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.

1. Preparación de poli (ácido 5-norborneno-2-carboxílico), PNBE (CO 2 H) <ol><li> Preparación de la NBE monómero (CO 2 H) <ol><li> Pesar ácido acrílico (AA) (327 g, 4,5 mol, 2 eq.) E hidroquinona (4,9 g, 4,5 x 10 -2 moles, 0,02 eq.) Y añadirlos a un matraz de 2 l de fondo redondo equipado con un condensador y una barra de agitación magnética. Se calienta el matraz a 150 ° C utilizando un baño de aceite de silicona. </li><li> Una vez que se resuelva el reflu...

<ol>
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El método propuesto aquí es simple y fácilmente susceptible de aumento de escala. Todos los productos químicos podrían ser utilizados como se recibieron sin purificación. Tenga en cuenta que la realización de la reacción a una escala más baja (por ejemplo, balanzas ≤1 g) por lo general tienen rendimientos más bajos debido a una pérdida inevitable de material durante la manipulación y la colección. Los catalizadores se forman in situ en la reacción de compues...

Norborneno, NBE, el aducto de Diels-Alder de etileno y ciclopentadieno (obtenido por &quot;cracking&quot; de diciclopentadieno (DCPD)), se polimeriza fácilmente usando polimerización por radicales libres, 1 polimerización catiónica, metátesis polimerización por apertura de anillo de 2 3 y la inserción catalítica polimerización. 4, 5, 6, 7 A diferencia de los otros mecanismos, la polimerización de inserción catalítico conduce a la formación de una temperatura muy alta de transición vítrea (Tg) del polímero mediante el cual se conserva la columna vertebral bicíclico de NBE. Una variedad de catalizadores tales como catalizadores de metaloceno y catalizadores de metales de transición finales se puede utilizar para promover la polimerización de NBE. 4, 5, 6, Tg, el homopolímero PNBE ha, que nosotros sepamos, nunca se encontró ningún uso. Polynorbornenes funcionales (PNBEs) han sido objeto de un escrutinio considerable durante los últimos 20 años, ya que combinan la alta Tg impartida por la unidad de repetición rígida bicíclico, así como propiedades deseables dotadas por sus funcionalidades. 8, 9, 10 monómeros NBE se obtienen de materias primas bastante simple y de bajo costo, utilizando una reacción de Diels-Alder de un solo paso entre el ciclopentadieno y un dienófilo funcionalizado. Sin embargo, la reacción de Diels-Alder conduce a dos estereoisómeros, endo y exo, que tienen muy diferentes reactividades. 11, 12 De hecho, el equipo de música endoisómero es menos reactivo que forma exo y desactiva el catalizador. 11, 12 Por lo tanto, en el pasado, la preparación de polynorbornenes funcionales requiere generalmente la separación de los estereoisómeros endo y exo, y se utilizó sólo el estereoisómero exo. Dicho procedimiento de separación era mucho tiempo, y dio lugar a la acumulación de estereoisómeros endo sin reaccionar como residuos indeseables. Recientemente hemos demostrado que la polimerización de NBEs funcionalizados que contienen ambos estereoisómeros es, de hecho, factible. 13 por lo que hemos sido capaces de preparar una variedad de PNBEs sustituidos, que contienen grupos funcionales tales como ésteres, anhídridos, aldehídos, alcoholes, imidas y dobles enlaces. Debido a su alto T g y funcionalidad, estos polímeros muestran propiedades deseables. Se describe aquí dos métodos para preparar polímeros funcionales. El primero conduce ala síntesis de la poli polímero soluble en agua (ácido 5-norborneno-2-carboxílico), PNBE (CO 2 H), utilizando un catalizador de Pd catiónico (Figura 1). 13, 14 El mismo método de polimerización puede usarse para preparar PNBEs funcionales con varias funcionalidades colgantes, tales como ésteres, alcoholes, imidas, bromo-alquilos, aldehídos y anhídridos. En nuestras manos, este catalizador Pd catiónico no se puede utilizar para NBEs que contienen dobles enlaces colgantes tales como 5-vinil-2-norborneno. En este caso, una inserción parcial del doble enlace colgante durante la polimerización conduce a la formación de un material reticulado. Por lo tanto, se presenta aquí un segundo método dedicado a la formación de poli (5-vinil-2-norborneno), PNBE (vinilo), usando Pd 2 (dba) 3: AgSbF 6: PPh 3 como un catalizador en situ. 14 Los grupos vinilo colgantes del polímero epoxidado son luego más allá, al llevar a THe formación de PNBE (epoxi) (Figura 1). Tanto PNBE (CO 2 H) y PNBE (epoxi) se han encontrado para conducir a la formación de resinas termoendurecibles con una Tg tan alta como 350 ° C. 14 Por lo tanto, el simple método descrito aquí permite a uno preparar eficientemente polímeros con una alta Tg y que tiene una variedad de grupos funcionales, que se pueden utilizar para numerosas aplicaciones. <img alt="Figura 1" src="/files/ftp_upload/54552/54552fig1.jpg" /> Figura 1: PNBEs funcionales preparados por Pd catalizada polimerización. (A) Preparación de PNBE (CO 2 H), (B) la preparación de PNBE (vinilo) y PNBE (epoxi). El enlace de trazos indica una mezcla de isómeros endo y exo. <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig1large.jpg" target="_blank">Haga clic aquí para ver una versión más grande de esta fi</a>gura.

