Name: ethylene polymerizations using parallel pressure reactors and a kinetic analysis of chain transfer polymerization
Uploaded: 2015-11-27T13:00:00
Description: Watch this Scientific Journal Video about Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization at JoVE.com

Den økonomiske støtte blev leveret af University of Minnesota (opstart fonde) og ACS Petroleum Research Fund (54225-DNI3). Udstyr køb for Kemi Institut NMR-faciliteten blev støttet gennem en bevilling fra NIH (S10OD011952) med matchende midler fra University of Minnesota. Vi anerkender Minnesota NMR Center for høj temperatur NMR. Finansiering af NMR instrumentering blev leveret af kontoret for vicepræsident for forskning, Medical School, College of Biological Science, NIH, NSF, og Minnesota Medical Foundation. Vi takker John Walzer (ExxonMobil) for en gave af PEEK højt gennemløb omrøring pagajer.

Forsigtig: Se venligst alle relevante materiale sikkerhedsdatablade (MSDS) før brug. Flere af de kemikalier, der anvendes i disse synteser er akut giftige og kræftfremkaldende, mens flere er pyrofore og antænde i luft. Brug venligst alle passende sikkerhedsforanstaltninger, når du udfører disse reaktioner herunder anvendelse af tekniske kontroller (stinkskab, Handskerum) og personlige værnemidler (sikkerhedsbriller, handsker, kittel, fuld længde bukser, lukket tå sko). Dele af de følgende fremgangsmåder involv...

<ol>
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En methyl-substitueret kationisk [α-diimin] NIBR 2 ethylen polymeriseringskatalysator aktiveret med MAO blev undersøgt for sin kompetence for ethylen kæde transfer polymerisationer. Reaktionerne blev overvåget via gasoptagelse målinger til at bestemme hastigheden og omfanget af polymerisering og katalysator levetid, og molekylvægten af de resulterende polymerer blev bestemt via gelpermeationskromatografi (GPC). I første omgang blev nikkelkatalysatoren testet over en...

Polyolefiner er en vigtig klasse af industrielle polymerer med anvendelser i termoplast og elastomerer. Betydelige fremskridt i udformningen af single-site katalysator til fremstilling af polyolefiner har ført til evnen til at tune molekylvægt, polydispersitet og polymer mikrostruktur, hvilket fører til en bred vifte af potentielle anvendelsesmuligheder. 1-3 For nylig, kædeoverførsel og kæde shuttling polymerisationer er blevet udviklet for at give en ekstra vej til at modificere egenskaberne af polymeren, uden at ændre katalysatoren. 4-6 Dette system anvender en enkelt-site overgangsmetalkatalysator og en kæde overførsel reagens (CTR), som typisk er en hovedgruppe metalalkyl. I løbet af denne polymerisation, den voksende polymerkæde er i stand til at overføre fra katalysatoren til CTR, hvor polymerkæden forbliver i dvale, indtil den overføres tilbage til katalysatoren. I mellemtiden kan alkylgruppen, der blev overført til katalysatoren initiere another polymerkæde. I en kædeoverførsel polymerisation, kan man katalysatoren sætte større antal kæder i forhold til en standard katalytisk polymerisation. Polymerkæderne termineres med kæden overførsel metal; derfor yderligere endegruppe-funktionalisering er mulig. Dette system kan anvendes til at ændre den molekylære vægt og molekylvægtsfordeling af polyolefiner, 7 at katalysere Aufbau-lignende alkylkæde vækst hovedgruppemetaller, 8 og til syntese af specialpolymerer involverer multicatalyst systemer, såsom blokcopolymerer. 9, 10 Kædeoverførselsmidler polymerisationer er blevet observeret hyppigst med tidlig overgangsmetaller (Hf, Zr) og alkylzinc eller alkylaluminiumforbindelser reagenser, selv om der findes eksempler på tværs overgangsmetallet serien. 5,7,8,11-16 I typiske tidlige overgangsmetalkatalysator systemer, kæde overførsel er hurtig, effektiv og reversibel fører til snævre molekylvægtsfordelinger. Chain overførsel / shuttling er blevet observeret i midten til slutningen af overgangsmetaller (f.eks Cr, Fe, Co og Ni) med gruppe 2 og 12 metalalkyler, selv om satserne for overførsel er meget varierende i forhold til begyndelsen af metaller. 4,7, 17-19 To hovedfaktorer er tilsyneladende nødvendig for en effektiv kædeoverførsel: et godt match af metal-carbon-binding dissociation energier for polymerisationskatalysator og kædeoverførsel reagens, og en passende sterisk miljø for at fremme dannelsen bimolekylære / brud på alkyl-bro bimetalliske mellemprodukter . 20 I tilfælde af sen overgangsmetaller, hvis katalysatoren ikke indeholder nok sterisk bulk, beta-hydrid (β-H) eliminering vil være den dominerende ophør pathway og vil generelt udkonkurrere kædeoverførsel. Heri vi rapportere om en undersøgelse af bimetallisk kæde overførsel fra nikkel til zink i en bis (2,6-dimethylphenyl) -2,3-butanediimine katalysator-system med diethylzink (ZNet 2) gennem small-skala med højt gennemløb reaktioner. Kædeoverførsel vil blive identificeret ved at undersøge ændringer i molekylvægt (Mw) og dispersitet indeks for den resulterende polyethylen gennem gelpermeationschromatografi analyse. Kædeoverførsel vil også identificeres ved 13C NMR-analyse af forholdet mellem vinyl mættede kædeender som en funktion af koncentration kædeoverføringsmiddel. En tilbundsgående kinetisk analyse af satserne for formering og kæde overførsel vil også blive præsenteret.

