CRYSTALLINE MORPHOLOGY IN A SERIES OF CH_(3)-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS

Crystalline morphology in a series of CH_(3)-substituted main chain thermotropic aromatic polyesters with even and odd numbered methylene spacers has been studied by polarizing optical microscopy(POM),scanning electron microscopy(SEM)and transmission electron microscopy(TEM).On crystallization from solution evaporation spherulites of radial structure were observed in the polymers with even numbered spacers,but spherulites with concentric rings form in the polymer with odd numbered spacers.Both spherulites have a lamellar structure,which is about 10 nm in thickness.On crystallization from nematic glassy state spherulites can not be grown;lamellar structure was only observed around disclinations in a specimen during crystallization.Ln the case of crystallization from nematic melt two types of spherulites can be observed far the sample with even numbered spacers.For the sample with add numbered spacers spherulites can not be formed,but only irregular crystallites.

MOLECULAR FIELD THEORY FOR NEMATIC LIQUID CRYSTAL POLYMER COMPRISING FLEXIBLE SPACER

Basea on the new model and concept of mtramolecular orientational order parameter, a molecular field theory was built up for main chain liquid crystalline polymer (MC-LCPs) with flexible spacers. The theory takes account of orientational correlation among all mesogens in a polymer chain and the relationship between the intramolecular orientation and spatial orientation of the mesogens. The free energy, temperature and entropy of the nematic-isotropic transition were determined with the theory and compared with experiments in current work. It was found that many unique transition properties of the MC-LCPs comprising flexible spacer are correctly predicted by the theory and the agreement of the theory with the experiments is impressive.

Synthesis and Liquid Crystalline Behavior of Side Chain Liquid Crystalline Polymers Containing Triphenylene Discotic Mesogens with Different Length Flexible Spacers

A series of side chain liquid crystalline polymers （SCLCPs） containing triphenylene （Tp） units in the side chains, denoted as PMTS （without spacer） and PMTnS （n = 2, 3, 4, 6, which is the number of the methylene units between the main chain and Tp moieties in the side chains）, with different lengths of spacers were synthesized through conventional free radical polymerization. The chemical structures of the monomers were confirmed by 1H/IaC-NMR, and the phase behaviors were examined by differential scanning calorimetry （DSC）, polarized optical microscopy （POM） and wide-angle X-ray diffraction （1D and 2D WAXD）. The molecular characterization of the polymers was performed with 1H-NMR, gel permeation chromatography （GPC） and thermogravimetric analysis （TGA）. The phase behaviors of the polymers have been investigated by a combination of techniques including DSC, POM, 1D and 2D WAXD. The results showed that the length of spacer has significant effects on the LC phase behavior of polymers. For PMTS and PMT2S, they displayed the columnar phase developed by the Tp moieties and the main chain as a whole due to the strong coupling effect of the Tp moieties and the main chain. For the PMT3S, PMT4S and PMT6S, they formed the symmetry hexagonal columnar （~n） phase owing to the decoupling effect. All of these indicated that the ＂decoupling effect＂ or ＂coupling effect＂ depended on the length of spacers, leading to the different LC phase formation mechanism.

Effects of Flexible Conjugation-Break Spacers of Non-Conjugated Polymer Acceptors on Photovoltaic and Mechanical Properties of All-Polymer Solar Cells

All-polymer solar cells(all-PSCs)possess attractive merits including superior thermal stability and mechanical flexibility for large-area roll-to-roll processing.Introducing flexible conjugation-break spacers(FCBSs)into backbones of polymer donor(P_(D))or polymer acceptor(P_(A))has been demonstrated as an efficient approach to enhance both the photovoltaic(PV)and mechanical properties of the all-PSCs.However,length dependency of FCBS on certain all-PSC related properties has not been systematically explored.In this regard,we report a series of new non-conjugated P_(A)s by incorporating FCBS with various lengths(2,4,and 8 carbon atoms in thioalkyl segments).Unlike com-mon studies on so-called side-chain engineering,where longer side chains would lead to better solubility of those resulting polymers,in this work,we observe that the solubilities and the resulting photovoltaic/mechanical properties are optimized by a proper FCBS length(i.e.,C2)in P_(A) named PYTS-C2.Its all-PSC achieves a high efficiency of 11.37%,and excellent mechanical robustness with a crack onset strain of 12.39%,significantly superior to those of the other P_(A)s.These results firstly demonstrate the effects of FCBS lengths on the PV performance and mechanical properties of the all-PSCs,providing an effective strategy to fine-tune the structures of P_(A)s for highly efficient and mechanically robust PSCs.

Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.