエン（DCPD）の「クラッキング」することによって得られる）は、エチレンとシクロペンタジエンのディールス-アルダー付加物は、容易にフリーラジカル重合、1カチオン重合、2開環メタセシス重合3および触媒挿入のいずれかを用いて重合され重合。 NBEの二環式骨格が保存される4、5、6、他の機構とは異なり7、触媒挿入重合は、非常に高いガラス転移温度（T g）ポリマーの形成をもたらします。このようなメタロセン触媒および後期遷移金属触媒のような触媒の様々なNBEの重合を促進するために使用することができます。 4、5、6、 <suPクラス= &quot;外部参照は&quot;&gt; 7は、しかし、その低い溶解性に起因し、非常に高いT gポリマーの処理に関連する困難に、PNBEホモポリマーは、我々の知る限り、任意の使用を発見したことがありません。 彼らは二環剛性繰り返し単位並びにそれらの機能に恵まれ望ましい特性により付与高いT gを組み合わせるための機能ノルボルネン（PNBEs）は、過去20年間、かなりの精査の対象となっています。 8、9、10 NBEモノマーは、シクロペンタジエンとジエノフィル官能間のワンステップディールス-アルダー反応を用いて、かなり簡単かつ安価な原料から得られます。しかしながら、ディールス-アルダー反応は、非常に異なる反応性を有する2つの立体異性体、 エンド及びエキソにつながります。実際には11、12、 エンドステレオ異性体は、 エキソ形よりも反応性が低いと触媒を不活性化します。 図11、 図12はこのように、過去に、機能的ポリノルボルネンの調製は、通常、 エンド及びエキソ立体異性体の分離を必要とし、唯一のエキソ立体異性体が使用されました。このような分離操作は、時間がかかりました、望ましくない廃棄物として未反応のエンド立体異性体の蓄積につながりました。 最近では、両方の立体異性体を含む官能基化NBEsの重合は、実際に実現可能であることを示しました。 13そこで我々は、そのようなエステル、無水物、アルデヒド、イミド、アルコールおよび二重結合などの官能基を含む、置換PNBEsの様々な調製することができました。その高いT gおよび機能性に、これらのポリマーは、所望の特性を示します。ここでは、機能性ポリマーを調製するための2つの方法を記載しています。一つ目はにつながりますカチオン性Pd触媒（ 図1）を使用して水溶性ポリマーであるポリ（5-ノルボルネン-2-カルボン酸）の合成、PNBE（CO 2 H）。 13、14と同じ重合方法は、エステル類、アルコール類、イミド類、ブロモアルキル、アルデヒド及び酸無水物のような種々のペンダント官能基を有する官能PNBEsを調製するために用いることができます。我々の手では、このカチオン性Pd触媒は、5-ビニル-2-ノルボルネンなどのペンダント二重結合を含むNBEsするために使用することができません。この場合には、重合時のペンダント二重結合の部分的な挿入は、架橋された材料の形成をもたらします。 インサイツ触媒とのPPh 3：AgSbF 6：したがって、我々は、Pd 2（DBA）3を用いて、PNBE（ビニル）、ここで、ポリの形成に専用の第二の方法提示（5-ビニル-2-ノルボルネン）。 14ポリマーのペンダントビニル基は、その後、さらに番目につながる、エポキシ化されていますPNBE（エポキシ）（ 図1）のE形成。 PNBE（CO 2 H）およびPNBE（エポキシ）の両方が、350℃などのT gと高いと熱硬化性樹脂の形成をもたらすことが見出されています。 図14はこのように、ここで説明する単純な方法は、1つは、効率的に、非常に高いT g及び多数の用途に使用することができる官能基の多様を有するポリマーを調製することができます。 <img alt="図1" src="/files/ftp_upload/54552/54552fig1.jpg" /> 図1：Pdをすることにより調製機能PNBEsは、重合触媒。 （A）PNBE（ビニル）及びPNBE（エポキシ）のPNBE（CO 2 H）、（B）製剤の調製。破線の結合は、 エンドおよびエキソ異性体の混合物を示しています。 <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig1large.jpg" target="_blank">このFiのの拡大版をご覧になるにはこちらをクリックしてください。</a>グレ。

