Formamide as the plasticizer for thermoplastic starch

As a novel plasticizer, formamide was tested in thermoplastic starch (TPS), in which native cornstarch granules were proved to transfer to a continuous phase by scanning electron microscope (SEM) and the hydrogen bond interaction between plasticizer and starch was proved by Fourier transform infrared (FTIR) spectroscopy. Mechanical tests showed that tensile strength and Young's modulus of formamide‐plasticized TPS (FPTPS) were lower than glycerol‐plasticized TPS (GPTPS) and elongation at break and energy break were higher. The effect of formamide and glycerol on the retrogradation of TPS was studied using X‐ray diffractometry. Formamide could effectively restrain the starch retrogradation at three different relative humidity (RH) environments, because it could form the more stable hydrogen bonds with the starch hydroxy group than glycerol. From these results, we found that the elongation at break, energy break, and the retrogradation of TPS were ameliorated by formamide. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1769–1773, 2004     

Preparation and properties of thermoplastic pea starch using N,N‐bis(2‐hydroxyethyl)formamide as the plasticizer

N,N‐bis(2‐hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new plasticizer for pea starch to prepare thermoplastic starch (TPS). The hydrogen bond interaction between BHF and pea starch was proven by Fourier‐transform infrared (FT‐IR) spectroscopy. As detected by scanning electron microscope (SEM), pea starch granules were completely disrupted, and the homogeneous materials were obtained. The crystallinity of pea starch and BHF‐plasticized thermoplastic pea starch (BTPS) was characterized by X‐ray diffraction (XRD). Rheological properties of TPS were analyzed. The water resistance of BTPS was better than that of glycerol‐plasticized thermoplastic pea starch (GTPS). At RH 33%, the tensile strength of BTPS was higher than that of GTPS for TPS containing 30% plasticizer. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Preparation and characterization of maleated thermoplastic starch‐based nanocomposites

Biodegradable nanoscale‐reinforced starch‐based products were prepared from an in situ chemically modified thermoplastic starch and poly(butylene adipate‐co‐terephthalate) (PBAT) through reactive processing. Natural montmorillonite (hydrophilic Cloisite Na) and organophilic Cloisite 30B were studied. In situ chemically modified thermoplastic starch (MTPS) was first prepared starting from (nano)clay (previously swollen in glycerol as plasticizer), and maleic anhydride (MA) as an esterification agent. Then, these nanoscale‐reinforced MTPS was reactively melt‐blended with PBAT through transesterification reactions promoted by MA‐derived acidic moieties grafted onto the starch backbone. The tensile and barrier properties of resulting (nano)composites were studied. High‐performance formulations with superior tensile strength (>35 MPa as compared with 16 MPa for the PBAT‐g‐MTPS copolymer) and break elongation (>800%) were obtained, particularly with Cloisite30B. Better water vapor and oxygen barrier properties of nanoscale‐reinforced MTPS‐g‐PBAT were achieved rather than the PRECURSORS. Wide angle X‐ray diffraction and transmission electronic microscopy analyses show that partial exfoliation of the clay platelets was observed within the PBAT‐g‐MTPS graft copolymer‐Cloisite 30B nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graft polymerization of acrylonitrile onto starch‐coated polyethylene film surfaces

Starch‐coated polyethylene (PE) films were prepared by immersing PE in a hot, jet cooked solution of starch. They were allowed to react with acrylonitrile (AN) in the presence of ceric ammonium nitrate initiator, and the graft polymerization that occurred produced starch‐g‐polyacrylonitrile (PAN) coatings that contained about 25 wt % grafted PAN. The starch‐g‐PAN coatings tightly adhered to the PE film surfaces. When grafted starch coatings were wetted with water and the surfaces vigorously rubbed, less than 20% of the coating was removed. The fact that PAN‐grafted coatings were not removed with boiling water provided further evidence for their strong adherence. When starch was removed from the coating by acid hydrolysis, the residual grafted PAN still remained adsorbed on the PE surface. Because the grafted coating was completely removed by treatment with refluxing 0.7N sodium hydroxide, there is apparently no chemical bonding between starch‐g‐PAN and PE. The dimensional changes associated with the evaporation of water from these PAN‐grafted coatings caused the films to curl during drying. Because the final shape of these coated films depends upon the presence or absence of water in the surrounding environment, these films may be considered to be a type of stimulus‐responsive polymer. Attempts to graft polymerize methyl methacrylate and methyl acrylate onto starch‐coated PE surfaces, under conditions similar to those used with AN, were unsuccessful. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3323–3328, 2003     

