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     

Castor oil-based hyperbranched polyurethanes as advanced surface coating materials

21st Century is treated as the century for highly branched macromolecules, because of their unique structural architecture and outstanding performance characteristics, in the field of polymer science. In the present study, castor oil-based two hyperbranched polyurethanes (HBPUs) were synthesized via A₂ + B₃ approach using castor oil or monoglyceride of the castor oil as the hydroxyl containing B₃ reactant and toluene diisocyanate (TDI) as an A₂ reactant along with 1,4-butane diol (BD) as the chain extender and poly(?-caprolactone) diol (PCL) as a macroglycol. The adopted ‘high dilution and slow addition’ technique offers hyperbranched polymers with high yield and good solubility in most of the polar aprotic solvents. Fourier transforms infra-red spectroscopy (FTIR) and nuclear magnetic resonance (NMR) analyses confirmed the chemical structure of synthesized polymers, while wide angle X-ray diffraction (WXRD) and scanning electron microscope (SEM) resulted the insight of their physical structures. The degree of branching was calculated from ¹H NMR and found to be 0.57 for castor oil based hyperbranched polyurethane (CHBPU), while it was 0.8 for monoglyceride based hyperbranched polyurethane (MHBPU). The studies showed that MHBPU and CHBPU exhibited tensile strength 11 MPa and 7 MPa, elongation at break 695% and 791%, scratch hardness 5 kg and 4.5 kg, gloss 84 and 72, respectively. Thermal properties like thermo stability, melting point, enthalpy, degree of crystallinity and glass transition temperature (T_g); and chemical resistance in different chemical media were found to be almost equivalent for both the polyurethanes. The measurements of dielectric constant and lost factor indicated that both the HBPUs behave as dielectric materials. Thus the synthesized HBPUs have the potential to be used as advanced surface coating materials.     

Bio-based elastomeric hyperbranched polyurethanes for shape memory application

The bio-based shape memory hyperbranched polyurethanes (HBPUs) have attracted tremendous attention both from academic and industrial researchers due to their strong potential in biomedical and other advanced applications. In the present investigation HBPUs have been synthesized from poly(??-caprolactone)diol as a macroglycol, butanediol as a chain extender, triethanolamine as a branch generating moiety, monoglyceride of Mesua ferrea L. seed oil as a bio-based chain extender, at different percentages and toluene diisocyanate by a two step one pot A₂?+?B₃ approach. The structure of the synthesized hyperbranched polyurethane was characterized by FTIR, ^IH NMR, XRD and SEM studies. ¹H NMR study indicates the formation of highly branched structure with degree of branching 0.93 for polyurethane with 5?wt% monoglyceride. TGA results indicated the increment of thermal stability from 185 to 240?°C with the increase of monoglyceride content from (0?C15) wt% for the HBPUs. The shape memory effect of the hyperbranched polyurethane increased with the increase of monoglyceride in the polymer. However, mechanical properties like tensile strength and elongation at break decreased from 19.31 to 11.48?MPa and 835 to 497%, respectively, with the increase in amount of bio-based component. Excellent impact strength and very good chemical resistance were also observed for the hyperbranched polymers. The studied bio-based HBPUs exhibit excellent shape fixity (95?C99)% as well as shape recovery 100%. Thus, the studied HBPUs have the potential to be used as advanced shape memory materials.     

Effect of branching in hyperbranched alkyd on the performance of alkyd polyurethane coating

Hyperbranched alkyd was synthesized by single‐step approach using trimethylolpropane, mono pentaerythritol as core material, and 2,2‐bis(methylol)propionic acid (DMPA), a combination of dehydrated castor oil fatty acid and coconut oil fatty acid as chain extender. A series of hyperbranched alkyds were prepared at different degree of branching in the alkyd structures by changing the amount of DMPA in the alkyd resin formulation. The resins were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance (NMR) spectroscopic technique. These hyperbranched alkyds were converted into polyurethane coating after reaction with hexamethylene diisocyanate trimer at a definite ratio in the presence of dibutyltin dilaurate as a catalyst. The effect of branching and polymeric chain entanglement on the glass transition temperature, T_g of the alkyd polyurethane coating (APUC) was studied by differential scanning calorimetry technique. The performance of such APUC in terms of gloss, gloss retention under accelerated QUV radiation, natural outdoor exposed condition, mechanical, and corrosion resistance properties were enhanced with the increase of polymeric chain entanglement, i.e., compactness or higher order of branching in the alkyd resin structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45835.     

