• Elastomers and Composites
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• v.27 no.3
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• pp.161-173
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• 1992

A series of polyurethane block copolymers based on hydroxyterminated poly(dimethyl siloxane), poly(propylene glycol) and poly(tetramethylene glycol) soft segments of molecular weights 1,809, 2,000 and 2,000, respectively, were synthesized. The hard segments consisted of 4,4'-diphenylmethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize poly(dimethyl siloxane)-based polyurethane(PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure PDMS-PU, poly(propylene glycol)-based polyurethane(PPG-PU) and poly(tetramethylene glycol)-based polyurethane(PTMG-PU), (mixed polyol)-based block copolymers and blends between PDMS-PU, PPG-PU and PTMG-PU were prepared, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based PU and in lower hard segment content blends, macro-phase separation was shown, but blends with higher hard segment contents showed significant reduction in amounts of phase separation.

• Elastomers and Composites
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• v.31 no.2
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• pp.104-110
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• 1996

The polyurethane was synthesized by the reaction of polycaprolactone diol(Mw 2000), 4,4'-diphenylmethane diisocyanate and 1,4-butanediol as the chain extender. Also, the modified polyurethane polymers based on liquid polybutadiene as a part of soft segment and dimethylolpropionic acid as a chain extender, giving polyurethane with various polarity, were synthesized. The thermal, mechanical, adhesion properties and water contact angles of the polyurethanes were examined. From the result of the water contact angle, the polarity of the acid modified PU containing 6% acid content was unchanged but mechanical and adhesion properties were improved. The water contact angles on polybutadiene modified PU films were increased with increasing polybutadiene content. The mechanical properties of the polybutadiene modified PU were higher than that of acid modified PU. However, the mechanical properties were reduced as polybutadiene content increased. The result is presumably due to phase separation between hard segment and soft segment. The peel strength of the polyurethane introduced with 5wt% polybutadiene was improved about 150% than that of unmodified PU. The same as the mechanical properties, the more polybutadiene was introduced, the lower peel strength was obtained.

• Macromolecular Research
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• v.10 no.4
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• pp.230-235
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• 2002

Alternating polyols of oxymethylene and oxyalkylene were synthesized and used as precursors for thermoplastic poly(ether-ester) elastomers (TPEs). The polyols were synthesized by reacting diols having different methylene units with dichloromethane in the presence of a phase transfer catalyst. The number of methylene units in the alkylene oxides was varied from 3 to 6. TPEs were prepared using the polyols as soft segments and poly(butylene terephthalate) units as hard segments. The polyols and TPEs synthesized were characterized using FTIR, NMR, GPC, DSC, and polarized optical microscopy. The polyols showed a profound odd-even effect on the melting (T$_{m}$) and glass transition temperatures (T$_{g}$). Polyols with odd numbers of methylene groups in the alkylene units have higher transition temperatures than polyols with odd number of methylene groups. The tendency is still kept in TPEs, even though the T$_{g}$ of soft segment in TPEs are slightly higher than those of corresponding neat polyols. The T$_{m}$ and T$_{g}$ of soft segments are almost constant in the range of 20 to 60 wt % contents of soft segments. On the other hand, the normalized heat of fusion of hard segment decreased with increasing the content of loft segment.ent.t.ent.

• 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.

• Elastomers and Composites
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• v.57 no.1
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• pp.13-19
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• 2022

Polycarbonate diol-based waterborne polyurethane (WPU) was prepared by prepolymer mixing process. The prepolymer mixture contained the polycarbonate diol, isophorone diisocyanate (IPDI), dimethylol propionic acid, triethylamine, and ethylenediamine (EDA). The NCO/OH ratio in the prepolymer was adjusted by controlling the molar ratio of IPDI, and its effects on the properties of WPU were studied. The structure of WPU was characterized by fourier transform infrared spectroscopy. The average particle size increased and viscosity decreased with increasing NCO/OH ratio and EDA content in WPU. The reduced phase separation between soft and hard segments increased glass transition temperature. The reduction in the thermal decomposition temperature could be attributed to the low bond energy of urethane and urea groups, which constituted the hard segment. Additionally, the polyurethane chain mobility was restricted, elongation decreased, and tensile strength increased. The hydrogen bond between the hard segments formed a dense structure that hindered water absorption.

