Comparison of the effects of linking diglycidyl ether‐terminated PDMS and BPA onto polyurethane with respect to the tensile and thermal properties

Flexible poly(dimethylsiloxane) (PDMS) or rigid bisphenol A (BPA) with diglycidyl ether end groups was linked to polyurethane (PU), which was composed of 4,4′‐methylenebis(phenyl isocyanate) as a hard segment and poly(tetramethylene ether)glycol as a soft segment. A control PDMS (CPDMS) series was prepared with an additional deprotonation step by NaH. The spectroscopic, thermal, tensile, shape memory, and low‐temperature flexibility properties were compared with those of plain PU to investigate the effects of linking the flexible PDMS or the rigid BPA on PU. The soft segment melting peaks were not affected by the PDMS content for the PDMS series but disappeared as the BPA content increased in the BPA series. The soft segment crystallization of PU was completely disrupted as the linked BPA content increased in the differential scanning calorimetry results and disappeared in the dynamic mechanical analysis results. The glass transition temperature (T_g) of the BPA series increased with increasing BPA content, whereas that of the PDMS series remained the same. The tensile strength of the PDMS series sharply increased with increasing PDMS content. The shape retention of the BPA series at ?25 °C sharply decreased as the BPA content increased. Finally, the BPA series linked with rigid aromatic BPA demonstrated excellent low‐temperature flexibilities compared with the PDMS series and plain PU. Compared with PUs linked with PDMS, PUs linked with rigid BPA demonstrated a significant change in the cross‐link density, thermal properties, shape retention, and low‐temperature flexibility. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43284.     

Structure and ionic conductive properties of polydioxolane–polyurethane‐based electrolytes

A series of polyurethanes (PUs) with different polyether soft segments [polydioxolane (PDXL), polyethylene glycol (PEG), or PDXL/PEG] were synthesized successfully, and solid polymer electrolytes based on PU/LiClO₄ complexes were prepared. The relations between structure and the ionic conductive properties of the PU‐based electrolytes were investigated by means of Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, and complex impedance analysis. Results showed that the glass‐transition temperature (T_g) of PDXL–PU was lower than that of PEG–PU. Doped lithium perchlorate (LiClO₄) salt could be dissolved well in soft segments of PDXL–PU. The ionic conductivity of the PDXL–PU/LiClO₄ complex could reach a value of 2 × 10^?5 S/cm at room temperature without the addition of an organic plasticizer. The system with PDXL/PEG as a soft segment had a higher T_g and a lower ionic conductivity than the one with PDXL as a soft segment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 103–111, 2002     

Synthesis and characterization of biodegradable polyurethanes based on L‐cystine/cysteine and poly(ϵ‐caprolactone)

Tunable biodegradable polyurethanes (PUs) with favorable mechanical properties were synthesized from 1,6‐hexamelthylene diisocyanate (HDI) as the hard segment, poly(?‐caprolactone) (PCL) as the soft segment, and L ‐cystine ester as chain extender. The structure of PUs was confirmed by FTIR and ¹H‐NMR. The results of differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical analysis, and tensile test revealed that the thermal and mechanical properties of PUs were strongly influenced by the molecular weight of soft segment PCL. In the presence of glutathione, the disulfide group cleaved into thiols, realizing the PUs degraded and the molecular weight decreased. For PU [550], it remained only 50% of the original M_w. Evaluation of cell viability demonstrated the nontoxicity of the PUs, which facilitated their potential in biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,properties, and dyeing application of nonionic waterborne polyurethanes with different chain length of ethyldiamines as the chain extender

This study deals with the synthesis of some nonionic waterborne polyurethanes (PUs), using ethyldiamines of different chain length, such as ethylenediamine (EDA) and diethyltriamine (DETA), as the chain extender in the reaction, and examines the thermal properties, mechanical properties, and dyeing properties of the PU products and their blends. As far as each PU by itself is concerned, we found that the T_g of the one made with DETA is the highest, followed by that with EDA, and the one with 1,4‐butanediol (1,4‐BD) is the lowest. The PU made with 1,4‐BD as the chain extender has no T_m, while the two others, using diamines as chain extenders, have a clear T_m, the one with DETA being higher than that with EDA. However, the enthalpy data are just the opposite. The tensile strengths of the two PUs, made with diamines as the chain extender, are larger than that made with 1,4‐BD, but their respective elongation properties are just the opposite. A comparison within PUs made with diamines showed that the one made with EDA is greater in both strength and elongation categories than that made with DETA. However, the one made with DETA is far superior to both of those made with 1,4‐BD and EDA in their dye‐exhaustion ratio, color yield (K/S), fixation rate, and color fastness. In respect to the various PU mixtures that we examined, we found that both PUs synthesized with EDA or DETA as the chain extender would have their T_g's greatly increased by blending in some PU made using 1,4‐BD as the chain extender. Among them, in particular, a blend of PU, made separately with DETA and 1, 4‐BD as the chain extender, showed great improvements in both tensile strength and elongation and also demonstrated better dyeability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2824–2833, 2003     

