Synthesis and shape memory effects of Si-O-Si cross-linked hybrid polyurethanes

A series of novel Si-O-Si cross-linked organic/inorganic hybrid polyurethanes (HYPUs) with shape memory effect were prepared from isophorone diisocyanate (IPDI), poly(ethylene oxide) (PEO), and a newly synthesized hybrid diol (HD) containing hydrolysable Si-OEt groups. After hydrolyzation and condensation of Si-OEt groups, the resulted films were characterized using wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and shape recovery test to get the insight into the relationship between shape memory behaviors and polymeric structures. The glass transition temperatures (T_g) and storage modulus increased with Si-O-Si cross-linking increasing in the hybrid polyurethanes. The hybrid polyurethanes can recover to their original shapes almost completely in less than 40 s in atmosphere and in less than 10 s in water, respectively, when heated at 25 °C above T_g. The shape memory mechanism is coming from the freezing at low temperature and activation at high temperature of micro-Brownian movement of amorphous molecular chains since the temperature ranges at which the sharpest changes of recovered curvature happened are found to be around their glass transition range. The high ratio of storage modulus below and above accounted for the temporary shape fixing at low temperature. The samples with more Si-O-Si cross-linking have higher storage modulus at high temperature, resulting in faster shape recovery speed but lower temporary shape fixing.     

Synthesis and characterization of rubber‐seed‐oil‐based polyurethanes

Novel biobased polyurethanes were synthesized from rubber seed oil (RSO), a renewable resource. The RSO monoglyceride, together with xylene and hexamethylene diisocyanate (HMDI), was employed to synthesize the desired urethane‐based prepolymer with isocyanate (NCO)‐terminated end groups followed by curing. The degrees of crosslinking of the polyurethane after curing were assessed with their swelling behavior. The properties of the resulting polyurethanes were found to be dependent on the type of diisocyanate and their molar ratios to the RSO monoglyceride. The network structures, which were assessed through swelling studies, showed that networks based on HMDI with an NCO/OH ratio of 1.50 were better crosslinked than with those toluene diisocyanate. The thermal properties of the samples analyzed by thermogravimetric analysis showed two and three decomposition stages in aliphatic‐ and aromatic‐based RSO polyurethanes, respectively. The highest stability with initial decomposition temperature (253°C) and percentage residual at 500°C (11.4%) was achieved with an aliphatic‐based RSO polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and shape‐memory behavior of shape‐memory polymer composites with hybrid fillers

Shape‐memory polymer (SMP) materials have several drawbacks such as low strength, low stiffness and natural insulating tendencies, which seriously limit their development and applications. Much effort has been made to improve their mechanical properties by adding particle or fiber fillers to reinforce the polymer matrix. However, this often leads to the mechanical properties being enhanced slightly, but the shape‐memory effect of reinforced SMP composites being drastically reduced. The experimental results reported here suggested that the mechanical resistive loading and thermal conductivity of a composite (with hybrid filler content of 7.0 wt%) were improved by 160 and 200%, respectively, in comparison with those of pure bulk SMP. Also, the glass transition temperature of the composite was enhanced to 57.28 °C from the 46.38 °C of a composite filled with 5.5 wt% hybrid filler, as determined from differential scanning calorimetry measurements. Finally, the temperature distribution and recovery behavior of specimens were recorded with infrared video in a recovery test, where a 28 V direct current circuit was applied. The effectiveness of carbon black and short carbon fibers being incorporated into a SMP with shape recovery activated by electricity has been demonstrated. These hybrid fillers were explored to improve the mechanical and conductive properties of bulk SMP. Copyright © 2010 Society of Chemical Industry     

Morphology and shape memory effect of segmented polyurethanes. Part ?: With crystalline reversible phase

A set of segment polyurethanes were synthesized and were proved to have interconnected, isolated and no hard-segmented domains. It was found that the shape fixity of the polyurethanes decreased with the increase of hard-segment content. The polyurethanes with hard-segment content from 30% to 50% had to be deformed at least to 100% strain to obtain good shape fixity. The segmented polyurethane having no hard-segment domains showed over 90% shape recovery under particular conditions. The segmented polyurethanes having interconnected hard-segment domains showed dramatically decreased shape recovery. The segmented polyurethanes having isolated hard-segment domains showed better shape recovery. When the polyurethanes were heated up to sufficiently high temperature they mostly recovered to their original shape. Stress relaxation would bring decrease to the shape recovery of the polyurethanes, especially to that of the segmented polyurethanes with low hard-segment content of 15% and 20%. For the segmented polyurethanes have isolated hard-segment domains the shape recovery decreased when the deformation amplitude increased from 50% to 200% and stopped decreasing as deformation amplitude increased to 250%. The shape recovery of the segmented polyurethanes could be enhanced nearly to 100% by a pre-deformation treatment.     

