Synthesis and characterization of nanocomposite organic/inorganic hybrid materials using living cationic polymerization

A series of novel chlorosilyl functional initiators have been prepared and applied for the first time in the living cationic polymerization of isobutylene (IB). Well-defined polyisobutylenes (PIBs) carrying mono-, di-, and trichlorosilyl head-group, and a tert-chloro end-group were synthesized using newly designed silyl-functional initiators in conjunction with TiCl4 in Hex:MeCl (60:40, v:v) at -80°C. End-group analysis by 1H NMR spectroscopy verified the product structure and the survival of the Si-Cl head-groups during the polymerization. The chlorosilyl functional initiators and chlorosilyl functional PIBs have been employed for the synthesis of PIB brushes on planar silicate substrates by the "grafting from" and "grafting to" techniques.; Structurally well-defined polymer/inorganic nanocomposites were prepared by surface-initiated living cationic polymerization of isobutylene (IB). The living cationic polymerization of IB was initiated from initiators self-assembled on the surface of silica nanoparticles in the presence of additional soluble "free initiator" with TiCl4 in hexanes/CH3Cl (60/40, v/v) at -80°C. The polymerization displayed the diagnostic criteria for living cationic polymerization and provided densely grafted polymers of controlled molecular weight with an approximate graft density of 3.3 chains/nm 2. The surface-initiated polymerization of IB without added "free initiator" also yielded grafted polymer chains with good molecular weight control and narrow molecular weight distribution (Mw/M n).; A series of novel hybrid poly(styryl-POSS), poly(isobutylene- b-(styryl-POSS)), and poly(isobutylene-b-(styryl-POSS)- b-isobutylene) are synthesized and characterized. Living cationic polymerization of styryl-POSS macromer was carried out using the 1-chloro-1-(4-methyphenyl)ethane (p-MeStCl)/TiCl4/MeChx:CH3Cl (60:40, v:v)/-80°C system in the presence of DTBP. Using these conditions, we have synthesized AB diblock, and ABA linear triblock copolymers containing polyisobutylene (PIB)-based rubbery mid block (B) with amorphous glassy poly(styryl-POSS) end blocks (A) by living cationic polymerization using sequential monomer addition. Well-defined PIB-b-P(styryl-POSS) and PIB- b-P(styryl-POSS)-b-PIB have been successfully prepared. The styryl-POSS based hybrid polymers were characterized by thermogravimetry and GPC measurements. (Abstract shortened by UMI.)...