High‐molecular‐weight polyurethanes prepared by one‐step miniemulsion polymerization

Through one‐step miniemulsion polymerization, hydrophobic polyurethane (PU) dispersions were prepared, with hexadecane (HD) as costabilizer in the oil phase and sodium dodecyl sulfate (SDS) as surfactant in the water phase. The oil phase, including isophorone diisocyanate, poly(oxytetramethylene) glycol, a costabilizer HD, a chain extender 1,4‐butanediol, a crosslinking agent trimethylol propane, and a catalyst dibutyltin dilaurate (SnDBL), was dispersed in the water phase containing SDS. The influences of experimental parameters, such as SnDBL, NCO/OH equivalents, and concentrations of surfactant, were discussed. The particle size and the molecular weight of PU polymer were measured by light scattering and gel permeation chromatography, respectively. With the addition of SnDBL and higher NCO/OH ratio, PU films with higher molecular weights were produced. The chemical structure of the PU polymer was identified by Fourier transform infrared spectrometer, and the adsorption of urethane group was observed. Thermal gravimetric analysis was used to characterize the thermal stability of PU. Furthermore, mechanical property was also investigated and characterized by tensile strength and elongation at break. With a higher NCO/OH ratio and the existence of SnDBL, the tensile strength of PU films was significantly increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Miscibility and properties of semi‐interpenetrating polymer networks based on polyurethane and nitroguar gum

Films from castor oil‐based polyurethane (PU) prepolymer and nitroguar gum (NGG) with different contents (10–70 wt %) were prepared through solution casting method. The networks of PU crosslinked with 1,4‐butanediol were interpenetrated by linear NGG to form semi‐interpenetrating polymer networks (semi‐IPNs) in the blend films. The miscibility, morphology, and properties of the semi‐IPNs coded as PUNG films were investigated with Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, wide‐angle X‐ray diffraction, density measurement, ultraviolet spectroscopy, thermogravimetric analysis, tensile, and solvent‐resistance testing. The results revealed that the semi‐IPNs films have good miscibility over the entire composition ratio of PU to NGG under study. The occurrence of hydrogen‐bonding interaction between PU and NGG played a key role in improvement of the material performance. Compared with the pure PU film, the PUNG films exhibited higher values of tensile strength (11.7–28.4 MPa). Meanwhile, incorporating NGG into the PU networks led to an improvement of thermal stability and better solvent‐resistance of the resulting materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4068–4079, 2007     

Preparation and properties of castor oil‐based polyurethane/α‐zirconium phosphate composite films

Novel castor oil‐based polyurethane/α‐zirconium phosphate (PU/α‐ZrP) composite films with different α‐ZrP loading (0–1.6 wt %) and different NCO/OH molar ratios were synthesized by a solution casting method. The characteristic properties of the PU/α‐ZrP composite films were examined by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and tensile testing. The results from Fourier transform infrared spectroscopy indicated that strong intermolecular hydrogen bonding formed between α‐ZrP and PU, XRD and SEM results revealed that the α‐ZrP particles were uniformly distributed in the PU matrix at low loading, and obvious aggregation existed at high loading. Because of hydrogen bonding interactions, the maximum values of tensile strength were obtained with 0.6 wt % α‐ZrP loading and 1.5 of NCO/OH molar ratio in the matrix. Evidence proved that the induced α‐ZrP used as a new filler material can affect considerably the mechanical and thermal properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of MDI-50 type polyurethane elastomer

以聚醚多元醇和MDI-50为原料,采用预聚物法合成预聚体,再和扩链剂MOCA进行扩链合成聚氨酯弹性体。研究了预聚体中不同异氰酸酯基（—NCO）质量分数对MDI-50型聚氨酯弹性体性能的影响。采用差示扫描量热分析（DSC）、热重分析（TG）、红外光谱（FTIR）及力学性能等测试方法对聚氨酯弹性体的结构与性能进行了表征和分析。结果表明：预聚体反应体系中NCO/OH摩尔比增大,预聚体中—NCO质量分数增加,预聚体的黏度降低,相应的聚氨酯弹性体的硬度和玻璃化转变温度提高,断裂伸长率降低,而拉伸强度和撕裂强度先增加后下降;当NCO/OH摩尔比为2.22时,聚氨酯弹性体力学性能较好;—NCO质量分数对聚氨酯弹性体的热稳定性影响不大。     

