• Textile Coloration and Finishing
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• v.8 no.1
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• pp.56-63
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• 1996

A number of thermotropic liquid crystalline polyurethanes with mesogenic unit were synthesized by polyaddition of a para-type diisocyanate such as 1, 4-phenylene diisocyanate(1,4-PDI) with 4, 4'-bis($\omega$-hydorxyalkoxy) biphenyls($BP{m}$) in DMF. The thermal and liquid crystab line properties were examined by differential scanning calorimetry(DSC), polarized optical microscopy, and wide-angle X-ray scattering(WAXS). Intrinsic viscosities of the polymers exbibited two endothermic peaks correspondinding to phase transitions of melting and isotropization. For example, polyurethane(1,4-PDI/($BP{11}$) ) was found to display a liquid crystalline phase between 177 to 205$^{\circ}C$. In order to know how the hydrogen bonding interaction affects the formation of mesophases in polyurethane 1, 4-PDI/($BP{8}$) / thermal processing FT-IR measurements were carried out. It was found that the stretches regarded as shift to higher frequency region with increasing temperature which showed grdually their liquid crystalline phase

• Proceedings of the Korean Fiber Society Conference
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• 1998.10a
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• pp.98-101
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• 1998

Segmented polyurethane elastomers are an important class of polymeric materials consisting of thermodynamically incompatible hard and soft segments. Due to the chemical structural difference between the hard and soft segments, a microphase separation occurs, consisting of crystalline hard domains and amorphous soft domains. (omitted)

• Applied Chemistry for Engineering
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• v.8 no.2
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• pp.339-346
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• 1997

Liquid crystalline polyurethanes were prepared from 1,4-bis(6-hydroxyhexoxy)benzene (BHB6) and 2,5-tolylene diisocyanate (2,5-TDI) solution polymerization in dimethylformamide produced intrinsic viscosities in the range 0.26 and $0.42d{\ell}/g$. The polyurethanes were investigated by DSC, Polarizing microscopy, X-ray, $^1H$-NMR and IR spectroscopy. Polyurethanes of two different molecular weights were studied in detail and these will be referred to as low molecular weight and high molecular weight. Polyurethane 2,5-TDI/BHB6 with $[{\eta}]=0.26d{\ell}/g$ prepared from BHB6 and 2,5-TDI, exhibited monotropic liquid crystallinity, although these polyurethanes contained no mesogenic core unit. For example, LCPU-L(low molecular weight) exhibited $T_{I-LC}$ of $122^{\circ}C$ $T_{LC-K}$ $89^{\circ}C$.

• Elastomers and Composites
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• v.41 no.2
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• pp.108-115
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• 2006

A series of thermotropic polyurethanes containing biphenyl units was synthesized by polyaddition reaction of diisocyanates such as 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,4-phenylene diisocyanate, and hexamethylene diisocyanate with 4,4'-Bis(9-hydroxynonoxy)biphenyl (BP9). 4,4'-bis(9-hydroxynonoxy)biphenyl exhibited a smectic type mesophase. Mesophase was found for all synthesized liquid crystalline polyurethanes except 1,4-PDI/BP9 based polyurethane. Structures of the monomer and the corresponding polymers were identified using FT-IR and $^1H-NMR$ spectroscopies. Their phase transition temperatures and thermal stability were also investigated by differential scanning calorimetry and optical polarizing microscopy.

• 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.

• 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.48 no.2
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• pp.141-147
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• 2013

Polyurethanes containing no mesogenic unit were prepared by polyaddition reaction of homo- and copolyurethanes based on para-type 1,4-phenylene diisocyanate (1,4-PDI), 2,6-bis($\omega$-hydroxypentoxy)naphthalene (BHN5) with 1,4-bis($\omega$-hydroxypentoxy)benzene (BHB5). All copolyurethanes showed monotropic liquid crystallinity, when measurements were performed under shearing. For example, a polyurethane Poly(50/50, mol%) with $[\eta]$=0.32 dL/g exhibited liquid crystallinity in the temperature range from $223^{\circ}C$ to $211^{\circ}C$ in the cooling stage. In contrast, two homopolyurethanes exhibited no explicit mesomorphic behavior, which was observed by DSC (Differental Scanning calorimeter) and measurement and polarized microscopic observation. The mesomorphic behavior of synthesized polyurethane was identified and characterized by differential scanning calorimetry, polarized optical microscope and X-ray.

• Textile Coloration and Finishing
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• v.8 no.3
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• pp.1-7
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• 1996

Mesogenic unit를 포함하고 있지 않는 1,4-phenylene diisocyanate, 2,6-bis(5-hydroxypentoxy)naphthalene, 1,4-bis(5-hydroxypentoxy)benzene을 重附加反應을 시킨 結果 生成된 co-polyurethane은 液晶性을 나타내었다. copolyurethane의 熱的 性質과 構造確認을 위하여 DSC, 編光顯微鏡, TG 및 FT-IR, $^{1}$H-NMR로 測定하였다. DSC 測定結果 Tm 및 Ti가 대부분 明確의 나타내었다. 특히 液晶 範圍는 copolyurethane은 homopolyurethane보다 약간 넓은 範圍에서 液晶性을 나타내었다. 예를 들면 copolyurethane(60/40) 및 home-polyurethane(0/100) 의 液晶 範圍는 각각 2$0^{\circ}C$ 및 11$^{\circ}C$이다. 이러한 것은 homopolyurethane이 copiktyretgabe보다 熱的 安定性이 적다는 것을 나타낸다. 그리고 TG의 測定에서도 homopolyurethane(100/0) 및 copolyurethane이 熱的으로 安定하다는 것을 알았다. 예를 들면 homopolyurethane(100/0) 및 copolyurethane(80/20)에서의 5%에서의 TG 測定結果 각각 312$^{\circ}C$ 및 327$^{\circ}C$였다. 이러한 結果는 copolyurethane이 homopolyurethane보다 分子間 水素結合의 影響으로 熱的 安定性을 가져오는 것을 確認 할 수 있었다.

• 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.

• 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.