Kinetic and microstructure studies of poly (ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts with constrained ligand geometry

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Abstract

This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4(SiMe2NtBu)]-TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-co-p-methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co-p-methylstyrene) copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol % of p-methylstyrene, the crystallinity of copolymer almost completely disappears.

Original languageEnglish (US)
Pages (from-to)1017-1029
Number of pages13
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume36
Issue number6
DOIs
StatePublished - Apr 30 1998

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Ethylene
Copolymers
Ligands
Microstructure
Catalysts
Kinetics
Geometry
Derivatives
Chemical analysis
Copolymerization
Melting point
Molecular weight
Nuclear magnetic resonance
ethylene
metallocene
vinyltoluene

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

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title = "Kinetic and microstructure studies of poly (ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts with constrained ligand geometry",
abstract = "This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4(SiMe2NtBu)]-TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-co-p-methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co-p-methylstyrene) copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol {\%} of p-methylstyrene, the crystallinity of copolymer almost completely disappears.",
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N2 - This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4(SiMe2NtBu)]-TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-co-p-methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co-p-methylstyrene) copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol % of p-methylstyrene, the crystallinity of copolymer almost completely disappears.

AB - This paper discusses the poly(ethylene-co-p-methylstyrene) copolymers prepared by metallocene catalysts, such as Et(Ind)2ZrCl2 and [C5Me4(SiMe2NtBu)]-TiCl2, with constrained ligand geometry. The copolymerization reaction was examined by comonomer reactivity (reactivity ratio and comonomer conversion versus time), copolymer microstructure (DSC and 13C-NMR analyses) and the comparisons between p-methylstyrene and other styrene-derivatives (styrene, o-methylstyrene and m-methylstyrene). The combined experimental results clearly show that p-methylstyrene performs distinctively better than styrene and its derivatives, due to the cationic coordination mechanism and spatially opened catalytic site in metallocene catalysts with constrained ligand geometry. A broad composition range of random poly(ethylene-co-p-methylstyrene) copolymers were prepared with narrow molecular weight and composition distributions. With the increase of p-methylstyrene concentration, poly(ethylene-co-p-methylstyrene) copolymer shows systematical decrease of melting point and crystallinity and increase of glass transition temperature. At above 10 mol % of p-methylstyrene, the crystallinity of copolymer almost completely disappears.

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