Thermo gravimetric analysis and morphological behavior of castor oil based polyurethane–polyester nonwoven fabric composites

Castor oil (CO) based polyurethane (PU)– polyester nonwoven fabric composites were fabricated by impregnating the polyester nonwoven fabric in a reactive composition containing CO and diisocyanate. Composites were fabricated with two different isocyanates such as toluene‐2, 4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). Thermogravimetric analysis (TGA) studies of the composites were performed to establish the thermal stability and their mode of thermal degradation. It was found that degradation of neat PU takes place in two steps and that of polyester nonwoven fabric reinforced PU composites takes place in three steps. From the TGA thermograms, a little improvement in thermal stability incase of polyester nonwoven fabric reinforced PU composites were noticed compared to unreinforced PUs. Degradation kinetic parameters were obtained for the composites using Broido, Coats and Redfern, and Horowitz and Metzger methods. Tensile fractured composite specimens were used to analyze the morphology of the composites by scanning electron microscopic technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Biobased chain extended polyurethane and its composites with silk fiber

The biobased chain extended polyurethane (PU) was synthesized by reacting castor oil based polyol with different diisocyanates [toluene‐2,4‐diisocyanate (TDI) and hexamethylene diisocyanate (HMDI)] and chain extender such as glutaric acid. Biocomposites have been fabricated by incorporating the silk fiber into both TDI‐ and HMDI‐based PUs. The effect of incorporation of silk fiber into TDI‐ and HMDI‐based neat PU on the physicomechanical properties such as density, surface hardness, tensile strength, and percentage elongation have been investigated. The dynamic mechanical properties and the thermal stability of neat PUs and the silk fiber incorporated PU composites have been evaluated. The TDI‐based neat PU has showed higher mechanical properties compared to HMDI‐based PU. The incorporation of 10% silk fiber into TDI‐ and HMDI‐based PU resulted in an enhancement of tensile strength by 1.8 and 2.2 folds, respectively. The incorporation of silk fiber into biobased chain extended PU increased the glass transition temperature (T_g) of the resultant biocomposites. The morphology of tensile fractured neat PUs and their biocomposites with silk fiber was studied using scanning electron microscope (SEM). POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Sorption and diffusion of water into melamine–formaldehyde‐incorporated poly(vinyl acetate)–polyester nonwoven fabric composites

A series of composites were fabricated by impregnating a polyester nonwoven fabric with melamine–formol (MF)‐incorporated poly(vinyl acetate) (PVAc) latex. The effect of different weight ratios of MF/PVAc, i.e. 0/100, 5/100, 10, 100, 15/100 and 20/100 (dry, wt/wt), on the water sorption and diffusion into the composites was evaluated. Water sorption studies were carried out at different temperatures, i.e. 30, 50 and 70 °C, based on the immersion weight gain method. From the sorption results, the diffusion (D) and permeation (P) coefficients of water penetrant were calculated. A significant increase in the diffusion and permeation coefficients was observed with an increase in the temperature of sorption. Drastic reductions in diffusion and permeation coefficients were noticed with increasing MF content in the composites. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport, and K, a constant which depends on the structural characteristics of the composite in addition to its interaction with water. The temperature dependence of the transport coefficients was used to estimate the activation energy parameters for diffusion (E_D) and permeation (E_p) processes from Arrhenius plots. Copyright © 2006 Society of Chemical Industry     

Molecular transport of n‐alkanes into PU/PBMA interpenetrating polymer network systems

The methylene diisocyanate (MDI) and toluene diisocyanate (TDI) based polyurethane/polybutyl methacrylate (PU/PBMA‐50/50) interpenetrating polymer network (IPN) membranes have been prepared. The molecular migration of n‐alkane penetrants such as hexane, heptane, octane, nonane, and decane through PU/PBMA (50/50) membranes has been studied at 25, 40, and 60°C using a weight gain method. From the sorption results, diffusion (D) and permeation (P) coefficients of n‐alkane penetrants have been calculated. Molecular migration depends on membrane‐solvent interactions, size of the penetrants, temperature, and availability of free volume within the membrane matrix. Attempts have been made to estimate the parameters of an empirical equation and these data suggest that molecular transport follows Fickian mode. From a study of temperature dependence of transport parameters, activation energy for diffusion (E_D) and permeation (E_P) have been estimated from the Arrhenius relation. Furthermore, sorption results have been interpreted in terms of enthalpy (ΔH) and entropy (ΔS) of sorption. The liquid concentration profiles have been computed using Fick's equation with appropriate initial and boundary conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 739–746, 2003     

