Synthesis and characterization of biodegradable polyurethanes based on L‐cystine/cysteine and poly(ϵ‐caprolactone)

Tunable biodegradable polyurethanes (PUs) with favorable mechanical properties were synthesized from 1,6‐hexamelthylene diisocyanate (HDI) as the hard segment, poly(?‐caprolactone) (PCL) as the soft segment, and L ‐cystine ester as chain extender. The structure of PUs was confirmed by FTIR and ¹H‐NMR. The results of differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical analysis, and tensile test revealed that the thermal and mechanical properties of PUs were strongly influenced by the molecular weight of soft segment PCL. In the presence of glutathione, the disulfide group cleaved into thiols, realizing the PUs degraded and the molecular weight decreased. For PU [550], it remained only 50% of the original M_w. Evaluation of cell viability demonstrated the nontoxicity of the PUs, which facilitated their potential in biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure‐property relationship in polyurethane elastomers containing starch as a crosslinker

Polyurethane elastomers were synthesized using polypropylene glycol (PPG 2000) as the polyol and starch as the multifunctional crosslinker in varying concentrations. Thermal and mechanical properties were measured by DSC, DMA and tensile tests. The morphology was examined by SEM. The swelling behavior of the polyurethanes in various solvents was investigated and the solubility parameter was determined. All these properties were compared with those of polyurethanes containing 1,1,1 ‐trimethylol propane (TMP) as the crosslinker. Starch‐based polyurethanes exhibited better mechanical properties. The effect of varying the starch:TMP ratio on the mechanical strength was also studied. With increasing starch content, the tensile strength and elongation increased. The starch‐based PUs exhibited two glass transitions, whereas TMP‐based PUs exhibited one T_g. No significant difference in the T_gs of the two PUs was observed. The activation energy of St‐PU calculated from DMA was 69 kcal/mol. Soil degradation tests indicated greater biodegradability in polyurethanes containing starch than in those containing TMP.     

Modified polyurethane with a covalent bond of dye molecule

In this article, we have successfully synthesized polyurethanes (PUs) with a covalent bond of dye molecule via a coupling agent of epichlorohydrin. The structure is proven by infrared (IR) spectra, which exhibits the absorption peak of dye molecule, as we expected. The dye‐grafted polyurethanes were used to evaluate their inherent viscosity, mechanical, and thermal properties and, also, their dyeing behavior. For the inherent viscosity, the PUs with the grafting of the dye molecule demonstrate a lower value of viscosity than those without grafting of the dye molecule. The tensile strength is found to decrease with the grafting of the dye molecule due to the further separation of intermolecular distance of the grafted PUs. But the elongation at break is increased with the grafting of the dye molecule. In consideration of the thermal properties, PUs with the grafting of dye molecule exhibit higher T_gh than those without dye molecule. However, their T_gs and T_ms of soft segment between dyed and undyed PU seem to be similar. For dye migration property, the PUs with the grafting of dye molecule are proven to be much lower thermal migration values (Mp%) than those of simple mixing of PU and dyestuff. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 245–253, 1999     

Synthesis and characterization of novel polyurethanes based on N1,N4‐bis[(4‐hydroxyphenyl)methylene]succinohydrazide hard segment

This article deals with the synthesis and characterization of novel polyurethanes (PUs) by the reaction between two aromatic diisocyanates (4,4′‐diphenylmethane diisocyanate and tolylene 2,4‐diisocyanate) and two aliphatic diisocyanates (isophorone diisocyanate and hexamethylene diisocyanate) with N¹,N⁴‐bis[(4‐hydroxyphenyl)methylene]succinohydrazide, which acted as hard segment. UV–vis, FTIR, ¹H NMR, ¹³C NMR, and DSC/TGA analytical technique has been used to determine the structural characterization and thermal properties of the hard segmented PUs. X‐ray diffraction revealed that PUs contained semicrystalline and amorphous regions that varied depending upon the nature of the backbone structures. PUs were soluble in polar aprotic solvents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Multifunctional,robust, and self-healable polyurethane coatings cross-linked by Diels–Alder reaction of calix[4] arenes containing furan groups

