Functionalization of polyethylene based on metallocene catalysis and its application to syntheses of new graft copolymers possessing polar polymer segments

Abstract

The control of hydroxylated polyethylene (PE) structures was investigated in the copolymerization of ethylene with allyl alcohol or 10‐undecen‐1‐ol with a specific metallocene, methylaluminoxane, and trialkyl aluminum catalyst system through changes in the copolymerization conditions. The incorporation of allyl alcohol into the PE backbones was controllable through changes in the trialkyl aluminum, leading to terminally hydroxylated PE or a copolymer possessing hydroxyalkyl side chains. The copolymerization of ethylene with 10‐undecen‐1‐ol gave copolymers with hydroxyalkyl side chains of various contents with a variety of molecular weights through changes in the copolymerization conditions. The obtained copolymers were useful as macroinitiators that allowed polar polymer segments to grow on the PE backbones, leading to the creation of graft copolymers that possessed PE and polar polymer segments. In this way, polyethylene‐g‐poly(propylene glycol) (PE‐g‐PPG) and polyethylene‐g‐poly(ϵ‐caprolactone) (PE‐g‐PCL) were synthesized. The 13C NMR analysis of PE‐g‐PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization, and transmission electron microscopy demonstrated nanoorder phase separation and indistinct phase boundaries. 13C NMR and gel permeation chromatography analyses indicated the formation of PE‐g‐PCL, in which 36–80 mol % of the hydroxyl groups worked as initiators for ϵ‐caprolactone polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3657–3666, 2003

The discovery and progress of MgCl2‐supported TiCl4 catalysts

“…Functionalized polyolefins are useful for synthesizing the hybrid polymers with them as macromonomers, macroinitiators, or reactive polymers. 35 MgCl 2 -supported TiCl 4 catalysts can contribute to it as an example that they were able to provide terminally hydroxylated iso-PP. 36 We believe in a bright future for MgCl 2 -supported TiCl 4 catalysts as well as their brilliant progress.…”

Synthesis and characterization of polypropylene-based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)

“…Their reactive groups can be easily converted to initiation sites for the various polymerization systems, such as transition-metal-catalyzed radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening anionic polymerization. The combination of these site-selective functionalized POs and various polymerization processes gave a variety of block and graft copolymers such as PE-b-PMMA block copolymers [2,3], PE-g-PMMA and PE-g-poly(n-butyl acrylate) graft copolymers [4], PE-g-poly(propylene glycol) and PEg-poly(3-caprolactone) graft copolymers [13]. In addition, there are some examples of the PO-based graft copolymers produced by radical or anionic polymerization with functionalized POs [5,6,14].…”

“…Recent advances in polyolefin (PO) chemistry have led to the creation of PO-based polymer hybrids between PO segments and other PO or polar polymer segments, which were prepared by several post-polymerization processes, such as radical [1][2][3][4][5][6][7][8][9][10], anionic [11][12][13][14], cationic [15,16] and coordination polymerizations [17][18][19], or a polymer coupling reaction using functionalized POs [20][21][22][23]. In particular, combinations of POs and polar polymers by chemical linkage have been attracting a lot of attention as PO hybrids between different segments such as crystalline/amorphous, polar/nonpolar or hydrophilic/hydrophobic segments.…”

Well-defined polymethylene-based block co/terpolymers by combining anthracene/maleimide diels–alder reaction with polyhomologation

“…[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] This method is a general one opening new horizons for the synthesis of well-defined PE-based polymeric materials with different macromolecular architectures.…”