Water absorption behavior of acrylonitrile‐butadiene (NBR) latex impregnated jute nonwoven fabric composites

Composites were fabricated by impregnating the jute nonwoven fabric in acrylonitrile–butadiene (NBR) latex. The effect of different pickup ratio (dry, wt/wt) of NBR latex to jute nonwoven fabric, viz., 0.5 : 1, 1 : 1.5, 1.5 : 1, 2 : 1, and 2.5 : 1 on the water absorption behavior of the composites were evaluated. Water absorption studies were carried out at different temperatures, viz. 30, 50, and 70°C, based on immersion weight gain method. From the sorption result, the diffusion (D) and permeation (P) coefficients of water penetrant have been calculated. Significant increase in the diffusion and permeation coefficients was observed with increase in the temperature of sorption experiments. Drastic reductions in diffusion and permeation coefficients were noticed with increase in the pickup ratio of NBR on to jute nonwoven fabric. Attempts were made to estimate the empirical parameters like n, which suggests the mode of transport, and K is a constant that depends on the structural characteristics of the composite in addition to its interaction with water. The temperature dependence of the transport coefficients has been used to estimate the activation energy parameter for diffusion (E_D) and permeation processes (E_p) from Arrhenius plots. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2045–2050, 2006     

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     

Poly(styrene‐co‐butyl acrylate) latex‐reinforced polyester nonwoven fabric composites: Thermal and morphological studies

A series of thermoplastic composites were fabricated by impregnating the polyester nonwoven fabric in poly(styrene‐co‐butyl acrylate) latex having different monomer compositions of styrene and butyl acrylate viz., 100/0, 90/10, 80/20, 70/30, 60/40, and 50/50 weight by weight. Thermogravimetric analysis (TGA) of the composites was performed to establish the thermal stability and their mode of thermal degradation. From TGA thermograms, a slight improvement in thermal stability of the composites was noticed compared to polyester nonwoven fabric. Degradation kinetic parameters were obtained for the composites using Broido and Coats–Redfern methods. The activation energy (E_a) of the composites for the thermal degradation process lies in the range 7.1–261 and 60–264 kJ/mol for Broido and Coats–Redfern methods respectively. Morphology of the tensile‐fractured composites was studied using scanning electron microscopic technique. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(urethane‐ester)s based on calcium salt of mono(hydroxybutyl)phthalate

Calcium‐containing poly(urethane‐ester)s (PUEs) were prepared by reacting diisocyanate (HMDI or TDI) with a mixture of calcium salt of mono(hydroxybutyl)phthalate [Ca(HBP)₂] and hydroxyl‐terminated poly(1,4‐butylene glutarate) [HTPBG₁₀₀₀], using di‐n‐butyltin‐dilaurate as catalyst. About six calcium‐containing PUEs having different composition were synthesized by taking the mole ratio of Ca(HBP)₂:HTPBG₁₀₀₀:diisocyanate (HMDI or TDI) as 3:1:4, 2:2:4, and 1:3:4. Two blank PUEs were synthesized by the reaction of HTPBG₁₀₀₀ with diisocyanate (HMDI or TDI). The polymers were characterized by IR, ¹H NMR, Solid state ¹³C‐CP‐MAS NMR, TGA, DSC, XRD, solubility, and viscosity studies. The T_g value of PUEs increases with increase in the calcium content and decreases with increase in soft segment content. The viscosity of the calcium‐containing PUEs increases with increase in the soft segment content and decreases with increase in the calcium content. X‐ray diffraction patterns of the polymers show that the HMDI‐based polymers are partially crystalline and TDI‐based polymers are amorphous in nature. The dynamic mechanical analysis of the calcium‐containing PUEs based on HMDI shows that with increase in the calcium content of polymer, modulus (g′ and g″) increases at any given temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1720–1727, 2006     

