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The synthesis of novel arborescent (arb; randomly branched, “tree‐like,” and often called “hyperbranched”) block copolymers comprised of rubbery polyisobutylene (PIB) and glassy polystyrene (PSt) blocks (arb‐PIB‐b‐PSt) is described. The syntheses were accomplished by the use of arb‐PIB macroinitiators (prepared by the use of 4‐(2‐methoxyisopropyl) styrene inimer) in conjunction with titanium tetrachloride (TiCl4). The effect of reaction conditions on blocking of St from arb‐PIB was investigated. Purified block copolymers were characterized by 1H NMR spectroscopy and Size Exclusion Chromatography (SEC). arb‐PIB‐b‐PSt with 11.7–33.8 wt % PSt and Mn = 468,800–652,900 g/mol displayed thermoplastic elastomeric properties with 3.6–8.7 MPa tensile strength and 950–1830% elongation. Samples with 26.8–33.8 wt % PSt were further characterized by Atomic Force Microscopy (AFM), which showed phase‐separated mixed spherical/cylindrical/lamellar PSt phases irregularly distributed within the continuous PIB phase. Dynamic Mechanical Thermal Analysis (DMTA) and solvent swelling of arb‐PIB‐b‐PSt revealed unique characteristics, in comparison with a semicommercial PSt‐b‐PIB‐b‐PSt block copolymer. The number of aromatic branching points of the arb‐PIB macroinitiator, determined by selective destruction of the linking sites, agreed well with that calculated from equilibrium swelling data of arb‐PIB‐b‐PSt. This method for the quantitative determination of branching sites might be generally applicable for arborescent polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1811–1826, 2005

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This article features macromolecular engineering via carbocationic polymerization, the focus of research of the recently established Macromolecular Engineering Research Centre (MERC) at the University of Western Ontario. The fundamental philosophy of MERC is interdisciplinary research with a strong industrial orientation, while emphasizing the quest for fundamental understanding of polymerization processes and polymer structure‐property relationships. First, a brief overview of living polymerizations in general, and living carbocationic polymerizations in particular will be given. This latter technique is of interest because some monomers (e. g., isobutylene) can be polymerized by cationic techniques only, to yield polymers with unique properties (e. g., polyisobutylene with superior chemical and oxidative stability, low permeability and high damping). This will be followed by an overview of our research strategy and a summary of our latest results. These include the development of a fiber‐optic mid‐FTIR method for the real‐time monitoring of low temperature polymerization processes, the discovery that selected epoxides initiate effectively the living carbocationic polymerization of isobutylene, fundamental studies into the mechanism and kinetics of living carbocationic polymerization, and the design and synthesis of various polymer architectures (e. g., branched homo‐ and block copolymers) with improved properties and nanostructured phase morphologies.

Blends of two or more polymers having appropriate reactive groups can be crosslinked through condensation or substitution reactions in the absence of crosslinking chemicals when molded at high temperatures for prolonged times. When at least one of the two polymers is a rubber, such blends are called “self-crosslinking rubber blends.” Self-crosslinking rubber/rubber blends included in this review are binary CSM/ENR, ENR/XNBR, CR/ENR, ENR/Zn-SEPDM, CSM/XNBR and CR/XNBR blends, and ternary CR/XNBR/ENR and CSM/XNBR/ENR blends. Self-crosslinking thermoplastic/rubber blends include binary PVC/XNBR, PVC/ENR, PVC/NBR, PVC/HNBR, PAA/CR and PAA/ENR blends, and a ternary PVC/ENR/XNBR blend. The formation of crosslinks in self-crosslinking blends is manifested in the rise of the rheometer torque with time. Solvent swelling studies and dynamic mechanical analysis support the self-crosslinking behavior of the blends. The extent of crosslinking depends on the amount and reactivity of the functional groups of the two blend components, the time and temperature of the reaction. In general, the self-crosslinked rubber/rubber blends behave like conventional rubber vulcanizates with respect to physical properties and can be reinforced by fillers. Infrared spectroscopy has been used to identify the chemical structures formed during self-crosslinking, allowing the elucidation of the mechanism of self-crosslinking.

The rheological and mechanical properties of a polystyrene‐polyisobutylene‐polystyrene (SIBS) block copolymer containing 30 wt% polystyrene (PS) and its blends with PS (SIBS/PS) were investigated. Atomic Force Microscopy (AFM) was used to visualize the nanostructured phase morphology of the SIBS, which is responsible for the mechanical strength of this thermoplastic rubber. The order‐disorder transition (ODT) for the SIBS block copolymer was found to be above 250°C. SIBS/PS blends with 10–30 wt% PS showed improved moduli and tensile strengths. Blends containing up to 40 wt% PS behaved as thermoplastic elastomers. In the region of linear viscoelasticity the blends revealed pronounced non‐Newtonian behavior and enhanced elasticity. This paper also reports the role of this styrenic block copolymer in the impact modification of PS.

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