Ethylene–co–norbornene copolymerization in the presence of a chain transfer agent

Boggioni, Laura; Sidari, Diego; Losio, Simona; Stehling, Udo; Auriemma, Finizia; Girolamo, Rocco Di; Rosa, Claudio De; Tritto, Incoronata

doi:10.1016/j.eurpolymj.2018.07.037

Cited by 17 publications

(27 citation statements)

References 38 publications

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“…The E-NB copolymers obtained over the homogeneous catalytic systems with the highest comonomer degree were amorphous ( Figure 5 a,c and Figures S28–S31 in the Supplementary File ). The similar results are observed in case of ethylene copolymerization with norbornene over homogeneous metallocene catalytic systems [ 6 ]. Noteworthy is that the E-NB copolymers synthesized using the immobilized catalytic systems ( SIL/C4 , SIL/C5 and SIL/C6 ) are characterized by generally increased intensity of melting peak, what is atypical behavior of the E-NB copolymers ( Figure 5 b,d and Figure S32 in the Supplementary File ).…”

Section: Resultssupporting

confidence: 85%

“…13 C NMR spectra were referenced internally to the 13 C resonances of the NMR solvent. The norbornene content in copolymers was calculated according to the formula [2 I ( C7 ) + I ( C1 – C2 ) + I ( C2 – C3 )] × 100/3 I (CH 2 ), where I (CH 2 ), I ( C7 ), I ( C1 – C2 ) and I ( C2 – C3 ) are the peak areas in the ranges 26–30, 30–36, 34–42 and 43–54 ppm of 13 C NMR spectra [ 6 , 47 ].…”

Section: Methodsmentioning

confidence: 99%

“…The COCs produced by copolymerization of ethylene with norbornene are one of few examples of copolymers industrially produced using metallocene catalysts with trade names TOPAS (by TOPAS Advanced Polymers GmbH) [ 3 , 4 ] and APEL (by Mitsui Chemicals, Inc.) [ 5 ]. Poly(ethylene-co-norbornene) materials show many interesting properties like a moisture barrier (4–5 times higher than low density polyethylene (LDPE)) [ 3 ], good solvent resistance, facile processability, high thermal stability, transparency and stiffness [ 6 ]. These copolymers are a promising class of thermoplastics, ranging from highly crystalline solids to elastomers, whose properties depend on the norbornene content and copolymer microstructure [ 7 , 8 , 9 , 10 ].…”

Section: Introductionmentioning

confidence: 99%

“…The main characteristics of these materials are directly linked to cyclic comonomer content, sequence distribution (isolated ENE units, alternating NEN units or presence of NN dyads and NNN triads), as well as a stereochemical arrangement of norbornene units. It is important to determine the microstructure of copolymers in order to understand their different polymer properties, so that to improve significantly their commercial use [ 6 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

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Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

et al. 2020

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The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discussed. In addition, the thermal properties of E-NB copolymers such as the melting and crystallization behavior, like also the heterogeneity of composition described by successive the self-nucleation and annealing (SSA) and the dispersity index (DI) were determined.

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Section: Resultssupporting

confidence: 85%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

et al. 2020

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“…Probably for these reasons, chain-shuttling copolymerization of norbornene (N) and ethylene (E), made possible by the discovery of metallocene catalysis by Kaminsky [25,26,27,28,29,30,31], has remained unexplored to date. For example, while there are significant studies on chain-growth termination and chain-transfer reactions for homo- and copolymerizations of α-olefins with transition metal catalysts, only one study on the exchange of ethylene- co -norbornene polymer chain between ansa-zirconocene catalysts and aluminum or zinc alkyls was found in the literature [32] before our recent studies [33].…”

Section: Introductionmentioning

confidence: 99%

Ethylene-co-norbornene Copolymerization Using a Dual Catalyst System in the Presence of a Chain Transfer Agent

et al. 2019

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Ethylene-co-norbornene copolymers were synthesized by a dual catalyst system at three concentrations of norbornene in the feed and variable amounts of ZnEt2, as a possible chain transfer agent. The dual catalyst system consists of two ansa-metallocenes, isopropyliden(η5-cyclopentadienyl)(η5-indenyl)zirconium dichloride (1) and isopropyliden(η5-3-methylcyclopentadienyl)(η5-fluorenyl)zirconium dichloride (2), activated with dimethylanilinium tetrakis(pentafluorophenyl)borate, in presence of TIBA. Values of norbornene content, molecular mass, glass transition temperature, and reactivity ratios r11 and r21 of copolymers prepared in the presence of 1+2 are intermediate between those of reference copolymers. The study of tensile and elastic properties of ethylene-co-norbornene copolymers (poly(E-co-N)s) gave evidence that copolymers were obtained in part through transfer of polymer chains between different transition metal sites. Mechanical properties are clearly different from those expected from a blend of the parent samples and reveal that copolymers obtained in the presence of 1+2 and ZnEt2 consist of a reactor blend of segmented chains produced by exchange from 2 to 1 and 1 to 2 acting as the ideal compatibilizer of chains produced by the chain transfer from 1 to 1, and from 2 to 2.

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Crystallinity in quasi‐alternating cycloolefin copolymers: Overcoming brittleness

Moon

Park

Baek

et al. 2020

Journal of Polymer Science

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Cycloolefin copolymers (COCs, which are produced via ethylene/cycloolefin copolymerization) and cycloolefin polymers (COPs, which are synthesized by a rather complicated two‐step process via ring‐opening metathesis polymerization and subsequent hydrogenation) are commercialized materials used especially widely in optical applications. Although a COP can be used after processing into a film, films made from conventional COCs are too brittle. Optical‐grade COCs and COPs are generally known as amorphous polymers. By contrast, here, a quasi‐alternating ethylene/norbornene copolymer (norbornene content 56 mol%), prepared from a constrained‐geometry Hf complex, shows some melting (Tm) signals in a broad temperature range (150–200°C) in the first heating scan of differential scanning calorimetry (DSC) when the samples are prepared by precipitation from a toluene solution. In the second heating scan, only glass transition (Tg) signals are observed at ~140°C with disappearance of Tm signals. The quasi‐alternating ethylene/norbornene copolymer has better mechanical properties (greater elongation at break) than random congeners, which do not show any melting signal, though elongation at break is still inferior to that of the COP which shows the melting signal in the first heating scan of DSC. The enhanced mechanical properties of the quasi‐alternating ethylene/norbornene copolymer and commercial‐grade COP may be ascribed to semicrystallinity observed in the first heating scan.

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Ethylene–co–norbornene copolymerization in the presence of a chain transfer agent

Cited by 17 publications

References 38 publications

Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

Ethylene-co-norbornene Copolymerization Using a Dual Catalyst System in the Presence of a Chain Transfer Agent

Crystallinity in quasi‐alternating cycloolefin copolymers: Overcoming brittleness

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