Structure–properties relationship of starch/waterborne polyurethane composites

The blend materials from waterborne polyurethane (WPU)/starch (ST) with different contents (10–90 wt %) were satisfactorily prepared by using the solution casting method. Their miscibility, structure, and properties were investigated by wide‐angle X‐ray diffraction (WAXD), scanning electron microscope (SEM), different scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and the tensile tests, respectively. The results indicated that tensile strength of composite materials not only depended on the starch content, but also related to the microstructure of WPU. The sample WPU2 (1.75 of NCO/OH molar ratio) exhibited hard‐segment order, but WPU1 (1.25 of NCO/OH molar ratio) had no hard‐segment order. The appropriate starch filled into WPU not only decreased the ordered region of soft‐segment matrix, but also hindered the formation of hard‐segment ordered structure. The blend material from 80 wt % WPU1 and 20 wt % starch exhibited better tensile strength (27 MPa), elongation at break (949%), and toughness than others. With an increase of starch content, the WPU matrix with dispersed starch in the blends transited to dual‐phase continuity and then to starch matrix with dispersed WPU. The results suggested that a certain extent of miscibility existed between WPU and starch in the blend materials on the whole composition ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3325–3332, 2003     

Preparation and characteristics of polyurethane made with polyhydric alcohol‐liquefied rice husk

The limited availability of fossil resource is causing the urgent need to get renewable chemicals. Solvent liquefaction can convert rice husk into bio‐based chemicals. Rice husk was liquefied in polyhydric alcohol catalyzed by sulfuric acid under atmospheric pressure. The viscosity, residue content, and weight average molecular weight (M_w) of liquefied rice husk were 3089 cps, 23.6% and 4100, respectively. Prolonging the liquefaction time decreased the residue content and increased the average molecular weight. Polyurethane (PU) foams were successfully prepared from the liquefied rice husk with different molar ratios of NCO to OH (NCO/OH). The mechanical properties of PU foams showed that the compressive strength in the vertical direction is higher than that in the horizontal direction. With Increase of the NCO/OH molar ratio from 1.0 to 2.0, compressive strength in the vertical direction of PU foams increased from 70.6 to 114.7 kPa at 10% strain. Thermal analysis results showed that thermal stability of liquefied rice husk‐based PU resins was better than that of fossil‐ and liquefied wood‐ based PU resins. Increasing the NCO/OH molar ratio and inorganic residue of rice husk can help to increase thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45910.     

Effects of nitrolignin on mechanical properties of polyurethane–nitrolignin films

Polyurethane‐nitrolignin (PUNL), a new network polymer, was synthesized from a castor oil based–polyurethane (PU) prepolymer and nitrolignin (NL) with a weight‐average molecular weight of 20.6 × 10⁴ and a content of 1.4–10%. The structure and miscibility of PUNL films prepared by solution casting were investigated by infrared spectroscopy and transmission electron microscopy. The results indicated that PUNL2 film, which had a 2.8% NL content, was the most miscible, and its tensile strength (σ_b) and breaking elongation (?_b) were 2 times higher than that of PU film. The crosslink densities of PUNL films increased with the increase of NL content until about 3%, similar to the variety of the mechanical properties. Thermogravimetric analysis revealed that the thermal stability of PUNL films was slightly higher than that of PU. Covalent bonds occurred between PU prepolymer and the NL in the PUNL films, forming crosslink networks, which resulted in the enhancement of mechanical properties and thermal stability. NL has a far higher reactivity with PU than nitrocellulose. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1213–1219, 2001     

Thermal effects in poly(hexamethylene adipamide) and polyoxymethylene at high hydrostatic pressures

The dynamic mechanical properties, transition behavior, and morphology of polycarbonate (PC)-polyurethane (PU) semi-interpenetrating polymer networks (semi-IPNs) and linear blends were studied by means of Rheovibron, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Two glass transition temperatures corresponding to polycarbonate and polyurethane were observed and microphase separation was further evident with TEM. In PC/PU semi-IPNs, two glass transition temperatures were shifted inwardly indicating that the interpenetrating network of polyurethane increases the mutual miscibility of PC and PU. The average phase domain was 500Å in semi-IPNs and the phase domains were in the range 1000–6000 Å in linear blends of the corresponding polymers. The compatibilities of PC and PU were greatly influenced by the molecular weight of polyols in PU prepolymer and the ratio of NCO/OH; lower molecular weight polyols and higher NCO/OH ratio resulted in better compatibility, and finer phase domains in PC and PU linear blends and semi-IPNs.     

