Network structure and properties of polyurethanes from soybean oil

Vegetable oils are very heterogeneous materials with a wide distribution of triacylglycerol structures and double‐bond contents. The hydrogenation of epoxidized soybean oil (ESO) produces polyols having a functionality distribution related to that of soybean oil. Therefore, these polyols are convenient substances for studying the impact of structural heterogeneity on network formation and properties. Polyols of hydroxyl numbers ranging from 225 to 82 mg KOH/g and weight‐average functionalities ranging from 4.4 to 2.7 were obtained by the variation of the time of hydrogenation of ESO. An analysis of the functionality distribution in polyols shows that gel points with diisocyanates vary from 54 to 76% conversion. The molecular weights of the network chains of polyurethanes prepared from these polyols and diphenyl methane diisocyanate varied from 688 to 1993. Polyols with hydroxyl numbers above 200 mg KOH/g gave glassy polymers, whereas those below that value gave rubbers. The heterogeneity of polyols had a negative effect on the elastic properties only at low crosslinking densities. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of the diisocyanate structure and the molecular weight of diols on bio‐based polyurethanes

Bio‐based polyurethanes (PU) containing poly(ε‐caprolactone) diol (PCL) and hydroxyl telechelic natural rubber (HTNR) were synthesized. The effect of the diisocyanate structure and the molecular weights of diols on the mechanical properties of PU were investigated. Three different molecular structures of diisocyanate were employed: an aliphatic diisocyanate (hexamethylene diisocyanate, HDI), an aromatic diisocyanate (toluene‐2,4‐diisocyanate, TDI) and a cycloalkane diisocyanate (isophorone diisocyanate, IPDI). Two molecular weights of each diol were selected. When HDI was employed, a crystalline PU was generated while asymmetrical structures of TDI and IPDI provided an amorphous PU. The presence of crystalline domains was responsible of a change in tensile behavior and physical properties. PU containing TDI and IPDI showed a rubber‐like behavior: low Young's modulus and high elongation at break. The crystalline domains in PU containing HDI acted as physical crosslinks, enhancing the Young's modulus and reducing the elongation at break, and they are responsible of the plastic yielding. The crystallinity increased the tear strength, the hardness and the thermal stability of PU. There was no significant difference between the TDI and IPDI on the mechanical properties and the physical characteristics. Higher molecular weight of PCL diol changed tensile behavior from the rubber‐like materials to the plastic yielding. Thermal and dynamic mechanical properties were determined by using DSC, TGA and DMTA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Recyclable bio‐based crosslinked polyurethanes with self‐healing ability

We report the synthesis of a linear bio‐based polyurethane (bio‐PU) containing furan ring by using renewable polylactide copolymer diol and 2,5‐furandimethanol as a soft segment and chain extender, respectively, in which the reversible crosslinked covalent bonds between hard segments were incorporated via Diels–Alder (D‐A) reaction between the furan ring of the chain extender and bismaleimide (BM) crosslinker. By simply controlling the amount of BM, mechanical properties of the obtained crosslinked bio‐PUs (CBPUs) were varied widely. In particular, the CBPU100 sample shows the highest tensile strength of 10.8 MPa, Young's modulus of 193 MPa, and an elongation of 155%. The differential scanning calorimetry experiments verify the recycle property of the CBPUs by the D‐A/retro‐D‐A reaction at the proper temperature. The thermal recyclability and remolding ability of these materials are demonstrated by two kinds of polymer processing methods, i.e., solution casting and hot‐compression molding. The recycled CBPUs display almost identical elongation and slightly decreased tensile strength compared to the as‐synthesized samples. Furthermore, the CBPUs also exhibit excellent self‐healing ability. Therefore, the resulting CBPUs possess tunable mechanical properties, good thermal recyclability, re‐mending, and self‐healing ability, which makes the bio‐based materials more eco‐friendly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46272.     