Study on polyethylene glycol/polydimethylsiloxane mixing soft‐segment waterborne polyurethane from different mixing processes

The surface structure and physical properties of polyethylene glycol series polyurethane (PEG‐PU) membranes, in which were introduced hydrophobic polydimethylsiloxane (PDMS) component by the procedure of PU blending or of soft‐segment copolymerization, were studied in this investigation. In the case of the blending process, the synthesized waterborne polyurethanes (WBPUs) of PEG–PU and of polydimethylsiloxane series polyurethane (PDMS–PU) were combined, whereas in the copolymerization process PEG and PDMS were taken as mixed soft segments to polymerize the WBPU. For the blending method, glass‐transition and melting temperatures increased rapidly when a small amount of PDMS–PU was added to PEG–PU and reached a maximum with 5% PDMS–PU mixed in. However, in the case of the copolymer method, thermal properties closely followed predicted values. From dynamic mechanical analysis studies it was found that a low PDMS–PU content ratio could increase the rubbery elasticity of PEG–PU membrane and improve its strength simultaneously in the blending method, and the copolymer method only caused PU to gain some natural complementary strength and elasticity. Electron spectroscopy for chemical analysis studies indicated that PDMS migrated to the surface much more easily in the blending method than in the copolymer method. The SEM studies also found that, in the blending method, the numbers of pores were less than those in the copolymer method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 233–243, 2003     

Study on the influence of thermal characteristics of hyperbranched polyurethane phase change materials for energy storage

A series of hyperbranched polyurethane (HB‐PU) phase change induced energy storage materials were prepared by polyethylene glycol (PEG), methylene diphenyl 4,4′‐diisocyanate (MDI), and hyperbranched polyester polyalcohol via a two‐step process. The influence of thermal characteristics of HB‐PU was investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). It has been found that the thermal characteristics of HB‐PU are affected by some factors. Such as the molecular weight and content of soft segment, once the M_n of PEG soft segments is larger than the critical M_n (2000 g/mol), both the phase change enthalpy and temperature increase as M_n of PEG soft segment and soft segment content (SSC) increase. The influence of the microstructure of hard segment originates from diisocyanate and hyperbranched polyester polyalcohol, HB‐PUs with regular microstructure and lower generation of hyperbranched polyester polyalcohol have high energy storage capability. Furthermore, the conditions of measurement affect the thermal characteristics of materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Thermo‐responsive polyurethane hydrogels based on poly(ethylene glycol) and poly(caprolactone): Physico‐chemical and mechanical properties

In this work, we present the synthesis and characterization of chemically crosslinked polyurethanes (PU) composed of poly(ethylene glycol) (PEG) and poly(caprolactone) diol (PCL‐diol), as hydrophilic and hydrophobic segments respectively, poly(caprolactone) triol (PCL‐triol), to induce hydrolysable crosslinks, and hexamethylene diisocyanate (HDI). The syntheses were performed at 45 °C, resulting in polyurethanes with different PEG/PCL‐diol/PCL‐triol mass fractions. All the PUs are able to crystallize and their thermal properties depend on the global composition. The water uptake capacities of the PU increase as the PEG amount increases. The water into hydrogels is present in different environments, as bounded, bulk and free water. The PU hydrogels are thermo‐responsive, presenting a negative dependence of the water uptake with the temperature for PEG rich networks, which gradually changes to a positive behavior as the amount of poly(caprolactone) (PCL) segments increases. However, the water uptake capacity changes continuously without an abrupt transition. Scanning electron microscopy (SEM) analyses of the hydrogel morphology after lyophilization revealed a porous structure. Mechanical compression tests revealed that the hydrogels present good resilience and low recovery hysteresis when they are subject to cycles of compression–decompression. In addition, the mechanical properties of the hydrogels varies with the composition and crosslinking density, and therefore with the water uptake capacity. The PU properties can be tuned to fit for different applications, such as biomedical applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43573.     

