Synthesis and Functionalization of Isotactic Poly(propylene) Containing Pendant Styrene Groups

Zou, Junfeng; Cao, Chengang; Dong, Jin; Hu, Youliang; Chung, T. C.

doi:10.1002/marc.200400284

Cited by 41 publications

(41 citation statements)

References 23 publications

(13 reference statements)

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“…[1,2] Because of the highly oxophilic nature of most metal catalyst systems for olefin coordination polymerization, the commercial production of functionalized polyethylenes is generally restricted to high-pressure radical processes by ethylene copolymerization with polar functional comonomers. [2,3] One recent research interest in this area is to combine catalytic olefin polymerization with successive living/ controlled polymerization of functional monomers (such as anionic polymerization, [4,5] atom transfer radical polymerization (ATRP), [5,6] nitroxide-mediated radical polymerization (NMRP), [7] reversible addition fragmentation chain transfer (RAFT), [8] etc.) to prepare functionalized polyolefins that contain blocks of functional comonomers and have well-defined architectures, such as star-shaped, comb-shaped, and block olefin copolymers.…”

Section: Introductionmentioning

confidence: 99%

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

Zhang

Wang

Subramanian

et al. 2007

Macromol. Rapid Commun.

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A one‐pot procedure for the synthesis of hyperbranched polyethylenes tethered with ATRP initiating sites by chain walking ethylene copolymerization with an acrylate‐type ATRP inimer, 2‐(2‐bromoisobutyryloxy) ethyl acrylate (BIEA) is reported. Because of its ability to incorporate acrylate‐type comonomers and tolerance toward the α‐bromoester group, the chain walking Pd‐diimine catalyst, [(ArNC(Me)(Me)CNAr)Pd(CH3)(NCMe)]SbF6 (Ar = 2,6‐(iPr)2C6H3), allowed the successful synthesis of a series of hyperbranched copolymers tethered with 2‐bromoisobutyryl groups at different densities. These copolymers may serve as polyfunctional macroinitiators for the ATRP of functional monomers to further synthesize core‐shell structured functionalized copolymers with a hyperbranched polyethylene core grafted with side chains of the functional monomers.magnified image

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Section: Introductionmentioning

confidence: 99%

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

Zhang

Wang

Subramanian

et al. 2007

Macromol. Rapid Commun.

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“…Currently, various reactive polyolefins, including polyolefins containing alkylborane groups, polyolefins containing p-methylstyrene units, a variety of unsaturated polyolefins have been synthesized using Ziegler-Natta or metallocene catalysts by the copolymerization of an α-olefin monomer with the corresponding reactive groupcontaining comonomers, which have been applied as 'intermediates' to prepare functional polyolefins having versatile functionalities (15)(16)(17)(18). Furthermore, a late metal catalyst system involving β-ketoamine ligand synthesized by our group has been reported as a successful initiator for the copolymerization of norbornene with styrene through a coordination polymerization mechanism (19)(20).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Norbornene and Methyl Methacrylate Graft Copolymers with High Norbornene Content by Using Mixed Catalytic System

Song

Hou

et al. 2008

Journal of Macromolecular Science, Part A

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A vinyl-type polymer of norbornene containing a few pendant styrene groups obtained by copolymerization of norbornene and 1,4-divinylbenzene (1,4-DVB) was used as a macroinitiator in the reverse atom transfer radical polymerization (RATRP) of methyl methacrylate in conjunction with CuCl 2 /2,2 -bipyridine/2,2 -azobisisobutyronitrile (AIBN) as a catalyst. In the first step of the reaction, the structural characterization of the copolymers showed that norbornene and 1,4-divinylbenzene copolymerizations occur as a coordination mechanism and that true copolymers are formed by random copolymerization. With the initiation of copper dichloride and AIBN in the second step, the pendant styrene groups in the copolymers were quantitatively polymerized with methyl methacrylates, which allowed the successful synthesis of polynorbornene-based graft copolymers by RATRP mechanism. The analyses of the product by 1 H-and 13 C-NMR and GPC gel permeation chromatography (GPC) gave the verification of 'true' copolymer. Varying the monomer feed ratio controlled the thermal property of the graft copolymer.

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“…In one research [13], Ziegler-Natta-catalyzed propylene polymerization was targeted at polypropylenes containing pendant styrene groups, which were then combined with either living anionic or controlled radical polymerization of polar monomers to reach side chain-functionalized PP with controlled functional group concentration while retaining the desired PP thermal properties such as high melting point and high crystallinity. In one research [13], Ziegler-Natta-catalyzed propylene polymerization was targeted at polypropylenes containing pendant styrene groups, which were then combined with either living anionic or controlled radical polymerization of polar monomers to reach side chain-functionalized PP with controlled functional group concentration while retaining the desired PP thermal properties such as high melting point and high crystallinity.…”

Section: Introductionmentioning

confidence: 99%

Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

Dong

2006

Front. Chem. China

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Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry Abstract Functionalization of polyolefins is an industrially important yet scientifically challenging research subject. This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization. In one approach, polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers. The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgCl 2 -supported TiCl 4 catalyst yielded polypropylenes containing pendant styrene moieties. Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites, generating polymeric benzyllithium and 1-chloroethylbenzene species. These species initiated living anionic polymerization of styrene (S) and atom transfer radical polymerization (in the presence of CuCl and pentamethyldiethylenetriamine) of methyl methacrylate (MMA), respectively, resulting in functional polypropylene graft copolymers (PP-g-PS and PP-g-PMMA) with controllable graft lengths. In another approach, chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metallocene catalyst through a selective aluminum chain transfer reaction. Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

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Synthesis and Functionalization of Isotactic Poly(propylene) Containing Pendant Styrene Groups

Cited by 41 publications

References 23 publications

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

Synthesis of Norbornene and Methyl Methacrylate Graft Copolymers with High Norbornene Content by Using Mixed Catalytic System

Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

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