Mesua ferrea L. seed oil‐based hyperbranched shape memory polyurethanes: Effect of multifunctional component

The bio‐based hyperbranched polyurethanes (HBPUs) have generated immense interest as advanced shape memory materials. In the present investigation, HBPUs were synthesized from poly(ε‐caprolactone)diol as a macroglycol, butanediol as a chain extender, monoglyceride of Mesua ferrea L. seed oil as a bio‐based chain extender, triethanolamine as a branch‐generating moiety (at different percentages), and toluene diisocyanate by a prepolymerization technique using A₂ + B₃ approach. The structure of the synthesized HBPU was characterized by different techniques. Nuclear magnetic resonance (proton) study indicated the formation of highly branched structure with degree of branching 0.9. The increment of thermal stability from 225 to 260°C and melting point from 50 to 53.5°C with the increase of triethanolamine content was observed. Tensile strength 4–8 MPa, elongation at break 614–814%, impact resistance 0.8–0.95 m, and scratch hardness 2–6 kg increased with the increase of multifunctional moiety content from 0 to 5 wt%. The shape recovery ratio increased with the increase of multifunctional moiety content from 0.21 to 0.95. Thus, the studied HBPUs have the potential to be used as advanced thermoresponsive shape memory materials. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

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     

Biobased polyisocyanates from plant oil triglycerides: Synthesis,polymerization, and characterization

In this study, an easy and efficient synthesis of unsaturated plant oil triglycerides having isocyanate groups is reported. In the first step of the synthesis, the triglyceride was brominated at the allylic positions by a reaction with N‐bromosuccinimide, and in the second step, these brominated species were reacted with AgNCO to convert them to isocyanate‐containing triglycerides. At the end of the reaction, approximately 60–70% of the bromine was replaced by NCO groups, and the double bonds of the triglyceride were not consumed. When the amount of AgNCO was increased, the yield also increased. The final products were characterized with IR and ¹H‐NMR, and polyurethanes and polyureas were obtained from these fatty isocyanates with alcohols and amines, respectively. The polymers were characterized by differential scanning calorimetry and thermogravimetric analysis. Differential scanning calorimetry curves showed that glycerin polyurethane showed a glass‐transition temperature at 19°C, castor oil polyurethane showed two glass‐transition temperatures at ?43 and 36°C, and triethylene tetraamine polyurea showed a glass‐transition temperature at 31°C. Some properties of the polymers, such as the tensile strength and swelling ratios, were also determined. The swelling rate of glycerin polyurethane was higher than that of castor oil polyurethane in dichloromethane. The equilibrium swelling ratio was highest for the castor oil polyurethane. The polyurethanes synthesized in this study had a Young's modulus around 50 kPa and a tensile strength around 0.01 N/mm² (100 kPa). The tensile strength of glycerin polyurethane was higher than that of castor oil polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and curing of millable polyurethanes based on castor oil

This paper presents the results of studies on the synthesis and curing of millable polyurethanes based on castor oil. To facilitate the preparation of millable urethanes, the hydroxy number of castor oil was modified to about two by acetylation. It was then used with tolylene diisocyanate (NCO/OH-ratios 1:0.9, 1:1 and 1:1.1, resp.) for polyurethane preparation. The dynamic curing of the synthesized polyurethanes was studied in a Brabender Plasticorder using various sulfur vulcanizing systems. The effect of stoichiometric ratio and choice of chain extenders on the dynamic curing behaviour was also studied. An NCO/OH ratio of 0.9 and 1,4-butanediol (30 wt.-%) as chain extender were found to favour the formation of a crosslinkable polyurethane. It was observed that a cure system containing sulfur, N-cyclohexyl-2-benzothiazole sulfenamide and mecraptobenzothiazole was a possible choice for the preparation of a sulfur-crosslinked polyurethane.     

