• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.39-43
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• 2006

The relaxed torsional potential of a liquid crystalline polymer containing an ester functional group in a mesogenic unit (hereafter 12-4 oligomer) has been calculated with the ab initio self-consistent-field using 6-31G$^*$ basis set. GIAO^{13}C NMR chemical shifts also have been calculated at the B3LYP/6-31G$^*$ level of theory for each conformational structure obtained from torsional potential calculation. The results show that the phenyl ring-ester linkages are coplanar with the dihedral angle of about 0$^{\circ}$ and the ring-ring linkages in the biphenyl groups are tilted with the dihedral angle of around 43-44$^{\circ}$ in the lowest energy conformer. The biphenyl ring has a comparatively lower energy barrier of internal rotation potential in the ring-ring than that of phenyl ring-ester. The ^{13}C chemical shifts of carbonyl carbons were found to move to upfield due to $\pi$ -conjugation with phenyl ring and slightly affected about 0.5 ppm by dihedral angle of the ring-ring linkage.

• Textile Coloration and Finishing
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• v.7 no.4
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• pp.8-15
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• 1995

A series of thermotropic Polyurethanes mesogenic unit were synthesized by polyaddition of a para-type diisocyanate such as 2,5-tolylene diisocyanate(2,5-TDI) with 4-4'-bis($\omega$-hydroxyalkoxy) biphenls(BPm: $HOCmH_{2m}OC_{6}H_{4}OC_{m}H_{2m}OH$ : m is the carbon number of the hydroxyalkoxy group) in DMF. Intrinsic viscosities of the polymers were in the range of 0.41~0.99dL/g DSC thermograms for these polymers exhibited two endothermic peaks corresponding to phase transitions of melting and isotropization. For examplem polyurethane 2,5-TDI/BPll with [η]=0.99 prepared from 2.5-TDI and 4,4'-bis[11-hydroxyundecaoxy biphenyl(BP11) a liquid crystalline phase from 156 to 173$^{\circ}C$. The thermotropic properites of liquid crystalline polyurethanes have been investigated by wide-angle X-ray scatter(WAXS), infrared (IR) spectroscopy, and differential scanning calorimetry (DSC). The mesomorphic behavior of the polyurethanes was concluded to be greatly dependent on the intermolecular hydrogen bonds through the urethane.

• Elastomers and Composites
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• v.40 no.1
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• pp.37-44
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• 2005

Novel polyurethanes containing no mesogenic unit were synthesized by the polyaddition reaction of para-type diisocyanates such as 2,5-tolylene diisocyanate (2,5-TDI) or 1,4-phenylene diisocyanate (1,4-PDI) with 2,6-bis(${\omega}$-hydroxyalkoxy)naphthalene (BHNm; m= 5, 6, 8, 11). Intrinsic viscosities of the polymers were in the range of 0.28-0.43 dL/g. The thermal properties of these polymers were studied by differential scanning calorimetry and polarizing microscopy. Polyurethanes prepared from BHNm and 2,5-TDI haying methyl substituent on the phenylene unit exhibited monotropic liquid crystallinity. However, in the series of polyurethanes prepared from 1,4-PDI and BHNm, no explicit mesomorphic behavior was observed by differential scanning calorimetry and polarizing microscopy.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.280-286
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• 2015

Two series of unsymmetric dimesogenic compounds containing a butylene or pentamethylene group as the flexible spacer were synthesized and their thermal and mesomorphic properties were studied. Mesogenic groups of the synthesized compounds consisted of a cholesteryl and an azobenzene group with lateral substituent. Chemical structures and mesomorphic properties of the synthesized compounds were investigated by FT-IR, $^1H$-NMR, differential scanning calorimeter (DSC), and polarizing optical microscope (POM). All synthesized compounds, apart from $D5-OCH_3$, showed enantiotropic liquid crystal phases. Compounds having an even number of carbon atoms in the flexible spacer exhibited wide mesophase temperature ranges and high isotropic transition temperatures. Regarding the effect of lateral substituents, compounds with bulky substituents exhibited decreased mesophase temperature ranges and isotropic transition temperatures, while those with polar substituents showed the increased thermal stability of the smectic phase.

• Korean Chemical Engineering Research
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• v.48 no.5
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• pp.615-620
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• 2010

In this study, five series of novel polyurethanes was synthesized by the polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate(2,6-TDI), 2,5-tolylene diisocyanate(2,5-TDI), 2,4-tolylene diisocyanate(2,4-TDI), and 1,4-phenylene diisocyanate(1,4-PDI), hexamethylene diisocyanate(HDI) with 4,4'-Bis(3-hydroxypropoxy)biphenyl (BP3), 4,4'-bis(3-hydroxypropoxy)biphenyl exhibited a smectic type mesophase. Monotropic mesophase was found for all synthesized liquid crystalline polyurethanes except HDI/BP3. In contrast, 1,4-PDI/BP3 without a methyl substituent in the phenylene unit exhibited no explicit mesomorphic behavior, which was confirmed by DSC and polarizing microscopy experiments. Structures of the compound were identified by FT-IR and $^1H$-NMR spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry(DSC), polarized optical microscopy(POM) and x-ray diffraction analysis.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.15 no.1
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• pp.575-580
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• 2014