D‐isosorbide and 1,3‐propanediol as plasticizers for starch‐based films: Characterization and aging study

In the present work, D‐isosorbide and 1,3‐propanediol are proposed as alternative plasticizers obtained from renewable resources. Plasticized starch films were prepared by solvent casting method. The influence of using different “green” plasticizers in the final properties of starch‐based films was analyzed. Besides, the characterization of the films was also performed after storage time in order to evaluate the effect of the plasticizer on aging. UV‐spectrophotometry results showed better optical properties for both glycerol and D‐isosorbide films with higher transparency. The thermal and mechanical properties resulted influenced by the nature of the plasticizer. It was demonstrated that water vapor permeability was governed by the starch‐water interactions, whereas the oxygen permeability depended on the plasticizer's nature. The storage time affected the surface, mechanical, and thermal properties of the plasticized starch films. Atomic force microscopy results concluded that the topography of the films changed due to aging. The use of D‐isosorbide as plasticizer reduced the evolution of the mentioned properties and enhanced the reliability of the material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44793.     

Urea and formamide as a mixed plasticizer for thermoplastic starch

Mixtures of urea and formamide were tested as plasticizers for thermoplastic starch (TPS). The hydrogen bonding interactions between urea/formamide and starch were investigated by using Fourier‐transform infrared spectroscopy (FT‐IR). The thermal stability, mechanical properties and starch retrogradation behavior were also studied by thermogravimetric analysis (TGA), tensile testing and X‐ray diffraction (XRD), respectively. TPS plasticized by urea (20 wt%) and formamide (10 wt%) showed better thermal stability and water resistance than conventional TPS plasticized by glycerol. Moreover, the tensile stress, strain and energy at break, respectively, reached 4.83 MPa, 104.6 % and 2.17 N m after storing in an atmosphere of relative humidity (RH) of 33 % for one week. At the same time, this mixed plasticizer could effectively restrain the retrogradation of starch. Copyright © 2004 Society of Chemical Industry     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermoforming starch‐graft‐polycaprolactone biocomposites via one‐pot microwave assisted ring opening polymerization

A thermoformable starch‐graft‐polycaprolactone biocomposite was prepared by initiating ring‐open polymerization of caprolactone monomer onto starch under microwave irradiation. In this case, the thermoplastic and hydrophobic modification of starch could be realized by one‐pot grafting PCL, where the grafted PCL chains acted as the “plasticizing” tails of thermoforming and as the hydrophobic species of water‐resistance. The resultant biocomposites were injection‐molded as the sheets and their structure and properties were investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical analysis, contact angle measurement, and tensile testing. In this case, the grafted PCL chains entangled each other, and hence contributed to the strength and elongation of biocomposites. This work provided a simple strategy of one‐pot thermoplastic and hydrophobic modification of starch, and may be applied in a continuous process of modification, compounding, and molding. Meanwhile, the resultant biocomposites containing starch are believed to have a great potential application as an environment‐friendly and/or biomedical material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and enzymatic degradation of thermoplastic starch–polycaprolactone blends

This study's aim was to evaluate the effect of processing conditions on the morphology and enzymatic degradation of 50/50 (w/w) thermoplastic starch–polycaprolactone blends. The blends, produced from native potato starch, glycerol, and polycaprolactone in a melt mixer using different mixing speeds and temperatures, were cocontinuous, and the blends were very homogeneous. Enzymatic hydrolysis was performed using Bacillus licheniformis alpha‐amylase and Aspergillus niger glucoamylase on both milled and intact samples. The thin layer of polycaprolactone (≈ 5 μm) formed on the surface of the thermoplastic starch–polycaprolactone blends during compression molding strongly reduced the rate of enzymatic hydrolysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2594–2604, 1999     