Bio-based hyperbranched polyurethanes for surface coating applications

High performance vegetable oil based hyperbranched polymers are not only interesting but also very useful with respect to current scenario of advanced coating materials. So in the present study hyperbranched polyurethanes have been synthesized from the monoglyceride of Mesua ferrea L. seed oil, poly(?-caprolactone)diol, 2,4-toluene diisocyanate and glycerol without using any catalyst by a two-step one pot A₂ + B₃ approach. The linear analog (neglecting little possible branching due to different components of monoglyceride) of the hyperbranched polyurethane has also been prepared by the same method without using glycerol, just to compare with hyperbranched polymer. The formation of polymers was confirmed by FTIR, ¹H NMR, UV and SEM studies and measurements of hydroxyl value, solubility and viscosity. TGA results indicated the high thermal stability of hyperbranched and linear polymers (210–220 °C). The properties like tensile strength, impact strength, hardness, adhesion, flexibility, gloss, elongation at break and chemical resistance were influenced by the hard segment content of the polymers. The hyperbranched polyurethane with 30% hard segment content showed the optimum properties. The values of hydrodynamic diameter of hyperbranched polymers compared to the linear analog support the hyperbranched formation. Thus it confirms the formation of mechanically strong and thermally stable hyperbranched polyurethane coating materials from a vegetable oil.     

Thermomechanical and water‐responsive shape memory properties of carbon nanotubes‐reinforced hyperbranched polyurethane composites

Shape memory composites of hyperbranched polyurethane (HBPU) and acid‐treated multi‐walled carbon nanotubes (MWNTs) were prepared using an in situ polymerization method. HBPUs with different hard segments contents were synthesized via the A₂ + B₃ approach using poly(ethylene glycol) (PEG) as a soft segment, 4,4′‐methylene bis(phenylisocynate), castor oil, and 1,4‐butanediol as hard segment. Compared to HBPU, the HBPU/MWNT composites showed faster shape recovery and double the shape recovery stress in the thermomechanical shape memory test, which was dependent on the MWNTs content and HBPU hard segment content. The water‐responsive shape memory effect of HBPU/MWNT composites was considered to result from the combined contribution of hydrophilic PEG and well dispersed MWNTs in highly branched HBPU molecules. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of polyurethane networks derived from new soybean oil‐based polyol and a bulky blocked polyisocyanate

BACKGROUND: Developing vegetable oil‐based polyols for polyurethane manufacturing is becoming highly desirable for both economic and environmental reasons. Most vegetable oils do not bear hydroxyls naturally. The objective of this work was to prepare a new soybean oil‐based polyol with high functionality of hydroxyl groups and built‐in (preformed) urethane bonds. RESULTS: A facile and improved method was developed for the transformation of epoxidized soybean oil into carbonated soybean oil under ambient pressure of CO₂ gas, with tetrabutylammonium bromide/calcium chloride as catalyst/co‐catalyst couple. Ring‐opening reaction of the carbonated oil with ethanolamine led to the desired polyol. A one‐pack polyurethane system was prepared via combination of the polyol and a blocked polyisocyanate. The polyol and final polyurethanes were fully characterized, and their physical, mechanical, viscoelastic and electrical insulating properties were studied. CONCLUSION: The application of this newly developed soybean oil‐based polyol for preparation of electroinsulating casting polyurethanes was examined. The prepared soy‐based polyurethanes offered excellent thermal and electrical insulating properties. Also, tunable physical and chemical properties for the final polyurethanes were achieved by replacing part of the soybean oil‐based polyol with poly(propylene glycol) (M_n = 1000 g mol^?1). Copyright © 2008 Society of Chemical Industry     