<table border="0" cellpadding="0" cellspacing="0" width="945">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">acrylic acid</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">147230</td>
			<td style="width:299px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">hydroquinone</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td>H9003</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">dicyclopendadiene</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td align="left">454338</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">palladium allyl dichloride dimer</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td>222380</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">silver hexfluoro antimonate</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">227730</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">liquid nitrogen</td>
			<td style="width:241px;">Local Facility</td>
			<td style="width:135px;">NA</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">ethyl acetate</td>
			<td style="width:241px;">Fischer Scientific</td>
			<td>E14520</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">5-vinyl-2-norbornene</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">148679</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">toluene</td>
			<td style="width:241px;">Fischer Scientific</td>
			<td>T290-4</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">palladium dba</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">227994</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">triphenyl phosphine</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">93090</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">silica gel 40-63 microns</td>
			<td style="width:241px;">Silicycle</td>
			<td style="width:135px;">Siliaflash</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">methanol</td>
			<td style="width:241px;">Fischer Scientific</td>
			<td>BPA412-20</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">dichloromethane</td>
			<td style="width:241px;">EMD Millipore</td>
			<td>DX08311</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">formic acid</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">F0507</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">acetic acid</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td>320099</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:271px;">hydrogen peroxide solution</td>
			<td style="width:241px;">Sigma-Aldrich</td>
			<td style="width:135px;">216763</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:271px;">acetone</td>
			<td style="width:241px;">Fischer Scientific</td>
			<td>A18-200</td>
			<td></td>
		</tr>
	</tbody>
</table>

a simple and efficient protocol for the catalytic insertion polymerization of functional norbornenes

ノルボルネン系二重結合を重合し、モノマーの二環式の性質が保存される挿入重合を含む様々な機構により重合することができます。得られた重合体、ポリノルボルネンは、非常に高いガラス転移温度、T gを、興味深い光学的および電気的特性を有します。しかし、このメカニズムによって機能ノルボルネンの重合は、 エンド置換ノルボルネンモノマーは、一般的に、非常に低い反応性を有するという事実によって複雑になります。さらに、 エキソモノマーからエンド置換モノマーの分離は面倒な作業です。カルボン酸またはペンダント二重結合のいずれかを保有する：（エキソ 約 80:20 エンド ）ここでは、置換ノルボルネンの重合のための単純なプロトコルを提示します。プロセスは、両方の異性体を分離することを必要とし、低い触媒充填量（0.01〜0.02モル％）で進行しません。ポリマーベアリング保留アリの二重結合は、更に、ペンダントエポキシ基を有するポリマーを得るために、高収率で変換することができます。これらの単純な手順は、例えば、エステル類、アルコール類、イミド類、二重結合、カルボン酸、ブロモアルキル、アルデヒドおよび無水物官能基の様々なノルボルネンを製造するために適用することができます。

NBEモノマーは、例えばアクリル酸（AA）は、DCPDの単純なディールス - アルダー反応及び適切なジエノフィルにより調製されます。通常、DCPDは、反応前に、シクロペンタジエン（CPD）を得割れています。 17たて割れCPDは、その後、ディールス・アルダー反応に従事しています。しかしながら、このプロトコルでは、両方の亀裂およびディールス - ア?...

Watch this Scientific Journal Video about A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes at JoVE.com

