Phase Identification in a Series of Liquid Crystalline TPP Polyethers and Copolyethers Having Highly Ordered Mesophase Structures. 6. Structure Changes from Smectic to Columnar Phases in a Series of Copolyethers Containing Odd and Even Numbers of Methylene Units in Equal Molar Composition

Abstract

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4‘-biphenyl)-2-(4-hydroxyphenyl)propane and different α,ω-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(n/m) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium. Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n = 11 to 5. In the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (ΦH) phase. A further decrease in temperature leads to a ΦH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (SF) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature ΦH phase to the low-temperature SF phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

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“…On the other hand, those of the low-temperature transition processes appear to exhibit cooling and heating rate dependence, indicating that the transitions at low temperatures may represent a transition that increases the structural order. [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] Fig. 3 shows a set of DSC cooling and subsequent heating diagrams for a compound of TQPP-[t-Bu] 2 -[OC 20 H 41 B] 4 with 20 carbons in the branched tails at different cooling and heating rates (2.5-40 C min À1 ).…”

“…Furthermore, the highest transition temperature (152.2 C) is substantially decreased compared with that of the linear alkyl tails (note that the tail lengths in this compound are close to that of TQPP-[t-Bu] 2 -[OC 16 H 33 ] 4 ). Based on DSC experiments alone, it may be expected that these two phase transitions must be associated with similar transition behaviors [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] as shown in Fig. 2 heating rate dependent in both transition temperature and heat of transition.…”

Phase Identification in a Series of Liquid Crystalline TPP Polyethers and Copolyethers Having Highly Ordered Mesophase Structures. 7. Phase Structures in a Series of Copolyethers Containing Odd and Even Numbers of Methylene Units of Different Compositions

“…The different spacer lengths may also significantly change the phase structures and transition behaviors. The current study has been particularly encouraged by our recent work on a series of coTPP( n / m )s containing a fixed even ( m = 12) and varying odd numbers ( n = 5, 7, 9, and 11) of methylene units with their compositions fixed at an equal molar ratio (5/5) . In that study, the SC phases are retained when the dissimilarity of the comonomer lengths is small, as in coTPP(11/12: 5/5).…”

6 Non-conventional soft matter

“…As a result the smectic layer structure is lost and a hexagonal columnar phase can be found before the transition to a nematic phase takes place. [411][412][413] In these columnar phases the columns are formed by the individual polymer chains arranged in a hexagonal lattice, similar to those of the polymers described in section 3.7 (Fig. 23(a)).…”