Studies on chain extension of a novel bio‐based engineering elastomer using 4,4‐diphenyl methane diisocyanate as a chain extender

A novel hydroxyl‐terminated bio‐based engineering elastomer (BEE) was synthesized from four bio‐based monomers by adding excess diol. Then the BEE was chain extended in Haake torque rheometer with 4,4‐diphenyl methane diisocyanate (MDI) as chain extender. The molar ratio of NCO/OH, reaction temperature and reaction time of the chain‐extension reaction were studied, and the optimum condition was determined by the gel permeation chromatography (GPC), soxhlet extraction, and fourier transform infrared spectroscopy (FTIR) results. After chain extension, (i) the number‐average molecular weight of BEE became about 3.5 times of the original BEE, (ii) the thermal stability was improved and the crystallization rate was lower, (iii) and the mechanical properties were significantly improved with nano‐SiO₂ as reinforcing filler. The chain‐extended BEE would have potential wide applications in engineering field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40756.     

Radiopaque polyurethanes with flexible iodine‐containing chain extender

Iodinated polyurethanes (IPUs) with radiopaque property were prepared using poly(oxytetramethylene) glycol, 4,4′‐diphenylmethane diisocyanate, and a novel chain extender. The chain extender, described as N‐(1,3‐dihydroxypropan‐2‐yl)‐2,3,5‐triiodobenzamide, was synthesized in two steps from 2‐aminopropane‐1,3‐diol and 2,3,5‐triiodobenzoic acid with a high yield. A thorough study on the chemical structure, mechanical properties, radiopacity, and physiological properties of the IPUs was conducted. It is revealed that with increasing content of chain extender, the molecular weights of IPUs decreased slightly while the tensile modulus and breaking strength of IPUs increased significantly, illustrating an excellent comprehensive performance. With iodine content high to about 16 wt %, the IPU sample is equal to the aluminum plate with the same thickness in X‐ray radiopacity, meaning that the synthesized polyurethanes are promising as radiopaque materials. The oxidative degradation and cytotoxicity tests illustrated a good performance of stability and biocompatibility for the IPUs. It confirmed that the as‐synthesized IPUs are promising for biomedicine applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42693.     

Polyester polyols and polyurethanes from ricinoleic acid

Triols of molecular weights (MWs) 1000–4000, suitable for flexible foams, were prepared by transesterification of methyl esters of ricinoleic acid with trimethylol propane. These polyols were noncrystallizing, relatively low‐viscosity liquids. They were reacted with diphenylmethane diisocyanate (MDI) to obtain elastomers having glass transition temperatures below ?60°C. Polymer networks from high‐MW polyols exhibited relatively high sol fractions suggesting that some cyclization occurred during polyol preparation. The low Shore hardness, relatively low strength and modest elongation of the elastomers were attributed to the specific structure of polyricinoleic chains and the presence of dangling chains, serving as plasticizers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and selected properties of polyurethanes with monodisperse hard segments based on hexane diisocyanate and three types of chain extenders

Poly(ethylene glycol) grafted octadecyl quaternized carboxymethyl chitosan (PEG-g-OQC) copolymers were synthesized to both improve the biocompatibility of OQC and form PEGylated cationic polymeric liposomes (CPLs), which composed of the mixture of OQC, cholesterol, and PEG-g-OQC. Structure of the copolymers was characterized by using Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H-NMR), and X-ray diffraction (XRD). The methyl tetrazolium (MTT) assay with L929 cell lines confirmed that PEGylation can decrease the cytotoxicity of OQC. PEGylated CPL nanoparticles (NPs) can be prepared by adding different weight ratio of PEG-g-OQC in the mixture. Paclitaxel was successfully incorporated into PEGylated CPLs with high drug encapsulating efficiency (>90%) and drug loading capacity (>15%). Physical stability experiment showed that paclitaxel-loaded PEGylated CPLs was stable with little change of particle size and size distribution in the condition of freeze-dried by adding mannitol or in high temperature and high pressure. Power or reagent of drug-loaded PEGylated CPLs showed a slow steady release profile for paclitaxel. These results show that PEG-g-OQC and CPLs have potential application as a drug delivery vehicle. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of novel natural rubber based cationic waterborne polyurethane—Effect of emulsifier and diol class chain extender

