Renewable resource modified polyol derived aliphatic hyperbranched polyurethane as a biodegradable and UV‐resistant smart material

Renewable resource tailored tough, elastomeric, biodegradable, smart aliphatic hyperbranched polyurethanes were synthesized using castor oil modified polyol containing fatty amide triol, glycerol, diethanolamine and monoglyceride of sunflower oil via an A_x + B_y (x , y ≥ 2) approach. To the best of our knowledge, this is the first report of the synthesis of solely aliphatic hyperbranched polyurethanes by employing renewable resources. The synthesized polyurethanes were characterized by Fourier transform infrared, NMR and XRD techniques. The hyperbranched polyurethanes exhibited good mechanical properties, especially elongation at break (668%), toughness (32.16 MJ m^?3) and impact resistance (19.02 kJ m^?1); also high thermal stability (above 300 °C) and good chemical resistance. Also, the hyperbranched polyurethanes were found to show adequate biodegradability and significant UV light resistance. Moreover, they demonstrated excellent multi‐stimuli‐driven shape recovery ability (up to 97%) under direct sunlight (10⁵ lux), thermal energy (50 °C) and microwave irradiation (450 W). The performance of the hyperbranched polyurethanes was compared with renewable resource based and synthetic linear polyurethane to judge the superiority of the hyperbranched architecture. Therefore, these new aliphatic macromolecules hold significant promise as smart materials for advanced applications. © 2017 Society of Chemical Industry     

New T-Shape Polyurethanes: Synthesis,Thermal and Mechanical Properties

A series of new T-shaped polyurethanes were prepared from various diisocyanates and 2,5-dihydroxybenzelidene aniline (azomethine bisphenol). The latter compound was synthesized by the reaction of 2,5-dihydroxy-benzaldehyde with aniline. The structures of azomethine bisphenol and T-shaped polyurethane were confirmed by FT-IR, ¹H-NMR, ¹³C-NMR Spectroscopy and elemental analysis (CHN). The mechanical properties were characterized by tensile strength, tear strength and shore hardness. Thermal properties were also studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Mechanical and thermal studies showed that the synthesized polyurethanes possess good mechanical and thermal properties.     

Development and scale-up of thermoplastic poly(ether-ester) glycol polyurethanes for flexography

This study presents an experimental essay on the production of thermoplastic polyurethanes for flexographic printing ink applications. Four formulations were obtained by step-growth polymerization reactions having the pre-polymer 4,4′-diphenylmethylene diisocyanate and Voranol 2120 L® catalyzed by dibutyltin dilaurate as common ground. In the chain extension step, ethanol or ethyl acetate was used as solvent, and the use or not of castor oil as a chain extender in addition to hexanedioic acid and 2,2′-oxydi(ethan-1-ol) was evaluated. The chemical structures of the synthesized thermoplastic polyurethanes (TPUs) were evaluated by Fourier transform infrared spectroscopy, ¹H NMR, gel permeation chromatography, differential scanning calorimetry, and rheological features were assessed by density and viscosity analysis. The TPU resins were used to produce flexographic printing inks and further tested by friction, adhesion, gloss, and Gardner viscosity essays. It was found that the castor oil presence enhanced ink viscosity in 66% (from 26,790 to 44,440 Pa s) as well as improved strength. Formulations using ethanol as solvent showed the best results. The experiments were carried in a 250 ml reactor and then, scaled up to 2000 ml, keeping the power transfer per unit of volume constant at around 0.8 W/L. The analytical results from the larger scale were as good as the obtained in scale one, showing promising application.     

Medical grade tubing: Criteria for catheter applications

In 1990 there were approximately 710 million catheter units produced world-wide from a variety of materials. This number is expected to increase 5–7% in 1991. Intravenous catheters are currently being produced from a myriad of materials including polyurethanes, polyvinylchloride, silicone rubber, and Teflon®, to name a few. Along with the ultimate end usage of a catheter, many other performance characteristics must be evaluated. Some of these characteristics are mechanical and physical properties, surface properties, hemocompatibility, biostability, and processability. The Vialon® biomaterial has a tensile strength of 520 kg/cm² which is over 50% higher than the other materials studied. This bioengineered material, which is a member of the broad class of polyurethanes, also gave better hemocompatibility properties, as measured by in vivo platelet deposition. In addition Vialon® is engineered such that the material softens in the body's moisture and heat rendering it biocompatible. The thermoplastic nature of this polymer also allows its ease of processing by such conventional means as thermal extrusion. A comparison of the aforementioned materials against these and other performance criteria was undertaken and will be presented.     

