Polynorbornene: synthesis, properties and simulations

Haselwander, Thomas; Heitz, Walter; Krügel, Stefan A.; Wendorff, Joachim H.

doi:10.1002/macp.1996.021971029

Cited by 186 publications

(162 citation statements)

References 26 publications

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“…Both spectra display two broad halos at 2u of 10 and 18.5Њ that can be attributed to a short range order. This is in agreement with the results reported by Haselwender et al [4]. No traces of Bragg reflections, characteristic of crystalline regions, are revealed.…”

Section: X-ray Diffraction and Polymer Packingsupporting

confidence: 94%

“…The polynorbornene is therefore non-crystalline. Haselwander et al [4] state that the two amorphous halos shown by polynorbornene are of intrachain nature, according to the specific structural information provided by the amorphous cell calculation. Nevertheless we tend to believe, in accordance with the investigations of polystyrene [14] and other polymers [15], that at least one amorphous halo, the one at relatively low angle, can be regarded as a reflection of the interchain or intersegment distance of the polymer.…”

Section: X-ray Diffraction and Polymer Packingmentioning

confidence: 99%

“…Haselwender et al reported a T g value of 220ЊC for an addition type polynorbornene obtained using a Pd based catalyst system [4]. …”

Section: Mdsc and Glass Transition Of Polynorbornenementioning

confidence: 99%

“…This peculiar structural feature suggests many interesting properties. For example, these polynorbornenes exhibit much higher glass transition temperatures than those obtained by the ROMP route: the T g value for the addition type polynorbornenes is above 220ЊC [4,7] while the one for ROMP polynorbornenes is 30ЊC [8]. Additionally, unusual diffusion and barrier properties are observed, which are an important asset in polymer design for gas permeation membranes.…”

Section: Introductionmentioning

confidence: 95%

“…Depending on the catalytic system and on the experimental synthesis conditions different polynorbornenes may be obtained ranging from amorphous to more stereoregular and crystalline ones. Based on molecular dynamic simulations Wendorff and collaborators [4][5][6] have shown that amorphous polynorbornene assumes a rigid random coil conformation. This peculiar structural feature suggests many interesting properties.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure

Zhao¹,

Ribeiro²,

Pinho³

et al. 2001

Polymer

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Polynorbornenes of different molecular weights were synthesised by addition polymerisation, using a nickel based catalyst. This polymerisation route leads to amorphous polymers that were shown to display unique properties: high glass transition temperature, rigid random coil conformation, and dense packing in the amorphous state. Gas permeation membranes were prepared from these addition type nonsubstituted polynorbornenes. A study of their gas transport properties was performed and compared with both substituted addition polynorbornenes and ring opening metathesis polymerised polynorbornenes. The observed behaviour, in terms of permeability and selectivity, is in accordance with the low free volume and the dense packing confirmed by positron annihilation spectroscopy and WAXD in these polymer structures. ᭧

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Section: X-ray Diffraction and Polymer Packingsupporting

confidence: 94%

Section: X-ray Diffraction and Polymer Packingmentioning

confidence: 99%

“…Haselwender et al reported a T g value of 220ЊC for an addition type polynorbornene obtained using a Pd based catalyst system [4]. …”

Section: Mdsc and Glass Transition Of Polynorbornenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure

Zhao¹,

Ribeiro²,

Pinho³

et al. 2001

Polymer

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Pd(II)‐catalyzed vinylic polymerization of norbornene and copolymerization with norbornene and copolymerization with norbornene carboxylic acid esters

Heinz

Alt

Heitz

1998

Macromol. Rapid Commun.

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The vinylic polymerization of norbornene and its copolymerization with norbornene carboxylic acid methyl esters were investigated. Norbornene was polymerized by us using di‐μ‐chloro‐bis‐(6‐methoxybicyclo[2.2.1]hept‐2‐ene‐endo‐5σ,2π)‐palladium(II) as catalyst. The polymerization time can be decreased by a factor of 100000 by activation of the catalyst with methylaluminoxane (MAO). With this palladium catalyst activated by MAO, 140 t of norbornene can be polymerized per mol palladium per h. This catalyst system was much more active than [Pd(CH3CN)4](BF4)2 (I). The polymerization of norbornene by (6‐methoxybicyclo[2.2.1]hept‐2‐ene‐endo‐5σ,2π)‐palladium(II) tetrafluoroborate was also possible but it was not as fast as the polymerization by Pd catalysts activated with MAO. We were also able to obtain copolymers of norbornene and 5‐norbornene‐2‐carboxylic acid methyl ester (exo/endo = 1/4 or 2/3) containing between 15 and 20 mol‐% ester units. The copolymerization of norbornene and 2‐methyl‐5‐norbornene‐2‐carboxylic acid methyl ester (exo/endo = 7/3) was faster than the copolymerization mentioned before. In contrast the homopolymerization of 2‐methyl‐5‐norbornene‐2‐carboxylic acid methyl ester was 10 times slower than that of 5‐norbornene‐2‐carboxylic acid methyl ester (exo/endo = 1/4).

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C1-symmetric metallocenes for olefin polymerisation, 1. Catalytic performance of [Me2C(3-tertBuCp)(Flu)]ZrCl2in ethene/norbornene copolymerisation

Arndt

Beulich

1998

Macromol. Chem. Phys.

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The mechanism of the alternating ethenehorbornene copolymerisation using [Me2C(3-'"'Bu-Cp)(Flu)]Xl2 with methylaluminoxane as catalyst is investigated. Copolymerisation models to describe the copolymerisation behavior in the presence of metallocenes with heterotopic sites for monomer coordination are given and applied. It is shown that the microstructure of the copolymers produced at 30°C is the result of a chain migratory insertion mechanism (alternating mechanism) and the sterical hindrance for norbornene insertion at one of the two heterotopic sites of the metallocene. Further investigations on the influence of the reaction parameters showed that an increase in temperature (to 60 "C) causes deviations from the alternating mechanism.

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Polynorbornene: synthesis, properties and simulations

Cited by 186 publications

References 26 publications

Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure

Structural characteristics and gas permeation properties of polynorbornenes with retained bicyclic structure

Pd(II)‐catalyzed vinylic polymerization of norbornene and copolymerization with norbornene and copolymerization with norbornene carboxylic acid esters

C1-symmetric metallocenes for olefin polymerisation, 1. Catalytic performance of [Me2C(3-tertBuCp)(Flu)]ZrCl2in ethene/norbornene copolymerisation

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