Effect of ultrasonic irradiation on ceric‐salt‐initiated grafting of methyl methacrylate onto regenerated cellulose film

Effect of ultrasonic irradiation on ceric salt (Ce⁴⁺)‐initiated grafting of methyl methacrylate (MMA) on regenerated cellulose film (thickness = 20 μm) was investigated under an air atmosphere in water solvent at 60°C. The grafting system with the ultrasonic irradiation was characterized by higher percentage of grafting and graft efficiency than the system without the irradiation. Reaction of cellulose with Ce⁴⁺ was also accelerated by the ultrasonic irradiation. No accelerating effect of grafting due to the ultrasonic irradiation was observed for the system under reduced pressure of 5 torr. The effect of the ultrasonic irradiation on the average molecular weight of MMA‐grafted chains was also studied. Moreover, the surface layer of the resulting grafted films was examined by attenuated total reflection–infrared (ATR–IR) measurement and scanning electron microscopy (SEM) observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 251–258, 1999     

Properties of extruded starch–poly(methyl acrylate) graft copolymers prepared from spherulites formed from amylose–oleic acid inclusion complexes

Mixtures of high‐amylose corn starch and oleic acid were processed by steam jet cooking, and the dispersions were rapidly cooled to yield amylose–oleic acid inclusion complexes as micron‐ and submicron‐sized spherulites and spherulite aggregates. Dispersions of these spherulite particles were then graft polymerized with methyl acrylate, both before and after removal of uncomplexed amylopectin by water washing. For comparison, granular, uncooked high‐amylose corn starch was also graft polymerized in a similar manner. Graft copolymers with similar percentages of grafted and ungrafted poly(methyl acrylate) (PMA) were obtained from these polymerizations. The graft copolymers were then processed by extrusion through a ribbon die, and the tensile properties of the extruded ribbons were determined. Although extruded ribbons with similar tensile strengths were obtained from the three starch–PMA graft copolymers, much higher values for % elongation were obtained from the spherulite‐containing systems. Also, the tensile properties were not significantly affected by removal of soluble, uncomplexed amylopectin by water washing before graft polymerization. These results are consistent with the observation that these PMA‐grafted starch particles did not melt during extrusion, and that continuous plastic ribbons were formed by fusing these particles together in the presence of small amounts of thermoplastic PMA matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40381.     

Dynamic mechanical and thermal properties of the composites of thermoplastic starch and lanthanum hydroxide nanoparticles

Nanostructured lanthanum (III)‐oxide (La₂O₃) particles were prepared by a polymer complex solution method and further used for the preparation of lanthanum hydroxide (La(OH)₃) nanoparticles. The La(OH)₃ nanopowder was mixed with glycerol‐plasticized maize starch and the effect of the filler on the thermal, mechanical, and viscoelastic properties of the matrix was investigated. It was expected that this nanofiller, which shows an affinity toward OH groups, would strongly affect the physical properties of thermoplastic starch (TPS). The pure TPS and the TPS‐La(OH)₃ nanocomposite films (with 1, 2, and 3 wt % filler) were conditioned at various relative humidities (RHs) (35, 57, 75, and 99% RH). After conditioning at 99% RH, the pure TPS films exhibited higher affinity toward water than the nanocomposites. Differential scanning calorimetric measurements showed that, due to retrogradation effects, the melting enthalpies of the films increased with increasing RH. Dynamic mechanical analysis revealed that the mechanical properties in the linear range strongly depend on both the humidity conditions and the concentration of the filler. The results also show that La(OH)₃ nanoparticles are good reinforcement for TPS films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Blends of thermoplastic starch and polyesteramide: processing and properties

