Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Abstract

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl2(PPh3)3 as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003

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

“…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.…”

Controlled radical polymerization with polyolefin macroinitiator: a convenient and versatile approach to polyolefin-based block and graft copolymers

“…Such polyolefin macroinitiators can be generally prepared by a multiple-step reaction consisting of preparing the functionalized polyolefin with reactive groups, such as hydroxyl, [11][12][13][14] glycidyl, [15] phenyl [16][17][18] and maleic anhydride group, [19] and subsequently their transformation into the initiation site. However, most of the functionalized polyolefins were prepared under unusual olefin polymerization conditions in the presence of specific chain transfer agents or polar monomers, which are poisonous for most olefin polymerization catalysts to retard the polymerization.…”

Syntheses, Structures and Functions of Polyolefin/non-Polyolefin Hybrids

“…In addition, surface coated PP sheets with poly(2-hidroxyethylmethacrylated) were successfully synthesized as new polyolefin materials. KEY WORDS Polyolefin / Non-Polyolefin / Block Polymer / Graft Polymer / Star Polymer / Functionalized Polyolefin / Compatibilizer / (Received June 21, 2007: Accepted September 13,2007) [ Kobunshi Ronbunshu, 64(12), 897-906 (2007)]…”