<table border="0" cellpadding="0" cellspacing="0" style="width:675px;" width="674">
	<tbody>
		<tr height="25">
			<td height="25" style="height:25px;width:209px;">Endeavor Pressure Reactor</td>
			<td style="width:119px;">Biotage</td>
			<td style="width:107px;">EDV-1N-L</td>
			<td style="width:240px;"></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Blade Impellers</td>
			<td>Biotage</td>
			<td>900543</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Glass Liners</td>
			<td>Biotage</td>
			<td>900676</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">2,3-butanedione, 99%</td>
			<td>Alfa Aesar</td>
			<td>A14217</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">2,6-dimethylaniline, 99%</td>
			<td>Sigma Aldrich</td>
			<td>D146005</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">formic acid, 95%</td>
			<td>Sigma Aldrich</td>
			<td>F0507</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">methanol, 99.8%</td>
			<td>Sigma Aldrich</td>
			<td>179337</td>
			<td>ACS Reagent</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">nickel (II) bromide, 99%</td>
			<td>Strem</td>
			<td>28-1140</td>
			<td>anhydrous, hygroscopic</td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;">triethylorthoformate, 98%</td>
			<td>Sigma Aldrich</td>
			<td>304050</td>
			<td>dried with K2CO3 and distilled</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">1,2-dimethoxyethane, 99.5%</td>
			<td>Sigma Aldrich</td>
			<td>259527</td>
			<td>dried with Na/Benzophenone and distilled</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">pentane, 99%</td>
			<td>Fisher</td>
			<td>P399</td>
			<td>HPLC Grade *</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">dichloromethane, 99.5%</td>
			<td>Fisher</td>
			<td>D37</td>
			<td>ACS Reagent *</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">toluene, 99.8%</td>
			<td>Fisher</td>
			<td>T290</td>
			<td>HPLC Grade *</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">methylaluminoxane</td>
			<td>Albemarle</td>
			<td>MAO</td>
			<td>pyrophoric, 30% in toluene</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">diethylzinc, 95%</td>
			<td>Strem</td>
			<td>93-3030</td>
			<td>pyrophoric</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">1,2,4-trichlorobenzene, 99%</td>
			<td>Sigma Aldrich</td>
			<td>296104</td>
			<td></td>
		</tr>
		<tr height="26">
			<td height="26" style="height:26px;">1,1,2,2-tetrachloroethane-D2, 99.6%</td>
			<td>Cambridge Isotopes</td>
			<td>DLM-35</td>
			<td></td>
		</tr>
	</tbody>
</table>

ethylene polymerizations using parallel pressure reactors and a kinetic analysis of chain transfer polymerization

Vi viser en fremgangsmåde til high-throughput screening katalysator bruger et parallelt trykreaktor fra det indledende syntese af en nikkel α-diimin ethylen polymerisationskatalysator. Indledende polymerisationer med katalysatoren fører til optimerede reaktionsbetingelser, herunder katalysatorkoncentration, ethylen tryk og reaktionstid. Ved hjælp af gas-uptake data for disse reaktioner, en procedure beregne den indledende sats for formering (k p) præsenteres. Brug af optimerede betingelser, evnen af nikkel α-diimin polymerisationskatalysator undergå kædeoverførsel med diethylzink (ZNet 2) under ethylenpolymerisation blev undersøgt. En procedure til at vurdere evnen af katalysatoren til at gennemgå kædeoverførsel (fra molekylvægt og 13 C-NMR-data), beregne graden af kædeoverførsel og beregne kæde overførselshastigheder (k e) præsenteres.

Forbruget ethylengas versus tid er vist i figur 1 for de forskellige testede ethylen tryk. Disse data anvendes til at bestemme optimerede reaktionsbetingelser. Forbruget ethylengas mod tiden er præsenteret i figur 2A til katalysatoren alene prøver, der anvendes til at beregne hastigheden af formering (k p). Figur 2B viser gelpermeationskromatografi (GPC) spor til kæde transfer polymeriseringer med 0-1,000 ækvivalenter af diethylz...

Watch this Scientific Journal Video about Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization at JoVE.com

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

En protokol for high-throughput analyse af polymerisationskatalysator, kædeoverførselsmidler polymerisationer, polyethylen karakterisering og reaktionen kinetisk analyse præsenteres.

Ethylen Polymeriseringer Brug Parallel Pressure reaktorer og en Kinetic Analyse af Chain Transfer Polymerisation

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

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