Study on the liquefied‐MDI‐based shape memory polyurethanes

A series of liquefied‐MDI‐based polyurethanes having shape memory behavior, with various soft segments, chain extenders, and micro‐phase separation promoters were synthesized. Their morphology and properties were investigated in terms of thermal properties, dynamic mechanical properties, and shape recovery behavior. The results indicate that the soft segment formed with longer chain segment incline to crystallize during the cooling scans and the resulting SMPU have the higher crystallinity. Meanwhile, the chain extenders, which can enhance the polarity of hard segment, incline to have excellent shape memory properties with bigger storage modulus in rubbery state too. It was also found that the micro‐phase separation promoters have great influence on the shape memory behavior due to the enhancement of micro‐phase separation of SMPU. Furthermore, it was proved again that SMPU with longer soft segment and lower hard segment contents usually showed good shape memory behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and Characterization of the Different Soy-Based Polyols by Ring Opening of Epoxidized Soybean Oil with Methanol, 1,2-Ethanediol and 1,2-Propanediol

Three soy-based polyols intended for application in polyurethanes were prepared by ring opening the epoxy groups in epoxidized soybean oil (ESO, 0.385 mol/100 g epoxy rings) with methanol, 1,2-ethanediol and 1,2-propanediol in the presence of tetrafluoroboric acid catalyst. The effect of the different opening reaction reagents, different low molecular weight alcohols, on the polyols was investigated by spectroscopic, chemical and physical methods. The viscosities, viscous-flow activation energies, molecular weight and melting point of the samples increased in the following order: polyol (3) > polyol (2) > polyol (1) > ESO [polyol (1); polyol (2) and polyol (3) represented the samples synthesized from the same epoxidized soybean oil generated by opening reactions with methanol, 1,2-ethanediol and 1,2-propanediol, respectively]. All the samples were crystalline solids below their melting temperature, displaying multiple melting point peaks. Compared with polyol (1), polyol (2) had a primary hydroxyl group, promoting the reactive activity of the polyol with isocyanates; polyol (3) contained large numbers of hydroxy groups, improving the properties of polyurethanes.     

Polyurethane coatings prepared from CNSL based polyols: Synthesis,characterization and properties

Conventional polyurethane chemistry based on polyol and isocyanate chemistry is widely used for many applications ranging from plastics to coatings, constructions, pharmaceuticals, foods, etc. The growing concern over depletion of petrochemical materials and their rising prices has led to search for environment friendly renewable materials. Cardanol derived from cashew nut shell liquid is one such renewable material which has reactive phenolic group and aliphatic double bond that could be tailor-made to produce novel functional materials for polymer and coating applications. This has previously been used for preparation of phenolics, epoxy resins and phenalkamine hardners. Diglycidyl ether of cardanol which is commercially available, is used as epoxy resin or modifier in epoxy formulations. In the present work, this was modified by simple one step ring opening reaction to produce polyols with different number of functionalities. The various polyols prepared were cured with polyisocyanate cross-linkers and applied on metallic substrates. The cured coatings were evaluated for physical, mechanical, chemical and thermal properties. The study conducted showed that the prepared polyols could be used as sole binder for coating formulation with overall excellent properties.     

Thermal,mechanical, and shape‐memory properties of nanorubber‐toughened,epoxy‐based shape‐memory nanocomposites

Epoxy‐based shape‐memory polymers (ESMPs) are a type of the most promising engineering smart polymers. However, their inherent brittleness limits their applications. Existing modification approaches are either based on complicated chemical reactions or done at the cost of the thermal properties of the ESMPs. In this study, a simple approach was used to fabricate ESMPs with the aim of improving their overall properties by introducing crosslinked carboxylic nitrile–butadiene nanorubber (CNBNR) into the ESMP network. The results show that the toughness of the CNBNR–ESMP nanocomposites greatly improved at both room temperature and the glass‐transition temperature (T_g) over that of the pure ESMP. Meanwhile, the increase in the toughness did not negatively affect other macroscopic properties. The CNBNR–ESMP nanocomposites presented improved thermal properties with a T_g in a stable range around 100 °C, enhanced thermal stabilities, and superior shape‐memory performance in terms of the shape‐fixing ratio, shape‐recovery ratio, shape‐recovery time, and repeatability of shape‐memory cycles. The combined property improvements and the simplicity of the manufacturing process demonstrated that the CNBNR–ESMP nanocomposites are desirable candidates for large‐scale applications in the engineering field as smart structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45780.     

