TY - JOUR
T1 - Early Transition Metal Catalysis for Olefin–Polar Monomer Copolymerization
AU - Chen, Jiazhen
AU - Gao, Yanshan
AU - Marks, Tobin J.
N1 - Funding Information:
Financial support was provided by NSF through Grant CHE-1856 619. Sijia Liu is acknowledged for cover design.
PY - 2020/8/24
Y1 - 2020/8/24
N2 - Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value-added applications. The metal catalyst-mediated copolymerization of non-polar olefins with polar comonomers represents the seemingly most straightforward, atom- and energy-efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)-catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co-monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.
AB - Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value-added applications. The metal catalyst-mediated copolymerization of non-polar olefins with polar comonomers represents the seemingly most straightforward, atom- and energy-efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)-catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co-monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.
KW - catalyst design
KW - early transition metal
KW - olefin
KW - polar monomer
KW - polymerization
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U2 - 10.1002/anie.202000060
DO - 10.1002/anie.202000060
M3 - Review article
AN - SCOPUS:85085570600
VL - 59
SP - 14726
EP - 14735
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 35
ER -