Novel cationic waterborne polyurethanes (cWPU) were synthesized by step‐growth polymerization of hydroxyl telechelic natural rubber, molecular weight of 2800 g mol^?1, toluene‐2,4‐diisocyanate, N‐methyl diethanolamine (NMDEA) as an emulsifier. The chemical structure of cWPU was confirmed by ¹H‐nuclear magnetic resonance and Fourier transform infrared spectroscopy. The amounts of NMDEA and ethylene glycol under isocyanate (NCO) index of 100 on the properties of cWPU were studied. It was found that cWPU was stable under the concentration of NMDEA more than 1.50 mol and the particle sizes decreased with increasing of NMDEA content. Also, contact angle shows more hydrophilic materials by increasing of NMDEA. Extended cWPU was found in two ranges of nano size. Chain extender has strongly affected cWPU film formation, increasing of mechanical properties, and thermal properties. In addition, stress–strain curve and scanning electron microscopy image shows the change of behavior from soft elastic to ductile plastic by adding ethylene glycol. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45715.     

Urethane‐forming reaction kinetics and catalysis of model palm olein polyols: Quantified impact of primary and secondary hydroxyls

Model palm olein natural oil polyols (NOPs) with varying ratios of primary to secondary hydroxyls were synthesized, characterized, and evaluated in reaction kinetics study with isocyanate in formation of polyurethanes. Reaction rate constants and activation energies associated with primary and secondary hydroxyls of NOPs were quantified. The kinetic study in toluene shows that the NOP containing primary hydroxyls have three times higher reaction rate constants in noncatalyzed reaction with 4,4′‐diphenylmethane diisocyanate (4,4′‐MDI) compared to the model NOP containing only secondary hydroxyls, which is associated with higher activation energy of secondary hydroxyls. However, the difference in reaction rate constants of primary and secondary hydroxyls in NOPs diminished in the reactions catalyzed with dibutyltin dilaurate. Bulk polymerization reaction confirms the kinetics results in toluene, showing that the model NOP containing primary hydroxyls reached gel time at a faster rate. Evaluation of elastomers from bulk polymerization shows low degree of phase separation of hard and soft segments for elastomers based on the model NOPs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42955.     

Elaboration and properties of renewable polyurethanes based on natural rubber and biodegradable poly(butylene succinate) soft segments

Natural rubber (NR) is a renewable bio‐based polymer, while poly(butylene succinate) (PBS) belongs to the family of biodegradable renewable polymers. In this article, novel polyurethanes (PUs) were prepared using hydroxyl telechelic natural rubber (HTNR) and hydroxyl telechelic poly(butylene succinate) (HTPBS) as soft segments, and using toluene‐2,4‐diisocyanate (TDI) and 1,4‐butanediol (BDO) as hard segment. HTPBS oligomers of = 2000 and 3500 g mol^?1 were synthesized by bulk polycondensation of succinic acid (SA) with BDO. The polyurethane materials were obtained by casting process after solvent evaporation. The influence of the hard segment content and the molecular weight of HTPBS on the materials’ thermo‐mechanical properties were investigated by means of tensile testing, DSC, TGA, and DMTA. The obtained polyurethanes were amorphous with phase separations between hard and soft segments as well as between HTNR and HTPBS segments, and they exhibited good physical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42943.     

Defining a strain‐induced time constant for oriented low shear‐induced structuring in high consistency MFC/NFC‐filler composite suspensions

Micro and nanofibrillated cellulose is an essentially one‐dimensional high aspect‐ratio particle material, which can undergo two‐dimensional layer (band) structuring under shear. Controlling the evolving rheological properties in aqueous suspension is essential for industrial applications in composite materials. This study focuses on an as yet considered to be unreported phenomenon of structure hardening under low shear. The timescale of the quasi gelation‐controlled structure formation under low shear is studied using the large gap vane‐in‐cup geometry of the Brookfield viscometer. It is proposed that localized structure forms within continuous shear bands, similar to quasi liquid‐crystal formation. By extrapolating a characteristic structure growth parameter to the rotation speed at which it becomes zero, the strain‐induced structure time constant, t_gel, can be obtained as (= f (Ω)) = 1/t_gel for the range Ω = 10–100/min. The time constant of low shear structure formation is shown to be separable from the static viscoelastic structure build under oscillation in concentrated composite suspension using plate‐plate geometry, which is manifest by a Weissenberg normal force response on switching to applied shear, when the time constant of structuration t_gel is long. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42827.     

