Application of statistical experimental strategies to the process optimization of waterborne polyurethane

A modified acetone process for the preparation of aqueous polyurethane (PU) dispersion is investigated. PU dispersions were prepared by polyaddition of isophorone diisocyanate (IPDI) to poly(tetramethylene ether glycol) (PTMG) and dimethylolpropionic acid (DMPA), followed by neutralization of pendant COOH groups with triethylamine (TEA). The resulting prepolymer chain was then extended through reaction with an ethylenediamine (EDA) derivative bearing sulfonate groups. The effect of such preparation conditions as catalyst (dibutyltin dilaurate, DBTDL) concentration, the acetone/PU ratio, phase-inversion temperature, agitation rate, and water-addition rate on the average particle size of aqueous PU anionomer dispersions is systematically studied using fractional factorial design and response surface methodology. Fractional factorial analysis indicates that the effects of the acetone/PU ratio, phase-inversion temperature, water-addition rate as well as the two factor interactions of DBTDL concentration and phase-inversion temperature, of the acetone/PU ratio and phase-inversion temperature, and of acetone/PU ratio and agitation rate are the key variables influencing average particle size of PU dispersions. Empirical models for average particle size are fitted and plotted using central composite experimental design as contour diagrams in order to facilitate examination of the average particle size results. The results show that for a 100 g PU anionomer containing 0.311 wt % COOH and 1.51 wt % SO₃H groups, a minimum number-average particle size of the dispersion ～ 25 nm can be obtained under an acetone/PU ratio, water-addition rate, phase-inversion temperature, catalyst concentration, and agitation rate of 3.65, 2 mL/min, 50°C, 150 ppm and 350 rpm, respectively.     

Synthesis and characterization of isocyanic acid,m‐phenylenediiso‐propylidene based poly(urethane‐urea) dispersions containing different amount of 2,2‐Bis(hydroxyl methyl)propionic acid

Isocyanic acid, m‐phenylenediiso‐propylidene (m‐TMXDI)‐based anionic poly(urethane‐urea) dispersions were prepared by the prepolymer mixing process. The equivalent ratio of NCO/OH was kept constant at 1.8, while 2,2‐bis(hydroxyl methyl) propionic acid (DMPA) used was varied from 3 to 10 wt %. The colloidal stability of poly(urethane‐urea) dispersions arose entirely from the presence of ionized carboxylic acid groups. The chemical structure of poly(urethane‐urea) dispersions with various amount of DMPA were identified by FTIR and ¹³C NMR analysis. The test results showed that the hydrophilicity of poly(urethane‐urea) dispersions were increased with increase in DMPA content. The degree of chain extension was much lower than the values predicted theoretically due to the side reaction of a small amount of hydrophilic isocyanate‐terminated prepolymer with water. The average particle size of poly(urethane‐urea) dispersions were decreased with an increase in DMPA content, and this lead to an increase in viscosity. Also, the thermal degradation behavior were measured and was shown that the initial degradation temperature shifted to lower temperature with an increase in DMPA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5737–5746, 2006     

FTIR, 1H‐NMR spectra,and thermal characterization of water‐based polyurethane/acrylic hybrids

Polyurethane (PU) polymer was synthesized following a prepolymer mixing process, by polyaddition of isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), 2‐hydroxyethyl methacrylate (HEMA), and 2,2‐bis(hydroxymethyl)propionic acid (DMPA). The PU anionomer having 2‐ethoxymethacrylate terminal groups was dispersed in water by prior neutralization of carboxylic acid groups of DMPA with triethylamine (TEA), chain extended with hydrazine (HZM) in water and a dispersion polymerization with methyl methacrylate/n‐butyl acrylate/acrylic acid mixture was performed. The above polymerization reactions lead to the formation of PU/acrylic hybrids having a chemical bond between PU and acrylic moieties. Acrylic content was varied from 0 to 50 wt % and samples were purified to eliminate oligomers and impurities before characterization. The FTIR and ¹H‐NMR spectra of these purified hybrid samples were obtained and bands and peaks assignments were discussed. Thermal properties (DSC and TGA) were also discussed. Breaking hydrogen bonds is the main reason for changes in properties with increasing acrylic content. Particle size data of dispersions is also presented and discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of thermoplastic water‐borne polycarbonate‐based polyurethane dispersions and cast films

