Ethylene polymerisation by Ni-diphosphine azine complexes

The properties of [NiX(PR2CH2C(But)NNC(But)CH2PR2)]+ complexes (where X = Br, and R = cyclohexyl (Cy), isopropyl (Pri), tert‐butyl (But), phenyl (Ph); X = Cl or I, and R = cyclohexyl) as catalysts for the polymerisation of ethylene were evaluated with or without the co‐catalysts methylaluminoxane...

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Veröffentlicht in:	Polymer international 2007-05, Vol.56 (5), p.613-620
Hauptverfasser:	Carvalho, Maria Fernanda Nascimento Neves, Cermák, Jan, Fernandes, Anabela Catarino, Ferreira, Ana Sofia, Galvão, Adelino Moura, Matos, Inês, Marques, Maria Mercês
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Schlagworte:	Applied sciences catalysis ethylene Exact sciences and technology Ni complexes Organic polymers Physicochemistry of polymers polyethylene polymerisation Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts theoretical calculations
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creator	Carvalho, Maria Fernanda Nascimento Neves Cermák, Jan Fernandes, Anabela Catarino Ferreira, Ana Sofia Galvão, Adelino Moura Matos, Inês Marques, Maria Mercês
description	The properties of [NiX(PR2CH2C(But)NNC(But)CH2PR2)]+ complexes (where X = Br, and R = cyclohexyl (Cy), isopropyl (Pri), tert‐butyl (But), phenyl (Ph); X = Cl or I, and R = cyclohexyl) as catalysts for the polymerisation of ethylene were evaluated with or without the co‐catalysts methylaluminoxane (MAO), diethylaluminium chloride, trimethylaluminium or tri(isobutyl)aluminium. Their efficiency depends on the characteristics of the halogen (X) and the R group of the diphosphine azine ligand. Bromide (X) strongly enhances the catalytic properties of the complexes within the R order Cy > Pri > Ph > But. Temperature, co‐catalyst ratio (Al/Ni) and complex concentration also influence the catalytic activity. The best results were obtained with [NiBr{PCy2CH2C(But)NNC(But)CH2PCy2}]Br activated by MAO (A = 25.8 kg (mol Ni)−1 bar−1 h−1). The polymers were characterised using NMR and differential scanning calorimetry as branched polyethylenes, the number of branches increasing with the temperature of polymerisation. The molecular weights of the polymers were estimated using NMR. A proposal for the catalyst active precursor is made on the basis of experimental data and molecular orbital calculations. Copyright © 2007 Society of Chemical Industry
doi_str_mv	10.1002/pi.2177
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Their efficiency depends on the characteristics of the halogen (X) and the R group of the diphosphine azine ligand. Bromide (X) strongly enhances the catalytic properties of the complexes within the R order Cy > Pri > Ph > But. Temperature, co‐catalyst ratio (Al/Ni) and complex concentration also influence the catalytic activity. The best results were obtained with [NiBr{PCy2CH2C(But)NNC(But)CH2PCy2}]Br activated by MAO (A = 25.8 kg (mol Ni)−1 bar−1 h−1). The polymers were characterised using NMR and differential scanning calorimetry as branched polyethylenes, the number of branches increasing with the temperature of polymerisation. The molecular weights of the polymers were estimated using NMR. A proposal for the catalyst active precursor is made on the basis of experimental data and molecular orbital calculations. 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Int</addtitle><description>The properties of [NiX(PR2CH2C(But)NNC(But)CH2PR2)]+ complexes (where X = Br, and R = cyclohexyl (Cy), isopropyl (Pri), tert‐butyl (But), phenyl (Ph); X = Cl or I, and R = cyclohexyl) as catalysts for the polymerisation of ethylene were evaluated with or without the co‐catalysts methylaluminoxane (MAO), diethylaluminium chloride, trimethylaluminium or tri(isobutyl)aluminium. Their efficiency depends on the characteristics of the halogen (X) and the R group of the diphosphine azine ligand. Bromide (X) strongly enhances the catalytic properties of the complexes within the R order Cy > Pri > Ph > But. Temperature, co‐catalyst ratio (Al/Ni) and complex concentration also influence the catalytic activity. The best results were obtained with [NiBr{PCy2CH2C(But)NNC(But)CH2PCy2}]Br activated by MAO (A = 25.8 kg (mol Ni)−1 bar−1 h−1). The polymers were characterised using NMR and differential scanning calorimetry as branched polyethylenes, the number of branches increasing with the temperature of polymerisation. The molecular weights of the polymers were estimated using NMR. A proposal for the catalyst active precursor is made on the basis of experimental data and molecular orbital calculations. Copyright © 2007 Society of Chemical Industry</description><subject>Applied sciences</subject><subject>catalysis</subject><subject>ethylene</subject><subject>Exact sciences and technology</subject><subject>Ni