Carbohydrate‐based polyurethanes: A comparative study of polymers made from isosorbide and 1,4‐butanediol

A set of linear polyurethanes containing isosorbide units were synthesized by polymerization in solution from HDI and MDI diisocyanates and 1,4‐butanediol (BD), isosorbide (Is) or diisosorbide diurethanes (Is₂HDI and Is₂MDI) as diols. The thermal transitions, thermal stability, and crystal structure of the polyurethane homopolymers and copolymers containing isosorbide were evaluated and compared with those displayed by their polyurethane analogues entirely made of BD. It was found that incorporation of Is units in the polyurethane chain produced significant changes in T_g, T_m, and T_d but no significant differences were noticed between copolymers made from Is or Is₂ monomers. Degradation assays revealed that the presence of Is units increased slightly the hydrolysis rate of polyurethanes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and structural peculiarities of 1,1‐dimethylhydrazine‐based polyurethanes

Novel polyurethanes (PUs) based on poly(oxytetramethylene glycol), 4,4′‐methylenediphenyl diisocyanate, and 1,1‐dimethylhydrazine (DMH) were prepared. Stoichiometric (1 : 1) and nonstoichiometric (2 : 1 to 20 : 1) prepolymer/DMH ratios were studied. The number‐average molecular masses and possible structures of the obtained polymers were evaluated by potentiometric nonaqueous titration analysis of terminal groups, the Kieldal method (the evaluation of the nitrogen atom content), the aminolysis method, viscosimetry, IR spectroscopy, rheology, and small‐angle X‐ray scattering. Only in the case of the stoichiometric (1 : 1) ratio was a low‐molecular‐mass PU with a linear structure formed, whereas for all studied nonstoichiometric ratios, PUs with branched structures were formed. The level of hard and flexible block segregation increased with the increase in the prepolymer/DMH ratio. Dielectric results for the dynamic glass transition and water sorption measurements provided additional support to the structural studies. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Renewable thermoset copolymers from tung oil and natural terpenes

The cationic copolymerization of tung oil, limonene, and myrcene as comonomers, initiated by boron trifluoride, is presented and discussed in this work. Dynamic mechanical analysis revealed that all copolymers behave as thermosets. FTIR spectra for both copolymers, after extraction with dichloromethane, suggested that the major component of the insoluble fraction was reacted tung oil (a cross‐linked triglyceride network). Likewise, unreacted tung oil was found to be the main component of the soluble phase. Also, all the copolymers showed only one tan δ peak, indicating no phase separation. Glass transition temperature (Tg) increased with the myrcene content and decreased almost linearly as the limonene content increased. Furthermore, the Fox and Loshaek model showed a relatively good prediction of the Tg values of the polymers. The Young's modulus ranged from 33.8 to 4.7 MPa for all tested thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41155.     

Polyurethanes containing a crystalline polyol and semiflexible urethane segments

Ultradrawing semicrystalline polymers is an intriguing approach to develop stiff, strong, and tough polymeric fibers. In the research field of polyurethane copolymer elastomers the term “soft segment” usually refers to the medium molecular weight glycol while the term “hard segment” stands for the urethane rich or isocyanate‐short glycol segments. Here we investigate the influence of semiflexible segment content in the urethane rich phase on the mechanical properties and morphology of polyurethanes synthesized with a crystalline polyol as a “soft” segment. Materials with lower semiflexible urethane segment content developed stiffer and stronger materials upon drawing. This was related to greater soft segment crystallization along the draw direction. Materials with a higher fraction of semiflexible urethane segments were more elastic (higher yield strains and strengths) but exhibited more brittle‐like fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41281.     

