• Fibers and Polymers
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• v.4 no.3
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• pp.114-118
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• 2003

The prepolymer and the final polyurethane (PU) block copolymer were synthesized by reacting 4,4-methylene bis(phenylisocyanate) with poly(tetramethylene glycol) and the prepolymer with 1,4-butanediol as a chain extender, respectively, to investigate the relation between phase separation and it's resulting properties. According to FT-IR data, the phase separation of hard and soft segments in the prepolymer and the PU block copolymer grew bigger by increasing the hard segment content, and the PU showed more dominant phase separation than the prepolymer. The heat of fusion due to soft segments decreased in both the prepolymer and the PU by increasing the hard segment content, whereas the heat of fusion due to hard segments increased in the PU did not appear in the prepolymers. The breaking stress and modulus of the prepolymer increased by increasing the hard segment content, and the elongation at break decreased gradually, and the PU showed the highest breaking stress and modulus at 58% hard segment content. However, the best shape recovery of the PU was obtained at 47% hard segment content due to the existence of proper interaction among the hard segments for shape memory effect. Consequently, the mechanical properties and shape memory effect of the PU were influenced by the degree of phase separation, depending on the incorporation of chain extender as well as the hard segment content.

• Proceedings of the Korean Fiber Society Conference
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• 1998.10a
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• pp.33-36
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• 1998

Segmented block copolyetheresters defined as copolymers having sequences of alternating polyester hard blocks and polyether soft blocks create labile physical cross-links upon crystallization of hard polyester blocks Since the nature of the physical interlocking is a crystallite formed exclusively from the crystallizable hard segment, the hard segment content (HSC) and hard segment length (HSL) will play an important role in determining the properties such as mechanical property and dynamic mechanical property. (omitted)

• Elastomers and Composites
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• v.54 no.4
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• pp.271-278
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• 2019

Polyurethane elastomers (PUEs) were synthesized using trans-1,4-bis(isocyanatomethyl) cyclohexane (1,4-H₆XDI), poly(oxytetramethylene) glycol, 1,4-butanediol (BD), and 1,1,1-trimethylol propane (TMP). To control the molecular aggregation state and mechanical properties of these PUEs, hard segment contents of 20 and 30 wt% and BD/TMP ratios of 10/0 and 8/2 were chosen. Differential scanning calorimetry and small-angle X-ray scattering measurements revealed that the degree of microphase separation increased with an increase in both hard segment content and BD ratio. The Young's modulus and strain at break of the 1,4-H₆XDI-based PUE were 6-20 MPa and 5-15, respectively. Incorporation of 20% TMP as a cross-linking agent into BD increased the melting temperature of the hard segment chains, that is, heat resistance, and decreased the Young's modulus. This could be due to the low density of the physical cross-linking network and the dispersion of hard segment chains in the soft segment matrix in the PUE in the presence of 20% TMP.

• Polymer(Korea)
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• v.24 no.2
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• pp.149-158
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• 2000

Oil-absorptive expanded polyurethane (EPU) was prepared with a lypophilic polyol, polypropyleneglycol (PPG) as the soft segment, and toluenediisocyanate (TDI) and $H_2O$ as the hard segment. PPGs haying various average molecular weights ((equation omitted) : 1000, 2000, 3000) were employed to investigate that the soft segment content was consequent on the oil-absorptivity and the mechanical properties of the EPUs. As (equation omitted) of PPG was decreased from 3000 to 1000, the oil-absorptivity and the tensile strength of the EPUs increased from 1460 to 3010% and from 0.26 to 0.55 $kg_{f}$ /$cm^2$ respectively. As the hard segment content ratio, ${\gamma}$ ([NCO]/[OH]) was increased from 1.0 to 1.2, the tensile strength of the EPUs increased from 0.56 to 0.95 $kg_{f}$ /$cm^2$, due to the formation of allophanate and/or biuret bondings. However, as the surfactant (S-A) content was increased from 1.0 to 2.5 pbw, the oil-absorptivity was decreased from 3634 to 3312%, due to the formation of closed cell structures.