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

機能性ノルボルネンの触媒挿入重合のためのシンプルで効率的なプロトコル

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

The overall goal of this synthetic procedure is to prepare functional insertion polynorbornenes, which are highly functional polymers with a very high glass transition temperature. The main advantage of this technique is that it's possible to access high performance polymers bearing highly reactive functional groups such as epoxy groups or acid groups via a simple experimental protocol. Generally, researchers that are new to catalytic polymer synthesis will struggle because the synthesis must be performed using very high standards of purity, but here, in the process we're going to describe, the synthesis can be performed easily with no special purification step.Demonstrating part of the procedure will be Moubarak Compaore, a graduate student in the Claverie laboratory. To begin this procedure, set up a one liter round bottom flask with a condenser and stir bar. Add 327 grams of acrylic acid and 4.9 grams of hydroquinone to the flask.Then use a heating block to heat the mixture to 150 degrees Celsius. Once the refluxing has settled, add 300 grams of DCPD. Then increase the temperature to 170 degrees Celsius for 16 hours.The solution color will change from clear to yellow-brown. Using a Pasteur pipette, extract a sample. Analyze by proton NMR, using deuterated chloroform as the solvent.Next, remove the condenser from the round bottom flask. Replace it with a simple distillation setup connected to a condenser circulating cold water. Place the reaction setup under vacuum and set the pressure to one millimeter mercury.Then heat to 100 degrees Celsius for approximately one hour. Collect and discard the clear liquid that boils off. Replace the collection flask with a 250 milliliter round bottom flask.Heat to 155 degrees Celsius for seven hours to distill the NBE carboxylic acid. Analyze the distilled liquid by proton NMR to determine the purity and endo to exo proportions. Then add 300 grams of NBE carboxylic acid to a 500 milliliter round bottom flask equipped with a magnetic stir bar.Degas the NBE carboxylic acid by bubbling nitrogen for 40 minutes using a slow stirring rate for the stir bar. Add 76 milligrams of allylpalladium(II)chloride dimer. Then add 180 milligrams of silver antimonate.Increase the stirring rate and heat the solution to 70 degrees Celsius under a slight nitrogen flux for 36 hours. Next, cool the flask with liquid nitrogen. Using a spatula, break the polymer into small pieces.Add 750 milliliters of ethyl acetate to a two liter beaker equipped with a magnetic stir bar. Then add the polymer chunks under vigorous stirring. Allow the solution to continue stirring for two hours.After stirring is complete, filter the solution using a Buchner funnel equipped with filter paper. Wash the polymer with 500 milliliters of ethyl acetate three times, then dry the polymer in a vacuum oven at 50 degrees Celsius for 12 hours. Separately degas 100 grams of toluene and 100 grams of NBE(vinyl)by bubbling with nitrogen gas for 30 minutes.After that, place both in the glove box. In the glove box, add the toluene into a 250 milliliter round bottom flask. Next, successively add 76 milligrams of PD2(DBA)3, 68 milligrams of silver antimonite and 43 milligrams of triphenylphosphine to the toluene solution.Then add the degassed NBE(vinyl)and stir at 70 degrees Celsius for 72 hours. Once stirring is complete, remove the solution from the glove box and transfer it into a one liter glass bottle equipped with a magnetic stir bar. Add 200 milliliters of fresh toluene and stir.Then add 10 grams of silica powder and continue stirring at room temperature for 16 hours. After stirring is complete, let the solution settle for two hours to allow the silica particles to sedimentate. Filter the settled solution through a Buchner funnel equipped with filter paper.Rinse the silica particles with fresh toluene and filter it through the Buchner funnel. Next, add 1.2 liters of methanol to a fresh four liter beaker equipped with a magnetic stir bar. Gradually add this solution of toluene and polymer to the beaker under vigorous stirring.Continue stirring for 30 minutes. After stirring is complete, filter the polymer using a Buchner funnel and filter paper. Wash the polymer with 400 milliliters of methanol three times.Analyze the polymer purity by proton NMR to determine if the residual monomer is present. If so, perform one additional wash with methanol. After washing is complete, dry the PNBE(vinyl)under vacuum at room temperature overnight.Add 150 grams of dichloromethane to a 500 milliliter round bottom flask equipped with a magnetic stir bar and a condenser. Then add 15 grams of PNBE(vinyl)with stirring. Once the polymer has completely dissolved, place the flask in an ice bath to cool for 15 minutes.In a fresh beaker, mix 30 grams of formic acid and five grams of acetic acid. Add this acid solution to the flask and let it cool for 15 minutes. Next, add 75 grams of a 30%aqueous solution of hydrogen peroxide and stir the solution for 18 hours.After this, remove a small sample. Precipitate the polymer with acetone and analyze with proton NMR as outlined in the text protocol. If the signal for the double bond has not decreased sufficiently, continue stirring the reaction, analyzing by proton NMR hourly.Once the signal for the double bond has decreased sufficiently, add 750 milliliters of acetone to a fresh four liter beaker equipped with a magnetic stir bar. Gradually add the polymer solution under vigorous stirring. Let the solution continue to stir for 15 minutes.After that, filter the polymer using a Buchner funnel and filter paper. Wash the polymer with 200 milliliters of acetone four times. Finally, dry the polymer under vacuum at room temperature overnight.In this procedure, polymers are obtained by catalyzed polymerization and collected in the form of dry powders. Representative results for the proton NMR analysis of the polymers can be seen here. This analysis confirms the epoxidation of PNBE(vinyl)The decreasing ratio between the integrals of the vinyl group and the other protons in the PNBE(epoxy)spectrum proves the efficacy of this epoxidation procedure, with 97%of PNBE(vinyl)being converted to PNBE(epoxy)FTIR spectroscopy is also used to confirm the outcome of the epoxidation reaction.This is seen by the apparition of a characteristic peak at 875 inverse centimeters and the disappearance of the 904 inverse centimeter and 992 inverse centimeter peaks, which are observed in the PNBE(vinyl)polymer. So once mastered, an ordinary scale of either polymer, be it polynorbornene epoxy or polynorbornene acid, can be prepared in less than a week with minimal manipulation time.

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