Biobased hyperbranched shape‐memory polyurethanes: Effect of different vegetable oils

Hyperbranched polyurethanes were synthesized from poly(ε‐caprolactone) diol as a macroglycol, butanediol as a chain extender, a monoglyceride of a vegetable oil (Mesua ferrea, castor, and sunflower oils separately) as a biobased chain extender, triethanolamine as a multifunctional moiety, and toluene diisocyanate by a prepolymerization technique with the A₂ + B₃ approach. The structure of the synthesized hyperbranched polyurethanes was characterized by ¹H‐NMR and X‐ray diffraction studies. M. ferrea L. seed‐oil‐based polyurethane showed the highest thermal stability, whereas the castor‐oil‐based one showed the lowest. However, the castor‐oil‐based polyurethane exhibited the highest tensile strength compared to the other vegetable‐oil‐based polyurethanes. All of the vegetable‐oil‐based polyurethanes showed good shape fixity, although the castor‐oil‐based polyurethane showed the highest shape recovery. Thus, the characteristics of the vegetable oil had a prominent role in the control of the ultimate properties, including the shape‐memory behaviors, of the hyperbranched polyurethanes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39579.     

A simple one‐step synthesis and polymerization of plant oil triglyceride iodo isocyanates

In this study, a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized with polyols, such as, castor oil, pentamethylene glycol, and glycerol to give the corresponding polyurethanes and with polyamines, such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and ¹H‐NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150°C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T_g around ?50°C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of metal‐containing polyurethanes with antibacterial activity

Metal salts of mono(hydroxypentyl)phthalate [M(HPP)₂, where M is Ca²⁺, Cd²⁺, Pb²⁺, or Zn²⁺] were synthesized by the reaction of 1,5‐pentane diol, phthalic anhydride, and metal acetate. A new series of metal‐containing polyurethanes containing ionic links in the main chain were synthesized by the reaction of hexamethylene diisocyanate or toluylene 2,4‐diisocyanate with the M(HPP)₂ salts. The structures of the monomers and polymers were confirmed with infrared, ¹H‐NMR, and ¹³C‐NMR spectra and elemental analysis. The polymers were also characterized with thermogravimetric analysis, differential scanning calorimetry, and solubility and viscosity measurements. The antibacterial activity of these polyurethanes was investigated with the agar diffusion method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1194–1206, 2002     

Early development of a biodegradable energetic elastomer

The expected depletion of oil resources and a greater awareness for the environmental impact of plastic products have created a strong interest toward energetic polymers that are not only biodegradable but also obtainable from renewable resources. In this work, a copoly(ester/ether) was synthesized from polyepichlorohydrin and sebacoyl chloride using pyridine as a Lewis‐base catalyst. The chlorinated polymer was azidified with NaN₃ in dimethyl sulfoxide solutions. The success of the reaction was confirmed by ¹H‐NMR, ¹³C‐NMR, and Fourier‐transform infrared spectroscopy. Two types of polyurethane networks were synthesized from the nonenergetic and the energetic copolymers, adding polycaprolactone triol and using L ‐lysine diisocyanate as a nontoxic curing agent. The two resulting polyurethanes were soft thermoset elastomers. The polyurethanes were chemically and mechanically characterized, and their biodegradability was evaluated in compost at 55°C. The nonenergetic and the energetic polyurethanes showed a glass‐transition temperature of −14°C, and −23°C, respectively. The weight loss of the polyurethanes during the composting experiments was monitored. It increased almost linearly with time for both materials. After 20 days, the nonenergetic samples lost about 50% of their mass because of the biodegradation mechanism. Instead, the energetic elastomers lost only about 25% of their initial mass after 25 days. The experimental results revealed that the azide pendant group in the soft segment (the polyether segments) is the main factor that controls the physical, mechanical, and degradation properties of these polyurethane networks. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new polyurethanes: influence of monomer composition

Different polyurethanes (PU) were synthesized from polycaprolactone diol, 1.6-hexamethylene diisocyanate and bis(2-hydroxyethyl)terephthalate, using a two- and one-step methods providing regular and random distributions of starting monomers in the polyurethane chains. Even with an identical molar monomer composition, the properties of obtained PU are different depending on the method of synthesis. The chemical structure of PU was characterized by ¹H and ¹³C NMR spectroscopy, as well as by FTIR and UV–Visible spectroscopy. The thermo-mechanical and hydrophilic properties of synthesized PU were also studied demonstrating the influence of aromatic ring in the macromolecular chain.     

