A powerful strategy to enhance the thermal conductivity of liquid crystalline epoxy resin (LCER) by simply replacing the conventional amine cross-linker with a cationic initiator was developed. The cationic initiator linearly wove the epoxy groups tethered on the microscopically aligned liquid crystal mesogens, resulting in freezing of the ordered LC microstructures even after curing. Owing to the reduced phonon scattering during heat transport through the ordered LC structure, a dramatic improvement in the thermal conductivity of neat cation-cured LCER was achieved to give a value ∼141% (i.e., 0.48 W/mK) higher than that of the amorphous amine-cured LCER. In addition, at the same composite volume fraction in the presence of a 2-D boron nitride filler, an approximately 130% higher thermal conductivity (maximum ∼23 W/mK at 60 vol %) was observed. The nanoarchitecture effect of the ordered LCER on the thermal conductivity was then examined by a systematic investigation using differential scanning calorimetry, polarized optical microscopy, X-ray diffraction, and thermal conductivity measurements. The linear polymerization of LCER can therefore be considered a practical strategy to enable the cost-efficient mass production of heat-dissipating materials, due to its high efficiency and simple process without the requirement for complex equipment.

A series of crown ether type binaphthyl derivatives (CEBDs) were synthesized and used as chiral dopants to induce chiral nematic (N*) liquid crystals (LCs). The twisting powers of the CEBDs for phenylcyclohexane (PCH)-derived nematic LCs were evaluated. It was found that the twisting powers of the CEBDs increased with decreasing ring size of the crown ether. Helical polyacetylenes were synthesized in the N*-LCs induced by the CEBDs. The relationship between the morphology of the helical polyacetylene and the helical structure of the N*-LC was investigated. The result showed that the interdistance between the fibril bundles of the helical polyacetylene was equal to a half-helical pitch of the N*-LC and the screw direction of the polyacetylene fibrils was opposite to that of the N*-LC.

We report an effective way to fabricate mechanically strong and multifunctional polyimide (PI) nanocomposites using aminophenyl functionalized graphene nanosheet (APGNS). APGNS was successfully obtained through a diazonium salt reaction. PI composites with different loading of APGNS were prepared by in situ polymerization. Both the mechanical and electrical properties of the APGNS/ PI composites were significantly improved compared with those of pure PI due to the homogeneous dispersion of APGNS and the strong interfacial covalent bonds between APGNS and the PI matrix. The electrical conductivity of APGNS/PI (3:97 w/w) was 6.6 × 10 −2 S/m which was about 10 11 times higher than that of pure PI. Furthermore, the modulus of APGNS/PI was increased up to 16.5 GPa, which is approximately a 610% enhancement compared to that of pure PI, and tensile strength was increased from 75 to 138 MPa. The water vapor transmission rate of APGNS/PI composites (3:97 w/w) was reduced by about 74% compared to that of pure PI. ■ INTRODUCTIONAromatic polyimide (PI) is a high-performance polymer with applications in the fields of microelectronics, optoelectronics, adhesives, and aerospace owing to its high thermal stability and favorable chemical and mechanical properties. 1,2 However, PI has a few limitations, such as electrostatic accumulation, poor heat dissipation, and low electrical conductivity for special applications. In recent years, much attention has been paid to PI composites with carbon nanomaterials because the incorporation of carbon nanofillers can effectively enhance the thermal, mechanical, and electrical properties of the nanocomposites. 2−6 Graphene, a one-atom-thick planar sheet of carbon atoms densely packed in a honeycomb crystal lattice, 7 has revolutionized the scientific frontiers of nanoscience and condensed matter physics due to its exceptional electrical, 8 physical, 9 and chemical properties. 10 The excellent properties of graphene have opened new pathways for developing a wide range of novel functional materials. In addition, graphene has a distinctive mechanical property with fracture strains of ∼25% and a Young's modulus of ∼1 TPa. 9 However, poor dispersion in organic solvents and weak interfacial interactions between graphene and the polymer matrix limit the widespread use of graphene. In contrast, graphene oxide (GO) produced by the oxidation of graphite can solve these issues. It is easily dispersed in water and polar solvents due to the functional groups, such as ketones, diols, epoxides, hydroxyls, and carbonyl, on its edges and basal planes. 11 Nevertheless, GO has limited compatibility with certain polymers and limited solubility in hydrophobic solvent owing to its hydrophilic nature, which can reduce the reinforcement effects of interfacial interaction in the polymer matrix. 12,13 Therefore, the key issue is to improve both the homogeneous dispersion and strong interfacial interaction between the polymer matrix and graphene for the development of high performance polymer/graphene nanocomposites. R...

We synthesized novel axially chiral binaphthyl derivatives with highly twisting powers by substituting phenylcyclohexyl (PCH) mesogenic moieties into 2,2' positions or 2,2',6,6' positions of binaphthyl rings. The di- and tetrasubstituted binaphthyl derivatives, abbreviated as D-1 and D-2, respectively, were adopted as chiral dopants to induce chiral nematic liquid crystals (N*-LCs) available for synthesis of helical polyacetylene. The helical twisting power (betaM) of D-2 was 449 microm(-1), which was ca. 2.6 times larger than that of D-1 (171 microm(-1)). We prepared two kinds of induced N*-LCs with 5 microm and 270 nm in helical pitch by adding the chiral dopants D-1 and D-2 into the host N-LCs, respectively. The helical polyacetylene synthesized in the N*-LC containing D-2 exhibited highly screwed fibrils, but not a bundle of fibrils. This result is in quite contrast to the usual fibril morphology, where the screwed fibrils are gathered to form the bundle of fibrils, as observed in the helical polyacetylene synthesized in the N*-LC containing a chiral dopant with moderate helical twisting power, such as D-1. It is of keen interest that the helical pitch (270 nm) of the N*-LC including D-2 is much smaller than the diameter (ca. 1 microm) of the bundle of fibrils, which should depress the formation of the bundle of fibrils. The morphology free from the bundle of fibrils might enable us to evaluate more precisely intrinsic electromagnetic properties of a single screwed fibril of helical polyacetylene.