The first example of a 3-alkene polymerization has been successfully achieved with 3-heptene in the presence of phenyl-substituted α- diimine nickel precatalysts activated by dMMAO, and compared with the corresponding linear alkenes, i.e., 1-pentene, 2-hexene and 4-octene polymerizations. The microstructures of the produced poly(3-heptene), which consists of ethyl , propyl and butyl branches indicated the 3,4- and 4,3-insertion, followed by chain-walking, with incorporation of a small fraction of long methylene sequences of 1,7-enchainment via monomer-isomerization. Late-transition metal catalyzed polymerization reactions of internal alkenes to synthesize novel polyolefin materials are highly important and also highly challenging. Upon activation with dried modified methylaluminoxane (dMMAO), the first example of a 3-alkene polymerization has been successfully achieved for 3-heptene catalyzed by phenyl-substituted α- diimine nickel complexes in comparison, and compared with the polymerizations of the corresponding linear alkenes, i.e., 1-pentene, 2-hexene and 4-octene. The results indicate that the polymerization of 3-heptene was achieved via chain-walking to generate branched amorphous polymers with glass transition temperature of ca. −68 °C. The microstructures of the produced poly(3-heptene) indicated the 3,4- and 4,3-insertion followed by chain-walking, the latter being predominant. The NMR analyses of the polymers showed that the obtained poly(3-heptene) possessed ethyl, propyl and butyl branches and a small amount of the long methylene sequence of 1,7-enchainment via monomer-isomerization. The branches structures were significantly dependent on the polymerization temperature, and the content of propyl branches derived from 3,4-insertion decreased with an increase in the polymerization temperature.
Tianheng Wang,Xiaoling Xu,Haisheng Zhang,Shaobin Wen,Liyuan Fan,Yanqiu Wang,Xinzhao Luo,Qiang Zhang,Yingquan Zou
Polyethylene is among the most widely-used coating materials due to the excellent physical and mechanical properties . However, the chemical inertness and poor solubility limit the application of polyethylene in coating. In this study, hyperbranched polyethylene-based graft copolymers containing functional oxetane groups (HBPE- g -POXMA) were synthesized via chain walking polymerization (CWP) and atom transfer radical polymerization (ATRP) in tandem. Macroinitiators were first synthesized via CWP of ethylene and trimethyl(undec-10-en-1-yloxy) silane following deprotection and esterification reaction. Subsequent ATRP of 3-ethyl-3-(methacryloyloxy) methyloxetane was performed to yield functional polyethylene with controlled molecular weight (MW), relatively narrow MW distribution, good solubility in organic solvents as well as pendant oxetane groups for photopolymerization . Finally, cationic photo-curing of HBPE- g -POXMA was conducted to build crosslinked polyethylene layers on polypropylene membrane surface. The composite membrane showed a narrow pore size distribution (0.03–0.63 μm) and an average pore size of merely 0.31 μm, which exhibited a retention ratio of over 90 % for different dyes. The strategy developed in this study could provide a synthetic route to hyperbranched polyethylene for functional coating via cationic photo-curing.
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