Synthesis and characterization of poly(urethane‐benzoxazine)/clay hybrid nanocomposites

Poly(urethane‐benzoxazine)/clay hybrid nanocomposites (PU/Pa–OMMTs) were prepared from an in situ copolymerization of a polyurethane (PU) prepolymer and a monofunctional benzoxazine monomer, 3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Pa), in the presence of an organophilic montmorillonite (OMMT), by solvent method using DMAc. OMMT was made from cation‐exchange of Na‐montmorillonite (MMT) with dodecyl ammonium chloride. The formation of the exfoliated nanocomposite structures of PU/Pa‐OMMT was confirmed by XRD from the disappearance of the peak due to the basal diffraction of the layer‐structured clay found in both MMT and OMMT. DSC showed that, in the presence of OMMT, the curing temperature of PU/Pa lowered by ca. 60°C for the onset and ca. 20°C for the maximum. After curing at 190°C for 1 h, the exothermic peak on DSC disappeared. All the obtained films of PU/Pa–OMMT were deep yellow and transparent. As the content of OMMT increased, both the tensile modulus and strength of PU/Pa–OMMT films increased, while the elongation decreased. The characteristics of the PU/Pa–OMMT films changed from plastics to elastomers depending on OMMT content and PU/Pa ratio. PU/Pa–OMMT films also exhibited excellent resistance to the solvents such as tetrahydrofuran, N,N‐dimethylformamide and N‐methyl‐2‐pyrrolidinone. The thermal stability of PU/Pa were enhanced remarkably even with small amount of OMMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4075–4083, 2003     

Physical Properties of Polyurethanes Produced from Polyols from Seed Oils: I. Elastomers

Polyols synthesized by ozonolysis and hydrogenation from canola oil were reacted with aliphatic 1,6-hexamethylene diisocyanates (HDI) to produce polyurethane (PU) elastomers. The properties of the materials were examined by dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), modulated differential scanning calorimetry (MDSC), and thermogravimetric analysis (TGA), and measurements were taken of tensile properties. The effect of dangling chains on network properties was assessed. The formation of hydrogen bonds was observed by FTIR. The measured properties were found to be strongly dependent on processing-dependent factors such as the crosslinking density and the molar ratio of polyols to HDI component. The glass transition temperatures (T _g) of the elastomers were found to increase as the OH/NCO molar ratio decreased. With the same OH/NCO molar ratio, T _g of canola-oil-based PU was higher than that of soybean-oil-based PU. The TGA thermographs showed two well-defined steps of degradation for all the elastomers. In the first step, up to 30% weight loss, the fastest rate of loss was found at 345 °C for canola-oil-based PU while soybean-oil-based PU lost most of the weight in the second step. With the same OH/NCO molar ratio, the elastomers made from canola-oil-based polyol showed slightly higher Young’s modulus and tensile strength.     

The influence of the NCO/OH ratio and the 1,6-hexanediol/ dimethylol propionic acid molar ratio on the properties of waterborne polyurethane dispersions based on 1,5-pentamethylene diisocyanate

1,5-Pentamethylene diisocyanate, a novel aliphatic diisocyanate formed from bio-based 1,5-pentamethylenediamine, has been used as a hard segmented material to synthesize polyurethane. In this study, several waterborne polyurethane (WPU) dispersions have been successfully prepared by a prepolymer process from 1,5-pentamethylene diisocyanate poly(polyether) with different NCO/OH ratios and 1,6-hexanediol (HDO)/dimethylol propionic acid (DMPA) molar ratios. The Fourier transfonn infrared (FTIR) spectra, thermogravimetric analysis, differential scanning calorimetry, X-ray diffiraction, and a mechanical tensile test were used to investigate the structures, thermal stability, phase separation, crystallinity, mechanical properties, and adhesive performance of the WPU dispersions. The FTIR results indicate that the degree of hydrogen bonding and the numbers of urea groups increase as the NCO/OH ratio and HDO/DMPA molar ratio increase. Furthermore, the phase separation increases and the thermal stability decreases as the NCO/OH ratio increases or the HDO/DMPA molar ratio decreases. Finally, WPU3.0-2.4 (NCO/OH = 3, HDO/DMPA = 2.4) exhibits a maximum tensile strength and shear strength, pointing to its possible use as an adhesive. These results could provide a very valuable reference for industrial applications of WPU.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

High‐strength and low‐stiffness composites of nanoclay‐filled thermoplastic polyurethanes