Synthesis and characterization of waterborne polyurethane dispersion from glycolyzed products of waste polyethylene terephthalate used as soft and hard segment

Waste polyethylene terephthalate (PET) bottles were collected, cleaned and then depolymerized by glycolysis with neopentyl glycol (NPG) and dipropylene glycol (DPG), in the presence of N-butyl titanate catalyst. The product, named glycolyzed oligoesters, obtained through the depolymerization, were employed respectively in hard segment and soft segment in the synthesis of novel waterborne polyurethane dispersions (PUDs) via a simple and environmentally benign process. In addition, a polyurethane dispersion without glycolyzed oligoesters was synthesized as a comparison. The bulk structure of PET glycolyzed oligoesters and PUDs films were characterized by Fourier transform infrared spectroscopy (FT-IR), H-nuclear magnetic resonance (¹H NMR) and Gel permeation chromatography (GPC). The results illustrated that glycolyzed oligoesters were successfully introduced into the hard and soft segment of the polyurethanes. Furthermore, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the PET glycolyzed oligoesters and PUDs films. The results showed that the thermal resistance of waterborne polyurethanes obtained with glycolyzed oligoesters increased due to lower degrees of phase separation. X-ray diffraction indicated that all synthesized polyurethanes exhibited reduced degrees of orientation. Due to the balance between hard-/soft-segment of the waterborne polyurethane dispersions, the formulations containing glycolyzed oligoesters within the hard segment sections of the polyurethanes provided the best performance.     

Synthesis,characterization, and antibacterial activity of metal‐containing polyurethanes

Metal salts of mono(hydroxyethoxyethyl)phthalate [M(HEEP)₂] (M = Ca²⁺, Cd²⁺, and Pb²⁺) were synthesized by the reaction of diethylene glycol, phthalic anhydride, and metal acetates. A series of metal‐containing polyurethanes (PUs) were synthesized by the reaction of hexamethylene diisocyanate or tolylene 2,4‐diisocyanate with Ca²⁺, Cd²⁺, and Pb²⁺ salts of mono(hydroxyethoxyethyl)phthalate using di‐n‐butyltin dilaurate as a catalyst. The PUs were well characterized by FTIR, ¹H, and ¹³C NMR, solid‐state ¹³C‐CP‐MAS NMR, viscosity, solubility, elemental, and X‐ray diffraction studies. Thermal properties of the polymers were also studied by using thermogravimetric analysis and differential scanning calorimetry. The antibacterial activities of these polyurethanes have also been investigated by using the agar diffusion method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 288–295, 2004     

Mechanical properties of polymer nanofibers revealed by interaction with streams of air

Electrospun nanofibers were captured directly between two steel rods that functioned as the “grips” of the tensile testing apparatus. Tension was applied to the selected nanofiber by displacing one of the grips at controlled rates or in steps. The stress was revealed by the deflection of a nanofiber, caused by the drag force from a broad stream of air, which flowed perpendicular to the fiber at a known velocity. The deflected position and shape of the nanofiber was observed with a light arrangement optimized to produce bright glints that were photographed with a camcorder. Image analysis of the catenary shapes of the nanofibers was combined with scanning electron microscopy measurements of the diameter of the ends of the tested fibers to evaluate the mechanical properties.Measurements of properties, including tensile strength, tensile modulus and elongation-to-break, of thin electrospun fibers were obtained on six chemically different polymers: nylon 6, poly(ethylene oxide), polyvinylpyrrolidone, poly(2-ethyl-2-oxazoline), Tecoflex^® and Tecophilic^® polyurethanes. To the best of our knowledge, this is the first report of tensile data on single polyvinylpyrrolidone and poly(2-ethyl-2-oxazoline) nanofibers. These soft nanofibers with low strain to break rarely survive the sample loading procedures where single fiber manipulation is involved. This method complements difficult mechanical measurements of polymer nanofibers and low strength microfibers made on miniature mechanical testing devices. Mechanical hysteresis curves were attained that show the recoverable and non-recoverable tensile deformation of PEO, nylon and Tecophilic^® polyurethane fibers.     