Development of transdermal drug‐delivery films with castor‐oil‐based polyurethanes

Two different types of polyurethanes (PUs) were prepared with castor oil, ethylene glycol, isophorene diisocyanate and castor oil, and isophoren diisocyanate and poly‐(ethylene glycol) (400 or 600). PU films were prepared and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and gel permeation chromatography. We prepared transdermal patches by loading different amounts of drug, plasticizer, and penetration enhancer. In vitro drug permeability through the castor‐oil‐based aliphatic PU patches was examined with a Keshary–Chien diffusion cell. The effect of castor oil on the film‐forming properties and the effect of penetration enhancers on diffusion characteristics of indomethacin (IDM) drug through the castor‐oil‐based PU were investigated. Prolonged release of IDM was observed from the prepared PU patches. In vitro drug diffusion revealed that slow and prolonged release of IDM was achieved in the absence of penetration enhancers. The use of penetration enhancers showed a significant effect on drug diffusion. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 779–788, 2007     

Co-extruded multilayer shape memory materials: Nano-scale phenomena

Shape memory polymers (SMPs), which demonstrate the ability to possess multiple shapes, are traditionally produced from copolymers and recently from blends. These materials often have phase separated morphologies that possess domain sizes on either the nano- or micro-scale. The observed properties, specifically the shape memory behavior, can be significantly altered by a change in the domain size; however, doing this often requires modification to the materials or material production process. Forced assembly multilayer co-extrusion was used to produce shape memory materials with a continuous layered structure that can be easily tailored to cover layer thicknesses ranging from the nano- to the micro-scale. Upon decreasing the layer thickness of polyurethane/polycaprolactone (PU/PCL) layered films, improvement in the shape fixity and recovery ratios tracked with layer thickness. The improvement in properties was attributed to a change in the PCL crystal orientation from randomly oriented in microlayers to in-plane lamella orientation in nanolayers.     

The effect of different palm oil‐based bio‐polyols on foaming process and selected properties of porous polyurethanes

Rigid polyurethane foams were successfully prepared by blending up to 70 wt% of two different palm oil‐based bio‐polyols with a petrochemical polyether polyol. The bio‐polyols were synthesized by epoxidation–oxirane ring‐opening process using water (PP102) and diethylene glycol (PP147), respectively. Due to the high viscosity of both bio‐polyols the reactive mixture was heated to start the foaming reaction at about 50 °C. Under these conditions, the gelling reactions speed up as the amount of PP147 increases but slow down to a great extent when PP102 is used. The thermal conductivity of modified foams is higher and the closed cell content lower compared to reference ones, even when the bio‐foams present a lower apparent density. However, all foams exhibit reduced water absorption, excellent dimensional stability and better thermal stability at temperatures up to 400 °C than the control foam. Conversely, their mechanical and dynamic mechanical properties become poorer as the PP147 concentration increases and even more so if PP102 is used instead. PP147 foams containing up to 50% bio‐polyol could be used as a green replacement of petroleum‐based ones in applications where excellent behaviour in compression (the most affected properties) is not fundamental, with the additional advantages of reduced density and increased content of bio‐derived components. © 2017 Society of Chemical Industry     

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.     