complexes</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>polyethylene</subject><subject>polymerisation</subject><subject>Polymerization</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><subject>theoretical calculations</subject><issn>0959-8103</issn><issn>1097-0126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><recordid>eNp10DFPwzAQhmELgUQpiL_QBRhQytlJ7HhEUEqrqjAUwWa5zlk1pEmIU9Hw60mVCiaWu-XRO3yEnFMYUgB2U7oho0IckB4FKQKgjB-SHshYBgmF8JiceP8OAImUskfkqF41GeY4KIusWWPlvK5dkQ-WzWDugtSVq8KXK9cC_b27pliXGW7Rn5IjqzOPZ_vfJy8Po8XdYzB7Gk_ubmeBCTmIgMvEypALGQGmjEVWo6YWeGKphiQBXPI4TjWLtUVmEU2aAhobhcIKHTET9sll1y2r4nODvlZr5w1mmc6x2HjFpGBMUtrCqw6aqvC-QqvKyq111SgKajeNKp3aTdPKi31Se6MzW-ncOP_HE86Bt1v1yXXnvlyGzX859TzZV4NOO1_j9lfr6kNxEYpYvc7Hai6mC37_NlPT8AcrS4CW</recordid><startdate>200705</startdate><enddate>200705</enddate><creator>Carvalho, Maria Fernanda Nascimento Neves</creator><creator>Cermák, Jan</creator><creator>Fernandes, Anabela Catarino</creator><creator>Ferreira, Ana Sofia</creator><creator>Galvão, Adelino Moura</creator><creator>Matos, Inês</creator><creator>Marques, Maria Mercês</creator><general>John Wiley & Sons, Ltd</general><general>Wiley</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7SR</scope><scope>8FD</scope><scope>F28</scope><scope>FR3</scope><scope>JG9</scope></search><sort><creationdate>200705</creationdate><title>Ethylene polymerisation by Ni-diphosphine azine complexes</title><author>Carvalho, Maria Fernanda Nascimento Neves ; Cermák, Jan ; Fernandes, Anabela Catarino ; Ferreira, Ana Sofia ; Galvão, Adelino Moura ; Matos, Inês ; Marques, Maria Mercês</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3607-698f9367940ed224faea1f068f1a0880eb655da25afe2feecdd0ecf437f7a42c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>Applied sciences</topic><topic>catalysis</topic><topic>ethylene</topic><topic>Exact sciences and technology</topic><topic>Ni complexes</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>polyethylene</topic><topic>polymerisation</topic><topic>Polymerization</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><topic>theoretical calculations</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Carvalho, Maria Fernanda Nascimento Neves</creatorcontrib><creatorcontrib>Cermák, Jan</creatorcontrib><creatorcontrib>Fernandes, Anabela Catarino</creatorcontrib><creatorcontrib>Ferreira, Ana Sofia</creatorcontrib><creatorcontrib>Galvão, Adelino Moura</creatorcontrib><creatorcontrib>Matos, Inês</creatorcontrib><creatorcontrib>Marques, Maria Mercês</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer international</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Carvalho, Maria Fernanda Nascimento Neves</au><au>Cermák, Jan</au><au>Fernandes, Anabela Catarino</au><au>Ferreira, Ana Sofia</au><au>Galvão, Adelino Moura</au><au>Matos, Inês</au><au>Marques, Maria Mercês</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ethylene polymerisation by Ni-diphosphine azine complexes</atitle><jtitle>Polymer international</jtitle><addtitle>Polym. Int</addtitle><date>2007-05</date><risdate>2007</risdate><volume>56</volume><issue>5</issue><spage>613</spage><epage>620</epage><pages>613-620</pages><issn>0959-8103</issn><eissn>1097-0126</eissn><abstract>The properties of [NiX(PR2CH2C(But)NNC(But)CH2PR2)]+ complexes (where X = Br, and R = cyclohexyl (Cy), isopropyl (Pri), tert‐butyl (But), phenyl (Ph); X = Cl or I, and R = cyclohexyl) as catalysts for the polymerisation of ethylene were evaluated with or without the co‐catalysts methylaluminoxane (MAO), diethylaluminium chloride, trimethylaluminium or tri(isobutyl)aluminium. Their efficiency depends on the characteristics of the halogen (X) and the R group of the diphosphine azine ligand. Bromide (X) strongly enhances the catalytic properties of the complexes within the R order Cy > Pri > Ph > But. Temperature, co‐catalyst ratio (Al/Ni) and complex concentration also influence the catalytic activity. The best results were obtained with [NiBr{PCy2CH2C(But)NNC(But)CH2PCy2}]Br activated by MAO (A = 25.8 kg (mol Ni)−1 bar−1 h−1). The polymers were characterised using NMR and differential scanning calorimetry as branched polyethylenes, the number of branches increasing with the temperature of polymerisation. The molecular weights of the polymers were estimated using NMR. A proposal for the catalyst active precursor is made on the basis of experimental data and molecular orbital calculations. Copyright © 2007 Society of Chemical Industry</abstract><cop>Chichester, UK</cop><pub>John Wiley & Sons, Ltd</pub><doi>10.1002/pi.2177</doi><tpages>8</tpages></addata></record>
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subjects	Applied sciences catalysis ethylene Exact sciences and technology Ni complexes Organic polymers Physicochemistry of polymers polyethylene polymerisation Polymerization Preparation, kinetics, thermodynamics, mechanism and catalysts theoretical calculations
title	Ethylene polymerisation by Ni-diphosphine azine complexes
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