Stable water‐borne polyurethane dispersions (PUDs) were prepared from bifunctional aliphatic polycarbonate‐based macrodiol, 2,2‐bis(hydroxymethyl)propionic acid (DMPA), 1,6‐diisocyanatohexane, 1,4‐butanediol (BD), and triethylamine. Water‐borne dispersion particles are thus solely formed from self‐assembled linear PU chains. Both PUDs and PUD‐based films were characterized with regards to the concentration of DMPA (ionic species content) and BD (hard‐segment content). Average particle size of PUDs decreased and their long‐term stability increased with increasing DMPA and decreasing BD concentration. Functional properties of cast films made from PUDs are substantially influenced by the character of the original colloidal particle dispersions. The swelling behavior of the films, their surface morphology, and mechanical properties are more influenced by DMPA than BD contents. At DMPA concentrations higher than 0.2 mmol g^?1 of the solid mass of polyurethane, distinct self‐organization of individual nanoparticles into fibril‐like structures was detected by atomic force microscopy and scanning electron microscopy. PU films made from PUD containing high BD as well as high DMPA concentrations have the best utility properties namely sufficient tensile properties and a very low swelling ability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42672.     

Performance of palm oil‐based dihydroxystearic acid as ionizable molecule in waterborne polyurethane dispersions

Waterborne polyurethane dispersions (WPUDs) containing a renewable palm oil‐based 9,10‐dihydroxystearic acid (DHSA) as an isocyanate‐reactive compound bearing ionizable carboxylic group to incorporate hydrophilic groups into the polymer chain have been successfully prepared. The WPUDs were prepared by using polyether and polyester polyols of 2000 molecular weight, DHSA and its traditional petroleum‐based counterpart 2,2‐bis(hydroxymethyl)‐propionic acid (DMPA), and an aliphatic diisocyanate (isophorone diisocyanate, IPDI). A comparison was made between the properties of WPUDs obtained using blends of DHSA and DMPA at different molar ratios and a reference WPUD based on DMPA. The particle size of polyester type WPUDs containing DHSA was reduced at a 0.5 to 0.5 molar ratio of DMPA to DHSA. A lower initial temperature was used in the preparation of NCO‐prepolymers with DHSA as compared to DMPA and this eased the preparation of WPUDs. The effect of molar ratio of DMPA to DHSA on the properties of films and coatings prepared with WPUDs was evaluated. The best properties were obtained with WPUDs prepared with a 0.5 to 0.5 molar ratio of DMPA to DHSA. The incorporation of renewable palm oil‐based DHSA into WPUDs improved water resistance (lower water uptake) and exhibited good combination of properties including hardness, adhesion strength, tensile strength, and elasticity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43614.     

Effects of the reagent molar ratio on the phase separation and properties of waterborne polyurethane for application in a water‐based ink binder

Waterborne polyurethane (WPU) dispersions with a high solid content and low viscosity were prepared successfully by a two‐step polymerization with isophorone diisocyanate, poly(propylene glycol), and dimethylol propionic acid as the main raw materials. The molar ratio of hard segments to soft segments was controlled to investigate its influence on the particle size, particle morphology, stability of dispersions, and final properties of the WPU films. Measurements including attenuated total reflectance/Fourier transform infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, polarizing optical microscopy, and contact angle tests were used to characterize the bulk structures, phase separation, thermal stability, crystallinity, and wettability of the WPU dispersions. The results indicate that all of the WPU dispersions with a high solid content (ca. 40 wt %) and low viscosity (ca. 20–50 mPa s) displayed excellent stability. The prepared WPU dispersions with acetone contents of 5–7 wt % could be used directly as an ink binder without removing the acetone; this is beneficial to industrial applications of water‐based ink binders. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45406.     