Synthesis and properties of liquid crystalline polyurethane elastomers

Novel type of mesogenic chain extenders used in this study are N,N′‐bis(4‐hydroxyphenyl)‐3,4,3′,4′‐biphenyldicarboxyimide (BPDI) and N,N′‐bis[4‐(6‐hydroxyhexyloxy) phenyl]‐3,4,3′,4′‐biphenyldicarboxyimide (BHDI). BHDI has a flexible spacer of 6‐methylene units but BPDI does not. The liquid crystalline polyurethane elastomers were synthesized from BPDI or BHDI as a mesogenic chain extender, 4,4′‐diphenylmethane diisocyanate, and poly(oxytetramethylene)glycol (MW 1000) as a soft segment. Polyurethane based on BHDI exhibited two melting transitions. However, any melting behavior was not shown in the BPDI‐based polyurethanes because of higher melting temperature than decomposition temperature. The composition of polyurethanes was varied as a means of manipulating liquid crystalline behavior and physical properties. The BHDI‐based polyurethanes containing above 50 wt % of hard segment content exhibited nematic liquid crystal behaviors. As the hard segment content of the BHDI‐based polyurethanes increased, the glass transition temperature (T_g), strength, modulus, and the amount of hydrogen bonding increased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 577–585, 2000     

Shape‐memory polyurethanes minimally crosslinked with hydroxyl‐terminated AB2‐type hyperbranched polyurethanes

A series of shape‐memory polyurethanes based on poly(ϵ‐caprolactone) diol were prepared with novel hydroxyl‐terminated hyperbranched polyurethanes as crosslinkers and were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, scanning electron microscopy, wide‐angle X‐ray diffraction, dynamic mechanical analysis, tensile testing, and shape‐memory testing. The molecular weight of the soluble polymers ranged from 5.1 × 10⁴ to 29.0 × 10⁴ g/mol. The differential scanning calorimetry and wide‐angle X‐ray diffraction data indicated that when the crystallinities of the crosslinked polymers were compared to that of linear polyurethane, this parameter was improved when the crosslinker was in low quantity. The storage modulus ratios obtained from the dynamic mechanical analyses data of the crosslinked polymers were also high compared to that of the linear polyurethane. As a result, crosslinked polymers showed better shape‐memory properties compared to the linear polyurethanes. Also, the that incorporation of the hyperbranched polymer as a crosslinker into the polyurethane chain improved the thermal and mechanical properties of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of triazole ring‐containing pentol chain extender and its effect on the properties of hyperbranched polyurethane‐urea coatings

This article describes the synthesis and property evaluation of different hyperbranched polyurethane‐urea (HBPUU) coatings based on a newly synthesized triazole ring‐based pentol chain extender. For this initially, the chain extender was synthesized using acetylene azide click reaction and the structure of the intermediate compounds were confirmed by ¹H‐, ¹³C‐NMR, FTIR, and ESI‐mass spectrometry. In the further steps, the required HBPUU coatings were prepared by a systematic three‐step reaction process. In the first step, a isocyanate terminated prepolymer resin was synthesized at NCO/OH ratio of 1.2 : 1, while the second and third step involves the partially chain extension followed by moisture curing. The excess NCO content in the prepolymer was calculated by standard dibutylamine titration method and partially (10, 20, 30, 50, and 70% of the excess NCO content) chain extended with the pentol chain extender and remaining was moisture cured. The structure property relation of different HBPUU coating films were analyzed by FTIR peak deconvulation technique using Gaussian curve fitting procedure while, their viscoelastic and thermo‐mechanical properties were measured by dynamic mechanical thermal analysis, thermo gravimetric analysis, differential scanning calorimetric, and universal testing machine instruments. These results showed that thermal stability, glass transition temperature (T_g), elongation at break increases but the storage and tensile modulus decreases with increasing the percent loading of the triazole chain extender. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Sustainable synthesis of bio‐based hyperbranched ester and its application for preparing soft polyvinyl chloride materials

In this study, bio‐based hyperbranched ester was synthesized from castor oil. The chemical structure of the bio‐based hyperbranched ester obtained was characterized with Fourier transform infrared and ¹H NMR spectra. Soft polyvinyl chloride (PVC) materials were prepared via thermoplastic blending at 160 °C using bio‐based hyperbranched ester as plasticizer. The performances including the thermal stability, glass transition temperature (T_g), crystallinity, tensile properties, solvent extraction resistance and volatility resistance of soft PVC materials incorporating bio‐based hyperbranched ester were investigated and compared with the traditional plasticizer dioctyl phthalate (DOP). The results showed that bio‐based hyperbranched ester enhanced the thermal stability of the PVC materials. The T_g of PVC incorporating bio‐based hyperbranched ester was 23 °C, lower than that of PVC/DOP materials at 28 °C. Bio‐based hyperbranched ester showed a better plasticizing effect, solvent extraction resistance and volatility resistance than DOP. The plasticizing mechanism is also discussed. © 2018 Society of Chemical Industry     

