Solid-State ¹³C and ¹⁵N NMR Analyses of Structure and Dynamics of Spacer Methylene Sequences and Mesogen Groups for Liquid Crystalline Polyurethanes with Different Spacer Lengths

Solid-state 13 C NMR analyses of the structure and dynamics have been performed for liquid crystalline polyurethanes with different spacer CH 2 lengths, which were polymerized from 3,3‘-dimethyl-4,4‘-biphenyldiyl diisocyanate, α,ω-alkanediols having various even numbers m of carbons, and 1-hexanol. Each sample was crystallized by cooling from the melt through the liquid crystalline phase at an appropriate cooling rate depending on its phase transition behavior detected by DSC. 13 C spin−lattice relaxation analyses have revealed that each CH 2 carbon resonance line contains three components with different T 1C values which are assigned to the crystalline, medium, and noncrystalline (supercooled liquid crystalline) components. For the polyurethane samples with m = 8 and 12, it has been found that the spacer CH 2 sequences for the noncrystalline component will adopt the alternate trans ( t ) and trans − gauche exchange ( x ) conformation in the central part whereas those of the crystalline and medium components may be in the all- trans conformation. Accordingly, the conformation of the spacer CH 2 sequences can be generally expressed as ttx ( tx ) 𝓁 tt (𝓁 = m /2 − 3) for 8 ≤ m ≤ 12, including the result for m = 10 reported previously. Furthermore, to examine molecular motion of the mesogen units in detail, 13 C CSA spectra have been measured at room temperature for the mesogen carbons by 2D SASS 13 C NMR spectroscopy and compared with those simulated by using the two-site exchange model for the flip motions of the phenylene group. As a result, it has been suggested that flip angles of fluctuations around the phenylene axis may be limited to less than about 20° without any 180° flip motion in all components, including the supercooled liquid crystalline component. Natural abundant CP/MAS 15 N NMR measurements also suggest that such rigidity of the mesogen groups may be due to the formation of intermolecular hydrogen bonding between NH and CO groups, and resulting segmental assemblies will induce the characteristic spacer conformation in the supercooled liquid crystalline component.