Cycloaliphatic polyolefins with functional groups were
obtained by Pd(II)-catalyzed homo-
and copolymerizations of norbornene derivatives.
Bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, the
corresponding methyl ester,
2-(hydroxymethyl)bicyclo[2.2.1]hept-5-ene, and the
corresponding octanoate and
decanoate were used as the monomers in these addition polymerizations.
Pd(II)−nitrile catalysts [Pd(RCN)4][BF4]2 (with R =
CH3 and C2H5) quite selectively
polymerized the exo isomers of the esters of
2-(hydroxymethyl)bicyclo[2.2.1]hept-5-ene.
Monomer mixtures containing an 80/20 ratio of
endo/exo
isomers were converted into polymers containing more than 50% of exo
units. 1H NMR studies showed
that the predominant fraction of the endo isomer remained unreacted.
The nitrile based Pd catalysts
were not sufficiently active to polymerize the monomers with
electron-withdrawing substituents linked
to the bicyclic unit at ambient temperature. In-situ prepared
(η3-allyl)palladium complexes with
associated
tetrafluoroborate and hexafluoroantimonate ions were found to be
substantially more active. They were
able to catalyze the addition polymerization of norbornene derivatives
containing a large proportion of
endo isomers. Quantitative monomer conversions were achieved for
aliphatic esters of 2-(hydroxymethyl)bicyclo[2.2.1]hept-5-ene. Random copolymers of
norbornene and the latter esters with molecular weights
M
n(GPC) above 100 000 were prepared.
The (η3-allyl)palladium compounds were suitable
for the
polymerization of bicyclo[2.2.1]hept-5-ene-2-carboxylic
acid methyl ester; high molecular weight materials
were obtained via copolymerization with norbornene. Furthermore,
addition polymers containing 0.2
carboxylic acid group per repeating unit were prepared by the
copolymerization of norbornene and bicyclo[2.2.1]hept-5-ene-2-carboxylic acid. The
hexafluoroantimonate-based (η3-allyl)Pd(II)
catalyst had a higher
polymerization activity than the Pd compound with the smaller
BF4
- counterion which was
rationalized
by a slightly stronger association of BF4
-
with the (η3-allyl)Pd(II) unit.
ansa-Metallocene derivatives XVII *. Racemic and meso diastereomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R ,S-Me 2 Si(3-t.Bu-5-MeC s H 2) 2ZrCI2
67Isotactic polypropene was prepared using rac-dimethyl-silylbis(2-methyl-4-t-butyl-cyclopentadienyl)zirconiumdichloride (1) and methyla!umoxane (MAO) at temperatures between 0 and 80°C and with Al/Zr ratios of 300 and 1500. The polymers, prepared at temperatures below 30°C had melting points of 162°C and above. The chain ends were determined by means of distortionless enhancement by polarization transfer (DEPT)-NMR spectroscopy. The pentad intensities were corrected according to the chemical shifts of the end groups. The intensity distributions are shown to arise from enantiomorphic site control of the chiral catalyst species.
Cycloaliphatic polyolefins with functional groups were prepared by the Pd(II)‐catalyzed addition polymerization of norbornene derivatives. Homo‐ and copolymers containing repeating units based on bicyclo[2.2.1] hept‐5‐en‐2‐ylmethyl decanoate (endo/exo‐ratio = 80/20), bicyclo[2.2.1]hept‐5‐ene‐2‐carboxylic acid methyl ester (exo/endo = 80/20), bicyclo[2.2.1]hept‐5‐ene‐2‐methanol (endo/exo = 80/20), and bicyclo[2.2.1]hept‐5‐ene‐2‐carboxylic acid (100% endo) were prepared in 49–99% yields with {(η3‐allyl)Pd(BF4)} and {(η3‐allyl)Pd(SbF6)} as catalysts. The catalyst containing the hexafluoroantimonate ion was slightly more active than the tetrafluoroborate based Pd‐complex.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.