Self-healing coatings can restore their performance after inevitable damage and are promising in the industry owing to their longer service life and lower repair cost. The use of Diels–Alder reaction bonds is well-known to generate thermally self-healing coatings. In this study, a series of cross-linked self-healing polyurethane (PU) coatings were synthesized through Diels–Alder reactions of p-tert-butyl calix[4]arene bearing furan groups (C4A-FA) as a new chain extender and a bismaleimide (BMI) polyether amine as a Diels–Alder cross-linking agent. Adding C4A-FA to PUs improves their mechanical properties, thermal stability, and self-healing ability. Additionally, these modifications can result in the formation of composite networks with PU that exhibit thermoreversibility and self-healing properties. These changes have led to PUs containing modified calix[4]arene (C4A-FA) having better properties compared with unmodified calix[4]arene PUs. The properties of prepared coatings were evaluated by Fourier transform infrared spectroscopy, scanning electron microscope, differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), and tensile tests compared with a typical PU sample. The tensile and TGA results show an improvement in the thermal and mechanical properties of the polymers by increasing the C4A-FA content. By replacing 15% of butandiol (BDO) with C4A-FA in PU pure, the tensile strength increased from 1.69 to 5.14 MPa. Furthermore, adding diels–alder (DA) bonds enhanced the tensile strength to 10.49 MPa for PU-C4A15-DA. According to DSC results, a broad endothermic peak from nearly 80–140°C confirmed the retro-DA reactions in the synthesized thermoreversible samples. The healing efficiency of the PU-C4A15-DA sample was obtained at 92.5% (measured by tensile test), which is the highest value among cross-linked self-healing PUs reported in the literature.     

Hydrolysis-resistant polyurethane elastomers synthesized from hydrophobic bio-based polyfarnesene diol

Hydrolytic stability is an essential requirement for polyurethanes (PUs) that are used in highly humid and aqueous environments. In this study, hydrolysis-resistant PU elastomers (PUEs) are synthesized based on hydrophobic bio-based polyfarnesene diol (PFD), which contains unique “bottle brushes” structure (with long branched hydrocarbon side chains). The effect of hard segment (HS) content, ranging from 30 to 50%, on the morphology and properties of PUEs is investigated by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, tensile, water absorption, and contact angle measurements. The results show that there are prominent phase separations in the synthesized PUEs. The PUEs show a three-stage degradation process and two T_g, one is at about −66 °C and the other 61 °C, which are related to the soft segment and HS, respectively. Water contact angles of PUEs increase from 98.6 to 105.2° with the increasing of PFD structural unit fraction. After being immersed in deionized water for 30 days, PUEs show no significant degradation of both tensile strength and elongation at break, and mass changes of all samples are less than 0.5%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47673.     

Synthesis and characterization of permanently antistatic polyurethanes containing ionic liquids

An in situ embed ionic liquid method is designed and employed in thermoplastic polyurethanes (PUs). Unlike the traditional physically incorporated antistatic polymers where conductive fillers do not firmly combined with the matrix. This permanently antistatic PUs are successfully synthesized by using a novel polyester diol bonded with ionic liquids (ILs), which are obtained by an esterification. The ILs and novel polyester polyol are successfully synthesized and subsequently characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectrum (¹H NMR), respectively. The effects of ILs content, temperature, and relative humidity (RH) on the surface resistivity of PUs are studied by surface resistivity tests. It is found that the surface resistivity of PUs dramatically decreases with the increment of ILs and are insensitive to surrounding environment. The surface resistivity of PUs with 5.96 wt% ILs reaches 10¹⁰ Ω cm^?2 order of magnitude. The crystalline properties, thermal decomposition behaviors and mechanical properties of synthesized PUs are investigated by X‐ray diffraction (XRD), thermal gravimetric analysis (TGA) and tensile test respectively. The crystallinity of PUs with ILs is lower than that of pure PUs. Moreover, we also investigate the effect of ILs on the surface morphology of the PUs. POLYM. ENG. SCI., 56:629–635, 2016. © 2016 Society of Plastics Engineers     

Tuning the Properties of Shape-Memory Polyurethanes via the Nature of the Polyester Switching Segment