In this study, bulk polymerized clay‐tethered thermoplastic polyurethane (TPU) composites were synthesized that offered much improved tensile strength with negligible changes in tensile modulus. These composites contained intercalated, tethered layered silicate particles and were synthesized by mixing low molecular weight prepolymer chains containing unreacted –NCO groups with reactive layered silicate clay followed by catalyzed chain extension reaction with butanediol. The molar ratio of –NCO and –OH functional groups in the composite was varied between 1.0 and 1.2. It was found that an appreciable amount of –NCO groups was consumed in reaction with moisture present in the clay and some in quaternary ammonium ion‐catalyzed dimerization and trimerization. Composites with –NCO to –OH molar ratio 1.1 provided the best improvement in mechanical properties—the composite with 5 wt% clay provided a 60% increase in tensile strength and 50% increase in strain at break, while the tensile modulus increased only by 15% over TPU. POLYM. ENG. SCI., 45:1532–1539, 2005. © 2005 Society of Plastics Engineers     

Synthesis and characterization of rubber‐seed‐oil‐based polyurethanes

Novel biobased polyurethanes were synthesized from rubber seed oil (RSO), a renewable resource. The RSO monoglyceride, together with xylene and hexamethylene diisocyanate (HMDI), was employed to synthesize the desired urethane‐based prepolymer with isocyanate (NCO)‐terminated end groups followed by curing. The degrees of crosslinking of the polyurethane after curing were assessed with their swelling behavior. The properties of the resulting polyurethanes were found to be dependent on the type of diisocyanate and their molar ratios to the RSO monoglyceride. The network structures, which were assessed through swelling studies, showed that networks based on HMDI with an NCO/OH ratio of 1.50 were better crosslinked than with those toluene diisocyanate. The thermal properties of the samples analyzed by thermogravimetric analysis showed two and three decomposition stages in aliphatic‐ and aromatic‐based RSO polyurethanes, respectively. The highest stability with initial decomposition temperature (253°C) and percentage residual at 500°C (11.4%) was achieved with an aliphatic‐based RSO polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of semi-interpenetrating polymer networks from polyurethane and benzyl konjac glucomannan

A series of semi-interpenetrating polymer network (semi-IPN) films coded as UB from castor oil-based polyurethane (PU) and benzyl konjac glucomannan (B-KGM) were prepared, and they have good or certain miscibility over entire composition range. Morphology, miscibility and properties of the UB films were investigated by using scanning electron microscopy (SEM), differential scanning calorimetry, dynamic mechanical analysis, ultraviolet spectrometer, wide-angle X-ray diffraction and tensile test. The results indicated that the UB films exhibited good miscibility when B-KGM content was lower than 15 wt%, resulting in relatively high light transmittance, breaking elongation and density. With an increase of the B-KGM content from 20 to 80 wt%, a certain degree of phase separation between PU and B-KGM occurred in the UB films. The tensile strength of the films UB increased from 7 to 45 MPa with an increase of B-KGM content from 0 to 80 wt%. By extracting the B-KGM with N, N-dimethylformamide from the semi-IPN, the morphology and phase domain size of the UB films were clearly observed by SEM. A continuous phase and dual-continuous phase model describing the semi-IPN were proposed to illustrate the morphology and its transition.     

Synthesis of polyurethanes from solvolysis lignin using a polymerization catalyst: Mechanical and thermal properties

Two methods of synthesis, namely, using a polymerization catalyst versus a non-catalytic route, were investigated to produce lignin-based polyurethanes. The films were characterized with respect to crosslink density, ultimate tensile behavior and glass transition temperature. The results indicated that use of the catalyst for polymerization is an effective way for producing films with consistent properties, even at lignin contents as high as 45 to 50 wt%. To illustrate the catalyst effectiveness, crosslink densities of catalyzed films with 20 wt% of lignin content increased drastically from 0.2-0.3 to 1.7-2.7 mmol/cm 3 when the NCO/OH molar ratio increased from about 1.3 to 3.0, without much increase in the corresponding crosslink densities of the non-catalyzed films. Also, when the NCO/OH molar ratio increased from 1.2 to 3.2, the tensile strength increased from 1.9 MPa to a maximum of 55 MPa (NCO/OH=2.6) before decreasing. Also, for same NCO/OH ratios, ultimate strain decreased drastically from 174.4% to 4.3%, with a corresponding increase in Young's Modulus from 0.03 GPa to 2.8 GPa. The glass transition temperatures of the catalyzed films also increased from 35°C to 89°C. Without the catalyst, only polyurethanes with low NCO/OH ratios, low lignin contents, and inferior mechanical properties, could be synthesized.     

