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. Fremstilling af poly (5-norbornen-2-carboxylsyre), PNBE (CO 2 H) <ol><li> Fremstilling af monomeren NBE (CO 2 H) <ol><li> Afvej acrylsyre (AA) (327 g, 4,5 mol, 2 ækv.) Og hydroquinon (4,9 g, 4,5 x 10 -2 mol, 0,02 ækv.) Og tilsæt dem til en 2 L rundbundet kolbe udstyret med en kondensator og en magnetisk omrører. Kolben opvarmes ved 150 ° C ved anvendelse af en siliconeolie bad. </li><li> Når tilbagesvaling er fast, tilsættes DCPD (300 g, 2,3 mol, 1 ækv.) I e...

<ol>
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Den her foreslåede metode er enkel og let modtagelige for opskalering. Alle kemikalier kunne anvendes som modtaget uden nogen oprensning. Bemærk at udføre reaktionen ved en lavere omfang (f.eks vægte ≤1 g) normalt giver lavere udbytte som følge af en uundgåelig tab af materiale under håndteringen og samlingen. Katalysatorerne dannes in situ ved omsætning af kommercielle Pd forbindelser med kationisering midler. I vores hænder, er udbyttet af reaktionen samt egens...

Norbornen, NBE, Diels-Alder-addukt af ethylen og cyclopentadien (opnået ved &quot;krakning&quot; af dicyclopentadien (DCPD)), let polymeriseres under anvendelse af enten fri radikal-polymerisation, 1 kationisk polymerisation, 2 ringåbnende metatese-polymerisation 3 og katalytisk insertion polymerisation. 4, 5, 6, 7 modsætning til de andre mekanismer, den katalytiske indsættelse polymerisation fører til dannelse af en meget høj glasovergangstemperatur (Tg) polymer, hvorved den bicykliske rygraden i NBE er bevaret. En række katalysatorer såsom metallocenkatalysatorer og sent overgangsmetalkatalysatorer kan anvendes til at fremme polymerisationen af ​​NBE. 4, 5, 6, Tg polymer, den PNBE homopolymer har, så vidt vi ved, aldrig fundet, enhver brug. Funktionelle polynorbornenes (PNBEs) har været genstand for betydelig kontrol for de sidste 20 år, fordi de kombinerer den høje Tg bibragt af bicykliske stive gentagelsesenhed samt ønskelige egenskaber etableres ved tilførsel af deres funktionaliteter. 8, 9, 10 NBE monomerer opnås fra temmelig enkle og billige råmaterialer, ved anvendelse af en ettrins Diels-Alder-reaktion mellem cyclopentadien og en funktionaliseret dienophil. Imidlertid Diels-Alder-reaktion fører til to stereoisomerer, endo- og exo, som har meget forskellige reaktiviteter. 11, 12 Faktisk endo stereoisomeren er mindre reaktiv end exo formular og deaktiverer katalysatoren. 11, 12 således i fortiden, fremstillingen af funktionelle polynorbornenes normalt kræves adskillelse af endo- og exo stereoisomerer, og kun exo stereoisomer blev anvendt. En sådan adskillelse procedure var tidskrævende, og førte til akkumulering af ikke-reagerede endo stereoisomerer som uønsket affald. For nylig har vi vist, at polymerisationen af ​​funktionaliserede NBEs indeholdende begge stereoisomerer er faktisk muligt. 13 Vi har således været i stand til at forberede en række substituerede PNBEs, der indeholder funktionelle grupper, såsom estere, anhydrider, aldehyder, imider, alkoholer og dobbeltbindinger. På grund af deres høje Tg og funktionalitet, disse polymerer viser ønskelige egenskaber. Vi beskriver her to metoder til fremstilling af funktionelle polymerer. Den første fører tilsyntesen af den vandopløselige polymer poly (5-norbornen-2-carboxylsyre), PNBE (CO 2 H), ved anvendelse af en kationisk Pd-katalysator (figur 1). 13, 14 Den samme polymerisation metode kan anvendes til fremstilling af funktionelle PNBEs med forskellige vedhæng funktionaliteter, såsom estere, alkoholer, imider, brom-alkyler, aldehyder og anhydrider. I vores hænder, kan dette kationiske Pd-katalysator ikke anvendes til NBEs indeholdende vedhængende dobbeltbindinger, såsom 5-vinyl-2-norbornen. I dette tilfælde en delvis indføring af pendant dobbeltbindingen under polymeriseringen fører til dannelsen af ​​en tværbundet materiale. Derfor præsenterer vi her en anden fremgangsmåde dedikeret til dannelsen af poly (5-vinyl-2-norbornen), PNBE (vinyl), ved anvendelse af Pd2 (dba) 3: AgSbF 6: PPh3 som et in situ-katalysator. 14 vedhæng vinyl grupper af polymeren er derefter yderligere epoxideret, at føre til the dannelse af PNBE (epoxy) (figur 1). Både PNBE (CO 2 H) og PNBE (epoxy) har vist sig at føre til dannelsen af termohærdende harpikser med en Tg så høj som 350 ° C. 14 Således er den simple metode beskrevet her tillader en at effektivt fremstille polymerer med en meget høj Tg og med en række forskellige funktionelle grupper, som kan anvendes til talrige anvendelser. <img alt="figur 1" src="/files/ftp_upload/54552/54552fig1.jpg" /> Figur 1: Funktionelle PNBEs fremstillet ved Pd-katalyseret polymerisation. (A) udarbejdelse af PNBE (CO 2 H), (B) udarbejdelse af PNBE (vinyl) og PNBE (epoxy). Den stiplede binding angiver en blanding af endo- og exo-isomerer. <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig1large.jpg" target="_blank">Klik her for at se en større version af denne fi</a>gur.

