Structure and mechanical properties of elastomeric block copolymers.

Abstract

This research presents the synthesis (by anionic polymerization and catalytic hydrogenation) and characterization of two types of block copolymers: CMC and XPX. In CMC, C is glassy poly(cyclohexylethylene) and M, the matrix, can be semicrystalline poly(ethylene) E, rubbery poly(ethylene-alt-propylene) P, or rubbery poly(ethylethylene) EE, or a combination to yield: CPC, CEEC, CEC, CPEEC and CEPC, with fC ≈ 0.18 – 0.30. XPX materials have X = CEC, fC ≈ fE, and fP ≈ 0.40 – 0.60. Block copolymer phase behavior and morphology were examined through a combination of DSC, rheology, SAXS, WAXS and TEM. CMC materials are meltordered due to block thermodynamic incompatibility with TODT > Tg (C) ≈ 147 °C and show lamellar or C cylinder morphologies. The design of XPX yields melt disordered materials up to high Mn with microphase segregation induced by E crystallization. Two high Mn XPX polymers are melt ordered above Tm(E) and show two correlation lengths in SAXS assigned to the C – E and X – P length scales. TEM images indicate that all XPX materials, irrespective of melt segregation, are characterized by composite glassy and crystalline hard domains dispersed in rubbery P at room temperature. Tensile and recovery testing at room temperature show that CMC and XPX materials, with the exception of plastic CEC, behave as thermoplastic elastomers with tunable properties. Interestingly, melt disordered XPX materials have competitive mechanical properties comparable to the strongest CMC polymers, but with advantageous processing. For melt ordered CMC, Tprocess > TODT, which is dependent on Mn, while for melt disordered XPX, Tprocess > Tm(E) ≈ 100 °C independent of Mn. The deformation of melt disordered XPX materials, probed by recovery studies and WAXS, suggests that deformation is first taken by P, then E and finally C, which causes ultimate failure, as agreed in the literature for conventional SBS and SIS thermoplastic elastomers. This implies that strain recovery in XPX materials can be comparable to that of CPC if materials contain low hard block content or are stretched to strains below the onset of E deformation. Finally, a collection of data of mechanical properties, namely modulus E, strain at break εb, tensile strength σTS and tension set εs, obtained from CMC, XPX and previously reported materials were examined. Most notably, E and εs were found to be strongly correlated with the volume fractions of C and E, as properties increase with (fC + fE)δ, where δ = 1 – 2.4. Ultimate properties such as σTS and εs are unaffected by changes in composition as failure is dictated by that of the hard domains and values are similar above a minimum amount of hard block. In addition, E, σTS, and εb are inversely correlated to rubber entanglement molecular weight Me, which implies that modulus and ultimate properties are affected by the ability of the rubber network to redistribute stress by entanglement slippage. However, εs is unresponsive to Me variations, which indicates that irrecoverable deformation in these materials results from deformation of the hard domains.