Effects of reaction and cure temperatures on morphology and properties of poly(ester‐urethane)

Poly(ester‐urethane) was synthesized from poly(ethylene glycol adipate) (PEG) and 2,4‐toluene diisocyanate (TDI) to study the effects of reaction temperature and cure temperature on the crystallization behavior, morphology, and mechanical properties of the semicrystalline polyurethane (PU). PEG as soft segment was first reacted with TDI as hard segment at 90, 100, and 110°C, respectively, to obtain three kinds of PU prepolymers, coded as PEPU‐90, PEPU‐100, and PEPU‐110. Then the PU prepolymers were crosslinked by 1,1,1‐tris (hydroxylmethyl) propane (TMP) and were cured at 18, 25, 40, 60, and 80°C. Their structure and properties were characterized by attenuated total reflection Fourier transform infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, and tensile testing. With an increase of the reaction temperature from 90 to 100°C, the crystallinity degree of soft segment decreased, but interaction between soft and hard segments enhanced, leading to the increase of the glass transition temperature (T_g) of soft domain and tensile strength. When the cure temperature was above 60°C, miscibility between soft and hard segments of the PEPU films was improved, resulting in relatively low crystallinity and elongation at break, but high soft segment T_g and tensile strength. On the whole, all of the PEPU‐90, PEPU‐100, and PEPU‐110 films cured above 60°C possessed higher tensile strength and elongation at break than that of the films cured at other temperatures. The results revealed that the reaction temperature and cure temperature play an important role in the improvement of the crosslinking structure and mechanical properties of the semicrystalline PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 708–714, 2006     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

PCL–PEG–PCL triblock ester–ether copolydiol-based waterborne polyurethane. II. Effect of NCO/OH mole ratio and DMPA content on the physical properties

This article was focused on the effects of the NCO/OH molar ratio and 2,2-bis(hydroxyl methyl) propionic acid (DMPA) content during prepolymerization on the physical properties of synthesized waterborne polyurethane (WBPU) by using the polycaprolactone–poly(ethyl glycol)–polycaprolactone triblock copolydiol (PCL–PEG–PCL) as the soft segment. The results showed that the particle size of the WBPUs' dispersion decreased with a decreasing NCO/OH molar ratio or increasing DMPA content. Regarding thermal and mechanical properties, the WBPUs had a higher T_g's and lower T_m's and a higher breaking stress and a lower breaking strain of film with the NCO/OH molar ratio or DMPA content increase. The increasing NCO/OH molar ratio was advantageous to the water vapor permeability (WVP)-breaking stress balance, but the effect of the DMPA content on the WVP was not significant. The WBPU with PCL–PEG–PCL as the soft segment had a smaller particle size in dispersion and a better WVP-breaking stress balance than those of WBPU with the blending PCL and PEG as the soft segment. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1301–1311, 1998     

Physical and potentiometric properties of polyurethane‐based cation‐selective membranes

Lipophilic salts based on tetraphenylborate derivatives [e.g., potassium tetrakis(p‐chlorophenyl)borate (KTpClPB), sodium tetraphenylborate (NaTPB), and cesium tetrakis(3‐methylphenyl)borate are essential ingredients used in the preparation of solvent polymeric cation‐selective membranes. The effects of such lipophilic salts on the physical properties of a polyurethane (PU) matrix comprising 4,4′‐diphenylmethane diisocyanate, 1,4‐butanediol, and poly(tetramethylene ether glycol) were examined. Differential scanning calorimetry measurements revealed that the sodium and potassium salts doped in PU increased the glass‐transition temperatures (T_g) of the matrix, while the film containing cesium salt exhibited slightly decreased T_g. The temperature dependence of the ionic conductivity for PU60 films doped with KTpClPB is well described by the Arrhenius‐type equation, and that doped with NaTPB is described by the Vogel–Tammann–Fulcher (VTF)‐type equation. The temperature dependence of the ionic conductivity on the VTF‐type equation suggests that the transport of sodium ions in the PU60 matrix is more strongly coupled to the soft segmental motion, and potassium ions are decoupled from the polymer host and transported by activated hopping. The effect of added salt on the internal structure of PU membranes was investigated by measuring the ratio between the free and hydrogen‐bonded CO bands at 1703 and 1730 cm⁻¹, respectively. The results showed that the ether oxygens in the soft segment chains are strongly coupled to the potassium or sodium, but much less to cesium. The potentiometric properties of these lipophilic additive doped PU membranes were characterized by incorporating valinomycin and 4‐tert‐butylcalix[4]arene‐tetraacetic acid tetraethylester as potassium‐ and sodium‐selective ionophores, respectively. Their response behavior could be explained by the observed physical characteristics. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 618–625, 2001     