Shape-memory polymers that contain semicrystalline domains with a melting temperature (T_m) above and a crystallization temperature (T_c) below physiological temperature as fixing elements are useful to create medical devices or implants that can be custom-shaped inside or around the body. With the goal to expand the palette of materials that exhibit such properties, a series of segmented polyurethanes (PUs) containing different crystallizable polyester segments is investigated. The nature of the polyester, its molecular weight, and the ratio of hard to soft segments are systematically varied and the effect on the mechanical, thermal, and shape-memory properties of the various PUs is studied. Poly(1,12-dodecylene dodecanoate), poly(1,6-hexylene dodecanoate), and poly(ethylene sebacate) (PES) are selected as crystallizable polyester segments. The PES-based PUs display T_c values of 25–35 °C and a T_m of 60–63 °C, and allow good shape fixing at 37 °C.     

Synthesis,characterization of novel dihydrazide containing polyurethanes based on N1,N2‐bis[(4‐hydroxyphenyl)methylene]ethanedihydrazide and various diisocyanates

Four novel types of polyurethanes (PUs) were prepared from N¹,N²‐bis[(4‐hydroxyphenyl)methylene]ethanedihydrazide with two aromatic diisocyanates (4,4′‐diphenylmethane diisocyanate and tolylene 2,4‐diisocyanate) and two aliphatic diisocyanates (isophorone diisocyanate and hexamethylene diisocyanate). The chemical structure of both diol and PUs was confirmed by UV–vis, fluoroscence, FTIR, ¹H NMR, and ¹³C NMR spectral data. DSC data show that PUs have multiple endotherm peak. X‐ray diffraction revealed that the PUs contained semicrystalline and amorphous regions that varied with the nature of the backbone structures. PUs were soluble in polar aprotic solvents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Electrostrictive effect in polyurethanes

Polyurethane electrostriction was investigated by measuring the tensile electromechanical coupling coefficients of structurally different materials. True values of the strain coefficients M₃₃₁₁, M₃₃₂₂, and M₃₃₃₃ were obtained for four types of polymer: one commercial polyurethane (DOW 2103‐80 AE) and three polyurethanes synthesized at the Naval Surface Warfare Center, including two phase‐separated (PS) materials with molecular weights of 1000 and 2000 and one phase‐mixed (PM) material with a molecular weight of 2000. Measurements were performed at 2 kHz under a bias field of 4 MV/m at room temperature. Measured values of M₃₃₃₃ ranged from ?9.4 × 10^?18 to ?74.6 × 10^?18 m²/V², with the PM material exhibiting the largest coefficient. The electrostatic interaction (Maxwell stress) did not account for more than 15% of the total electromechanical activity in any of the materials. Furthermore, at the macroscopic level, an empirical relationship was established to predict the values of the electrostrictive coefficients from the dielectric constants and the compliance coefficients of the material. Finally, results indicated that, at the microscopic level, the phenomenon of electrostriction in polyurethanes could be best explained by the presence of charges inside the material (space–charge theory). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 399–404, 2003     

Segmented and nonsegmented polyurethanes: Polyaddition products of 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether and 1,6‐hexanediisocyanate

New linear polyurethanes (PUs) derived from 4,4′‐bis(2‐hydroxyethoxy)diphenyl ether (4‐HEDE) and 1,6‐hexanediisocyanate (HDI) were synthesized by either melt or solution polymerization. We found that the properties of PUs obtained are dependent mainly on the kind of organic solvent, contribution of the catalyst, and concentration of the monomers used. Good results are obtained using aprotic solvent‐N,N‐dimethylformamide, ∼ 30 wt % concentration of monomers, dibutyltin dilaurate as a catalyst, and conducting the process at 90–100°C for 4 h. This article presents basic properties of the series of PUs obtained. Thermal properties of the polymers were investigated by means of thermal gravimetric analysis and differential scanning calorimetry. Molecular weight distribution was determined by gel permeation chromatography. Shore hardness and tensile test results are also presented. The structure of the resulting products was confirmed by elemental analysis, Fourier transform infrared spectroscopy and X‐ray diffractometry. We also present the properties of copolyurethanes type 4‐HEDE/HDI/1,6‐hexanediol or 4‐HEDE/HDI/polytetramethylene oxide containing variable amounts of 1,6‐hexanediol or polytetramethylene oxide (M _n ∼ 650) synthesized in the optimal conditions established earlier for PU 4‐HEDE/HDI. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 83–91, 1999     

