Macromonomer Chain Growth in the Radical Polymerization of MMA by Cobalt(II) Catalyzed Chain Transfer

Properties of the radical polymerization of methyl methacrylate in the presence of cobalt(II) tetraphenylporphyrin ((TPP)Co^II•) as a chain transfer catalyst are reported. Reversible addition of (L)Co‐H to macromonomers gives living character to the oligomer olefins that grow to higher molecular weight without altering the primary polymer structural features. Incorporation of reversible termination of oligomer radicals in the mechanistic model for chain transfer catalysis by (L)Co^II• complexes is an essential feature of the catalytic chain transfer process.

Average degree of polymerization as a function of monomer conversion for the (TPP)Co^II• mediated CCT polymerization of MMA in C₆D₆ initiated by AIBN at different concentrations of (TPP)Co^II•.     

Synthesis and Characterization of Long‐Chain‐Branched Polyolefins with Metallocene Catalysts: Copolymerization of Ethylene with Poly(ethylene‐co‐propylene) Macromonomer

Poly(ethylene‐co‐propylene) macromonomer (EPM) was synthesized in a high‐temperature continuous stirred tank reactor (CSTR) with [C₅Me₄(SiMe₂N^tBu)]TiMe₂ (CGC‐Ti) as the catalyst system. PE samples with EPM long chain branching (LCB) were produced by semi‐batch copolymerization of ethylene and EPM with CGC‐Ti. The LCB frequencies were up to 21.8 EPM side chains per PE backbone. The effects of temperature and ethylene pressure on the degree of EPM grafting and catalyst activity were examined.

Incorporation of EPM into a growing PE chain forming an LCB polymer.     

Thermo‐Responsive Solid‐Phase Extraction Using Poly(methyl vinyl ether)–Containing Segmented Polymer Networks

Segmented polymer networks containing poly(methyl vinyl ether) (PMVE) segments were prepared by free‐radical‐initiated copolymerization of PMVE‐α,ω‐dimethacrylate with styrene or 2‐hydroxyethyl methacrylate (HEMA). These networks were evaluated as thermo‐responsive solid‐phase extraction materials. Suspension‐derived polymer networks consisting of 80% of PMVE and 20% of HEMA adsorb toluene from an aqueous solution at 40°C and release the adsorbed toluene quantitatively at 20°C.     

Macromonomers and coordination polymerization

The present work discusses the synthesis of well-defined comb-shaped polymers or graft copolymer structures based on coordination (co)polymerization of macromonomers. Polystyrene macromonomers with various polymerizable entities were synthesized first by induced deactivation reactions. The homopolymerization of these macromonomers in the presence of selected early or late transition metal catalysts was examined. Comb-shaped polymers could be obtained over a large range of DP values. The results were compared to those obtained by anionic homopolymerization. Some results on the copolymerization of these PS macromonomers with ethylene in the presence of VERSIPOL^TM type catalysts were presented.     

Swelling,elasticity and structure of hydrogels prepared via bis-macromonomers of poly(ethylene oxide)

The effect of swelling on the shear modulus was studied for hydrogels prepared by radical polymerization of methacrylate-terminated poly(ethylene oxide) (PEO) bis-macromonomers of different molecular weight. Gels made of long chains (M = 12000 or 6000) display classical softening upon swelling, whereas gels made of shorter chains (M = 4000 or 2000) remain rigid or even stiffen. The abnormal behaviour is explained by a specific character of network junctions presented by polymethacrylate chains in which each unit is linked with a PEO network chain. It is assumed that the interactions among densely grafted PEO chains result in their stretching on polymerization and non-affine deformation on swelling, which stiffen the gel. This is verified by the data on copolymer (macromonomers - 2-hydroxyethyl methacrylate) gels that have lesser densities of PEO chains attached to the junctions and show weaker stiffening on swelling. The osmotic pressure of gels was estimated from the swelling pressure and shear modulus. Similar to the mixing pressure of equivalent PEO solutions, it varies as the 9/4 power of polymer concentration. At the same time, it is lower than the mixing pressure. This indicates that the junctions make only quantitative changes in the osmotic properties of macromonomer chains.