• Fibers and Polymers
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• v.1 no.1
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• pp.12-17
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• 2000

Thermotropic polyurethanes were synthesized from 1,6-hexane diisocyanate (HDI) as a diisocyanate, 1,6-hexane diol (HD), and rigid diols containing imide unit such as N,N＇-bis(4-hydroxyphenyl)-3,4,3＇,4＇-biphenyl-dicarboxyimide (BPDI) or bis-N-(4-hydroxyphenyl)-4,4＇-oxydiphthalimide (ODPI). The effects of structure difference between BPDI and ODPI and composition of HD/BPDl (ODPI) on the thermal and liquid crystalline behavior were studied. Thermotropic polyurethanes with an inherent viscosity of 0.59~0.70 were obtained. The melting temperature of BPDI-based polyurethanes were in the range of 150~$290^{\circ}C$, however, those of ODPI-based polyurethanes were in the range of 150~$190^{\circ}C$. All the polyurethanes based on ODPI (25~100 mole %) clearly exhibited a stable liquid crystalline phase, and BPDI-based polyurethane having 5-25% of BPDT showed a mesophase. The melting and isotropization temperatures ($T_m$, $T_i$) and ΔT($T_i$ - $T_m$) increased with increasing BPDI and ODPI content. The polyurethanes based on BPDI has higher melting points and thermal stability compared to ODPI-based polyurethanes.

• Proceedings of the Korean Fiber Society Conference
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• 1998.04a
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• pp.9-13
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• 1998

A number of papers concerning the preparation and physical properties of thermotropic polyurethanes have been reported,$^{1.2}$ since thermotropic polyurethanes were first reported by Iimura and coworkers.$^3$ We have been studying the synthesis of thermotropic para-type aromatic polyurethanes containing alkylene spacers.$^{4.7}$ .(omitted)

• Elastomers and Composites
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• v.34 no.4
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• pp.292-298
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• 1999

Lactide oligomer with number averagae molecular weight of 460 was synthesized and reacted with poly(oxyteramethylene)glycol(PTMG, Mn = 650) to obtain oligolactide oligomer-terminated PTMG. Polyurethanes were synthesized from the oligolactide-terminated PTMG, 4,4'-diphenylmethane diisocyanate, and 1,4-butanediol. The mechanical and thermal properties of the polyurethanes and PTMG based polyurethane as control were measured by means of DSC and tensile tester. Degradation behavior of these polyurethanes put into a compost was evaluated by variation of mechanical properties, surface state, and weight loss. Modulus and weight significantly decreased with increasing time. The surface of the oligolactide polyurethane put into the compost during 6 weeks had a number of voids. On the other hand, These properties of the PTMG based polyurethane as control did not change. These results suggest that the novel polyurethanes incorporated oligolactide easily degrade under biodegradable condition.

• Macromolecular Research
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• v.16 no.3
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• pp.194-199
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• 2008

Four novel polyurethanes were prepared from 4-{(4-hydroxyphenyl)iminomethyl} phenol by reactions with two aromatic diisocyanates, 4,4'-diphenylmethane diisocyanate and toluene 2,4-diisocyanate, and two aliphatic diisocyanates, isophorone diisocyanate and hexamethylene diisocyanate. The polyurethanes formed were characterized by UV-vis, fluorescence, FT-IR, $^1H$-NMR, $^{13}C$-NMR, differential scanning calorimetry, thermogravimetry, and X-ray diffraction. The polymers were semi-crystalline and all polymers were soluble in polar aprotic solvents.

• Polymer(Korea)
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• v.29 no.3
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• pp.253-259
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• 2005

Polyurethanes, synthesized by polyester polyols and aliphatic or aromatic diisocyanates for a crease resist finishing agent, were prepared by two-step reactions, that is, prepolymer synthesis and chain extension. The structures of synthesized polyurethanes were confirmed by the measurement of FT-IR and $^1H$-NMR spectrometer. The number average molecular weight ($\bar{M}_n$) and the weight average molecular weight ($\bar{M}_w$) of the polyurethane with aromatic diisocyanate (MDI) were higher than those of the synthesized polyurethanes with aliphatic diisocyanate (HDI, $H_{12}MDI$). The glass transition temperatures ($T_g$) of soft segments in polyurethanes with MDI, HDI, $H_{12}MDI$ were -25,-42 and -50$^{circ}C$, respectively. In the polyurethanes obtained by two-step reaction, thermal stability and tensile strength increased with increasing hard segment contents, whereas elongation at break decreased with increasing hard segment contents.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.841-844
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• 2005

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.811-816
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• 2008

2,5-Di-(2'-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and polymerized with 2,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate to yield novel T-type polyurethanes 4 and 5 containing 2,5-dioxybenzylidenemalononitrile, nonlinear optical (NLO)-chromophores as part of the polymer backbones. Polyurethanes 4 and 5 were soluble in common organic solvents such as acetone and N,Ndimethylformamide and showed a thermal stability up to $250{^{\circ}C}$ with glass-transition temperatures ($T_g$) in the range $119-146{^{\circ}C}$. The second harmonic generation (SHG) coefficients ($d_{33}$) of poled polymer films at 1064 nm fundamental wavelength were around $5.82{\times}10^{-9}$ esu. The dipole alignment exhibited high thermal stability up to $T_g$, and there was no SHG decay below $140{^{\circ}C}$ due to the partial main-chain character of the polymer structure, which was acceptable for nonlinear optical device applications.

• Elastomers and Composites
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• v.44 no.3
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• pp.329-335
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• 2009

Four series of novel liquid crystalline polyurethanes were 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) with 4,4'-bis(5-hydroxypentoxy)biphenyl (BP5). 4,4'-bis(5-hydroxypentoxy)biphenyl exhibited a smectic type mesophase. Mesophase was found for all synthesized liquid crystalline polyurethanes except 1,4-PDI/BP5. The structures and the thermal properties of polyurethanes were studied by using FT-IR and ^1H$ NMR spectroscopy, DSC measurements and a polarizing microscope equipped with a heating stage.

• Macromolecular Research
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• v.14 no.3
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• pp.373-382
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• 2006

A series of crosslinkable, waterborne polyurethanes (I-WBPUs) were prepared by in-situ polymerization using isophorone diisocyanate (IPDI)/poly(tetramethylene oxide) glycol (PTMG, $M_n$=2,000)/dimethylol propionic acid (DMPA)/ethylene diamine (EDA)/triethylamine (TEA)/aminoplast[hexakis(methoxymethyl)melamine (HMMM)] as a crosslinking agent. Typical crosslinkable, waterborne polyurethanes (B-WBPUs) blended from WBPU dispersion and aqueous HMMM solution was also prepared to compare with the I-WBPUs. The crosslinking reaction between WBPU and HMMM was verified using FTIR and XPS analysis. The effect of the HMMM contents on the dynamic mechanical thermal, thermal, mechanical, and adhesion properties of the I-WBPU and B-WBPU films were investigated. The storage modulus(E'), glass transition temperatures of the soft segment ($T_{gs}$) and the amorphous regions of higher order ($T_{gh}$), melting temperature ($T_m$), integral procedural decomposition temperature (IPDT), residual weight, $T_{10%}$ and $T_{50%}$ (the temperature where 10 and 50% weight loss occurred), tensile strength, initial modulus, hardness, and adhesive strength of both I-WBPU and B-WBPU systems increased with increasing HMMM content. However, these properties of the I-WBPU system were higher than those of the B-WBPU system at the same HMMM content. These results confirmed the in-situ polymerization used in this study to be a more effective method to improve the properties of the WBPU materials compared to the simple blending process.

• 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.