Structure–property relationships of polycarbonate diol‐based polyurethanes as a function of soft segment content and molar mass

Segmented thermoplastic polyurethanes (PUs) have been synthesized with polycarbonate diol as soft segment and 4,4′‐diphenylmethane diisocyanate and butanediol as hard segment. Two different series employing two different soft‐segment molar mass, 1000 and 2000 g/mol, and by changing the hard‐segment content from 32 to 67% have been investigated with the aim to elucidate the effect of the different content variations on the properties. Morphological, thermal, and mechanical properties have been studied by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), wide angle X‐ray diffraction, atomic force microscopy, tensile and tear strength, hardness, and specific gravity tests. Properties have been explained from the standpoint of miscibility between hard‐ and soft‐segment microdomains of the tailored segmented PUs through an exhaustive analysis. FTIR, DSC, and DMA measurements revealed that miscibility between hard and soft microdomains increases as the molar mass of the macrodiol decreases. An increase in hard‐segment content entailed the formation of larger hard domains with higher crystallinity what results in superior mechanical properties such as higher tensile stress and tear strength, and hardness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41704.     

The chain extender content and NCO/OH ratio flexibly tune the properties of natural rubber‐based waterborne polyurethanes

The effects of chain extender content (ethylene diamine, EDA) and NCO/OH ratio on the properties of natural rubber‐based waterborne polyurethanes (WPUs) were investigated experimentally. The particle size of WPU increased significantly with the NCO/OH ratio, in the presence of the EDA chain extender, while it was unaffected by the EDA content. The water uptake of WPU film increased with the EDA content, while the swelling in various solvents decreased. In a thermal analysis, the second decomposition stage of a WPU film increased with the EDA content and with the NCO/OH ratio that also positively affected the dynamic mechanical and mechanical properties. These factors in WPU films had no the effect on the T_g. The stress–strain curves clearly showed the change in WPU films from soft elastomeric materials to ductile and hard plastics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42505.     

Polyols and polyurethane foams from acid‐catalyzed biomass liquefaction by crude glycerol: Effects of crude glycerol impurities

The effects of crude glycerol impurities on acid‐catalyzed biomass liquefaction by crude glycerol were investigated. Salts (i.e., NaCl and Na₂SO₄) decreased biomass conversion ratios and negatively affected the properties of polyols produced. Regression models were developed and validated as appropriate for describing the relationships between organic impurities and biomass conversion ratios and between organic impurities and the hydroxyl number of polyols. Polyols produced from crude glycerol containing 0–45% organic impurities showed the hydroxyl number varying from 1301 to 700 mg KOH/g, acid number from 19 to 28 mg KOH/g, viscosity from 2.4 to 29.2 Pa s, and molecular weight (M_w) from 244 to 550 g/mol. Crude glycerol containing 40–50 wt % of organic impurities was suitable to produce polyols with suitable properties for rigid and/or semi‐rigid polyurethane (PU) foam applications. The produced PU foams showed density and compressive strength comparable to those derived from petrochemical solvent‐based liquefaction processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40739.     

Polyols and polyurethanes prepared from epoxidized soybean oil ring‐opened by polyhydroxy fatty acids with varying OH numbers

Bio‐based polyols from epoxidized soybean oil and different fatty acids were successfully prepared using a solvent‐free method in order to investigate the effect of the polyols' OH numbers on the thermal and mechanical properties of the polyurethanes prepared using them. Epoxidized soybean oil/epoxidized linseed oil was ring‐opened by methanol/glycol followed by saponification to prepare polyhydroxy fatty acids. These fatty acids and epoxidized soybean oil were then used for further solvent‐free ring‐opening reactions with DBU as catalyst, which facilitated the carboxylic ring‐opening. Gel permeation chromatography revealed that a molar ratio of carboxylic acid from polyhydroxy fatty aicds and epoxy group of 0.5 : 1 resulted in optimized polyols containing the smallest amounts of residual starting materials. The obtained polyols had varying OH numbers and the acquired polyurethane films were comprehensively characterized. With increasing OH number of the polyols the PUs displayed an increase in crosslinking density, glass transition temperature (T_g), tensile strength and Young's modulus, and a decrease in elongation and toughness. This work provides Supporting Information on the effect of OH number of polyols obtained via a solvent‐free ring‐opening method on the mechanical and thermal properties of polyurethanes, of particular interest when designing PU products for specific purposes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41213.     

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.