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     

Synthesis and Properties of Polyurethane Elastomers with Castor Oil as Crosslinker

Castor oil–polyurethane elastomers were prepared by reacting poly (1,4-butane diol) (Terathane 1400) with aliphatic 1,6-hexamethylene diisocyanate. The prepolymers were chain-extended with bifunctional precursor chains and/or with castor oil as a trifunctional crosslinker at stoichiometric ratios. These resulted in a series of crosslinked polyurethane elastomers with different structures of the hard segment. The properties of the material were measured by differential scanning calorimetry, thermogravimetric analysis, atomic force microscopy, as well as tensile properties measurements. The effect of stoichiometric balance (i.e., OH/NCO molar ratio) on the final properties was evaluated. The formation of hydrogen bonds was observed by Fourier transform infrared.spectroscopy The measured properties were found to be strongly influenced by the molar ratio of chain extenders to the diisocyanate component. The glass transition temperatures (T _g) for the polyurethanes with OH_polyol/NCO/OH_{chain extender} having molar ratios of 1:2:1 and 1:4:3 were found to be −70 and −57 °C, respectively. The polyurethanes networks with a OH/NCO molar ratio of 1:2:1 had excellent mechanical properties, indicating that this is the optimum ratio to be used in castor oil polyurethane elastomer formulations. The objective of this work was to study the effect of the castor oil crosslinker on the morphology of the resulting crosslinked polyurethanes and to correlate the morphology with the properties of these bio-based crosslinked polyurethanes.     

Synthesis,properties, and dyeing application of nonionic waterborne polyurethanes with different chain length of ethyldiamines as the chain extender

This study deals with the synthesis of some nonionic waterborne polyurethanes (PUs), using ethyldiamines of different chain length, such as ethylenediamine (EDA) and diethyltriamine (DETA), as the chain extender in the reaction, and examines the thermal properties, mechanical properties, and dyeing properties of the PU products and their blends. As far as each PU by itself is concerned, we found that the T_g of the one made with DETA is the highest, followed by that with EDA, and the one with 1,4‐butanediol (1,4‐BD) is the lowest. The PU made with 1,4‐BD as the chain extender has no T_m, while the two others, using diamines as chain extenders, have a clear T_m, the one with DETA being higher than that with EDA. However, the enthalpy data are just the opposite. The tensile strengths of the two PUs, made with diamines as the chain extender, are larger than that made with 1,4‐BD, but their respective elongation properties are just the opposite. A comparison within PUs made with diamines showed that the one made with EDA is greater in both strength and elongation categories than that made with DETA. However, the one made with DETA is far superior to both of those made with 1,4‐BD and EDA in their dye‐exhaustion ratio, color yield (K/S), fixation rate, and color fastness. In respect to the various PU mixtures that we examined, we found that both PUs synthesized with EDA or DETA as the chain extender would have their T_g's greatly increased by blending in some PU made using 1,4‐BD as the chain extender. Among them, in particular, a blend of PU, made separately with DETA and 1, 4‐BD as the chain extender, showed great improvements in both tensile strength and elongation and also demonstrated better dyeability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2824–2833, 2003     

Chlorogenic Acid Containing Bioinspired Polyurethanes: Biodegradable Medical Adhesive Materials

Highly adhesive bioinspired polyurethanes (PUs) based on the chlorogenic acid (CLA) were prepared from 4,4′-methylenebis(cyclohexyl isocyanate) (MCI) and polyethylene glycol 200 (PEG 200). The polyurethanes exhibited the lowest glass transition temperature (T_g), improved thermal stability and good adhesive properties. The highest adhesion strength was found as 373.3 ± 47.5 kPa for 10% CLA containing PUs. The polyurethanes were observed to be biodegradable and were in the range of 19–24% for 8 weeks as depending on chlorogenic acid containing of PUs. As a result, prepared biocompatible-adhesive bioinspired polyurethanes are good candidates for medical applications as a tissue adhesive material.     