The physical properties of aqueous cationic–nonionic polyurethane with poly(ethylene glycol methyl ether) side chain and its blend with aqueous cationic polyurethane

The cationic–nonionic dispersing centers with different chain lengths of poly ethylene glycol methyl ether (N‐PDEA 750, N‐PDEA 2000) were prepared from N‐diethanol amine (NDEA), isophorone diisocyanate (IPDI), and poly(ethylene glycol methyl ether) (PEO M_w = 750 and 2000), whereas aqueous cationic–nonionic polyurethane (N‐PDEA PU) with different side chain lengths were prepared by N‐PDEA 750 (or N‐PDEA 2000), 4,4‐methylene bis(isocyantocyclohexane) (H₁₂MDI), polytetramethylene glycol (PTMG 2000), ethylene diamine (EDA), and glycolic acid (GA) as cationic–nonionic dispersing center, hard segment, soft segment, chain extender, and quarternizing agent, respectively. The thermal and mechanical properties of PU casting film were then discussed. We also used N‐methyldiethyolamine (N‐MDEA) without PEO as cationic dispersing center to synthesize aqueous cationic PU (N‐MDEA PU). The PU blends were blending N‐PDEA 750 PU and N‐MDEA PU by different weight ratios and the physical properties of casting films and coated fabric of PU and PU blends were investigated. Regarding the thermal properties, we have found out that the cationic–nonionic PU (N‐PDEA 750 PU, N‐PDEA 2000 PU) has lower T_gs, T_ms, T_mH, and ΔH_H than N‐MDEA PU, apart from ΔH_s. The N‐PDEA 2000 PU with longer side‐chain PEO has lower T_gs, higher T_ms and ΔHs than N‐PDEA 750 PU. As for mechanical property, N‐PDEA PU has lower tensile strength of casting film compared with N‐MDEA PU. Regarding the comparison of side chain length of PEO, N‐PDEA 2000 PU with longer side chain has higher tensile strength than N‐PDEA 750 PU with shorter side chain length. In addition, N‐PDEA 2000 PU group that shows hard property in stress–strain curve, whereas N‐PDEA 750 PU shows soft property. The tensile strength of PU blends decreases as the content of N‐PDEA 750 PU increases. When the low‐blend ratio of N‐PDEA 750 PU (e.g., 5%), the tensile strength of casting film only shows less influence that can improve the elongation effectively. In terms of coating‐treated fabrics, cationic–nonionic PU‐coated fabrics show lower waterproof capacity (WP) than those treated by cationic PU. However, the water vapor permeability (WVP) and antiyellowing of the N‐PDEA 750 PU coated fabrics are significantly better than the one treated by cationic polyurethane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2963–2974, 2006     

Thermal stability of polyurethane elastomers before and after UV irradiation

In this work, we investigated the thermal degradation behavior of segmented polyurethane (PUR) elastomers before and after UV irradiation. The thermal degradation of PUR elastomers was studied over the temperature range of 25–600°C in an atmosphere of nitrogen using thermal gravimetric analysis (TGA). Four series of PUR elastomers derived from poly(oxytetramethylene)glycol (PTMO) of 1000 and 2000 molecular weight and poly(caprolactone glycol) (PCL) of 1250 molecular weight, 4,4′‐diphenylmethane diisocyanate (MDI), and 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI) and 1,4‐butanediol as an chain extender were synthesized by the prepolymer method. The derivative thermogravimetric (DTG) peaks observed in the experiments indicated that PUR elastomers degraded through two steps. We attributed the first step to degradation of the hard segment. The second degradation step could be ascribed to degradation of the soft segment. We found that the PUR elastomers based on poly(ester polyol) and aromatic diisocyanate exhibit better thermal stability than that of PUR elastomers based on the poly(ether polyol) soft segment in both steps of degradation. The thermal degradation is more prevalent in PUR elastomers based on cycloaliphatic diisocyanate. The higher values of the temperature of initial decomposition (Tⁱ) indicate a higher thermal stability of UV‐exposed elastomers on the beginning of degradation. This may be due to the formation of a crosslinking structure in the presence of UV irradiation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 864–873, 2001     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