The blending of thermoplastic starch (TPS) with other biodegradable polyesters such as polyesteramide could be an interesting way to produce new biodegradable starch‐based materials. Different mixes of wheat starch and polyesteramide (BAK) were melt blended by extrusion. After pelletization, granules were injection molded to produce test specimens. A range of blends was studied with glycerol (plasticizer)/starch content ratios varying from 0.14 to 0.54. BAK concentrations were up to 40 wt %, TPS remaining as the major phase in the blend. Various properties were examined with mechanical, thermomechanical (dynamic mechanical thermal analyzer) and thermal (differential scanning calorimetry) analysis. Hydrophobicity was determined with contact angle measurements. Thanks to the knowledge of the properties of each polymeric system, we analyzed the blends' behavior by varying each component concentration. The material aging was also studied. We showed that structural changes occurred during several weeks after injection. We noticed a certain compatibility between both polymeric systems. The addition of BAK to TPS matrix allowed us to overcome the weaknesses of pure thermoplastic starch: low mechanical properties, high moisture sensitivity, and high shrinkage in injection, even at 10 wt % BAK. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1117–1128, 2000     

Ring‐opening graft polymerization of L‐lactide onto starch granules in an ionic liquid

A room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([AMIM]Cl) was a promising direct solvent for starch and nonderivitizing solvent for starch‐effective dissolution, in which the ring‐opening graft polymerization (ROGP) of L ‐lactide (L ‐LA) onto starch chains was carried out homogeneously. The obtained starch grafted poly(L ‐lactide) (starch‐g‐PLLA) was characterized by FTIR, ¹³C NMR, DSC, and WAXD, and the good adhesion between the two components was evidenced by SEM observations although the chains of grafted PLLA were not long. The grafting efficiency of PLLA reached 30% when the ROGP proceeded at 100°C for 10 h with L ‐LA/starch 0.5 : 1 (wt/wt) and stannous octoate (Sn(Oct)₂) as a catalyst, which was calculated according to a standard curve newly created by FTIR method. The homopolymerization of L ‐LA and the disconnection of grafted PLLA from starch‐g‐PLLA were the main competition reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tensile properties of thermoplastic starch‐PVB blends

Blends of thermoplastic starch and recycled polyvinylbutyral from automotive windscreens were investigated. Mechanically compatible blends are formed at low to intermediate starch content. However, scanning electron microscopy and dynamic‐mechanical analysis revealed a phase‐separated nature for all blend compositions investigated. Tensile properties are negatively affected by aging in a high humidity environment and they deteriorate rapidly when the samples are soaked in water. Synergistic property enhancement was observed for a compound containing 22% thermoplastic starch. It features a higher tensile strength, shows better water resistance, and is significantly less affected by aging. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1751–1755, 2006     

Preparation and properties of polymerizable 1,8‐naphthalimide fluorescent dye grafted linear low‐density polyethylene

Light converting greenhouse films are novel plastic films for agriculture. In this study, 4‐methoxy‐N‐allyl‐1,8‐naphthalimide (MOANI) was grafted onto linear low‐density polyethylenes (LLDPE‐g‐MOANI) by melt reactive mixing. The effects of monomer concentration, chamber temperature, and reaction time on grafting degree were systematically studied. Evidence of the grafting reaction was determined by ¹HNMR, FTIR, UV–Vis, and fluorescence spectrometry. Dynamic rheological properties, isothermal crystallization kinetics, surface morphologies of LLDPE, LLDPE‐g‐MOANI, and blends of LLDPE and MOANI (LLDPE/MOANI) were also analyzed. In addition, mechanical and fluorescent properties of unpurified LLDPE‐g‐MOANI films were further studied after the UV condensation weathering and acceleration migration test, respectively. We demonstrated that the cross‐linking of LLDPE could be inhibited effectively by the graft of MOANI; the grafted MOANI acted as a nucleation agent to accelerate crystallization; the grafted MOANI effectively inhibited the aging process of LLDPE and the migration of free MOANI to the surface of the unpurified LLDPE‐g‐MOANI film. The modified LLDPE showed the potential application in long‐term light converting films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42172.     