Structure and properties of semiinterpenetrating polymer networks based on polyurethane and nitrochitosan

Two semiinterpenetrating polymer networks (semi‐IPNs) based on trihydroxyl methylpropane–polyurethane (T‐PU) or castor oil–polyurethane (C‐PU) were prepared by curing the mixed solution of the polyurethane prepolymer and nitrochitosan (NCH). During the curing process, crosslinking and grafting reaction between the molecules of the PU prepolymer and NCH occurred, because of the high reactivity of remaining hydroxyl groups in the NCH with ? NCO groups of PU. The structure of the original semi‐IPN sheets and the sheets treated with acetone were studied by infrared, ¹³C‐NMR, scanning electron microscopy, and dynamic mechanical analysis, showing interpenetration of NCH molecules into the PU networks. When nitrochitosan content (C_NCH) was lower than 10 wt %, the semi‐IPN sheets T‐PU and C‐PU had higher density and tensile strength (σ_b) than the systems with C_NCH more than 20%. The trihydroxymethyl propane‐based PU reacted more readily with nitrochitosan to form the semi‐IPNs than castor oil‐based PU. The semi‐IPN coatings T‐PU and C‐PU were used to coat cellophane, resulting in intimate interfacial bonding. The mechanical strength and water resistivity of the cellophane coated with T‐PU coating were improved remarkably. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3109–3117, 2001     

Smart secondary polyurethane dispersions

Secondary dispersions of cationic segmented polyurethanes (PUs) with thermoresponsivity (upper critical solution temperature (UCST) in water), high solid contents and antibacterial properties are highlighted in this paper. PUs were prepared by polyaddition reactions and subsequent quaternization with methyl iodide. No additional stabilizers, organic solvents or special procedures were required to obtain stable aqueous dispersions containing up to 10 wt% PU; in contrast, stable dispersions were straightforwardly accessed by a combination of UCST behavior and repulsive electrostatic forces among the positively charged segments, which meets the requirements of a green chemistry process. Particle size and UCST strongly depended on the solid content of the dispersions and the content of poly(ethylene glycol) segments in the copolymers. The dispersions exhibited fast‐acting antibacterial properties against Escherichia coli. © 2013 Society of Chemical Industry     

Preparation and Properties of Water-borne Polyurethanes

Following a prepolymer mixing process, polyurethane (PU) anionomer dispersions were prepared from polyethylene adipate glycol (PEA), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and dimethylol propionic acid (DMPA) as a potential ionic centre. Effects of prepolymer molecular weight, PEA molecular weight, hard segment content, DMPA content, degree of neutralization and mixed diisocyanates have been studied in terms of particle size and viscosity of emulsion, and surface, mechanical and dynamic mechanical properties of the emulsion-cast films. Particle size decreased and emulsion viscosity increased with increase in prepolymer molecular weight and PEA molecular weight, DMPA content, the degree of neutralization and IPDI content in mixed isocyanate systems. The decrease in particle size was due to increased chain flexibility and/or hydrophilicity of the PU. The mechanical and dynamic mechanical properties of the PU ionomer dispersions were interpreted in terms of soft segment–hard segment phase separations, hard segment content, chain flexibility and coulombic forces. © of SCI.     

Urushiol/polyurethane–urea dispersions and their film properties

A series of aqueous polyurethane–urea (PUU) dispersions having urushiol were synthesized by in situ step polymerization of isophorone diisocyanate (IPDI), poly(ethylene glycol) (PEG, M_n = 1000 g/mol), urushiol, dimethylol propionic acid (DMPA), and ethylene diamine (EDA). Urushiol was extracted with acetone from the purified lacquer of Toxicodendron vernicifluum and the different concentrations (0, 11.8, 17.6, and 22.2 wt.% based on the total solids) of urushiol were introduced during the PU prepolymer synthesis. Thermal stability, mechanical strength, antimicrobial, and anticorrosive properties of the urushiol/PUU films were investigated in terms of urushiol concentration.     