Structure‐property relationship in polyurethane elastomers containing starch as a crosslinker

Polyurethane elastomers were synthesized using polypropylene glycol (PPG 2000) as the polyol and starch as the multifunctional crosslinker in varying concentrations. Thermal and mechanical properties were measured by DSC, DMA and tensile tests. The morphology was examined by SEM. The swelling behavior of the polyurethanes in various solvents was investigated and the solubility parameter was determined. All these properties were compared with those of polyurethanes containing 1,1,1 ‐trimethylol propane (TMP) as the crosslinker. Starch‐based polyurethanes exhibited better mechanical properties. The effect of varying the starch:TMP ratio on the mechanical strength was also studied. With increasing starch content, the tensile strength and elongation increased. The starch‐based PUs exhibited two glass transitions, whereas TMP‐based PUs exhibited one T_g. No significant difference in the T_gs of the two PUs was observed. The activation energy of St‐PU calculated from DMA was 69 kcal/mol. Soil degradation tests indicated greater biodegradability in polyurethanes containing starch than in those containing TMP.     

Effects of polyurethane soft segment and crosslink density on the morphology and mechanical properties of polyurethane/poly(allyl diglycol carbonate) simultaneous interpenetrating polymer networks

Tough, optically clear simultaneous interpenetrating polymer networks (SINs) of polyurethane (PU) and poly(allyl diglycol carbonate) (ADC) at different compositions were synthesized. The effects of the molecular weight of PU soft segment on the morphology, mechanical properties, and thermal transition behavior of the SINs at two levels of crosslinking agent were studied. The miscibility of PU/ADC SINs, studied by TEM and DMA, was greatly influenced by the SIN composition and the molecular weight of poly(caprolactone) diol (PCL) as the PU soft segment. A single‐phase morphology at a PU concentration of 10% changed to a very fine microheterogeneous morphology as the molecular weight of PCL changed from 530 to 1250. The two‐phase morphology of the PU10/ADC90 SIN based on higher PCL molecular weight (PCL 1250) was also confirmed by DMA, which displayed a sharp peak for the ADC‐rich phase and a small shoulder for the PU‐rich phase transition in the tan δ plot. The SINs at 20–30% PU composition exhibited co‐continuous phase morphology in the transmission electron micrographs, in which the phase regions grew larger as the PCL molecular weight increased from 530 to 1250. All the SIN samples possessed excellent optical transparency except two samples with 30% PU composition based on PCL 1250, which showed a hazy appearance. The tensile strength, modulus, and toughness of the SINs decreased by increasing the molecular weight of PCL from 530 to 1250, whereas the elongations at break remained nearly unchanged. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1583–1595, 2003     

Thermal and Mechanical Properties of Polyurethanes Derived from Mono- and Disaccharides

Thermal and mechanical properties of polyurethane (PU) sheets pre-pared from the glucose/fructose/sucrose–polyethylene glycol (PEG)–diphenylmethane diisocyanate (MDI) system were examined by differential scanning calorimetry, thermogravimetry, dynamic mechanical analysis and tensile tests. The saccharide content was varied at a constant NCO: OH ratio of 1·0. The glass transition temperature (T_g) increased with increasing saccharide content. The incorporation of saccharides into the PU structure results in a higher crosslinking density and a higher content of hard segments. The thermal decomposition was dependent on the saccharide content, an increase leading to a lower thermal decomposition temperature (T_d). The dissociation of saccharide OH groups and NCO groups is a major part of the thermal decomposition of these PUs. Dynamic mechanical analysis revealed two kinds of relaxation: the high temperature relaxation corresponds to main chain motion and the other is a local mode relaxation due to non-reacted isocyanate groups. The tensile stress and Young’s modulus increased with the saccharide content. © of SCI.