Infrared spectra of polymer solutions. I. Conformational stability of isotactic polymer chains in solution

The infrared spectra of isotactic polystyrene, polypropylene, and poly-p-chlorostyrene were measured in dilute solutions or gels at various temperatures ranging from room temperature to ?100°C. For isotactic polystyrene and polypropylene, all the absorption bands characteristic of the helical conformation of the molecules increase in intensity with decreasing temperature, and show intensities at low temperature as strong as in the highly crystallized samples. This suggests that the molecules can assume very regular conformations even in solution. Similar temperature dependence of the spectra was observed for a homogeneous gel of isotactic poly-p-chlorostyrene, which is believed to be noncrystalline. These experimental facts lead to the conclusion that the stability of the TG type helical conformation of these isotactic polymers may be ascribed to the intramolecular forces within a molecule. The fact that these spectral changes are reversible has permitted a thermodynamic treatment of the conformational regularity in solution on the basis of the infrared data. The temperature dependence of the absorption intensities has been interpreted quantitatively by a simple statistical mechanical model, and the enthaply and the entropy differences between the helical and the random states of the monomeric residue in the molecular chain have been estimated.     

Structural studies of pressure-crystallized polymers. I. Heat treatment of oriented polymers under high pressure

A convenient pressure apparatus was designed for crystallization of high polymers under hydrostatic pressure up to 5000 atm. Melt crystallization as well as heat treatment under various temperatures and pressures was carried out on several polymers, and the effects of pressure on the molecular and crystal structures of the samples are discussed. Heat treatment of syndiotactic polypropylene under high pressure yields a new crystal modification rather than the previously known helix and planar zigzag modifications. Of the three modifications of poly(vinylidene fluoride), modification III was found as a high-pressure phase for specimens in the unoriented state, while modification I was obtained as the most stable one on heat treatment of oriented specimens under high pressure. Heat treatment under high pressure converts ordinary isotactic poly-4-methylpentene-1 with a lower density than the noncrystalline value, to a new crystal modification with higher density. As is reasonable, the dense modification is stable in a high-pressure range. For these three cases, the orientation of specimens was found to remain unchanged during the transitions, which must therefore occur in the solid state.     

Preliminary communication Liquid crystalline cardanyl β-D-glucopyranosides

Two novel aryl glycosides were synthesized, which varied in the extent of unsaturation in the lipophilic part, from plant/crop-based renewable resource materials. Their liquid crystalline properties were characterized by optical polarizing microscopy, differential scanning calorimetry and X-ray diffraction. All the mesophases are identified as lamellar in structure.     

Crosslinking polymerization leading to interpenetrating polymer network formation. I. Polyaddition crosslinking reactions of poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate)s with ethylene glycol resulting in polyurethane networks

At the start of our research program concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article deals with the polyaddition crosslinking reaction leading to PU network formation. Therefore, 2‐methacryloyloxyethyl isocyanate (MOI) was radically copolymerized with methyl methacrylate (MMA) in the presence of CBr₄ as a chain‐transfer agent. The resulting poly(MMA‐co‐MOI)s, having pendant isocyanate (NCO) groups as novel multifunctional polyisocyanates, were used for polyaddition crosslinking reactions with ethylene glycol as a typical diol. The second‐order rate constants depended on both the functionality of poly(MMA‐co‐MOI) and the NCO group concentration. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation; the deviation of the actual gel point from the theoretical value became more remarkable for a greater functionality of poly(MMA‐co‐MOI) and at a lower NCO group concentration or at a lower poly(MMA‐co‐MOI) concentration. These are discussed mechanistically, with consideration given to the significance of intramolecular cyclization and intramolecular crosslinking reactions leading to the shrinkage of the molecular size of the prepolymer, along with the data of the intrinsic viscosities of resulting prepolymers and the swelling ratios of resulting gels. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 606–615, 2003     

Exponents for the excluded volume problem as derived by the dynamic renormalization group method

By regarding the contour length L of a polymer chain as “time”, we derive the mean-square end-to-end distance 〈x²〉 for the polymer chain with excluded volume by means of the dynamic renormalization group. The result to first order in ? = 4 ? d (d is the dimension of the space) is $\text{〈x}{}^2\text{〉 =}\text{const}\text{× L}{}^{\mathrm{<mtext>1+?</mtext><mtext>8</mtext>}}$.