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1.
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.  相似文献   

2.
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 (Tg), 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 Tg 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  相似文献   

3.
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  相似文献   

4.
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 Tg 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  相似文献   

5.
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.  相似文献   

6.
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  相似文献   

7.
(Na1?xKx)NbO3 (NKN) platelets synthesized at 600°C for 12 h have an Amm2 orthorhombic structure. However, the structure of NKN platelets synthesized at 500°C is a mixture of R3m rhombohedral and Amm2 orthorhombic structures. The formation of a rhombohedral structure is attributed to the presence of OH? and H2O defects in the NKN platelets. The piezoelectric strain constant (d33) of NKN platelets synthesized at 600°C for 12 h is 100 pmV?1, whereas that of NKN platelets synthesized at 500°C is lesser (50 pmV?1) due to the presence of these defects. Piezoelectric nanogenerators (PNGs) are fabricated using composites consisting of NKN platelets and polydimethylsiloxane. A large output voltage of 25 V and output current of 2.7 μA were obtained for the PNG with NKN platelets synthesized at 600°C for 6 h. This PNG shows a high output electrical energy of 3.0 μW at an external load of 5.1 MΩ.  相似文献   

8.
Hyperbranched polymer was synthesized from pentaerythritol (as the central core), 1,2,4‐trimellitic anhydride, and epichlorohydrin, and then hyperbranched polymer electrolytes with terminal ionic groups were prepared by the reaction of hyperbranched polymer with N‐methyl imidazole. The chemical structure, thermal behavior, and ionic conductive property of the hyperbranched polymer electrolytes were investigated by 1H‐NMR, FTIR, differential scanning calorimetry, thermogravimetric analyzer, and complex impedance analysis, respectively. The ionic conductivity of hyperbranched polymer electrolyte was up to 2.4 × 10?4 S cm?1 at 30°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

9.
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  相似文献   

10.
Flame retardant hyperbranched polyurethanes were prepared by reacting phosphorous containing triol, tris(bisphenol-A) mono phosphate, castor oil, and polyethylene glycol with different diisocyanates like TDI, IPDI and HMDI via A2+B3 method. In this method A2 reactants were diisocyanates along with castor oil and polyethylene glycol whereas phosphorous containing triol was used as B3 reactant and dibutyltin dilaurate (DBTDL) was used as catalyst. Synthesized polyurethans were characterized by gel-permeation chromatography (GPC), elemental analysis, Fourier transform infrared spectroscopy (FTIR) and 1H NMR spectroscopic techniques. Neat polyurethanes were used for preparing films. Nano-clay composites were prepared with various concentration of organomodified montmorillionite nano-clay. Flame retardant, Thermal and mechanical properties of these hyperbranched polyurethanes and their nano-composites were found out. The polyurethanes and their formulations with nano-clay were also used for the coating of mild steel panels. Scratch, pencil, and impact hardness, flexibility and adhesion properties of coated panels were also determined. Observations show an increase in the scratch hardness and flexibility with the introduction of clay. All the coatings show excellent chemical resistance properties compare to their linear counterpart.  相似文献   

11.
Two series of hyperbranched polymers (HP), polyurethanes and polyureas, with aromatic and aliphatic structures, are synthesized in one-pot method using commercially available monomers. The obtained HP samples were characterized by 1H Nuclear Magnetic Resonance (NMR) spectroscopy, Gel Permeation Chromatography (GPC), Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA) measurements. Molecular dynamics in these systems were investigated by combining Thermally Stimulated Depolarization Currents (TSDC) and broadband Dielectric Relaxation Spectroscopy (DRS) techniques. High conductivity contribution in dielectric loss does not allow the study of the segmental α relaxation associated with the glass transition. In the glassy state two secondary relaxation mechanisms have been investigated, the γ and the β mechanism. The γ relaxation mechanism, at low temperatures/high frequencies, is attributed to motions of the end groups (-OH for polyurethanes and -NH2 for polyureas), and has been found faster in the hyperbranched polyureas. In addition, our results reveal that γ relaxation mechanism in both series depends on the chemical structure, being faster for aliphatic structures. The β relaxation mechanism, at higher temperatures/lower frequencies, is attributed to the motions of branched ends with polar groups. Our study suggests that this mechanism may be a typical relaxation process for hyperbranched polyurethanes structures, not existed in the linear counterparts. All the systems exhibit dc conductivity at temperatures higher than Tg which shows Arrhenius-like temperature dependence and is characterized by rather high activation energies (in the order of 200 kJ/mol). At temperatures lower than Tg all the systems studied exhibit remarkably high charge mobility. In particular, aliphatic hyperbranched polyureas exhibit dc conductivity which has been found to be of VTF type concerning the temperature dependence. This result implies that the conduction mechanism is coupled with molecular motions in the glassy state of the polymer.  相似文献   

12.
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.  相似文献   

13.
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  相似文献   

14.
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 (Tg); 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.  相似文献   