Novel method to prepare charged mosaic membrane by using dipole‐like microspheres. I. Preparation and characterization of poly(4‐vinylpyridine/n‐butyl acrylate) seed latex with high solid content by soap‐free emulsion polymerization

The stable latex of poly(4‐vinylpyridine‐co‐n‐butyl acrylate) (P4VP/nBA) with a solid content as high as 10 wt % was prepared by a modified soap‐free emulsion polymerization. A mixture of water and organic solvents was employed as the continuous phase for increasing the solid content of the latex. Several organic solvents were investigated and, among them, ethyl acetate (EA) and diethyl ether (DE) were effective. The stable latex with 10 wt % solid content was prepared by charging 10 wt % EA or a EA/DE mixture (5 wt % each); however, more than 10 wt % solid content of the stable latex could not be obtained even by charging more than 10 wt % EA or a EA/DE mixture. The stable latex with 10 wt % solid content, which was crosslinked with less than 0.5 wt % (based on monomer) of ethylene glycol dimethacrylate, was prepared by charging 10 wt % of EA. In this case, however, the pH of the continuous phase had to be adjusted to lower than 4. The effects of EA on the characteristics of the resulting uncrosslinked latex were investigated by employing ζ‐potential measurements and scanning electron microscopy. It was found that the mass of coagulum decreased as the EA increased. At 8 wt % of EA, a stable latex of 10 wt % solid content without any coagulum was obtained. The ζ potential of particles increased from −100 up to 45.7 mV as the EA increased from 0 to 10 wt %. The effects of batch and semicontinuous copolymerization on the morphology of the microspheres were investigated by using DSC and ultrathin cross‐sectional transmission electron miscroscopy photos. A core–shell structure was not found, despite the batch copolymerization of 4VP(1)/nBA(2) (r₁ = 4.3, r₂ = 0.23), even with disparate reactivity ratios. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1731–1740, 2000     

Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I)

A series of waterborne polyurethanes (WBPU) containing different amount of 2,2‐bis(hydroxymethyl) propionic acid (DMPA) were synthesized using prepolymer mixing process. Relationships between the DMPA content and physical, mechanical, and thermal properties as well as adhesive behavior at different condition were investigated. Stable aqueous dispersions of WBPU were obtained when the DMPA content was more than 10 mol %. At higher DMPA content, the particle size of the WBPU dispersion was lower but the viscosity of the dispersion was higher. Water swelling and tensile strength of the films increased with increasing of DMPA content. The optimum adhesive strength of WBPU adhesives was found to be depended on the DMPA content, pressing temperature, and pressure on adhesion process. The adhesive strength of WBPU adhesives increased with increasing DMPA content. The optimum pressing temperature decreased with increasing DMPA content. The adhesive strength of WBPU adhesives increased with increasing pressure up to 15 kg f/cm² and then leveled off. The optimum pressing temperature of WBPU adhesives samples containing 24.02, 22.05, and 17.05 mol % DMPA was about 100, 120, and 140°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5684–5691, 2006     

Surface modification with waterborne fluorinated anionic polyurethane dispersions

