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

• Elastomers and Composites
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• 제57권1호
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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.

• Elastomers and Composites
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• 제57권3호
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• pp.100-106
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• 2022

Waterborne polyurethane-acrylate(WPUA) dispersions were prepared by surfactant-free emulsion polymerization in a two-step process. In the first step, polytetrahydrofuran, isophorone diisocyanate, dimethylol proponic acid, and 2-hydroxyethyl methacrylate were used to synthesize a vinyl-terminated polyurethane prepolymer. In the second step, styrene, methyl methacrylate, butyl acrylate, and different multi-functional crosslinkers were copolymerized. 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate were used as the crosslinkers, and their effect on the mechanical and thermal properties of WPUA was investigated. Overall, as the number of functional groups of the cross-linker increased, the gel fraction improved to 79.26%, the particle size increased from 75.9 nm to 148.7 nm, and the tensile strength was improved from 5.86 MPa to 12.40 MPa. In thermal properties, the glass transition temperature and decomposition temperature increased by 9.9℃ and 18℃, respectively. The chemical structures of the WPUA dispersions were characterized by Fourier-transform infrared spectroscopy. The synthesized WPUA has high potential for applications such as coatings, leather coatings, adhesives, and wood finishing.

• Advances in materials Research
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• 제13권2호
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• pp.129-140
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• 2024

This study evaluates the ratio of Toluene di-isocyanate (TDI) functional group isocyanate (NCO) to the binder functional hydroxyl group (OH) in HTPB/AP/Al-based propellants on their mechanical properties, flow rate, and viscosity to determine the limitations of NCO/OH in the composition of solid propellants. The propellants consisted of hydroxyl-terminated polybutadiene (HTPB) polyurethane (PU), aluminum (Al) and tri-modal ammonium perchlorate (AP). The tri-modal AP consisted of 30% of coarse AP, 30% of medium AP, and 8% of fine AP. The ratio of NCO/OH varies from 0.73 to 0.85, with two binder percentages of 10.5% and 12%. An increase in NCO/OH ratio with 10.5% binder provided 20%, 95%, and 8 to 9% increments in UTS, modulus, and hardness, respectively. However, the propellant elongation, density, and flow rate decreased by 170%, 0.2%, and 11-12%, respectively. Viscosity increased 20% based on initial hour reading. The 12% binder provides 27%, 47%, and 5~6% an increment of UTS, modulus and hardness respectively. However, the propellant elongation, density, and flow rate decreased by 47%, 0.17% and 27%, respectively. The viscosity increased 30% based on initial hour reading. This study suggests the NCO/OH value of 0.77 and 10.5~11% binder content in propellant based on the mechanical properties, flow rate, and viscosity for better processing and pot life.

• 폴리머
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• 제34권2호
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• pp.104-107
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• 2010

가교제인 trimethylol propane(TMP)의 함량변화에 따라 다양한 폴리우레탄(PU) 평판을 제작하였다. DMA 측정을 통하여 TMP 함량에 따라서 PU의 $T_g$는 34.8 $^{\circ}C$에서 49.9 $^{\circ}C$로 증가를 확인하였다. TMP의 함량이 4%에서 12%까지 증가함에 따라 탄성률은 322 MPa에서 423 MPa로 증가하였고, 인장강도는 10.6 MPa에서 14.8 MPa로 다소 증가하였으며, 신율은 62.8%에서 49%로 감소하였다. 음향특성의 경우, TMP의 함량이 증가함에 따라 가교 정도가 높아지며, 음속은 증가하였으나 음향감쇠계수는 감소하였다. 제작한 PU 평판은 4주간 수중에서 안정적임을 보여 주었다.

• Toxicological Research
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• 제17권
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• pp.305-307
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• 2001

Toluene diisocyanate (TDI) is widely used in the manufacture of polyurethanes and is a recognized cause of occupational asthma. Although extensive investigations have been undertaken, the molecular mechanism(s) of the disease is still unclear. We hypothesized that inflammatory cytokines are required during both the sensitization and elicitation phases of the disease and have utilized TNF-R knock-out (KO) mice to address the hypothesis. Black C57 TNFR knock-out mice were exposed to TDI by sc injection and challenged by inhalation of 100 ppb TDI vapor. Control animals included: wild type C57 animals, sham-exposed animals that were challenged with TDI, and animals that were injected with anti-TNF antibodies prior to sensitization and again prior to challenge. Total IgE was increased in the knock-out animals compared with the wild type sensitized and challenged animals whereas TDI-specific IgG antibodies did not differ significantly in KO and wild type animals. There was less inflammation in the nares and trachea in KO animals compared with the wild type animals exposed to TD1 as well as less goblet cell hyperplasia and epithelial damage. Airway reactivity was assessed in animals treated with anti-TNF$\alpha$ antibody and found to be substantially reduced compared with that in sensitized and challenged animals. These results indicate that TNF$\alpha$ plays a role in the immunologic and physiologic responses and in airways inflammation in this animal model and suggests a role for TNF in occupational asthma due to TDI.