• Fibers and Polymers
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• v.2 no.3
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• pp.141-147
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• 2001

The effect of compositions of isophorone diisocyanate (IPDl)/4.4'-diphenylmethane diisocyalate (MDI) and polypropylene oxide diol (PPG, $M_w$: 3000)/1,4-butane diol (BD) on the properties of UV-cured polyurethane acrylate films based on 2-hydroxyethyl acrylate (HEA) was examined. UV-curable polyurethane acrylates were formulated from the prepolymer. trimethylol propane triacrylate (TMPTA) as a reactive diluent, and 1-hydroxycyclohexyl ketone (Irgacure 184) as a photoinitiator. Dynamic mechanical thermal properties and elastic properties of UV-cured polyurethane acrylates was fecund to depend on the chemical composition of IPDl/MDl and PPG/BD. As the BD content increased, the tensile storage modulus of all series samples increased significantly. The storage modulus increased in the order of samples A (IPDI based samples)> samples B (IPDI/MDl (7/3 molar ratio) based samples) > samples C (IPDI/MDl (5/5 molar ratio) based samples at the same composition. Two distinct louts modulus peaks for all samples are observed owing to the softs segment glass transition temperature ($T_gh$) and hard segment glass transition temperature ($T_gh$). The difference between $T_gh$, and $T_gh$, (Δ$T_g$) increases in the order of A > B > C at the same composition. In cycle test, the initial onset strain (%) was found to decrease with increasing BD content in PPG/BD and with increasing MDI content in IPDI/MDl.

• Polymer(Korea)
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• v.38 no.5
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• pp.602-612
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• 2014

Polyurethanes containing poly(dimethyl siloxane) (PDMS) unit, PU-Si, were synthesized and their thermal and shape memory properties were investigated. Various amounts of PDMS units were incorporated via a solution polymerization method using mixed diols of poly(tetramethylene ether glycol) (PTMEG) and PDMS-diol as the soft segment (SS) and methylene diphenyl diisocyanate and 1,4-butanediol as the hard segment (HS). Two series of PU-Si samples with an HS content of 23% or 32% were prepared and analyzed. For PU-Si with an HS content of 23%, both the cold crystallization temperature ($T_{cc}$) and melt crystallization temperature of the SS domain moved higher temperature with increasing PDMS content, while the melting temperature ($T_m$) of the SS domain remained unaffected. The increase in HS content from 23% to 32% resulted in the increased $T_m$ and disappearance of $T_{cc}$. The shape recovery of PU-Si flim with an HS content of 32% increased while its shape retention decreased as PDMS content increased.

• Polymer(Korea)
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• v.24 no.6
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• pp.744-750
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• 2000

Oil gelling agent was synthesized with PPG, PTMG and TDI at 7$0^{\circ}C$ for 4hours. PPGs and PTMGs having various average molecular weights (M$_{n}$: 1000, 2000, 3000) were employed to investigate the ratio of oil gelation and water gelation. As M$_{n}$ of PPG, in result, was decreased from 3000 to 1000, the ratio of oil gelation was increased from 130% to 290% for PPG and from 250% to 310% for PTMG. Ratio of oil gelation was increased approximately two times when EG was added. As the amount of hydrophilic compound in the prepolymer was increased, ratio of oil gelation was increased from 290% to 1120% for PPG and increased from 310% to 1310% for PTMG, due to the increased dispersion of prepolymer in the water/oil mixture.ure.

• Textile Coloration and Finishing
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• v.34 no.4
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• pp.261-271
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• 2022

Waterborne polyurethane(WPU) is greatly affected by its properties depending on the average particle size. In this study, by analyzing the characteristics of WPUs with different average particle sizes according to the DMPA content and we confirmed that the WPU-Ms have different properties from the physical properties of WPU by mixing two types of WPU with different particle sizes in the same volume. At this time, we mixed WPU at an ideal ratio of 7:3 through literature research. In the thermal characteristic analysis, it was confirmed that the thermal decomposition temperature decreased and Tg increased as the content of DMPA, which is the hard segment, increased. In addition, the average particle size of WPU decreased as DMPA increased, and physical properties and adhesive strength were improved due to increased interaction. When mixed with each other in a weight ratio of 7:3, it was observed that adhesion and mechanical properties were improved compared to only WPU.

• Membrane Journal
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• v.15 no.1
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• pp.44-51
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• 2005

Polyurethane-polysiloxanes (PU/PDMS) was synthesized using 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) to overcome the weakness to the organic chemicals. The composite membranes were prepared onto porous poly(tetrafluoroethylene) (PTFE) supports. In vapor permeation experiments, the flux increased with increasing operating temperatures and feed concentrations while the separation factors showed the opposite trend, so-called 'trade-off'. In this study, the effect of the flux on the operating temperatures was not severe since the content of the soft segments is fairly higher than that of the hard segments. The composite membrane type of PU/PDMS maintained high flux and separation factor as well when comparing with the dense type membranes.