Waterborne fluorinated anionic polyurethane dispersions (FAPUDs) were synthesized from tris(6‐isocyanatohexyl) isocyanurate, N‐ethyl‐N‐2‐hydroxyethyl‐perfluorooctanesulfonamide, poly(oxytetramethylene glycol) (PTMG), dimethylolpropionic acid (DMPA), hexamethylene diisocyanate, 1,4‐butanediol, and two different neutralizing agents (triethylamine and sodium carbonate). Waterborne polyurethane dispersions (PUDs) were synthesized from isophorone diisocyanate, PTMG, DMPA, and ethylenediamine as chain extenders. The particle size of the FAPUDs, based on the fluorine content and degree of neutralization (DN), was measured with dynamic light scattering. So that the surface modification and morphology variations of the PUDs through the addition of the FAPUDs could be observed, the surface energy and thermal properties of the blending films [fluorine PUD mixtures (FPMs)] were measured with contact‐angle analysis and differential scanning calorimetry. The particle size of the FAPUDs increased as the fluorine content in the FAPUDs increased and decreased as the DN increased. The surface energy of the FPM films made from the blending of the FAPUD T series (neutralization with triethylamine) gradually decreased above the critical fluorine concentration (0.02797 wt %). However, for the blending of the FAPUD 25Na series (neutralization with sodium carbonate), the surface energy increased above the critical fluorine concentration (0.02797 wt %) because of the increase in Na salts. The FAPUDs showed the native thermal behavior of the fluorine. However, the thermal properties of the blending films were like those of pure PUDs. This showed that the morphology of the PUDs was rarely unchanged when the FAPUDs were added. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3322–3330, 2002     

Influence of aqueous dispersions in place of organic solvents during the synthesis of shape memory polyurethanes on their structure and properties

In this work, the effect of synthesizing shape memory polyurethanes in aqueous dispersions instead of in organic solvents on the structure and properties of the obtained polymers was investigated. Shape memory polyurethanes based on polycaprolactone diol and isophorone diisocyanate were synthesized by two routes: (1) aqueous dispersion (PU/SM_WATER) and (2) dissolution in THF (PU/SM_THF). The samples were analyzed by infrared spectroscopy (FTIR), X‐ray diffraction (XRD), static light scattering (SLS), atomic force microscopy (AFM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and mechanical tests. The aqueous dispersion method led to the production of polyurethanes with a higher degree of phase separation and a higher degree of crystallinity. The morphology of the obtained polyurethanes demonstrated that PU/SM_WATER displays a structure with better defined phase separated domains. The polyurethanes exhibited similar average molar masses, soft segment glass transitions (T_gs) and mechanical properties. The lower degrees of phase separation and crystallinity of the PU/SM_THF led to lower values for the shape memory properties (shape recovery ratio (R_r)). The observed changes in the structure of the polyurethanes due to the replacement of organic solvent by an aqueous dispersion during their syntheses confirmed the preparation of shape memory polyurethanes with enhanced shape memory properties. POLYM. ENG. SCI., 57:432–440, 2017. © 2016 Society of Plastics Engineers     

Preparation of poly(propylene carbonate)/nano calcium carbonate composites and their supercritical carbon dioxide foaming behavior

Biodegradable polymer foams are attracting extensive attention in both academic and industrial fields. In this study, an emerging biodegradable polymer, poly(propylene carbonate) (PPC), was compounded with nano calcium carbonate (nano‐CaCO₃) and foamed via supercritical carbon dioxide for the first time. Four concentrations of nano‐CaCO₃, 1, 3, 5, and 10 wt %, were used and the thermal properties of PPC/nano‐CaCO₃ composites were investigated. The glass‐transition temperature and thermal decomposition temperature of the PPC/nano‐CaCO₃ composites increased with the addition of nano‐CaCO₃. The morphologies of the PPC/nano‐CaCO₃ composites and the rheological results showed that homogeneous dispersions of nano‐CaCO₃ and percolated nano‐CaCO₃ networks were achieved at a nano‐CaCO₃ content of 3 wt %. Therefore, the finest cell diameter (3.13 μm) and highest cell density (6.02 × 10⁹ cells/cm³) were obtained at the same nano‐CaCO₃ content. The cell structure dependences of PPC and PPC with a nano‐CaCO₃ content of 3 wt % (PPC‐3) foams on the foaming pressure and temperature were investigated as well. The results suggested that the cell structure of PPC‐3 was more stable at different foaming conditions due to the networks of nano‐CaCO₃. Moreover, the change in pressure was more influential on the cell structure than the temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42248.     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

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     

The effect of change of ionomer/polyol molar ratio on dispersion stability and crystalline structure of films produced from hydrophilic polyurethanes

