• 한국염색가공학회지
• /
• 제8권1호
• /
• pp.56-63
• /
• 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

• 폴리머
• /
• 제28권6호
• /
• pp.538-544
• /
• 2004

Z-라이신 올리고머를 사슬연장제로 하고 D-다이페닐이소시아네이트와 폴리테트라메틸글리콜을 반응시켜 주사슬에 L-라이신 분절을 함유하는 폴리우레틴 (PULL)을 합성하였다. PULL 표면의 아민기와 인슐린의 공유 결합으로 인슐린 고정화 폴리우레탄 (PULL-In)을 제조하였다. Bradfold법으로 측정한 고정화 인슐린의 양은 약 0.30 nmol/$\textrm{cm}^2$이였다. $^3$H-thymidine 분석방법과 광학 현미경법으로 NIH/3T3 섬유아세포와 표면 개질된 PULL의 상호작용을 조사하였다. 그 결과 PULL-In 필름 표면에서의 세포 성장 속도는 다른 기질에서보다 높았다. 또한 고정화된 인슐린에서의 세포증식이 배양액에 용해된 인슐린에서와 거의 유사한 특성을 나타내었다.

• 접착 및 계면
• /
• 제18권4호
• /
• pp.179-182
• /
• 2017

본 연구에서는 polycaprolactone diol, castor oil과 4,4'-methylene dicyclohexyl diisocyanate 를 소프트 도메인으로, dimethylol butanoic acid를 내부 유화제로, trimethylamine을 중화제로 사용하여 다른 분자량을 가지는 prepolymer를 기초로 castor oil 기반의 수분산 폴리우레탄을 성공적으로 합성하였다. 분자량 변화에 따른 기계적인 물성 변화(UTM), 표면의 친수성 확인(contact angle), castor oil 유무에 따른 표면개질 변화(FE-SEM) 등을 평가 분석하였다. Castor oil 기반의 수분산 폴리우레탄의 경우 표면 친수성 향상 및 개질 변화를 기대할 수 있으며, 다양한 접착제 분야에 적용될 유망한 후보 물질로 여겨질 수 있을 것으로 예상된다.

• Fibers and Polymers
• /
• 제3권4호
• /
• pp.153-158
• /
• 2002

A series of waterborne polyurethanes (WBPU) were prepared from 4,4-dicyclohexylmethane diisocyanate ($H_{12}$MDI),2,2-bis(hydroxylmethyl) propionic acid (DMPA), othylenediarnine (EDA), triethylamine (TEA), and triblock glycol [TBG, ($\varepsilon$-caprolactone)$_{4.5}$-poly(tetramethylene ether) glycol (MW= 2000)-($\varepsilon$-caprolactone)$_{4.5}$: $(CL)_{4.5}$-PTMG-$(CL)_{4.5}$, MW=3000] as a soft segment. Two melting peaks of TBG at about 14$^{\circ}C$ and 38$^{\circ}C$ were observed indicating the presence of two different crystalline domains composed of CL and PTMG dominant component. The effect of soft segment content (60-75 wt%) on the colloidal properties of dispersion, and thermal and mechanical properties of WBPU films, the water vapor permeability (WVP) and water resistance (WR) of WBPU-coated Nylon fabrics, and the adhesive strength of WBPU- coated layer and Nylon fabrics was investigated. As soft segment contents increased, the water vapor permeability of WBPU- coated Nylon fabrics increased from 3615 to 4502 g/$m^2$day, however, the water resistances decreased from 1300 to 500 mm$H_2$O.O.

• Elastomers and Composites
• /
• 제55권1호
• /
• pp.13-19
• /
• 2020

4,4'-Methylenebis(2-chlorobenzenamine) (MOCA)-free fast curing polyurethanes were prepared. In this study, the processibility of a fast curing polyurethane system was characterized by assessing the pot life. The obtained pot life of the polyurethane was 6-8 s, indicating that this prepolymer-curative system is appropriate for ribbon flow casting. The influence of the NCO index on the viscosity and mechanical properties was evaluated. The viscosity, tensile strength, tear strength, and hardness of the as-prepared polyurethanes showed an increasing trend, with an increase in the NCO index, whereas the elongation at break increased initially and then decreased with an increase in the NCO index. The gel fraction and crosslink density showed a direct correlation with the NCO index, which substantiated the improved mechanical properties at the higher NCO index. The coefficients of friction and abrasion deteriorated with an increase in the NCO index.

• Transactions on Electrical and Electronic Materials
• /
• 제18권4호
• /
• pp.211-216
• /
• 2017

The dielectric properties of two polyurethanes (PUs) with different hard segments, i.e., aromatic methylene di-p-phenyl diisocyanate (MDI) and aliphatic hexamethylene diisocyanate (HDI), were investigated in the temperature range of -100 to $100^{\circ}C$ and in the frequency range of 1 Hz to 3 kHz. The ${\alpha}$-relaxations induced by the glass transition of the equivalent soft segments in the two PUs occurred at relaxation times of ${\tau}=3.46{\times}10^{-3}s$ for MDI-PU and ${\tau}=3.39{\times}10^{-2}s$ for HDI-PU at $-20^{\circ}C$, in accord with the temperature-frequency superposition principle, resulting in similar shifting factors. However, different I-relaxations were observed for the two PUs. The I-relaxation of MDI-PU occurred due to the mobility of the chain extenders near $80^{\circ}C$ with a slower shifting rate than the ${\alpha}$-relaxation. On the other hand, I-relaxation arising from both the extender and the unconstrained hard segments of HDI-PU occurred at $70{\sim}100^{\circ}C$, indicating complicated dielectric behavior due to partial interaction with the ${\alpha}$-relaxation at high frequencies. Thus, the I-relaxation of HDI-PU did not follow the superposition principle. The dielectric behaviors of the PUs were mainly influenced by their phase transitions, which were affected by the structure and components of the materials.