• 한국염색가공학회지
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• 제28권1호
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• pp.40-47
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• 2016

As a coating material for loudspeaker dampers, resilient polyurethane/epoxy hybrid resins were synthesized to replace conventional phenol resin and examined the physical properties, which are not only environmentally friendly but also not harmful to human. Five types of polyurethane resins were synthesized in the step-shot method using methylene diisocyanate, three polyols such as poly tetramethylene ether glycol(PTMEG, MW:2000), poly(1,4-buthylene adipate(PBAP, MW:2000), and poly carbonatediol(PCD, MW:2000), and three chain extenders such as ethylene glycol(EG), neopentyl glycol(NPG), and 1,4-buthandiol(1,4-BD). The five types of synthesized polyurethane resins and commercially available bisphenol A type epoxy resin were blended in weight ratios of 90:10, 70:30, and 50:50 to synthesize 15 types of polyurethane/epoxy hybrid resins. Among the polyurethane resins, the one that was synthesized using PCD and 1,4-BD showed excellent tensile strength, 100% modulus, low extension, and relatively high viscosity. Polyurethane/epoxy hybrid resins with higher epoxy resin contents showed better thermal properties and water resistance while those with higher polyurethane contents showed higher flexibility. The polyurethane/epoxy hybrid resin made by blending the polyurethane based on PCD and 1,4-BD with a bisphenol A type epoxy resin in a weight ratio of 70:30 was identified to be the most suitable to be used in speaker dampers.

• Journal of Pharmaceutical Investigation
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• 제41권2호
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• pp.95-102
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• 2011

An amphiphilic cationic branched methoxy poly (ethylene glycol)-branched polyethylenimine - poly(L-phenylalanine) (mPEG-bPEI-pPhe) block copolymer was successfully synthesized by ring-opening polymerization (ROP) of N-carboxyanhydride of L-phenylalanine (Phe-NCA) with mPEG-bPEI for the preparation of more stable polyelectrolyte complex (PEC) included a hydrophobic interaction. mPEG-bPEI was firstly prepared by the coupling of mPEG and bPEI using hexamethylene diisocyanate (HMDI). The structural properties of mPEG-bPEI-pPhe copolymers were confirmed by $^1H$ NMR. The copolymers exhibited a self-assemble behavior in water above critical aggregate concentration (CAC) in the range of 0.01-0.14 g/L. The CAC of copolymers obviously depended on the hydrophobic block content in the copolymers (the value decreased with the increase of the pPhe block content). The cationic copolymers have the ability to form multi-interaction complex (MIC) with bovine serum albumin (BSA) and plasmid DNA through multi-interaction (electrostatic and hydrophobic interaction). The physicochemical characterization of the complex was carried out by the measurement of zeta potential and particle size. Their zeta-potentials were positive (approximately +10 mV) and their sizes decreased with increasing pPhe contents in the copolymers (PPF/BSA wt% ratio = 2). The complex showed good stability at high ionic strength. Therefore, mPEG-bPEI-pPhe block copolymer was considered as a potential material to enhance the stability of complex including biotherapuetic drugs.

• 한국응용과학기술학회지
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• 제23권1호
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• pp.77-84
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• 2006

Modified polyesters (TTBA-10C, -20C, -30C) that contain phosphorus and chlorine were synthesized by the condensation polymerization of tetramethylene bis(orthophosphate), neohexanediol trichlorobenzoate, 1,4-butanediol and adipic acid, in which tetramethylene bis(orthophosphate) and neohexanediol trichlorobenzoate were prepared previously in our laboratory. In this study, two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/ HDI-trimer= TTHD-20C, TTBA-30C/HDI-trimer= TTHD-30C) were obtained by curing at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vertical and horizontal combustion method, and $45_{\circ}$ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.

• 한국응용과학기술학회지
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• 제22권2호
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• pp.123-135
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• 2005

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate)(TBOP) were synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-S, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. Network structured PU flame-retardant coatings (APHD) were prepared by curing the synthesized benzoic acid modified polyesters containing phosphorus (APT B - 5 , -10, -15) with hexamethylene diisocyanate (HDI)-timer. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures. With the introduction of BZA, the film viscosity and film hardness of APHD decreased. With the introduction of caprolactone group, the flexibility, impact resistance, accelerated weathering resistance of APTBs increased. Flame retardancy of the coatings was tested. In a vertical burning method, APHD shows 210$^{\sim}$313 seconds, which indicates that the coatings are good flame-retardant coatings. Moreover, the amount of afterglow and flame retardancy of the coatings are decreased with increasing BZA content.