• Applied Chemistry for Engineering
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• v.30 no.6
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• pp.673-680
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• 2019

GAP or GAP-co-BO based energetic thermoplastic elastomers (ETPEs) were synthesized by changing the hard segment content percent in the range of 30~45% by 5% difference. Thermal and mechanical properties of GAP-co-BO based ETPEs were compared to those of GAP based ETPEs. FT-IR results showed that the capability of forming hydrogen bond increases with increasing the hard segment content in GAP/GAP-co-BO based ETPE, and also the GAP-co-BO based ETPEs are stronger than GAP based ETPEs in the hydrogen bond formation. DSC and DMA results showed that the glass transition temperature (T_g) of GAP based ETPEs increased with the increment of the hard segment content, while the T_g of GAP-co-BO based ETPEs was maintained even the hard segment content increased. The storage modulus at room temperature of the GAP-co-BO based ETPEs was higher than that of the GAP based ETPEs. This was due to the strong phase separation behavior of the hard and soft segment of GAP-co-BO based ETPEs, which further resulted in the stronger breaking strength and lower tensile elongation at break point for GAP-co-BO based ETPE than the GAP based one.

• Transactions of the Korean Society of Automotive Engineers
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• v.22 no.5
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• pp.5-12
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• 2014

Weatherstrip coatings of urethane and silicon type which are fit to EPDM and thermoplastic materials are used in sealing systems for automotive applications for noise reduction and high slip characteristics for external applications, respectively. Polyurethane binder was successfully synthesized from poly(butyladiphate)diol (PBAD), poly(tetramethylene)glycol (PTMG) and isocyanate as starting materials. Then, polyurethane coating agents were prepared by using various additives. To investigate effects of segment types on the abrasion resistance of polyurethane coating agents, thin films based on polyurethane coating materials were fabricated. With increasing the amount of hard segment in the coating agent, abrasion resistance, modulus and tensile strength of the coating films were improved, but the elongation of the coating films was decreased.

• Proceedings of the Membrane Society of Korea Conference
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• 1999.10b
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• pp.23-26
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• 1999

• Polymer(Korea)
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• v.29 no.2
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• pp.140-145
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• 2005

Effects of the polyol type and the hard segment content of thermoplastic polyurethane (TPU) on the crystallization of hard segments in TPUs were studied employing differential scanning calorimetry. Diols used for the preparation of TPUs were poly(tetramethylene ether glycol) (PTMEG), poly(propylene glycol) (PPG), polycaprolactone (PCL), poly(butylene adipate) (PBA) the molecular weights of which were 2000 and the hard segments contents of TPUs were $35\~44\;wt\%$. We found that crystallization of hard segments in TPUs were observed at higher temperatures and became faster with increasing hard segment contents of TPUs. The crystallization rate of TPU was also affected by the types of polyols used for the preparation of TPUs. It is postulated that lower miscibility of soft segments and hard segments results in higher crystallization rate and increase of cooling crystallization temperatures due to better hydrogen bending between hard segments in melts.

• Journal of the Korean Institute of Gas
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• v.2 no.1
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• pp.59-65
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• 1998

Morphology and thermal properties of polyurethane synthesized from 4,4'-diphenylmethane diisocyanate (MDI), polyester polyol, and 1,4-butane diol are investigated using fourier transform infrared spectroscopy (FT-IR), differential scanning calorimeter (DSC), and dynamic mechanical thermal analysis (DMTA). From the FT-IR study, it is found that the stretching peaks of hydrogen bonded N-H and C=O are shifted to the low frequencies with the increase of hard segment content of the polyurethanes. The shift of the stretching peaks of hydrogen bonded N-H and C=O indicates that the degree of hydrogen bonding is increased. From the DSC study, it appears that the glass transition temperature ($T_g$) of the polyurethanes is increased with the increase of the hard segment content. Also, it is found that the polyurethanes investigated in this study have the homogeneous network structure due to the high functionality of the MDI. From the DMTA study, transition of the soft segment was not found. Therefore it is concluded that the polyurethanes investigated in this study have the one-phase morphology which is consistent with the DSC results.

• Proceedings of the Korean Fiber Society Conference
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• 1996.10a
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• pp.465-467
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• 1996

A series of thermoplastic polyurethane copolymers were prepared from polypropyleneglycol(PPG, MW 3000), 1,4-butanediol, Isophorone diisocyanate(IPDI) and dibutyltin dilaurate(BBT) as catalyst. Studies have been made on the effects of molar ratio of isocyanate /polyol/chain extender on the properties such as tensile and thermal properties. By varying the ration of hard to soft segments, TPU ranging from soft elastomeric polymer to relatively hard elastoplastics and be obtained. The storage modulus and glass transition temperature of TPU increased with increasing the hard segment content.