Synthesis and coating characteristics of novel calcium‐containing poly(urethane ethers)

Calcium salt of mono(hydroxypentyl)phthalate [Ca(HPP)₂] was synthesized by the reaction of 1,5‐pentanediol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ethers) (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or toluylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HPP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. We synthesized a series of calcium‐containing PUEs with different compositions by taking the molar ratio of Ca(HPP)₂ : PEG₃₀₀ or PEG₄₀₀ : diisocyanate (HMDI or TDI) as 2 : 2 : 4, 3 : 1 : 4, and 1 : 3 : 4 to study the coating properties of the PUEs. Blank PUEs without a calcium‐containing ionic diol were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by fourier transform infrared spectroscopy, ¹HNMR, ^?13C‐NMR, solid‐state cross‐polarity/magic‐angle spinning ¹³C‐NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as a top coat on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, including tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 710–721, 2004     

Polyurethane composites based on oil palm empty fruit bunches: Effect of isocyanate/hydroxyl ratio and chemical modification of empty fruit bunches with toluene diisocyanate and hexamethylene diisocyanate on mechanical properties

This study focuses on the effect of isocyanate (NCO)/hydroxyl (OH) group ratios and chemical modification of oil palm empty fruit bunches (EFBs) with toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI) on the mechanical properties of EFB–polyurethane (PU) composites. The tensile, flexural, and impact properties are affected by the NCO/OH ratios. The tensile strengths, flexural strengths, and toughness increase as the NCO/OH increases; however, the modulus decreases. The reduction in the modulus is attributable to the increased flexibility of the PU linkages. Chemical modification of the EFBs increases the tensile strength, flexural strength, and toughness; however, the modulus is lowered as the percentage of treated EFB is increased. Impact strength results show that the strength increases as the NCO/OH ratio is increased. At NCO/OH ratios of 1.0 and 1.1, the composites with HMDI‐treated fibers exhibit higher impact strength than those with TDI‐treated and untreated fibers, respectively. This may be due to the longer and more flexible chain length of HMDI as compared to TDI, which enables the composites to absorb more energy before failure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Molecular mobility and hydration properties of segmented polyurethanes with varying structure of soft‐ and hard‐chain segments

The molecular mobility and hydration properties of model segmented polyurethanes from either poly(propylene glycol) (PPG) or poly(butylene adipate) (PBAD), both of molecular weight 2000 (soft segments), and three different diisocyanates (all‐trans 4,4′‐dicyclohexylmethane diisocyanate, 100% t,t HMDI; HMDI with 20% of trans isomers, 20% t,t HMDI; and 4,4′‐diphenylmethane diisocyanate, MDI) (hard segments) were investigated using differential scanning calorimetry (DSC), thermally stimulated depolarization currents (TSDC) measurements, ac dielectric relaxation spectroscopy (ac DRS), equilibrium water‐sorption isotherms (ESI), and dynamic water‐sorption isotherms (DSI). No effects of the structure and of the amount of the soft segments on the overall degree of microphase separation (DMS) into microphases rich in soft and hard segments, respectively, were observed. On the contrary, DMS depends on the composition of the diisocyanates used and systematically increases in the order MDI, 20% t,t HMDI, 100% t,t HMDI as indicated by DSC, TSDC, and ac DRS. The PPG‐based polyurethanes are characterized by larger values of water content at saturation, h, and smaller values of the diffusion coefficient of water, D. h increases with temperature, indicating that the sorption process is endothermic. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1209–1221, 1999     

Chain-extended polyurethanes—Synthesis and characterization

Thermoset polyurethane (PU) elastomers were prepared using hydroxyl-terminated polybutadiene (HTPB), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). The effects of various diamines and diols on the mechanical and thermal properties of polyurethanes are discussed. The average molecular weight between crosslinks (M?/_c) was determined by swelling studies. The properties imparted by the extenders are explained on the basis of the groups present in the diamines and the number of methylene carbons in the diols.     