<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

Norborneno puede ser polimerizado por una variedad de mecanismos, incluyendo la polimerización de inserción mediante el cual el doble enlace se polimeriza y la naturaleza bicíclico del monómero se conserva. El polímero, polinorborneno resultante, tiene una temperatura muy alta de transición vítrea, Tg, y propiedades ópticas y eléctricas interesantes. Sin embargo, la polimerización de norbornenos funcionales por este mecanismo es complicado por el hecho de que el monómero de norborneno endo sustituido tiene, en general, una reactividad muy baja. Además, la separación del monómero endo sustituido a partir del monómero exo es una tarea tediosa. A continuación, presentamos un protocolo sencillo para la polimerización de norbornenos sustituidos (endo: exo ca. 80:20) que lleva un ácido carboxílico o un doble enlace colgante. El proceso no requiere que pueden separar los dos isómeros, y procede con cargas de catalizador bajas (0,01-0,02% en moles). Los pend cojinete de polímerodobles enlaces de hormigas pueden ser transformados adicionalmente con un alto rendimiento, para proporcionar un cojinete de polímero de grupos epoxi colgantes. Estos procedimientos simples se pueden aplicar para preparar polynorbornenes con una variedad de grupos funcionales, tales como ésteres, alcoholes, imidas, dobles enlaces, ácidos carboxílicos, bromo-alquilos, aldehídos y anhídridos.

Los monómeros NBE se preparan por simple reacción de Diels-Alder de DCPD y un dienófilo adecuado, por ejemplo ácido acrílico (AA). Normalmente, DCPD está agrietada para dar ciclopentadieno (CPD) antes de la reacción. 17 CPD recién abierto entonces se dedica a la reacción de Diels-Alder. Sin embargo, en este protocolo, ambos pasos de craqueo y de Diels-Alder se realizan de forma concomitante, en una reacción en un solo recipiente. Por lo tanto, tan pronto...

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.

Un protocolo simple y eficaz para la inserción catalítico de polimerización norbornenos funcionales

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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A Simple and Rapid Protocol for Measuring Neutral Lipids in Algal Cells Using Fluorescence

Un simple y protocolo Rapid para Medir lípidos neutros en las células de algas Utilizando Fluorescencia

Algae are considered excellent candidates for renewable fuel sources due to their natural lipid storage capabilities. Robust monitoring of algal ...

Investigación

Química

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

Síntesis y rendimiento catalítico de Oro intercalados en las Murallas de sílice mesoporoso

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties ...

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization

Preparación Facile y Eficiente de la glicopolímeros fluorescentes Tri-componentes a través de polimerización BALSA controlado

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and ...

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

Las polimerizaciones de etileno utilizando reactores de presión paralelas y un análisis cinético de la cadena de transferencia de polimerización

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel ...

A Protocol for the Production of Gliadin-cyanoacrylate Nanoparticles for Hydrophilic Coating

Un protocolo para la producción de nanopartículas gliadina-cianoacrilato para el recubrimiento hidrofílico

This article presents a protocol for the production of protein-based nanoparticles that changes the hydrophobic surface to hydrophilic by a simple spray ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Síntesis Facile de micelas similares a gusanos de luz visible mediada por dispersión Polimerización con catalizador Photoredox

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

Un protocolo optimizado para el radiomarcaje eficaz de nanopartículas de oro mediante el uso de una<sup&gt; 125</sup&gt; Azida grupo prostético marcado con I

Here, we demonstrate a detailed protocol for the radiosynthesis of a 125I-labeled azide prosthetic group and its application to the efficient ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Paladio<em&gt; N</em&gt; -Heterocíclicos de los complejos de carburo: Síntesis a partir de sales de benzimidazolio y actividad catalítica en las reacciones de formación de enlaces carbono-carbono

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

Método de precipitación química para la síntesis de Nb2O5 modificado a granel catalizadores de níquel con alta superficie específica

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of ...

Fabrication and Testing of Catalytic Aerogels Prepared Via Rapid Supercritical Extraction

Fabricación y pruebas de Aerogels catalíticos preparados vía rápida extracción supercrítica

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three ...