Hyperbranched polymer living polymerization

Hyperbranched polymers have also been prepared via living anionic polymerization. The reaction of poly(4-methylstyrene)-fo-polystyrene lithium with a small amount of divinylbenzene, afforded a star-block copolymer with 4-methylstyrene units in the periphery [200]. The methyl groups were subsequently metalated with s-butyllithium/tetramethylethylenediamine. The produced anions initiated the polymerization of a-methylstyrene (Scheme 109). From the radius of gyration to hydrodynamic radius ratio (0.96-1.1) it was concluded that the second generation polymers behaved like soft spheres. 

Ishizu et al.194 synthesized hyperbranched macromolecules that resemble dendrimers. The synthetic approach involved the preparation of poly(4-methyl-styrene-b-PS-b-poly(4-methylstyrene) triblock copolymer by using naphthalene lithium as difunctional initiator. The 4-methyl groups of the terminal blocks were metalated with s-BuLi/tetramethylethylenedi-amine (TMEDA) complex in a molar ratio of 1 2. After removal of the excess s-BuLi by repeated precipitation of the living polymer and transfer of supernatant solution to another flask under high vacuum conditions, the polymer was dissolved in THF and was used as the initiator of a-methylstyrene at —78 °C. After the polymerization of a-methylstyrene, a small amount of 4-methylstyrene was added. The procedure of metalation of the a-methyl groups and polymerization of a-methylstyrene can be repeated many times to form a dendritic type hyperbranched polymer (Scheme 99). The characterization of the inter-... 

Michel Schappacher is Senior Research Engineer at the French National Center for Scientific Research (CNRS). He was educated at the Univereity Louis Pasteur (ULP), Strasboui France, where he received a "Doctorat d Universite in 1981 in synthetic organic chemistry under the supervision of Prof. R. Weiss. In 1988 he joined Dr. A. Deffieux s team at the Laboratoire de Chimie des Polymdes Oi aniques, University of Bordeaux France. He worked on modular synthetic approaches using living polymerization reactions for the precise design of new polymer architectures including maaocyclic polymere, star-like polymers, copolymer brushes, hyperbranched polymers, and their AFM visualization and characteriza-... 

A-P(MeOx)-AA MMA Living cationic DS in water and acetone -P(EtOx)-A polymerization, free DS in water, toluene, and acetone, DSC, DMTA radical Chemical reaction between hydrophobic hyperbranched polymers or dendrimers and hydrophilic linear chains 90... 

The complexation of DNA and polycations is a function of the intrinsic properties of the two components. For instance, from the use of synthetic polycations for complexing DNA also arises the problem of polydispersity of polymers (a polymer sample is usually composed of macromolecular species of differing molar masses) compared with DNA, which is monodisperse. Because the polydispersity of the polycation could be an issue in studies of IPECs, sugar-based polymers (usually polydisperse except if fractionated), conjugated polymers (polydispersity, Mw/Mn > 2), branched PEI derivatives, and hyperbranched polymers are out of the scope of this review, as already mentioned. Only polymers synthesized via controlled or living polymerization methods will be discussed [55-57]. 

In conclusion, by overcoming the disadvantage of the previous synthetic methods for the preparation of hyperbranched polymers, we designed an all-new Seesaw-type macromonomer strategy to construct perfect hyperbranched model samples with uniform subchains. In onr stndy, we successfully prepared various kinds of Seesaw-type macromonomers, snch as homopolymers, triblock copolymers and diblock copolymers. Using these maCTomonomers as precursors, we have further prepared a series of perfect hyperbranched homopolymers, block copolymers, graft copolymers and hetero-snbchain copolymers by a combination of controlled/ living polymerization and click chemistry. Various solution properties of these novel hyperbranched (co) polymers in dilnte and semidilute solntions have been studied in detail. More specifically, the main achievements of this work are as follows ... 

Hirao, A., Sugiyama, K., Matsuo, A. et al. (2(X)8) Synthesis of weU-defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations. Polymer International, 57,554—570. 

The development of PPE synthetic chemistry makes the synthesis of PPEs with various structures possible. Recently, PPE-based polymers with different topological structures including linear random copolymers, block copolymers, star polymers, miktoarm polymers, and brush and hyperbranched polymers have been synthesized. Among them, linear homopolymers or random copolymers of PPEs are perhaps the most studied. Different block copolymers with AB, ABA, and ABC architectures have been synthesized by controlled ROP. By the combination of ROP of PPE with other controlled polymerization methods, such as living radical polymerization, or click chemistry, more complex architectures including miktoarm, comb, or graft copolymers can be synthesized. The richness of structures has allowed the convenient adjustment of material properties of PPE for biomedical applications. 

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