15.
BACKGROUND: Bio‐ethanol production from renewable sources, such as sugar cane, makes it a biofuel that is both renewable and environmentally friendly. One of the strategies to reduce production costs and to make ethanol fuel economically competitive with fossil fuels could be the use of wild yeast with osmotolerance, ethanol resistance and low nutritional requirements. The aim of this work was to investigate the kinetics of ethanol fermentation using Saccharomyces cerevisiae ITV‐01 yeast strain in a batch system at different glucose and ethanol concentrations, pH values and temperature in order to determine the optimum fermentation conditions. RESULTS: This strain showed osmotolerance (its specific growth rate (µmax) remained unchanged at glucose concentrations between 100 and 200 g L?1) as well as ethanol resistance (it was able to grow at 10% v/v ethanol). Activation energy (Ea) and Q10 values calculated at temperatures between 27 and 39 °C, pH 3.5, was 15.6 kcal mol?1 (with a pre‐exponential factor of 3.8 × 1012 h?1 (R2 = 0.94)) and 3.93 respectively, indicating that this system is biologically limited. CONCLUSIONS: The optimal conditions for ethanol production were pH 3.5, 30 °C and initial glucose concentration 150 g L?1. In this case, a maximum ethanol concentration of 58.4 g L?1, ethanol productivity of 1.8 g L?1 h?1 and ethanol yield of 0.41 g g?1 were obtained. Copyright © 2010 Society of Chemical Industry  相似文献   

16.
Hyperbranched polyesters with thioether linkages were facilely prepared from methyl 10‐undecenoate, a castor oil‐derived renewable chemical. The monomer was obtained in excellent yield through thiol–ene click chemistry in the presence of catalytic amounts of photoinitiator under UV irradiation. Subsequent bulk polycondensation via a transesterification process catalyzed by Ti(OBu)4, Sb2O3 or Zn(OAc)2 gave hyperbranched polyesters with high molecular weights and unusual crystalline properties. The degree of branching in the range 0.45 ? 0.54 calculated from quantitative 13C NMR spectroscopy and low inherent viscosities of 0.16 ? 0.25 dL g?1 strongly confirmed the hyperbranched structures of the resultant polymers. © 2012 Society of Chemical Industry  相似文献   

17.
In this work, a number of urethane-modified polyesteramide (UmPEA) films were developed from mahua and castor oils, which are renewable resources. Mahua oil and diethanolamine were reacted to form mahua fattyamide, which was then reacted with itaconic acid to prepare polyesteramide. In order to make the UmPEA films, different proportions of polyesteramide and castor oil as polyols were reacted with isophoronediisocyanate. The UmPEA films showed excellent chemical resistance against water, acid, alkali, salt, and organic solvents and were found insoluble in common organic solvents. The thermal stability of the UmPEA films was investigated through TGA and DSC analyses, and their Tg values are between 69.1°C and 56.1°C for UmPEA films, which indicated that a higher content of CO enhances the Tg, and it was also found that the films were highly stable up to 230°C. The Ea values [224 kJ mol−1 (Tp1) and 226 kJ mol−1 (Tp2)] indicate that the castor oil enhances the thermal stability of the films due to better cross-linking density occurring through the high hydroxyl groups of CO as the polyol which also showed better flame retardancy in the synthesized UmPEA films. Our findings demonstrate that the newly developed UmPEA films can be potent coating materials.  相似文献   

18.
In this work, a novel series of zwitterionic gemini surfactants with different hydrophobic tails were synthesized and characterized. The physico‐chemical properties of these products (such as surface tension, oil/water interfacial tension, foaming ability, and the wetting ability of paraffin‐coated sandstone) were fully studied. The CMC of the synthesized surfactants ranged from 2.17 × 10?4 mol L?1 to 5.36 × 10?4 mol L?1 and corresponding surface tension (γCMC) ranged from 26.49 mN m?1 to 29.06 mN m?1, which showed excellent efficiency among the comparison surfactants. All the products can reduce the interfacial tension to a relatively low level of about 0.1–1.0 mN m?1. Additionally, results from applying different hydrocarbons suggested that the synergy will be clearer and oil/water interfacial tension will be lower if the oil components are similar to the surfactants. Contact angle and foaming measurements indicated that the surfactants exhibited good wetting and foaming abilities. The results of oil flooding experiments using an authentic sandstone microscopic model showed that C‐12 and CA‐12 could effectively improve the displacement efficiency by 21–29 %.  相似文献   

19.
A series of alkyl sulphobetaine Gemini surfactants Cn‐GSBS (n = 8, 10, 12, 14, 16) was synthesized, using aliphatic amine, cyanuric chloride, ethylenediamine, N,N′‐dimethyl‐1,3‐propyldiamine and sodium 2‐chloroethane sulfonate as main raw materials. The chemical structures were confirmed by FT‐IR, 1H NMR and elemental analysis. The Krafft points differ markedly with different carbon chain length, for C8‐GSBS, C10‐GSBS and C12‐GSBS are considered to be below 0 °C and C14‐GSBS, C16‐GSBS are higher than 0 °C but lower than room temperature. Surface‐active properties were studied by surface tension and electrical conductivity. Critical micelle concentrations were much lower than dodecyl sulphobetaine (BS‐12) and decreased with increasing length of the carbon chain from 8 to 16, and can reach a minimum as low as 5 × 10?5 mol L?1 for C16‐GSBS. Effects of carbon chain length and concentration of Cn‐GSBS on crude oil emulsion stability were also investigated and discussed.  相似文献   

20.
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.  相似文献   

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