• 한국산업보건학회지
• /
• 제22권3호
• /
• pp.209-216
• /
• 2012

Objectives: Polyurethanes are usually formed by the reactions of liquid diisocyanate components with liquid polyol resin components. Although polyurethanes have advantageous properties, such as their versatility, the manufacturing process generates diisocyanates, which can cause asthma and respiratory irritation in exposed workers. This study compared the differences in diisocyante concentrations between two different (molded foam and slabstock foam) polyurethane foam manufacturing methods. Materials and Methods: Active samples and direct reading samples of diisocyanates (MDI, TDI) were collected in five polyurethane foam manufacturing companies. Results: Workers' exposure concentrations of diisocyanate (GM: 4.078 ppb, range: 1.190~23.770 ppb) in a slabstock foam manufacturing company were much higher than those (GM: 0.011 ppb, range: 0.001~0.055 ppb) in molded foam manufacturing companies. The results of the direct reading samples of diisocyanate indicated that the rapid reaction zone of the slabstock foam processes emitted large amounts of diisocyanates. Conclusions: The exposure levels of diisocyanates for all molded foam workers were much lower than the occupational exposure standard (5 ppb); however, exposure levels for many slabstock foam workers exceeded the standard.

• Elastomers and Composites
• /
• 제54권3호
• /
• pp.225-231
• /
• 2019

Bio-based polyester polyol was synthesized via esterification between azelaic acid and isosorbide. After esterification, bio-based polyurethanes were synthesized using polyester polyol, 1,3-propanediol as the chain extender, and 4,4'-diphenylmethane diisocyanate, in mixing ratios of 1:1:1.5, 1:1:1.8, 1:1:2, and 1:1:2.3. The bio TPU (Thermoplastic Polyurethane) samples were characterized by using FT-IR (Fourier Transform Infrared Spectroscopy), TGA (Thermal Gravimetric Analysis), DSC (Differential Scanning Calorimetry), and GPC (Gel Permeation Chromatography). The mechanical properties (tensile stress and hardness) were obtained by using UTM, a Shore A tester, and a Taber abrasion tester. The viscoelastic properties were tested by an Rubber Processing Analyzer in dynamic strain sweep and dynamic frequency test modes. The chemical resistance was tested with methanol by using the swelling test method. Based on these results, the bio TPU synthesized with the ratio of 1:1:2.3, referred to as TPU 4, showed the highest thermal decomposition temperature, the largest molecular weight, and most compact matrix structure due to the highest ratio of the hard segment in the molecular structure. It also presented the highest tensile strength, the largest elongation, and the best viscoelastic properties among the different bio TPUs synthesized herein.

• Bulletin of the Korean Chemical Society
• /
• 제22권2호
• /
• pp.194-198
• /
• 2001

In order to look for polymeric materials applicable to the oxygen electrode membranes of biosensors, polyurethanes (PUs) were synthesized from poly(butylene succinate) diol (Mn 1150), poly(ethylene glycol) (Mn 200), and 4,4'-methylenebis(cyclohexyl isocyanate). The PUs (Mn 15000-100000) underwent the crystallization and melting transitions in the temperature range of 20-30 $^{\circ}C$ and 90-110 $^{\circ}C$, respectively. The oxygen permeability for the PU membranes prepared by the solution casting method could not be measured since oxygen simply leaked through the membranes with an audible noise. However, when the PUs were blended with carboxylated poly(vinyl chloride) (CPVC), the permeability could be measured. The oxygen permeability coefficient (Po2) of the PU/CPVC $(96}4)$ membranes (6.4 Barrer) was high enough for the application as the electrode membranes. The Po2 decreased dramatically when the CPVC content increased from 4 to 5 wt%, but decreased very slowly and approached to that of CPVC (~0.26 Barrer) when the CPVC content increased further. The scanning electron micrographs of the membranes revealed that the PU membranes were composed of large crystal grains with many pores, but the size of the PU crystal grains and pores decreased progressively with increasing the CPVC content.

• 청정기술
• /
• 제25권2호
• /
• pp.114-122
• /
• 2019

최근 재생자원으로부터 바이오 폴리올을 합성하는 것이 주목을 받고 있다. 특히 고분자의 합성에서 이러한 바이오 폴리올을 활용하는 것은 대단히 중요한 과제이다. 폴리카보네이트 폴리올/바이오 폴리올(PO3G: 옥수수 당의 발효에 의해 제조된 1,3-프로판 디올로부터 제조된 폴리트리메틸렌 에터 글리콜), 메틸렌디페닐디이소시아네이트 및 1,4-부탄디올을 사용하여 일련의 디메틸포름아미드(DMF) 기반 폴리우레탄을 합성하였다. 본 연구에서는 폴리우레탄 필름의 특성과 습식 인조피혁의 셀(cell) 특성을 조사하였다. 폴리카보네이트 폴리올/바이오 폴리올에서 바이오 폴리올의 함량이 증가할수록 폴리우레탄 필름의 인장강도는 감소하지만 연신율은 증가하였으며, 유리전이온도는 낮아짐을 알 수 있었다. 또한 습식공법에 의한 인조피혁 단면을 분석한 결과 폴리카보네이트 폴리올 함량이 증가함에 따라 인조피혁에 형성된 셀의 수와 균일성이 증가함을 알 수 있었다. 이 결과로부터 적정량의 바이오 폴리올을 사용한 DMF 기반 폴리우레탄의 경우에 충분히 인조피혁에 사용할 수 있음을 알 수 있었다. 바이오 탄소 함량은 폴리우레탄의 제조에 사용한 바이오 폴리올의 함량 증가에 따라 비례하여 증가하였다.