Synthesis of Low Density Poly(ethylene) Using Nickel Iminophosphonamide Complexes

Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with T...

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Published in:Macromolecules 2007-05, Vol.40 (9), p.2993-3004
Main Authors: Stapleton, Russell A., Chai, Jianfang, Nuanthanom, Anuttra, Flisak, Zygmunt, Nele, Marcio, Ziegler, Tom, Rinaldi, Peter L., Soares, Joao B. P., Collins, Scott
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Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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cited_by cdi_FETCH-LOGICAL-a289t-8f62ea2967f02c5fe28d7cd11d5ebe09566367eb25d10440df30c8caf76483f33
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creator Stapleton, Russell A.
Chai, Jianfang
Nuanthanom, Anuttra
Flisak, Zygmunt
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Ziegler, Tom
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Collins, Scott
description Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with T m < 100 °C. High field 13C NMR spectra reveal the presence of methyl branches (ca. 10−15 per 1000 C atoms), branches longer than six C atoms (15−20 per 1000 C atoms) and trace levels of ethyl, propyl, n-butyl, and sec-butyl branches (total
doi_str_mv 10.1021/ma062332f
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P. ; Collins, Scott</creator><creatorcontrib>Stapleton, Russell A. ; Chai, Jianfang ; Nuanthanom, Anuttra ; Flisak, Zygmunt ; Nele, Marcio ; Ziegler, Tom ; Rinaldi, Peter L. ; Soares, Joao B. P. ; Collins, Scott</creatorcontrib><description>Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with T m &lt; 100 °C. High field 13C NMR spectra reveal the presence of methyl branches (ca. 10−15 per 1000 C atoms), branches longer than six C atoms (15−20 per 1000 C atoms) and trace levels of ethyl, propyl, n-butyl, and sec-butyl branches (total &lt;2 per 1000 C atoms). The branching distribution changes modestly in response to changes in ethylene pressure in a manner consistent with a chain-walking mechanism. Analysis of high MW polymers by GPC-light scattering reveals the presence of sparse long-chain branching (g M = 0.78−0.93 with &lt;1 long-chain branch per molecule); the branched PE formed is thus similar to low-density PE. Addition of α-olefin during polymerization leads to enhanced activity but is accompanied by chain transfer. The only evidence of α-olefin incorporation is at the chain-ends in the case of 4-methylpentene, and there is little change to the branching distribution in the presence of α-olefin. A sterically hindered nickel iminophosphonamide (PN2) complex (Me3Si)2NP(Me)(NSiMe3)2NiPh(PPh3) (2) was prepared and characterized by X-ray crystallography. This complex oligomerizes ethylene to branched material with a microstructure very similar to that observed using the catalysts derived from phosphorane 1 and Ni(COD)2 or (π-allyl)2Ni. DFT modeling of the active catalyst, coupled with stochastic simulation of chain growth, reveals that a chain-walking vs insertion mechanism can account for the short-chain branching distributions observed. Kinetic modeling of the observed branching distribution can account for relative intensity of the short branches (≤C5) as well as those of the longer branches. However, in order to fit the intensity of the Hx+ branches, one of the key parameters in the model, the probability of chain-walking for higher secondary Ni−R groups, converges to a value ∼ 1. 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P.</creatorcontrib><creatorcontrib>Collins, Scott</creatorcontrib><title>Synthesis of Low Density Poly(ethylene) Using Nickel Iminophosphonamide Complexes</title><title>Macromolecules</title><addtitle>Macromolecules</addtitle><description>Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with T m &lt; 100 °C. High field 13C NMR spectra reveal the presence of methyl branches (ca. 10−15 per 1000 C atoms), branches longer than six C atoms (15−20 per 1000 C atoms) and trace levels of ethyl, propyl, n-butyl, and sec-butyl branches (total &lt;2 per 1000 C atoms). The branching distribution changes modestly in response to changes in ethylene pressure in a manner consistent with a chain-walking mechanism. Analysis of high MW polymers by GPC-light