Toughening of polylactide via in situ formation of polyurethane crosslinked elastomer during reactive blending

Polylactide (PLA)/polyurethane (PU) composites were prepared by reactive blending method with in situ formation of PU particles via the reaction between polyester polyol (PPG) and toluene‐2,4‐diisocyanate (TDI). The interfacial compatibility and adhesion between the PLA and PU phases were greatly improved by the reaction of the terminal hydroxyl groups of PLA and N?C?O groups of TDI forming graft copolymer, as confirmed by FTIR spectroscopy. The elongation at break and notch impact strength of PLA/PU composites increased considerably with increasing PU content, and the tensile strength of PLA/PU composites decreased slightly compared with that of pure PLA. Upon addition of 12 wt % PU, the elongation at break and notch impact strength increased to 175.17% and 10.96 kJ/m², respectively, about 27 times and 5.4 times greater than the corresponding values for the pure PLA. The tensile strength decreased only slightly to 48.65 MPa. The excellent interfacial adhesion, the dispersed PU elastomeric particles acting as stress concentration areas, and the triggering of large matrix shear yield as well as many fibrils by internal cavitation were the main mechanical toughening mechanisms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44383.     

Studies on polyurethanes and polyurethane–ureas derived from divalent metal salts of mono(hydroxybutyl) hexolate

Divalent metal salts of mono(hydroxybutyl)hexolate [M(HBH)₂), M=Ca²⁺, Mn²⁺or Pb²⁺] were synthesized by the reaction of 1,4‐butanediol, 5,6,7,8,10,10‐hexachloro‐3a,4,4a,5,8,8a,9,9a‐octahydro‐5,8‐methanonaphtho‐[2,3‐C]‐furan‐1,3‐dione and divalent metal acetates. Hexamethylene bis [N′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (HBHMPU) and tolylene 2,4‐bis[N ′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (TBHMPU) were synthesized by reacting 2‐amino‐2‐methyl‐propan‐1‐ol with hexamethylene diisocyanate (HMDI) and tolylene 2,4‐diisocyanate (TDI), respectively, in toluene solvent. Flame‐retardant metal‐containing polyurethanes were synthesized by the solution polymerization of HMDI with M(HBH)₂ and the polyurethane–ureas by reacting HMDI with 1:1 mixture of M(HBH)₂ and HBHMPU or TBHMPU, respectively, in DMSO as solvent. The polymers have been characterized by elemental analysis, solubility, viscosity and IR and ¹H NMR spectroscopy. The thermal stability of the polymers has been studied by thermogravimetry. The flame‐retardant property of the polymers has been investigated by measuring limiting oxygen index values. © 2000 Society of Chemical Industry     

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     

Various properties of diimide–diacid-modified saturated polysters

Polyesterdiimide prepolymers containing synthesized diimide–diacid monomer (DIDAn) were synthesized under conditions previously under conditions previously reported. One-component varnishes were obtained by mixing the synthesized prepolymers with phenol-blocked toluene diisocyanate (TDI) and/or hexamethylene diisocyanate (HMDI). The solubility parameter of diimidemodified polyester prepolymer was investigated using an intrinsic viscosity measurement. Thermal behavior and pyrolysis activation energy were also investigated using thermogravimetric analysis. The thermal stability increased with an increase in the content of DIDA. The diimide-modified polyester one-component varnishes coated onto an aluminum panel were found to be acceptable, according to the specification of ASTM D-3794. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(urethane‐co‐imidine)s having pendent phenyl and benzylidene groups using bisphthalides,bislactones and blocked polyurethane prepolymers