不同直链含量热塑性淀粉的制备及性能研究

利用转矩流变仪,以丙三醇为增塑剂对不同来源的淀粉进行改性制备热塑性淀粉（TPS）。采用X射线衍射仪（XRD）、热重分析仪（TG）、水接触角测量仪、傅里叶变换红外光谱仪（FTIR）和扫描电子显微镜（SEM）等对获得的热塑性淀粉进行了表征。结果表明,4种热塑性淀粉均含有颗粒状和颗粒状碎片,并且在热塑性木薯淀粉中所含比例更高;淀粉在增塑过程中达到稳态的扭矩依次为木薯淀粉（23 N·m）>玉米淀粉（21 N·m）>马铃薯淀粉（17.8 N·m）>蜡质玉米淀粉（15.2 N·m）,这与不同种类来源淀粉的直链淀粉比例差异直接相关;不同类型的淀粉与增塑剂形成氢键的能力存在差异,蜡质玉米淀粉的能力最强;4种热塑性淀粉的亲水性依次为热塑性木薯淀粉（75.9 °）>热塑性玉米淀粉（69.2 °）>热塑性马铃薯淀粉（67.9 °）>蜡质玉米淀粉（64.9 °）。     

Polybenzimidazole‐graft‐polyvinylphosphonic acid—proton conducting fuel cell membranes

A new method for the preparation of polybenzimidazole (PBI)‐based membranes, containing high concentrations of immobilized phosphonic acid groups, has been developed. The procedure used is carried out in two steps: (1) Synthesis of modified PBIs, containing 1,2‐dihydroxypropyl groups and preparation of films there from; (2) Introduction of vinylphosphonic acid (VPA) and initiator (cerium ammonium nitrate) in the film, subsequent grafting of VPA from the active sites of the PBI backbone. Membranes with different length of the grafted polyvinylphosphonic acid chains were prepared. The molar ratio grafted VPA units per PBI repeating unit reaches 7.8. Proton conductivity was measured at 120°C and relative humidity (RH) 20–100%. For the membrane with highest concentration of phosphonic acid groups the proton conductivity was 35 mS cm^?1 at 100% RH and 8 mS cm^?1 at 20% RH. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of processing on the melt degradation of starch‐filled polypropylene

Compounded polypropylene powders with various concentrations of corn starch were processed in a Haake torque rheometer at constant temperature, 180 °C, for different times in a closed system. A scanning electron micrograph of 5‐min processed sample shows a fine dispersion of starch particles in the polypropylene (PP) matrix. A good distribution and interaction of the starch particles are seen with increasing processing time (up to 15 min). Infrared spectroscopy evidence on the extracted films shows that most interactions between PP and starch are obtained after about 10 min processing. The presence of 2–6 wt% starch in the PP has a melt‐stabilising effect by reducing melt flow index and increasing apparent viscosity with a good correlation. However, 6 wt% starch gives complete inhibition of the PP melt degradation up to 20 min processing. Carbonyl groups are not formed during processing of PP containing 6 wt% starch. This is also an indication of a starch stabilising effect on the PP chemical structure. An increase in elongation at break of PP films having 6 wt% starch, when compared with the controls, is observed, while their ultimate tensile strength remains almost the same. © 1999 Society of Chemical Industry     

The influence of layered compounds on the properties of starch/layered compound composites

Glycerol‐plasticized starch films were modified by addition of various layered compounds as fillers, two being of natural origin (kaolinite, a neutral mineral clay, and hectorite, a cationic exchanger mineral clay) and two synthetic (layered double hydroxide, LDH, an anionic exchanger, and brucite, having a neutral structure). The effects of the filler type and the plasticizer were analyzed by X‐ray diffraction, dynamic mechanical analysis and thermogravimetry. The storage modulus was higher for kaolinite > brucite > hectorite than for LDH starch composites. However, only the hectorite filler presented a shift of the interplanar basal distance to higher values, which represents the intercalation of glycerol molecules between the clay layers. The glycerol intercalation is minimized in plasticized–oxidized starch films where the oxidized starch chains are preferentially intercalated. Copyright © 2003 Society of Chemical Industry