scattering reveals the presence of sparse long-chain branching (g M = 0.78−0.93 with &lt;1 long-chain branch per molecule); the branched PE formed is thus similar to low-density PE. Addition of α-olefin during polymerization leads to enhanced activity but is accompanied by chain transfer. The only evidence of α-olefin incorporation is at the chain-ends in the case of 4-methylpentene, and there is little change to the branching distribution in the presence of α-olefin. A sterically hindered nickel iminophosphonamide (PN2) complex (Me3Si)2NP(Me)(NSiMe3)2NiPh(PPh3) (2) was prepared and characterized by X-ray crystallography. This complex oligomerizes ethylene to branched material with a microstructure very similar to that observed using the catalysts derived from phosphorane 1 and Ni(COD)2 or (π-allyl)2Ni. DFT modeling of the active catalyst, coupled with stochastic simulation of chain growth, reveals that a chain-walking vs insertion mechanism can account for the short-chain branching distributions observed. Kinetic modeling of the observed branching distribution can account for relative intensity of the short branches (≤C5) as well as those of the longer branches. However, in order to fit the intensity of the Hx+ branches, one of the key parameters in the model, the probability of chain-walking for higher secondary Ni−R groups, converges to a value ∼ 1. 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P.</au><au>Collins, Scott</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Low Density Poly(ethylene) Using Nickel Iminophosphonamide Complexes</atitle><jtitle>Macromolecules</jtitle><addtitle>Macromolecules</addtitle><date>2007-05-01</date><risdate>2007</risdate><volume>40</volume><issue>9</issue><spage>2993</spage><epage>3004</epage><pages>2993-3004</pages><issn>0024-9297</issn><eissn>1520-5835</eissn><coden>MAMOBX</coden><abstract>Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with T m &lt; 100 °C. High field 13C NMR spectra reveal the presence of methyl branches (ca. 10−15 per 1000 C atoms), branches longer than six C atoms (15−20 per 1000 C atoms) and trace levels of ethyl, propyl, n-butyl, and sec-butyl branches (total &lt;2 per 1000 C atoms). The branching distribution changes modestly in response to changes in ethylene pressure in a manner consistent with a chain-walking mechanism. Analysis of high MW polymers by GPC-light scattering reveals the presence of sparse long-chain branching (g M = 0.78−0.93 with &lt;1 long-chain branch per molecule); the branched PE formed is thus similar to low-density PE. Addition of α-olefin during polymerization leads to enhanced activity but is accompanied by chain transfer. The only evidence of α-olefin incorporation is at the chain-ends in the case of 4-methylpentene, and there is little change to the branching distribution in the presence of α-olefin. A sterically hindered nickel iminophosphonamide (PN2) complex (Me3Si)2NP(Me)(NSiMe3)2NiPh(PPh3) (2) was prepared and characterized by X-ray crystallography. This complex oligomerizes ethylene to branched material with a microstructure very similar to that observed using the catalysts derived from phosphorane 1 and Ni(COD)2 or (π-allyl)2Ni. DFT modeling of the active catalyst, coupled with stochastic simulation of chain growth, reveals that a chain-walking vs insertion mechanism can account for the short-chain branching distributions observed. Kinetic modeling of the observed branching distribution can account for relative intensity of the short branches (≤C5) as well as those of the longer branches. However, in order to fit the intensity of the Hx+ branches, one of the key parameters in the model, the probability of chain-walking for higher secondary Ni−R groups, converges to a value ∼ 1. This finding is not anticipated by the DFT results and suggests that the longer branches present in these materials do not form by a chain-walking vs insertion mechanism.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ma062332f</doi><tpages>12</tpages></addata></record>
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subjects Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
title Synthesis of Low Density Poly(ethylene) Using Nickel Iminophosphonamide Complexes
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