The liquid crystalline copolymers were synthesized through direct polycondensation using 4-[4-(4-hydroxyphenoxy)butoxy]benzoic acid (HBBA) and p-hydroxy benzoic acid (HBA) as monomers. The structure and properties for synthesized copolymers were investigated by $^1H$-NMR, FT-IR, differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and polarizing optical microscope (POM). As result of investigations, inherent viscosities (${\eta}_{inh}$) of polymers were measured as 0.77~1.60 dL/g in phenol/p-chlorophenol/1,1,2,2-tetrachloroethane (25/40/35=w/w/w). Except for P-80, the ranges of the transition and mesophase temperature of copolymers were increased with increasing the amount of HBA. These properties of polymers were presumably due to increasing of the irregularity and rigidity of polymer chains.

• Textile Coloration and Finishing
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• v.8 no.2
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• pp.1-7
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• 1996

Thermotropic liquid-crystalline polyurethanes were synthesized by the polyaddition reaction of such para-substiuted diisocyanate monomer as 1,4-phenylene diisocyanate(1,4-PDI) and 2,5-tolylene diisocyanate(2,5-TDI), with 4,4'-bis($\omega$-hydroxyalkoxy)biphenyls(BPm: $HOC_{m}OC_{6}H_{4}C_{6}H_{4}OC_{m}H_{2m}OH$; m is the carbon number of the hydroxyalkoxy group). These polyurethanes have mesogenic biphenyl units in the main chain. Properties of polymers were studied by differential scanning calorimetry, wide-angle X-ray scattering, thermogravimetic analysis, polarizing microscopy, and infraed spectroscopy. DSC thermograms for these polymers exhibited two endothermic peaks corresponding to phase transitions of melting and isotropization. Mesomorphic behavior of the polyurethanes were also observed under the polarizing microscope. For example, polyurethane 2,5-YDI/BP5 with [$\theta$]=0.44 prepared from 2,5-TDI and BP5 exhibited a liquid crystalline phase from 194 to 205$^{\circ}C$. Infrared spectrum study indicated that the hydrogen bonding between urethane linkages affected the mesomorphism. The thermostabilities of polyurethanes 2,5-TDI/BP5 and 1,4-PDI/BP5 were measured at a heating rate of 1$0^{\circ}C$/min in air. The temperatures of 5% weight loss for 2,5-TDI/BP5 and 1,4-PDI/BP5 were 297 and 334$^{\circ}C$, respectively.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.176-180
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• 2005

The liquid crystalline properties of a series of main chain liquid crystalline polymers and four series compounds consisting of aromatic type Schiff base mesogenic units and polymethylene flexible spacers were studied. The thermal and liquid crystalline properties were investigated by differential scanning calorimetry and on the hot stage of a polarizing microscope. The nature of the liquid crystalline phase of the polymers and compounds depended greatly on the length of the central polymethylene spacer and on the terminal alkoxy groups. Polymers I and Series III exhibited an even-odd effect in melting and isotropization temperatures but Series II and Series IV exhibited an even-odd effect in isotropization temperatures. They formed nematic and smectic mesophases in melts as judged by their optical textures observed through a polarizing microscope.

• Elastomers and Composites
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• v.48 no.4
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• pp.306-311
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• 2013

A series of liquid crystalline polyesters containing the 4-chloro benzoate group on the hydroquinone unit of rigid group were synthesized through solution polymerization of 2,5-di(4-chlorobenzoate)hydroquinones and 4,4'-dicarboxy-${\alpha},{\omega}$-diphenoxy alkane. The structure and properties for synthesized polymers were investigated by $^1H$-NMR, FT-IR, DSC, TGA, and POM. As result of investigations, The presence of the methylene group and bulky lateral groups in polymer chain have a great influence on the properties of polymers such as solubilities and thermal transitions. The optical textures of polymers revealed a weak birefringence in the melt and indicated that they form nematic mesophase. All polymers have very narrow mesophase temperature ranges.

• Polymer(Korea)
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• v.24 no.1
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• pp.16-22
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• 2000

Poly(butylene terephthalate- co-oxybenzoate)(PBOT) containing mesogenic oxybenzoate units in the main chain was synthesized through ester exchange reaction by melt mixing of poly(butylene terephthalate)(PBT) and p-acetoxybenzoic acid (ABA). From the kinetics of the copolymerization reaction, the activation energies and the rate constants of homopolymerization and copolymerization, k$_{h}$ and k$_{c}$, could be determined. From the reaction conditions of different compositions, 4/6, 5/5, and 6/4 of PBT/ABA, at 250, 260, and 27$0^{\circ}C$, it was revealed that copolymerization between PBT and ABA proceeds on a pseudo-second order reaction if the ABA content and its conversion are low. In this case, the ratio of rate constants of homopolymerization to copolymerization was in the range from 1.08 to 3.17, indicating that the copolymer with more notable block character was obtained at the higher mole fraction of ABA and at higher temperature.e.e.