Effect of crosslinking on mechanical and viscoelastic properties of semiinterpenetrating polymer networks composed of poly(vinyl chloride) and isocyanate crosslinked networks

Semiinterpenetrating polymer networks (SIPNs) of PVC/isocyanate/poly‐triol were prepared by premixing small (150 μm dia.) porous (30% voids) unplasticized PVC particles, 10% by weight of isocyanate, and a triol at different OH/NCO mol ratios. Three types of isocyanates (methylene bis‐phenyl diisocyanate (MDI), oligomeric MDI isocyanates (PAPI), and toluene diisocyanate (TDI) prepolymer/polytriol) were used. Two‐roll milling was followed by hot‐press curing. The tensile, flexural, and impact strengths increased when small amounts of crosslinked isocyanate networks were created in PVC. The isocyanate/polyol hydroxyl stoichiometry was varied, and the effects of crosslinking on the tensile, impact, and flexural strengths of PVC/isocyanate/triol SIPNs were examined. The strength increments were greater when the OH/NCO mole ratio went from 0 to 0.25, than when it went from 0.25 to 1.0. In many cases, increasing OH/NCO mol ratio from 0.5 to 1.0 decreased tensile, impact, and flexural strengths. Both PAPI and MDI (30% NCO content) gave bigger improvements in the these mechanical strengths than the TDI (only 9.7% NCO). These SIPN blends exhibited lower tan δ peak temperatures and a single distinct loss modulus, E″, peak values at lower temperatures than those of PVC that had been exposed to the same processing temperatures. Substantial amounts of isocyanate networks exist in SIPN phases according to DMTA studies. The OH/NCO ratio did not generally correlate with the decreases in the glass transition temperatures in these three sets of blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1402–1411, 2000     

Structure and properties of regenerated cellulose films coated with polyurethane–nitrolignin graft‐IPNs coating

A regenerated cellulose film (RC) was coated with a graft‐IPNs coating, which was composed of castor oil‐based polyurethane and 2.8 wt % nitrolignin (NL), to obtain water‐resistant films. The effects of NCO/OH molar ratio and different polyols, such as 1,4‐butanediol (BDO) and trimethanol propane (TMP), on the structure and properties of the coated RC films were investigated. With an increase of the NCO/OH molar ratio, the tensile strength of the coated films increased, but the water resistivity and size contraction hardly changed. The coated films with TMP exhibited the higher breaking elongation at 1.5 of the NCO/OH molar ratio, while those with BDO have more excellent tensile strength, water resistivity, and dimensional stability. The coated films with the graft‐IPNs coating exhibited superior water resistivity and dimensional stability. The light transmittance of the coated films was more excellent than that of the RC film. Moreover, the results from the IR and electron probe microanalysis (EPMA) showed that the chemical bonding occurred between cellulose and coating, and the introduction of NL plays an important role in the enhancement of the interface adhesion of the coated films. Atomic force microscopy (AFM) depicted the flat and dense surface of the coated films, which restricted the water vapor penetration and the size contraction, resulting in the enhancement of water resistivity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1799–1806, 2002     

Effects of NCO/OH ratio and catalyst concentration on structure,thermal stability,and crosslink density of poly(urethane‐isocyanurate)

Poly(urethane‐isocyanurate)s were synthesized by reacting toluene diisocyanate and poly(propylene glycol) with various stochiometric ratios (1–3) in the presence of different concentrations of dibutyltin dilaurate (DBTDL) and ferric acetylacetonate (FeAA). The influence of the NCO/OH ratio and the catalyst type and concentration on the extent of urethane and isocyanurate formation were examined using Fourier transform IR spectroscopy. No trimer formation was observed in the presence of the FeAA catalyst. The percentage of the trimer group and the trimer/urethane content were found to be increased with increasing the stochiometric ratio or DBTDL concentration. The thermal decomposition of the copolyurethanes in an inert atmosphere was studied by means of thermogravimetry (TG). The TG curves showed three decomposition steps with the principal degradation temperature at about 355–385°C. The effects of the NCO/OH ratio, catalyst type and concentration, and heating rate on the thermal stability of the copolyurethanes were determined. The Flynn–Wall, Kissinger, and Ozawa methods were used to calculate the activation energies of thermal decomposition. The swelling behavior of solid copolyurethanes in toluene showed that, as the DBTDL concentration and/or NCO/OH ratio increased, the swelling ratio and average molecular weight between crosslinks were decreased whereas the crosslink density was increased. The sol fraction of solid copolyurethanes was examined and found to be reduced when the percentage of DBTDL or the stochiometric ratio was raised. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 963–972, 2003