Effect of chain extender structure on the properties and morphology of polyurethanes based on H12MDI and mixed macrodiols (PDMS–PHMO)

The effect of chain extender structure on properties and morphology of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS) and poly(hexamethylene oxide) (PHMO) mixed macrodiol‐based aliphatic polyurethane elastomers was investigated using tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). All polyurethanes were based on 50 wt % of hard segment derived from 4,4′‐methylenecyclohexyl diisocyanate (H₁₂MDI) and a chain extender mixture. 1,4‐Butanediol was the primary chain extender, while one of 1,3‐bis(4‐hydroxybutyl)tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)tetramethyldisiloxane (BPTD), hydroquinonebis(2‐hydroxyethyl)ether (HQHE), 1,3‐bis(3‐hydroxypropyl)tetramethyldisilylethylene (HTDE), or 2,2,3,3,4,4‐hexafluoro‐1,5‐pentanediol (HFPD) each was used as a secondary chain extender. Two series of polyurethanes containing 80 : 20 (Series A) and 60 : 40 (Series B) molar ratios of primary and secondary chain extenders were prepared using one‐step bulk polymerization. All polyurethanes were clear and transparent and had number‐average molecular weights between 56,000 and 122,100. Incorporation of the secondary chain extender resulted in polyurethanes with low flexural modulus and high elongation. Good ultimate tensile strength was achieved in most cases. DSC and DMTA analyses showed that the incorporation of a secondary chain extender disrupted the hard segment order in all cases. The highest disruption was observed with HFPD, while the silicon‐based chain extenders gave less disruption, particularly in Series A. Further, the silicon chain extenders improved the compatibility of the PDMS soft segment phase with the hard segment, whereas with HFPD and HQHE, this was not observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2979–2989, 1999     

Biobased chain extended polyurethane and its composites with silk fiber

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

Polyurethane networks from formiated soy polyols: Synthesis and mechanical characterization

Polyurethanes can be prepared using polyols obtained from vegetable oils in natura, such as castor oil, or from functionalized vegetable oils, such as hydroxylated soybean oil. These polyurethanes have different valuable properties, determined by their chemical composition and cross-linking density. In this study, soy epoxy polyols with different OH contents were prepared through a one-step reaction using the method of in situ performic acid generation. Polyols with OH functionalities from 1.9 to 3.2 were reacted in bulk with different diisocyanates at a NCO/OH molar ratio of 0.8 and 60°C for 24 h. Mechanical properties of the polyurethanes were determined by dynamic mechanical thermal analysis, hardness (Shore A), and swelling measurements. Polymer networks with glass-transition temperatures (T _g ) from −13 to 48°C were obtained. We observed that the higher the OH functionality of the polyols, the higher the T _g and cross-linking density of the polyurethane network. The influence of diisocyanate structure (rigid or flexible chain), curing temperature, and curing reaction time on mechanical properties was also investigated.     

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.     

Shape memory effect of poly(L‐lactide)‐ based polyurethanes with different hard segments

A series of biodegradable polylactide‐based polyurethanes (PLAUs) were synthesized using PLA diol (M_n = 3200) as soft segment, 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI) as hard segment, and 1,4‐butanediol as chain extender. The structures and properties of these PLAUs were studied using infrared spectroscopy, differential scanning calorimetry, tensile testing, and thermomechanical analysis. Among them, the MDI‐based PLAU has the highest T_g, maximum tensile strength, and restoration force, the TDI‐based PLAU has the lowest T_g, and the IPDI‐based PLAU has the highest tensile modulus and elongation at break. They are all amorphous. The shape recovery of the three PLAUs is almost complete in a tensile elongation of 150% or a twofold compression. They can keep their temporary shape easily at room temperature (20 °C). More importantly, they can deform and recover at a temperature below their T_g values. Therefore, by selecting the appropriate hard segment and adjusting the ratio of hard to soft segments, they can meet different practical demands for shape memory medical devices. Copyright © 2007 Society of Chemical Industry