Flame-retarding materials—I. Syntheses and flame-retarding property of alkylphosphate-type polyols and corresponding polyurethanes

In this research, oligomeric polyalkyl phosphate-type polyols (P% = 14–17) were synthesized from ethylene glycol or 1,4-butanediol (PBE or PBB) by means of butyl phosphorodichloridate, which was prepared from phosphorus oxychloride and butanol. These polyols were then reacted with isocyanate to form the corresponding polyurethanes (PETD and PBTD). These polyols were characterized by FTIR, ¹H-NMR, and ³¹P-NMR, and the thermal stabililties were measured by thermogravimetry analysis. The degradation phenomena were traced by FTIR and interpreted in terms of the degradation and formation of bonds. The corresponding polyurethanes were also characterized by FTIR and ¹H-NMR, and their thermal stability was also studied by thermogravimetry analysis. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1635–1643, 1998     

Synthesis of bio‐based polyurethanes from epoxidized soybean oil and isopropanolamine

Epoxidized soybean oil (ESO) and isopropanolamine were used to synthesize a new polyol mixture for preparation of bio‐based polyurethanes. The chemical synthetic route for reaction of ESO with isopropanolamine was analyzed by ¹H‐NMR. The results suggested that both ester groups and epoxy groups in ESO had reacted with amino group of isopropanolamine through simultaneous ring‐opening and amidation reactions. Epoxy groups in various situations exhibited different reactivity, and the unreacted epoxy groups were further opened by hydrochloric acid. The synthesized polyol mixture had high hydroxyl number of 317.0 mg KOH/g. A series of polyurethanes were prepared by curing the synthesized polyol mixture with 1,6‐diisocyanatohexance along with different amount of 1,3‐propanediol (PDO) as chain extender. Tensile tests showed that yield strengths of the polyurethanes ranged from 2.74 to 27.76 MPa depending on the content of PDO. Differential scanning calorimetry analysis displayed one glass transition temperature in the range of 24.4–28.7°C for all of the polyurethane samples, and one melt peak at high content of PDO. Thermogravimetric analysis showed that thermal degradations of the polyurethanes started at 240–255°C. In consideration of simple preparation process and renewable property of ESO, the bio‐based polyurethane would have wide range of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Extruder synthesis of a new class of polyurethanes: Polyacylurethanes based on poly(ε-caprolactone) oligomers

Using a micro-extruder a new class of polyurethanes, polyacylurethanes (PAUs), based on poly(ε-caprolactone) (PCL) oligomers and terephthaloyl diisocyanate was synthesized. These polymers are anticipated to have potential for biodegradable and/or biomedical applications. Therefore, PAUs were synthesized without the use of any, possibly toxic, catalysts.PCL diols of different molecular mass were used, namely 750, 1000, 1250, 1500, 2000, 3000 and 4000 g/mol. These diols were synthesized by thermal polymerization at 150 °C without the use of any catalyst. The PAUs of terephthaloyl diisocyanate were synthesized by reactive extrusion using a micro-extruder of 5 cm³ at 130 °C.The PAUs obtained were characterized using DSC, GPC, DMTA, SAXS and tensile testing.Surprisingly, PAUs based on PCL chains of 750, 1000, 1250 and 1500 g/mol were found to show microphase separation/micro crystallization as proven by SAXS data combined with DSC. This microphase separation creates elastomeric properties as is known from polyurethanes.In the PAUs based on PCL chains of 2000, 3000 and 4000 g/mol part of the PCL was found to crystallize and no evidence of any phase separation of the acylurethane block was found.     

Synthesis of L-Lactide-Based Segmented Polyurethanes

A series of segmented polyurethanes with polylactidediols soft segments and methylene-diphenyl-diisocyanate/1,4-butanediol hard segments with molecular weights in the range of 6.18 × 10³ to 9.36 × 10³ Da were synthesized. Stannous octoate was the catalyst for the reactions. These polymers were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, gel permeation chromatography, and thermogravimetric analyzer. Fourier transform infrared analyses revealed the formation of urethane groups and complete curing of polyurethane. The thermal degradation temperatures were in the range of 248.55–257.09°C. X-ray diffraction studies confirmed the segmented structure of polyurethanes.     

