Dilute solution properties of poly(di-tert-butyl fumarate)

Abstract

The mean-square radius of gyration 〈S 2 〉 and second virial coefficient A 2 are determined from static light scattering (LS) measurements for six samples of poly(di-tert-butyl fumarate) (PDtBF) for a range of weight-average molecular weight M w from 4.35 × 10 4 to 1.73 × 10 5 in tetrahydrofuran at 30.0°C. The intrinsic viscosity [η] and translational diffusion coefficient D are also determined from viscosity and dynamic LS measurements for those samples under the same solvent conditions. From a simultaneous analysis of 〈S 2 〉 and A 2 based on the Kratky-Porod (KP) wormlike chain with excluded volume, the stiffness parameter λ − 1 and the reduced excluded-volume strength λB are determined to be 350 Å and 0.024, respectively, where we assume the shift factor M L for PDtBF to be 101 Å − 1 on the analogy of the main-chain structure of poly(diisopropyl fumarate) previously studied. For PDtBF with such a large λ − 1 , it is found that the intramolecular excluded-volume effect for 〈S 2 〉 is negligibly small in the range of M w examined. As for [η] and D, their behavior may be well explained by the corresponding KP theories using the model parameter values consistent with those determined from 〈S 2 〉 and A 2 , and the intramolecular excludedvolume effect for them can be ignored, as in the case of 〈S 2 〉.

Reversible addition‐fragmentation chain transfer polymerization of diisopropyl fumarate using various dithiobenzoates as chain transfer agents

“…Dialkyl fumarates (DRFs) as 1,2‐disubstiuted ethylene monomers undergo radical polymerization to give high‐molecular‐weight poly(DRF)s with a rigid chain structure due to their unique poly(substituted methylene) backbone by introduction of bulky alkyl groups, such as isopropyl, cyclohexyl, and tert ‐butyl . It is noteworthy as features of DRF polymerization that propagation and termination rate constants are much smaller than those for conventional vinyl monomers .…”

Stiff and hierarchical chain nature of atactic and stereoregular poly(substituted methylene)s

“…The linearity of atactic PPMO in an unperturbed state is abnormal compared to general synthetic polymers 17,18,[21][22][23][24]29,32 and biopolymers. 25,26 Despite the absence of steric hindrance in its structure, such as that induced by the chirality of polysilanes 33 and by the side chain bulkiness of poly(di-tert-butyl fumarate), 34 atactic PPMO exhibits a rod conformation under Θ conditions. In contrast, stereoregular PPMO in an unperturbed state shows secondary (i.e.…”

Synthesis of transparent block copolymers consisting of poly(diisopropyl fumarate) and poly(2‐ethylhexyl acrylate) segments by reversible addition‐fragmentation chain transfer polymerization using trithiocarbonates as the chain transfer agents

“…High‐temperature and transparent polymer materials have become important for information and electronics applications, such as coating, disk, fiber, display, electronic devices, solar cells, and so on . The radical polymerization of dialkyl fumarates provides rigid poly(substituted methylene)s as some of the transparent acrylic polymers . Recently, we reported the reversible addition‐fragmentation chain transfer (RAFT) polymerization of diisopropyl fumarate (DiPF) as the most suitable method for the controlled polymerizations of the fumarates by living radical polymerization techniques .…”