Ethene−Norbornene Copolymerization with Homogeneous Metallocene and Half-Sandwich Catalysts:  Kinetics and Relationships between Catalyst Structure and Polymer Structure. 3. Copolymerization Parameters and Copolymerization Diagrams

Ruchatz, Dieter; Fink, Gerhard

doi:10.1021/ma971043b

Cited by 127 publications

(95 citation statements)

References 14 publications

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“…Although the activities of 12 and 13 were lower than that of 7 (but at a higher or similar level compared to CGC and DSBI), the results thus clearly indicate that the chlorinated phenoxy-modified Cp analogues, especially 12 and 13, showed the most efficient NBE incorporation compared with the others under these conditions. The 2,4,6-Cl3C6H2 analogue (13) showed higher catalytic activity than that of the 2,6-Cl2C6H3 analogue (12), whereas 12 showed better NBE incorporation than 13 under the same conditions (e.g., run 1 vs run 4). The activity (on the basis of polymer yields) of 13 at 40-60 °C was higher than that conducted at 25 °C; the activity of 12 at 40 °C was higher than that conducted at 25 °C.…”

Section: Efficient Norbornene (Nbe) Incorporation In Ethylene/nbe Copmentioning

confidence: 99%

“…Many have reported on ethylene copolymerization with norbornene (NBE) using ordinary metallocenes [10][11][12][13][14][15][16][17], half-titanocenes [18][19][20][21][22][23][24][25][26], and others [27][28][29][30], however, successful examples of the efficient synthesis of random, high molecular weight copolymers with high Tg values (high NBE content) have been limited. Ethylene copolymers with tetracyclododecene (TCD, dimethanooctahydronaphthalene) are also known as promising materials [9], and are produced by using classical Ziegler-type vanadium catalyst systems (VOCl3, VO(OEt)Cl2-EtAlCl2•Et2AlCl, etc.)…”

Section: Introductionmentioning

confidence: 99%

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Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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Abstract:Selected results for the synthesis of cyclic olefin copolymers (COCs)-especially copolymerizations of norbornene (NBE) or tetracyclododecene (TCD) with ethylene and α-olefins (1-hexene, 1-octene, 1-dodecene)-using group 4 transition metal (titanium and zirconium) complex catalysts have been reviewed. Half-titanocenes containing an anionic ancillary donor ligand, Cp'TiX 2 (Y) (Cp' = cyclopentadienyl; X = halogen, alkyl; Y = anionic donor ligand such as aryloxo, ketimide, imidazolin-2-iminato, etc.), are effective catalysts for efficient synthesis of new COCs; ligand modifications play an important role for the desired copolymerization. These new COCs possess promising properties (high transparency, thermal resistance (high glass transition temperature), low water absorption, etc.), thus it is demonstrated that the design of an efficient catalyst plays an essential role for the synthesis of new fine polyolefins with specified properties.

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Section: Efficient Norbornene (Nbe) Incorporation In Ethylene/nbe Copmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Zhao

Nomura

2016

Catalysts

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“…Different approaches have been described in the literature for determining the copolymerization parameters 2) . One of them is the linear method introduced by Kelen and Tüdös 3) , which we applied to ethene-norbornene copolymers in a previous paper 4) . Alternatively, the copolymerization parameters can be derived from the triad distribution, which can be determined by 13 C NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

13C NMR studies of ethene-norbornene copolymers: assignment of sequence distributions using13C-enriched monomers and determination of the copolymerization parameters

Wendt

Mynott

Hauschild

et al. 1999

Macromol. Chem. Phys.

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SUMMARY: Ethene and norbornene were copolymerized using metallocene catalysts that produce copolymers having isolated norbornene units or microblocks with a maximum of two norbornene units. The resonances of the norbornene C 5/6 and the ethene carbon atoms, which overlap extensively in the 13 C NMR spectrum, were differentiated and assigned by comparing the 13 C NMR spectra of the copolymers obtained from monomers having 13 C at natural abundance with those prepared from feedstocks containing 13 C 1 -enriched ethene or 13 C 5/6 -enriched norbornene. The NMR analysis revealed that the chemical shifts of the norbornene C 5/6 carbon atoms are triad sensitive and those of the ethene carbon atoms are pentad sensitive. 13C NMR analysis of copolymers containing isolated norbornene units in various proportions allowed the resonances of the norbornene C 5/6 and the ethene carbon atoms to be assigned to the respective triads and pentads. The complete triad distributions of these copolymers determined in this way were used to calculate the copolymerization parameters for a representative metallocene catalyst.

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“…Thermoplastic polymers recently synthesized by means of metallocene-based catalysts have attracted the attention of many researchers and producers. Particular interest has been focused on the synthesis and characterization of cycloolefin copolymers (COCs) [5][6][7][8][9][10][11][12][13], which are amorphous thermoplastics obtained by copolymerization of norbornene and ethylene.…”

Section: Introductionmentioning

confidence: 99%

Linear low density polyethylene/cycloolefin copolymer blends

Dorigato¹,

Pegoretti²,

Fambri³

et al. 2011

Express Polym. Lett.

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Abstract. Linear low density polyethylene (LLDPE) was melt compounded with various amounts of a cycloolefin copolymer (COC). Scanning and transmission electron microscopy evidenced, at qualitative level, some interfacial adhesion between LLDPE and COC. Another indication of interactions between the components was the increase of crystallinity degree with rising COC content and the enhancement of COC glass transition temperature with the LLDPE fraction. In order to explain this behaviour, the incorporation of ethylene segments of COC into the LLDPE crystalline phase, leading to an increased number of norbornene units in the remaining COC component undergoing the glass transition, was hypothesized. The thermo-oxidative degradation stability of LLDPE was substantially enhanced by COC introduction for filler contents higher than 20 wt%, especially when an oxidative atmosphere was considered. An increasing fraction of COC in the blends was responsible for an enhancement of the elastic modulus and of a decrease in the strain at break, while tensile strength passed through a minimum, in agreement with the model predictions based on the equivalent box model and equations provided by the percolation theory. The introduction of a rising COC amount in the blends increased the maximum load sustained by the samples in impact tests, but decreased the blend ductility. Concurrently, a significant reduction of the creep compliance of LLDPE was observed for COC fractions higher than 20 wt%.

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Ethene−Norbornene Copolymerization with Homogeneous Metallocene and Half-Sandwich Catalysts: Kinetics and Relationships between Catalyst Structure and Polymer Structure. 3. Copolymerization Parameters and Copolymerization Diagrams

Cited by 127 publications

References 14 publications

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

Design of Efficient Molecular Catalysts for Synthesis of Cyclic Olefin Copolymers (COC) by Copolymerization of Ethylene and α-Olefins with Norbornene or Tetracyclododecene

13C NMR studies of ethene-norbornene copolymers: assignment of sequence distributions using13C-enriched monomers and determination of the copolymerization parameters

Linear low density polyethylene/cycloolefin copolymer blends

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