Blending polypropylene with glycidyl methacrylate‐containing polymer to improve adhesion to elastomers

BACKGROUND: Polypropylene (PP) is one of the most widely used polyolefins but gets restricted in surface applications due to its non‐polar nature. Surface properties of films made of PP were modified to improve their adhesion to elastomeric polymers such as thermoplastic polyurethanes (TPU), especially to Pebax^® [poly(ether‐block‐amide)]. RESULTS: Surface modification of PP was brought about by blending it with glycidyl methacrylate (GMA)‐containing polymer to increase its surface energy. Films of modified PP were analyzed to determine the blending efficiency and characterized using contact angle measurements, differential scanning calorimetry, X‐ray photoelectron spectroscopy and scanning electron microscopy. Molecular dynamics simulations were done to determine surface and bulk properties of PP blended with GMA. The computational results correlated very well with the experimental data and revealed that the changes in the surface energy can be linked to the position of the functional group within the sample. T‐Peel tests indicated a 2.4 times increase in adhesion to Pebax^® and only 1.7 times increase in adhesion to TPU compared to unmodified PP. CONCLUSION: The surface energy and enhanced adhesion proved that PP was successfully modified and its surface made more polar. Copyright © 2008 Society of Chemical Industry     

Synthesis and Comparative Physico-chemical Study of Polyester Polyols Based Polyurethanes of Bisphenol-A and Bisphenol-C Epoxy Resins

Polyester polyols of epoxy resins of bisphenol-A and bisphenol-C were synthesized by reacting corresponding 0.02 mol epoxy resin, and 0.04 mol ricinoleic acid by using 1,4-dioxane (30 ml) as a solvent and 0.5 g triethyl amine as a catalyst at reflux temperature for 4–5 hr. Polyurethanes have been synthesized by reacting 0.0029 mol of polyester polyols with 0.004 mol toluene diisocyanate at room temperature and their films were cast from solutions. The formation of polyester polyols and their polyurethanes are supported by IR spectral data (1732.9–1730.0 cm^?1 ester and urethane and 3440.8–3419.6 cm^?1 OH and NH str). The densities of polyurethane of bisphenol-A (PU-A) and polyurethane of bisphenol-C (PU-C) were determined by a floatation method. The observed densities of PU-A and PU-C are 1.2190 and 1.2308 g/cm³, respectively. Slightly high density of PU-C is due to structural dissimilarity of two bisphenols. The tensile strength, electric strength, and volume resistivity of PU-A and PU-C are 34.7, 18.7 MPa; 80.7, 44.4 kv/mm; and 1.7 × 10¹⁵, 2.2 × 10¹⁵ ohm cm, respectively. PU-A and PU-C are thermally stable up to about 182–187°C and followed three step degradation. Incorporation of cyclohexyl cardo group in polyurethane chain did not impart any change in thermal properties but it caused drastic reduction in tensile and electric strength due to rigid nature of PU-C chains. PU-C has excellent chemical resistance over PU-A. Both polyurethanes possess good resistance against water, 10% each of aqueous acids (HCl, HNO₃, and H₂SO₄), alkalis (NaOH and KOH) and NaCl. Good thermo-mechanical, excellent electrical properties, and good chemical resistance of polyurethanes signify their usefulness in coating and adhesive, electrical and electronic industries.     

Synthesis and nonlinear optical properties of novel y‐type polyurethanes containing different concentrations of chromophore

A new series of Y‐type polyurethanes containing different concentrations of nonlinear optical (NLO) chromophore with aniline donor and tricyanofurane (TCF) acceptor have been successfully prepared, and characterized by FTIR, UV‐Vis, and ¹H‐NMR spectra. New polyurethanes were synthesized with different chromophore contents by introducing diol N, N‐dihydroxyethylaniline or 4‐[N, N‐(dihydroxyethyl)amino]benzaldehyde. These NLO polyurethanes exhibit good film forming property and high thermal stability up to 281°C. The highest electro‐optic coefficient (r₃₃) of polymers is up to 39 pm V^?1 measured by simple reflection technique at 1310 nm, and the temporal stability of the poling‐induced order at elevated temperature of 80°C was much improved through the introducing of hydrogen bonding interaction in this system. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Physical properties of crosslinked polyurethane

Polyester based polyurethanes were synthesized from low molecular weight polyester (M_n 2000) and 4,4′-methylene bis(phenyl isocyanate) (MDI) with butanediol as a chain extender and glycerol as a crosslinker. The polyester was synthesized from adipic acid and glycol which was a mixture of 1,6-hexanediol and 1,2-propanediol. The effect of the crosslinker content on the degree of H-bond formation in the hard segments and the physical properties of polyurethanes were studied by differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), Fourier transform infrared spectroscopy (FTIR) and mechanical testing. The experimental results revealed that incorporation of a triol crosslinker into the hard segments of polyurethane results in a decrease of hard segment H-bond formation. The mechanical data indicate that the mechanical properties of polyurethanes depend on the concentrations of physical and chemical crosslinks and that there is an optimum concentration of triol crosslinker for the tensile stress and elongation properties. © 1998 Society of Chemical Industry