• 한국염색가공학회지
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• 제8권1호
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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

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 1998년도 가을 학술발표회논문집
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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)

• 공업화학
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• 제8권2호
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• pp.339-346
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• 1997

액정 polyurethane은 DMF 용매중 1,4-bis(6-hydroxyhexoxy)benzene (BHB6)과 2,5-tolylene diisocyanate (2,5-TDI)를 중부가 반응에 의해서 합성하였다. 고유점도는 0.26, $0.42d{\ell}/g$였다. 생성된 polyurethane의 열적성질 및 구조확인은 DSC, 편광현미경, X-ray회절 그리고 $^1H$-NMR 및 FT-IR에 의해 확인하였다 특히 분자량이 서로 다른 polyurethane 2,5-TDI/BHB6의 열적성질 및 물성에 대해서 비교 검토하였다. 고유점도가 [${\eta}$]=0.26인 polyurethane 2,5-TDI/BHB6는 monotropic 액정성을 나타내었다. 이러한 것은 구조적으로는 mesogen을 포함하고 있지 않다. 예를 들면 LCPU-L(저분자량)은 $T_{I-LC}$(등방성액체상전이점-액정) 및 $T_{LC-K}$(액정-결정)은 $122^{\circ}C$부터 $89^{\circ}C$까지 관찰되었다.

• Elastomers and Composites
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• 제41권2호
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• pp.108-115
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• 2006

비페닐기를 함유하는 새로운 형태의 액정성 폴리우레탄을 신규로 합성한 4,4'-Bis(9-hydroxynonoxy)biphenyl (BP9)와 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,4-phenylene diisocyanate 및 hexamethylene diisocyanate의 중부가 반응에 의해 합성하였다. 단량체 BP9은 스멕틱상을 형성하였으며 1,4-PDI/BP9을 제외한 나머지 폴리우레탄에서는 모두 액정성을 나타내었다. 합성된 단량체와 중합체들의 구조는 적외선분광분석기 및 핵자기공명분석기를 사용하여 확인하였으며, 그들의 열적 상전이 온도 및 안정성들은 시차주사 열량분석기와 편광현미경으로 조사하였다.

• Elastomers and Composites
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• 제44권3호
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• pp.329-335
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• 2009

4종류의 새로운 형태의 열방성 액정폴리우레탄을 4,4'-Bis(5-hydroxypentoxy)biphenyl (BP5)와 2,6-tolylene diisocyanate (2,6-TDI), 2,5-tolylene diisocyanate (2,5-TDI), 및 2,4-tolylene diisocyanate (2,4-TDI), 1,4-phenylene diisocyanate (1,4-PDI) 의 중부가 반응에 의해 합성하였다. 단량체 BP5은 스멕틱상을 형성하였으며 1,4-PDI/BP5을 제외한 나머지 폴리우레탄에서는 모두 액정성을 나타내었다. 생성된 폴리우레탄의 구조는 FT-IR과 ^1H$ NMR 스펙트럼으로 확인하였고 열적 성질은 DSC와 편광현미경으로 관찰하였다.

• 한국염색가공학회지
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• 제7권4호
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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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• 제48권2호
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• pp.141-147
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• 2013

메소겐(Mesogen) 단위가 포함되어 있지 않는 para- 형태의 1,4-phenylene diisocyanate (1,4-PDI)와 2,6-bis(${\omega}$-hydroxypentoxy)naphthalene (BHN5) 또는 1,4-bis(${\omega}$-hydroxypentoxy)benzene (BHB5)을 단일과 공중합폴리우레탄을 부가중합에 의해 합성하였다. 모든 공중합폴리우레탄에서는 전단변형의 측정에서 단방성 액정상을 나타내었다. 예를 들면, 고유점도가 $[\eta]$=0.32 dL/g인 폴리우레탄 Poly(50/50, mol%)은 $223^{\circ}C{\sim}211^{\circ}C$에서 냉각 시 액정성을 나타내었다. 그러나 두 개의 단일폴리우레탄에서는 DSC (Differental Scanning calorimeter) 측정 및 편광현미경 관찰에서도 액정상을 전혀 관찰 할 수 없었다. 합성된 폴리우레탄의 액정성은 시차주사열량분석기, 편광현미경과 X-ray에 의해 확인하였다.

• 한국염색가공학회지
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• 제8권3호
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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.

• 한국염색가공학회지
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• 제8권2호
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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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• 제1권1호
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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.