Synthesis and Mechanical Properties of Polypropylene-based Polymer Hybrids via Controlled Radical Polymerization

Isotactic polypropylene-based graft copolymers linking poly(methyl methacrylate), poly(n-butyl acrylate) and polystyrene were successfully synthesized by a controlled radical polymerization with isotactic polypropylene (iPP) macroinitiator. The hydroxylated iPP, prepared by propylene/10-undecen-1-ol copolymerization with a metallocene/methyl-aluminoxane/triisobutylaluminum catalyst system, was treated with 2-bromoisobutyryl bromide to produce a Br-group containing iPP (PP-g-Br). The resulting PP-g-Br could initiate controlled radical polymerization of methyl methacrylate, n-butyl acrylate and styrene by using a copper catalyst system, leading to a variety of iPP-based graft copolymers with a different content of the corresponding polar segment. These graft copolymers demonstrated unique mechanical properties dependent upon the kind and content of the grafted polar segment.     

Construction of α-phosphonolactams via rhodium (II)-catalyzed intramolecular C?H insertion reactions

The Rh(II)-catalyzed intramolecular C H insertion reactions of N,N-dialkyl-α-diazo-α-(diethylphosphono)acetamides 2a , f–j in CHCl₃ or ClCH₂CH₂Cl were found to give monocyclic and bicyclic α-phosphono-β-lactams, 3a and 3f–j , in 43–67% yields via regiospecific α-C H insertion of the N-alkyl groups. Similar treatment of N-benzyl-N-isopropyl-α-diazo-α-(diethylphosphono)acetamide ( 2b ) and the corresponding N-isobutyl-N-methylacetamide 2d in ClCH₂CH₂Cl afforded mixtures of β-lactams 3b (35%) and and 3b ′ (16%), β-lactam 3d (47%), and γ-lactam 4d (10%), respectively, each of which is formed by the competitive C H insertion reaction between benzylic and isopropyl α-C H bonds and between methyl α-C H and methine β-C H bonds, respectively. For the formation of β-lactams, the selectivity in the rhodium-mediated C H insertion in ClCH₂CH₂Cl follows the order methyl > methine > benzylic α-C H bond on N-substituents. The N,N-dibutyl-α-diazo homologue 2c and Nα[α-diazo-α-(diethylphosphono)acetyl]-2-methylindoline ( 2k ) exclusively produced γ-lactams 4c (67%) and 4k (81%) via insertion into the methylene β-C H and methyl β-C H bonds. tert-Butyl N-[α-diazo-α-(dibenzylphosphono)acetyl]-piperidine-2-carboxylate ( 2m ) on similar treatment, followed by deprotection of the benzyl ester afforded the 7-phosphono carbacepham 6 in 32% overall yield. Similar Rh(II)-catalyzed cyclization of N-methyl-N[4-benzyloxy-α-(diethylphosphono)-phenyl(diethyl-phosphono)methyl]-α-diazo-acetamide ( 2n ) led to 1-[4′-benzylphenyl(diethylphosphono)methyl] -3-(diethyl-phosphono)azetidin-2-one ( 3n ) in 78% yicld. The phosphono group at C-7 of 3f was converted into the acetylamino group via a four-step reaction. Application of chiral rhodium(II) carboxylates 12a–c to the insertion reactions of 2b , c produced α-phosphono-β-and γ-lactams, 3b and 4c , in 6–24% ee and 25–29% ee, respectively.