Chain‐extended polyurethanes—Synthesis and characterization

Chain‐extended polyurethanes (PUs) were prepared using castor oil and different diisocyanates such as toluene‐2,4‐diisocyanate and 4,4′‐methylene bis(phenylisocyanate) as a crosslinker and different aromatic diamines like 4,4′‐diaminodiphenyl methane and 4,4′‐diaminodiphenyl sulphone as chain extenders. The effect of aromatic diamines on the swelling and thermal degradation behavior of PU have been discussed. A thermogravimetric analyzer (TGA) curve shows that all the chain‐extended PUs are stable up to 194°C and that maximum weight loss occurs at 490°C. The TGA thermograms show that the thermal degradation of the PUs was found to proceed in two steps. The average molecular weight between crosslinks (M?_c) was determined by swelling studies. The properties imparted by the aromatic chain extenders are explained on the basis of groups present in the diamines. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 359–369, 2002; DOI 10.1002/app.10347     

Catalytic Synthesis of Carbonated Soybean Oil

Carbonated soybean oil (CSBO) can be used as intermediate for the synthesis of non-isocyanate polyurethanes (NIPUs). In this work, CSBO was prepared by the reaction of epoxidized soybean oil (ESBO) with carbon dioxide (CO₂) using a novel composite catalyst comprising SnCl₄ · 5H₂O and tetrabutylammonium bromide (TBABr). The evolution of the reaction process and structure of CSBO were studied by means of IR, ¹H-NMR, and GPC techniques. Effects of catalyst formulation and various reaction conditions on the reaction were examined. The results showed that the obvious improvement in ESBO conversion using the present composite catalyst under mild conditions was achieved. Moreover, it was interesting to note that very high purity of CSBO was not a prerequisite for the synthesis of NIPUs with good performance.     

Role of isophorone diisocyanate in the optimization of adhesion tendency of polyurethane pressure sensitive adhesives

The present work describes the role of accurate selection of diisocyanate on the adhesion strength of polyurethanes (PUs). The concentration of diisocyanate induces the hard segment (HS) in the main architecture of PUs which decides the viscoelastic properties of the polymers. A balanced ratio of viscoelastic properties ultimately determines the adhesion strength. The composition of the polymers consists of a blend of macrodiol of hydroxyl-terminated polybutadiene and polypropylene glycol with different molecular weights. Isophorone diisocyanate (IPDI) is used to develop the urethane linkages by maintaining its contribution from 28 to 67% as HS contents. It determines the adhesion strength of the final product. The adhesion strength is evaluated by texture analyzer and 180° peel test. The probe tack analysis shows maximum adhesion energy of 156.2 J cm⁻² and 180° peel test shows 18.80 N/25 mm peel force. The glass-transition (T _g) values obtained through differential scanning calorimetry are in good agreement with theoretically calculated Flory–Fox temperature. The proportion of the loss tangent to the storage modulus (tan δ/E′) shows the optimum value of 2.80 MPa⁻¹. The ideal concentration of IPDI results to achieve better adhesion properties of PU pressure sensitive adhesives. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47124.     

Biodegradable polyurethane based on random copolymer of L‐lactide and ϵ‐caprolactone and its shape‐memory property

A series of biodegradable polyurethanes (PUs) are synthesized from the copolymer diols prepared from L ‐lactide and ε‐caprolactone (CL), 2,4‐toluene diisocyanate, and 1,4‐butanediol. Their thermal and mechanical properties are characterized via FTIR, DSC, and tensile tests. Their T_gs are in the range of 28–53°C. They have high modulus, tensile strength, and elongation ratio at break. With increasing CL content, the PU changes from semicrystalline to completely amorphous. Thermal mechanical analysis is used to determine their shape‐memory property. When they are deformed and fixed at proper temperatures, their shape‐recovery is almost complete for a tensile elongation of 150% or a compression of 2‐folds. By changing the content of CL and the hard‐to‐soft ratio, their T_gs and their shape‐recovery temperature can be adjusted. Therefore, they may find wide applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4182–4187, 2007