Homogeneous metallocene/MAO-catalyzed polymerizations of polar norbornene derivatives: copolymerizations using ethene, and terpolymerizations using ethene and norbornene

Abstract

Terpolymerizations of norbornene derivatives containing different functional substituents were carried out with ethene and norbornene using the homogeneous catalyst system iPr[CpInd]ZrCl2/MAO. The norbornene derivatives 5‐norbornene‐2‐methanol and 5‐norbornene‐2‐carboxylic acid were prereacted with triisobutylaluminium to prevent the deactivation of the catalyst. 13C NMR studies revealed the composition of the polymer. The incorporation rate was 5–12 mol‐% at a content of 50 mol‐% of the norbornene derivative in the monomer feedstock. IR‐GPC coupled experiments confirmed the homogeneous composition of the polymer. In addition, we investigated the ethene copolymerization and the ethene/norbornene terpolymerization using the trialkylsilyl protected norbornene derivates such as 5‐norbornene‐2‐methyleneoxytriethylsilane and 5‐norbornene‐2‐methyleneoxy‐tert‐butyldimethylsilane. These norbornene derivatives reveal an incorporation rate of 5–6 mol‐% in the polymer at a content of 20 mol‐% in the monomer feedstock.

Metal catalysts for the vinyl/addition polymerization of norbornene

“…For the ethene copolymerization and the ethene/norbornene terpolymerization with 5-methyleneoxytriethylsilane-2-norbornene and 5-methyleneoxytert-butyldimethylsilane-2-norbornene their incorporation rate in the polymer was 5-6 mol% at a content of 20 mol% in the monomer feedstock ( Fig. 3) [74].…”

Ethene Co- and Terpolymerizations with TIBA-Protected Norbornenemethanol and TIBA-Protected Norbornenecarboxylic Acid Using Homogeneous Metallocene/MAO Catalyst Systems

“…[8,10] The polymerization activities observed were noticeably lower in comparison with the activities of ethene copolymerizations using norbornenemethanol. However, during the investigations of ethene/norbornene/ norbornenecarboxylic acid terpolymerizations that have recently been published, an enhancement of polymerization activities had been detected by means of a prereaction of norbornenecarboxylic acid with TIBA at a molar ratio of 1 : 2, instead of an equimolar ratio.…”

“…However, during the investigations of ethene/norbornene/ norbornenecarboxylic acid terpolymerizations that have recently been published, an enhancement of polymerization activities had been detected by means of a prereaction of norbornenecarboxylic acid with TIBA at a molar ratio of 1 : 2, instead of an equimolar ratio. [10] Therefore, the formula of a TIBA-norbonenecarboxylic acid complex as presented in Scheme 3 has been suggested. The complexed carbonyl group was detected by IR spectroscopic analysis.…”

“…[10] Alternatively, norbornenecarboxylic acid was also used as a polar norbornene derivative. So far only the homogeneous catalyst system iPr[CpInd]ZrCl 2 /MAO has been clearly investigated for the co-and terpolymerizations mentioned above.…”

“…Formula of a possible structure of the norbornenecarboxylic acid prereacted with TIBA; [TIBA]/[norbornenecarboxylic acid] = 2 : 1 [10]. …”