Poly(epichlorohydrin) (PECH) was modified to a considerable extent with mesogenic acids, namely 4′-(ω-alkenoxy)-4-biphenylcarboxylic acids and 6-(ω-alkenoxy)-2-naphthalenecarboxylic acids, which leads to side chain liquid crystalline polymers which can be cross-linked through their terminal double bonds in a further step. Cleavage and cross-linking side reactions, which have been reported elsewhere, were observed. The polymers were characterized by NMR, IR, SEC-MALLS, viscosimetry, elemental analysis, DSC, and TGA. The thermal stability of the modified polymers was higher than that of the starting PECH. The mesophases were identified by DSC, light-polarized optical microscopy, and X-ray diffraction. The biphenyl derivatives show smectic A mesophases consisting of a bilayer or partial bilayer structure, which is modulated for the 4′-(5-hexenoxy)-4-biphenylcarboxylic acid derivatives (S A ˜). The 6-(5-hexenoxy)-2-naphthalenecarboxylic acid and the 6-(10-undecenoxy)-2-naphthalenecarboxylic acid derivatives show nematic and smectic C mesophases, respectively.

Novel hybrid organic–inorganic materials were prepared from 10‐undecenoyl triglyceride and methyl 3,4,5‐tris(10‐undecenoyloxy)benzoate via hydrosilylation. 1,4‐Bis(dimethylsilyl)benzene, tetrakis(dimethylsilyloxy)silane, and 2,4,6,8‐tetramethylcyclotetrasiloxane were used as crosslinkers. The hydrosilylation reaction was catalyzed by Karstedt's catalyst [Pt(0)–divinyltetramethyldisiloxane complex]. The networks were structurally characterized by Fourier transform infrared spectroscopy, 13C NMR, and 29Si magic‐angle‐spinning NMR. The thermal properties of these hybrids were studied with differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The obtained materials showed good transparency and promising properties for optical applications. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6295–6307, 2005

We modified poly(epichlorohydrin) (PECH) with biphenyl carboxylic and naphthalene carboxylic acid derivatives which contains propargyloxy moieties. The linear polymers were characterized by NMR and IR spectroscopy, elemental analysis, DSC and TGA. We obtained only one side chain liquid crystalline. A smectic A mesophase of this biphenyl derivative was identified by DSC, light polarized optical microscopy and X‐ray diffraction. Thermal crosslinking of the aryl propargyl ether group via sigmatropic rearrangement took place while the material was in the isotropic phase. Partially curing this reactive liquid crystalline polymer resulted in the formation of an anisotropic elastomer when the curing was radically initiated in the range of mesophase stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3883–3892, 2002

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b, but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P4 and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and 1H and 13C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C2 mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006

Two series of vinyl‐terminated side‐chain liquid‐crystalline polyethers containing ethylene oxide or glycidyl aromatic carboxylates as spacers were synthesized. The mesogenic cores were 4,4′‐biphenyl or 2,6‐naphthalene moieties. The polymers were synthesized by chemically modifying poly(epichlorohydrin) or poly(epichlorohydrin)‐poly(ethylene oxide) with the corresponding mesogenic carboxylic acids or with mixtures of these acids and the nonmesogenic non‐crosslinkable analogous 4‐biphenyl‐ and 2‐naphthalenecarboxylic acids. In most cases the degree of modification achieved was higher than 90%. The polymers were characterized by chlorine analysis, IR, and 1H and 13C NMR spectroscopies; viscosimetry; size exclusion chromatography; multi‐angle laser light scattering; and thermogravimetric analysis. The liquid‐crystal behavior, shown by most polymers, was examined by differential scanning calorimetry, polarized optical microscopy (POM), and X‐ray diffraction on mechanically oriented samples. The crosslinking of most polymers was done by peroxide‐type initiators that led to liquid‐crystal thermosets or elastomers. The freezing of the mesophase organization on the crosslinked materials was confirmed by POM and X‐ray diffraction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3893–3908, 2002