Bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) was used successfully as a novel coupling agent cum accelerator to co-vulcanize the elastomer blend comprising highly unsaturated natural rubber (NR) and ethylene propylene diene rubber (EPDM) of low unsaturation content. The blend vulcanizates produced exhibit improved physical properties that can be further enhanced by implementing a two-stage vulcanization technique, as well as by judicious selection of the NR-to-EPDM ratio. The results indicate coherency and homogeneity in the blend composition of two-stage vulcanizates. The cure-rate mismatch problem could thus be solved through the formation of rubberbound intermediates with a multifunctional rubber additive (i.e., DIPDIS), thereby restricting the curative migration from lower to highly unsaturated rubber. The blend morphology as revealed by SEM studies accounts for significant improvement in physical properties, particularly in two-stage vulcanizates.
Time-of-flight mass spectra of cyclopentanone and its clusters cooled in a supersonic jet expansion have been measured following 4-, 3-, and 2-photon ionizations by the 2nd, 3rd, and 4th harmonic wavelengths, respectively, of a Q-switched Nd:YAG laser. The mass spectra reveal signatures of energetically favored keto to enol tautomerization of the molecular ion leading to intermolecular proton transfer, and this observation is found sharply dependent on the ionization wavelengths used. Electronic structure calculation predicts that in spite of the energetic preference, keto-enol conversion barrier of isolated molecular ion is high. However, the barrier is significantly reduced in a CH⋯O hydrogen-bonded dimer of the molecule. The transition states associated with tautomeric conversion of both cyclopentanone monomer and dimer cations have been identified by means of intrinsic reaction co-ordinate calculation. In a supersonic jet expansion, although a weakly bound dimer is readily generated, the corresponding cation and also the protonated counterpart are observed only for ionization by 532 nm. For other two ionization wavelengths, these species do not register in the mass spectra, where the competing reaction channels via α-cleavage of the ring become dominant. In contrast to the report of a recent study, we notice that the intact molecular ion largely survives fragmentations when ionized from the 2-photon resonant 3p Rydberg state as intermediate using nanosecond laser pulses, and the corresponding resonant 3-photon ionization spectrum has been recorded probing the intact molecular ion.
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