<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

Norbornen kan polymeriseres ved en række forskellige mekanismer, herunder ilægning polymerisation hvorved dobbeltbindingen er polymeriseret og den bicykliske karakter af monomeren er bevaret. Den resulterende polymer, polynorbornen, har en meget høj glasovergangstemperatur, Tg, og interessante optiske og elektriske egenskaber. Imidlertid er polymerisationen af funktionelle norbomener ved denne mekanisme kompliceret af den omstændighed, at endo substitueret norbomen monomer har generelt en meget lav reaktivitet. Endvidere adskillelsen af endo substitueret monomer fra exo-monomeren er en kedelig opgave. Her præsenteres en simpel protokol til polymerisation af substituerede norbornener (endo: exo ca 80:20) bærer enten en carboxylsyre eller et vedhæng dobbeltbinding. Processen kræver ikke, at begge isomerer adskilles, og fortsætter med lave katalysatorfyldninger (0,01 til 0,02 mol%). De polymere bærende veant dobbeltbindinger kan yderligere omdannes i højt udbytte, hvilket gav en polymer bærende vedhæng epoxygrupper. Disse enkle procedurer kan anvendes til fremstilling af polynorbornenes med en række forskellige funktionelle grupper, såsom estere, alkoholer, imider, dobbeltbindinger, carboxylsyrer, brom-alkyler, aldehyder og anhydrider.

De NBE monomerer fremstilles ved simpel Diels-Alder-reaktion af DCPD og en egnet dienophil, fx acrylsyre (AA). Normalt er DCPD krakket til opnåelse cyclopentadien (CPD) inden reaktionen. 17 Frisk krakket CPD derefter engageret i Diels-Alder-reaktionen. Men i denne protokol, udføres både revner og Diels-Alder-trin samtidigt, i en one-pot-reaktion. Således så snart CPD er dannet, det reagerer med AA til dannelse 5-norbornen-2-carboxylsyre, NBE (CO 2 ...

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.

En enkel og effektiv protokol til katalytisk Indsættelse polymerisation af funktionelle norbornener

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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