In this study, we report the effect of the DMPA/PTHF molar ratio on dispersion properties of the MDI‐based hydrophilic polyurethane dispersions. In addition, the effect of the DMPA/PTHF molar ratio on the crystallinity and thermal properties of the polyurethane films prepared from dispersions are also discussed. The variation in stability was studied using a particle size analyzer. DSC and XRD analyses were used to study variations in crystallinity of films with the change of DMPA/PTHF molar ratio. FT‐IR spectra were used to monitor the formation of hydrogen bonds through urethane linkages to produce hard‐segment crystalline areas. The zeta potential increased with the increase of DMPA/PTHF molar ratio (hard‐segment content), while particle size of polyurethane particles decreased. Hence, the stability of dispersions was increased with DMPA/PTHF molar ratio due to the increase of hydrophilicity in polymer chain. Crystallinity of the films was increased with DMPA/PTHF molar ratio due to the increase of interchain interactions through Coulombic interactions and hydrogen bonding. Consequently, crystalline melting temperature was increased with the increase of DMPA/PTHF molar ratio. However, molten films formed crystalline soft segments instead of crystalline hard segments during slow cooling. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44475.     

Preparation,mechanical properties of waterborne polyurethane and crosslinked polyurethane‐acrylate composite

The waterborne polyurethane (PU) prepolymer was first prepared based on isophorone diisocyanate, polyether polyol (NJ‐210), dimethylol propionic acid (DMPA), and hydroxyethyl methyl acrylate via in situ method. The crosslinked waterborne polyurethane‐acrylate (PUA) dispersions were prepared with the different functional crosslinkers. The chemical structures, optical transparency, and thermal properties of PU and PUA were confirmed by Fourier transform infrared spectrometry, ultraviolet–visible spectrophotometry, and differential scanning calorimetry. Some physical properties of the aqueous dispersions such as viscosity, particle size, and surface tension were measured. Some mechanical performances and solvent resistance of PUA films were systemically investigated. The experimental results showed that the particle sizes of the crosslinked PUA aqueous dispersions were larger than the PU and increased from 57.3 to 254.4 nm. When the ratios of BA/St, BA/TPGDA, and BA/TMPTA were 70/30, PUA films exhibited excellent comprehensive mechanical properties. The tensile strength and elongation at break of the film were 2.17 MPa and 197.19%. When the ratio of BA/St was 30/70, the film had excellent water resistance and was only 6.47%. The obtained PUA composites have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings, and wood finishes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermomechanical characteristics of benzoxazine–urethane copolymers and their carbon fiber‐reinforced composites

Copolymers of polybenzoxazine (BA‐a) and urethane elastomer (PU) with three different structures of isocyanates [i.e., toluene diisocyanate (TDI), diphenylmethane diisocyanate, and isophorone diisocyanate], were examined. The experimental results reveal that the enhancement in glass transition temperature (T_g) of BA‐a/PU copolymers was clearly observed [i.e., T_g of the BA‐a/PU copolymers in 60 : 40 BA‐a : PU system for all isocyanate types (T_g beyond 230°C) was higher than those of the parent resins (165°C for BA‐a and ?70°C for PU)]. It was reported that the degradation temperature increased from 321°C to about 330°C with increasing urethane content. Furthermore, the flexural strength synergism was found at the BA‐a : PU ratio of 90 : 10 for all types of isocyanates. The effect of urethane prepolymer based on TDI rendered the highest T_g, flexural modulus, and flexural strength of the copolymers among the three isocyanates used. The preferable isocyanate of the binary systems for making high processable carbon fiber composites was based on TDI. The flexural strength of the carbon fiber‐reinforced BA‐a : PU based on TDI at 80 wt % of the fiber in cross‐ply orientation provided relatively high values of about 490 MPa. The flexural modulus slightly decreased from 51 GPa for polybenzoxazine to 48 GPa in the 60 : 40 BA‐a : PU system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009