Macromolecules 2003, 36, 9763-9774
9763
Complex Macromolecular Architectures Utilizing Metallocene Catalysts Christos Batis, Giorgos Karanikolopoulos, Marinos Pitsikalis, and Nikos Hadjichristidis* Industrial Chemistry Laboratory, Department of Chemistry, University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece Received October 22, 2003
ABSTRACT: Graft copolymers having poly(methyl methacrylate), PMMA, backbone and polystyrene, PS, polyisoprene, PI, poly(ethylene oxide), PEO, poly(2-methyl-1,3-pentadiene), P2MP, and PS-b-PI branches were prepared using the macromonomer methodology and high-vacuum techniques. The methacrylic macromonomers, mMM, were synthesized by anionic polymerization, whereas their homopolymerization and copolymerization with MMA were performed by metallocene catalysts. Relatively high macromonomer conversions were obtained in all cases. The parameters affecting the polymerization characteristics were examined. Well-defined poly(butyl methacrylate)-b-poly(methyl methacrylate) block copolymers were prepared for the first time by sequential addition of monomers starting from n-butyl methacrylate. The samples were characterized by size exclusion chromatography, SEC, 1H and 13C NMR spectroscopy, low-angle laser light scattering, LALLS, and differential scanning calorimetry, DSC.
Introduction Recent advances in polymer chemistry have led to the synthesis of several complex macromolecular architectures by a variety of techniques such as anionic,1 cationic,2 group transfer,3 nitroxide mediated,4 atom transfer radical,5 and reversible addition-fragmentation chain transfer polymerization.6 These developments stimulated tremendous efforts to study the structureproperties relationships and opened a new era in material science, introducing macromolecular architecture as one of the most important parameters influencing materials properties.7 Among the different polymerization techniques, metallocene and related transition metal catalyzed polymerizations have attracted a continuously growing academic interest leading to numerous industrial applications.8 Most of the efforts are dedicated to the polymerization of olefins,9 but increasing interest has been developed in the past decade in the synthesis of polymethacrylates,10 especially after the appearance of the mechanistic studies reported by Collins.11 Several efforts for the synthesis of complex architectures utilizing metallocene catalysts have been previously reported in the literature. Chung and collaborators developed a route for the synthesis of block and graft copolymers of olefinic monomers with methyl methacrylate, MMA, using borane chemistry.12 Copolymerization of ethylene and 5-hexenyl-9-BBN was performed using Et(Ind)2ZrCl2/MAO, Cp2ZrCl2/MAO, or TiCl3/EtAlCl2 to yield a linear polyethylene, PE, chain having borane side groups. By selective oxidation of the borane groups, free radical centers were created along the chain from which the polymerization of MMA was initiated to afford PE-g-PMMA graft copolymers.13 Polypropylene, PP, having a vinyl end group was prepared using Et(Ind)2ZrCl2/MAO as the catalyst system through the termination of the polymerization by β-hydrogen elimination. The olefinic chain end was hydroborated by 9-BBN, and the borane end group was then transformed by oxidation to a polymeric radical, which was used as a macroinitiator to polymerize MMA, thus leading to the synthesis of PP-b-PMMA diblock copolymers.14
Waymouth and Hawker et al. combined metallocene chemistry and nitroxide mediated living radical polymerization to synthesize PP-g-PS and PE-g-PS as well as PE-g-(PS-b-PBd), PE-g-(PBd-b-PS), PE-g-(PS-b-PBuA), and PE-g-(PBuA-b-PBd) graft copolymers where PS is polystyrene, PBuA poly(butyl acrylate), and PBd polybutadiene.15 The procedure involves the copolymerization of olefins with monomers containing nitroxide functions able to initiate the radical polymerization of styrene or other monomers leading to the formation of the graft structures. Products with broad molecular weight or bimodal distributions were obtained from this method. Henschke et al. prepared PP-g-PS graft copolymers by the copolymerization of propene with allyl-terminated PS macromonomers using the [Me2Si(2-Me-Benzind)2]ZrCl2/MAO system.16 The macromonomers were prepared by anionic polymerization through the termination of living polystyryllithium with allyl bromide at -78 °C. Moderate macromonomer conversions up to 50% were reported for macromonomers having molecular weights ranging from 4000 to 41000. Shiono and collaborators prepared atactic PP macromonomers through the polymerization of propene with bis(pentamethylcyclopentadienyl)zirconium dichloride/ MAO, Cp2*ZrCl2/MAO, and termination by β-hydrogen elimination.17 The PP macromonomers were copolymerized with propene using rac-[Me2Si(2-Me-Benzind)2]ZrCl2/MAO as the catalytic system to produce atactic PP-g-isotactic PP stereo-comb polymers. The macromonomer method was also employed by Endo et al. to prepare syndiotactic PS-g-atactic PS stereo-combs.18 Anionic polymerization was used to prepare vinylbenzyl-terminated PS macromonomers, which were subsequently copolymerized with styrene using CpTiCl3/MAO as the catalyst. Low copolymerization yields (