Poly(urethane‐co‐imidine)s were prepared using amine blocked polyurethane (PU) prepolymer. The PU prepolymer was prepared by the reaction of poly(propylene glycol) (PPG₂₀₀₀) and 2,4‐tolylene diisocyanate (TDI) and end capped with N‐methyl aniline. The PU prepolymer was then reacted with bisphthalides and bislactones, until the evolution of carbon dioxide ceased. Polymerization reactions with bispthalides and bislactone took more time than with dianhydrides. Polymers were characterized by FTIR, GPC, TG and DSC analyses. Molecular weights of the poly(urethane‐co‐imidine)s were found to be lower than that of poly(urethane‐co‐imide)s. Compared to poly(urethane‐co‐imide)s all poly(urethane‐co‐imidine)s showed high glass transition temperature and crystallization peak in DSC. The thermal stability of the polyurethanes was found to increase with the introduction of imidine component. © 2001 Society of Chemical Industry     

Structure–property relationship of blocked diisocyanates: synthesis of polyimides using imidazole‐blocked isocyanates

Imidazole, 2‐methylimidazole and benzimidazole‐blocked aromatic and aliphatic diisocyanates have been prepared and polymerized with pyromellitic dianhydride in the presence of a basic catalyst. The polymers are characterized with FTIR, ¹H NMR and ¹³C NMR spectroscopy and GPC, DSC and TGA. The structure–property relationship of blocked diisocyanates are discussed in terms of molecular weight of the polyimides obtained. Considering the blocking agent, GPC results show that the benzimidazole blocked adduct yields higher molecular weight polymer than the 2‐methylimidazole‐blocked adduct which, in turn, yields higher molecular weight polymer than the imidazole‐blocked adduct. Considering the structure of the isocyanate, the molecular weight of polymer increases from isophorone diisocyanate to hexamethylene diisocyanate and to toluene diisocyanate (TDI). DSC traces of the polymers derived from TDI show glass transitions (T_g) in the temperature range 152–180 °C and the values increase from the polymer based on imidazole‐blocked TDI to 2‐methylimidazole‐blocked TDI and to benzimidazole‐blocked TDI. © 2000 Society of Chemical Industry     

SMC中不饱和聚酯树脂增稠及贮存性能的研究

本文以甲苯二异氰酸酯（TDI）及其预聚物PU400、PU200为增稠剂对端羟基的不饱和聚酯进行增稠，通过树脂的粘度变化、螺线流动实验对这种新型增稠体系的增稠性能和片材的贮存稳定性进行了研究。并与以MgO为增稠剂的片材进行了对比研究，结果表明：（1）异氰酸酯预聚体的增稠性能优于异氰酸酯单体。（2）增稠剂PU400的质量百分数Wpu应该小于10％。在相同的－NCO浓度下，不饱和聚酯树脂的增稠速度随分子量的提高而加快；在273K下，不饱和聚酯树脂能在4天内完成增稠，在323K下，能在8小时内完成增稠。（3）聚酯片材贮存三个月后，由异氰酸酯增稠体系制备的片材的螺线长度，低于氧化镁增稠体系的下降幅度。     

Preparation and properties of a p‐aramid fabric composite impregnated with a magnetorheological fluid for body armor applications

A polyurethane (PU)‐magnetorheological fluid (MRF)/p‐aramid fabric composite was fabricated, and its mechanical properties were subsequently investigated. The contribution of the PU‐MRF matrix to the impact resistance of the system was then discussed. MRFs consist of stable suspensions of magnetite particles within a carrying fluid. Therefore, when an external magnetic field is applied, the MRFs exhibit drastic and reversible changes in rheological properties as a result of the field‐induced ordering of the particulate phase. We then attempted to develop new and enhanced bulletproof materials by incorporating MRF and PU in a p‐aramid fabric. It was found that when a magnetic field was applied, the mechanical properties of the PU‐MRF/p‐aramid fabric composite improved. It was also found that adding a PU matrix improves the impact performance of the PU‐MRF/p‐aramid fabric composite, relative to a neat p‐aramid fabric and a MRF/p‐aramid fabric composite with similar areal density. The improved impact performance of the PU‐MRF/p‐aramid fabric composite appears to be because the PU film and MRF enable different energy absorbing mechanisms, including particle friction, fabric/matrix debonding, matrix cracking, and delamination, which are not observed in neat p‐aramid fabric systems. The findings of this study are thought to be important from a design viewpoint of soft armors. POLYM. ENG. SCI., 55:729–734, 2015. © 2013 Society of Plastics Engineers