Thermomechanical characterization of thermoset urethane shape‐memory polymer foams

The shape‐memory polymer performance of urethane foams compressed under a variety of conditions was characterized. The foams were water‐blown thermosets with a closed‐cell structure and ranged in density from about 0.25 to 0.75 g/cm³. Compressive deformations were carried out over a range of strain levels, temperatures, and lateral constraints. Recovery stresses measured between fixed platens were as high as 4 MPa. Recovery strains, measured against loads up to 0.13 MPa, demonstrated the effects of various parameters. The results suggest that compression near the foam glass‐transition temperature provided optimal performance. Foams with densities of about 0.5 g/cc and compressed 50% provided a useful balance (time, strain, and load) in the recovery performance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of linseed oil‐based nanocomposites

The nanocomposites from conjugated linseed oil, acrylic acid, and divinylbenzene are synthesized using modified montmorillonite clay and characterized for thermal properties. The wide angle X‐ray diffraction results clearly show the distortion of the platy nanolayers of the nanofiller in the polymer matrix as the peak due to the clay disappears in the nanocomposite samples. The dynamic mechanical analysis results show the enhanced storage modulus and transition temperature compared with the pristine polymer. At the glass transition temperature, the storage modulus of nanocomposites is in the range of 17–79 MPa, whereas the pristine polymer shows a storage modulus of 2.1 MPa. The melting peak temperature ranges from 230 to 260°C, which is further confirmed by thermogravimetric analysis (TGA) results. The samples are stable up to 200°C and show a two‐stage degradation. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of novel polyurethanes based on fluorine‐containing polyphosphazene

Fluorine‐containing poly[bis‐(2,2,3,3,4,4,5,5‐octafluoro‐1‐pentanol)_1.6 (4‐hydroxybutaneoxy)_0.4 phosphazene] (OFHBP) was synthesized and characterized by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The obtained OFHBP was used as a cross‐linker to prepare a series of novel polyurethanes (PUPFs). The composition of the PUPFs was confirmed by FTIR and elemental analysis (EA). The crystalline structure and microstructure of the PUPFs were examined by X‐ray diffraction (XRD) and atomic force microscopy (AFM). The thermal and tensile properties of the PUPFs were characterized by differential scanning calorimetry (DSC) and tensile testing. In addition, the surface energy of the PUPFs was also evaluated by contact angle measurements (CA). The results showed that glass transition temperature of the PUPF‐4 was decreased by 15°C, elongation at break was improved by 61% and a 41% decrease in surface energy in comparison with conventional polyurethane. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of phosphorus-containing polyurethanes

Phenylbis(hydroxyalkyl)phosphonates were prepared by treating excess glycol(ethylene glycol or diethylene glycol) with phenylphosphonic dichloride (PPD). Phosphorus-containing homopolyurethanes were synthesized by low temperature solution polyaddition by phenylbis (hydroxyalkyl)phosphonates with tolylene diisocyanate (TDI). Copolyurethanes with various phosphorus content were prepared by copolymerization of tolylene diisocyanate with polypropylene glycol (PPG, MW = 3000), and phenylbis(hydroxyalkyl)phosphonate. All polymers were characterized by elemental analysis, infrared (IR), differential scanning calorimeter (DSC), differential thermal analysis (DTA), and thermogravimetric analysis (TGA). Thermal properties of the polyurethane were compared with that of the common polyurethane. Phosphorus containing homopolyurethanes and copolyurethanes had lower decomposition temperatures and higher char yield residue than the corresponding common polyurethane.     

Synthesis and molecular weight characterization of rubber seed oil‐modified alkyd resins

Alkyd resins of 40% (I), 50% (II), and 60% (III) oil length (OL) were prepared with rubber seed oil (RSO), phthalic anhydride (PA), and glycerol (GLY), employing the two‐stage alcoholysis method. Changes in the physical characteristics of the reaction medium were monitored by determination of the acid value and the number‐average molecular weight, M_n , of in‐process samples withdrawn at different stages of the reaction. The mode of variation of these properties denotes that the preparation of RSO alkyds is complex. Molecular weight averages and the molecular weight distribution (MWD) of the finished alkyds were determined by GPC, cryoscopy, and end‐group analysis. Molecular weight averages and the MWD vary with differences in the formulation, with sample II exhibiting the narrowest size distribution. Values of M_n with the corresponding polydispersities in brackets are 3234 (1.91), 1379 (1.56), and 3304 (2.56) for samples I, II, and III respectively. M_n values obtained by cryoscopy are comparable to those obtained by gel permeation chromatography (GPC), while end‐group analysis seems to grossly overestimate their molecular weights. Correlation of M_n and the MWD with the quality of the finished alkyds shows that the narrower the size distribution the better the quality of the alkyd. Properties such as the rate of drying and resistance of the alkyds are optimum at 50% OL. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2431–2438, 2001