Adv Polym Sci (2013) 258: 233–278
DOI: 10.1007/12_2013_209
# Springer-Verlag Berlin Heidelberg 2013
Published online: 19 April 2013
Functional Polyolefins: Synthesis and Energy
Storage Applications
T.C. Mike Chung
Abstract This chapter discusses our research into the functionalization of
polyolefins (PE, PP etc.) that contain polar groups (such as OH and NH 2 ) in the
side chains and chain end, as well as polyolefin graft and block copolymers
containing both a polyolefin block and functional polymer blocks (acrylic and
methacrylate polymers). In the late 1980s, our research on the functionalization
of polyolefins was inspired by the development of homogeneous, single-site
metallocene catalysts that showed excellent copolymerization capabilities and a
well-controlled polymerization mechanism. We were curious to know how to apply
this newly available technology to the direct polymerization (in-reactor) process to
circumvent the inevitable deactivation of the transition metal cationic active site by
functional (polar) groups containing basic O, N, and halides. Throughout the past
two decades, we have developed an effective approach that is centered on specially
designed “reactive” comonomers and chain transfer agents. These can deliver three
essential properties during the polymerization process: (1) stability (no side reaction) of the active site; (2) solubility in the polymerization media for effective
incorporation; and (3) versatility for interconversion to desirable functional groups
under mild reaction conditions after polymerization (preferably a one-pot process).
With the conjunction of suitable metallocene catalysts, a broad range of polyolefins
with “reactive” sites in the side chains or chain end were prepared, and the
incorporated reactive groups were interconverted into functional groups to form
side-chain- or chain-end-functionalized polyolefins. Some active sites were also
transformed into “living” radical or anionic initiator to initiate graft-from polymerization of polar monomers to obtain polyolefin graft and block copolymers (such as
PP-g-PMMA and PP-b-PMMA). The resulting functional polyolefins show many
desirable properties and applications. This chapter focuses on applications in the
area of energy storage. Specifically, I will discuss the usage of new functional
T.C.M. Chung (*)
Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, PA 16802, USA
e-mail: chung@ems.psu.edu
DOI: 10.1007/12_2013_209
# Springer-Verlag Berlin Heidelberg 2013
Published online: 19 April 2013
Functional Polyolefins: Synthesis and Energy
Storage Applications
T.C. Mike Chung
Abstract This chapter discusses our research into the functionalization of
polyolefins (PE, PP etc.) that contain polar groups (such as OH and NH 2 ) in the
side chains and chain end, as well as polyolefin graft and block copolymers
containing both a polyolefin block and functional polymer blocks (acrylic and
methacrylate polymers). In the late 1980s, our research on the functionalization
of polyolefins was inspired by the development of homogeneous, single-site
metallocene catalysts that showed excellent copolymerization capabilities and a
well-controlled polymerization mechanism. We were curious to know how to apply
this newly available technology to the direct polymerization (in-reactor) process to
circumvent the inevitable deactivation of the transition metal cationic active site by
functional (polar) groups containing basic O, N, and halides. Throughout the past
two decades, we have developed an effective approach that is centered on specially
designed “reactive” comonomers and chain transfer agents. These can deliver three
essential properties during the polymerization process: (1) stability (no side reaction) of the active site; (2) solubility in the polymerization media for effective
incorporation; and (3) versatility for interconversion to desirable functional groups
under mild reaction conditions after polymerization (preferably a one-pot process).
With the conjunction of suitable metallocene catalysts, a broad range of polyolefins
with “reactive” sites in the side chains or chain end were prepared, and the
incorporated reactive groups were interconverted into functional groups to form
side-chain- or chain-end-functionalized polyolefins. Some active sites were also
transformed into “living” radical or anionic initiator to initiate graft-from polymerization of polar monomers to obtain polyolefin graft and block copolymers (such as
PP-g-PMMA and PP-b-PMMA). The resulting functional polyolefins show many
desirable properties and applications. This chapter focuses on applications in the
area of energy storage. Specifically, I will discuss the usage of new functional
T.C.M. Chung (*)
Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, PA 16802, USA
e-mail: chung@ems.psu.edu