Ethanolamine as a novel plasticiser for thermoplastic starch

Ethanolamine plasticised thermoplastic starch (ETPS) was prepared using a novel plasticiser ethanolamine. SEM images show that the native starch granules were destroyed, and the ethanolamine made them come into a uniform continuous phase. FTIR spectroscopy showed that the hydrogen bonds between the ethanolamine and starch molecules weakened the strong effect of starch intermolecular and intramolecular hydrogen bonds. The ETPS successfully restrains the re-crystallization of traditional thermoplastic starch plasticised by glycerol (GTPS), which was proved by XRD. The mechanical properties of ETPS, such as Young's modulus and breaking energy and the water absorption were improved. The glass-transition temperature (T_g) and thermal stability were also studied by DSC and TGA.     

The processing of starch as a thermoplastic

The thermoplastics processing of native starch in the presence of water is a recent development with very wide possible applications. Eventually, oil-based polymer materials have to be replaced in many applications by sustainable, inexpensive, natural materials from renewable resources. As with conventional thermoplastics, starch-water melts may be processed by injection moulding and extrusion. The present contribution focuses on injection moulding. The bases of the processing and the thermal and molecular changes occurring are described. In addition, the rheological behaviour of the starch-water melts during processing is analysed quantitatively to give apparent melt viscosities. The dimensional, thermal and mechanical properties of moulded thermoplastic starch polymer (TSP) materials and the products presently being produced from them are discussed.     

Enzymatic synthesis and properties of novel biodegradable and biobased thermoplastic elastomers

Novel biodegradable and biobased thermoplastic elastomers, poly[dodecanolide-12-hydroxystearate (12HS)], poly(pentadecanolide-12HS) and poly(hexadecanolide-12HS) with M_ws of 140,000-290,000 g mol⁻¹ were prepared by the enzymatic copolymerization of a macrolide as the hard segment and methyl 12HS as the soft segment. Their thermal properties, such as T_m and T_c, were measured by DSC. Physicochemical and mechanical properties, such as crystallinity, were also measured. The polymer structures were analyzed with respect to the sequence of the two monomers by ¹H NMR spectroscopy using an europium shift reagent. The randomness of the two monomer units in the polymer chain increased with the polymerization time. Both Young’s modulus and tensile strength decreased with increasing 12HS content in the copolymer. In contrast, elongation at break increased with increasing 12HS content, thus demonstrating the copolymers’ elastomeric properties. These copolymers showed biodegradabilities by activated sludge, which also increased with increasing 12HS content.     

Mechanical properties and enzymic degradation of thermoplastic and granular sago starch filled poly(ε-caprolactone)

The mechanical, morphological and biodegradation properties of two types of poly(ε-caprolactone)/sago starch (PCL/sago) composites were investigated i.e. dried granulated sago starch and undried thermoplastic sago starch (TPSS). Thermoplastic starch was extruded with a twin screw extruder model Haake Rheomix (TW100 attached to a Haake Rheometer (Haake Rheodrive 5000). The composites were compounded with a Haake internal mixer (Haake Rheomix 3000) attached to the Haake Rheometer. Tensile properties were determined with the Monsanto Tensometer T10. A Shimadzu UV-160A visible UV spectrophotometer was used to monitor the liberation of carbohydrate as a consequence of starch hydrolysis by α-glucoamylase. Determining the weight loss of composites as well as the acid liberated from PCL also monitored biodegradation. The results indicate that dried granulated sago starch function better as fillers in terms of mechanical properties and the ease of biodegradation. However, TPSS imparted better yield strength to the composites. Poor wetting of starch accounts for the decreased mechanical properties at higher starch concentration as agglomeration occurs. While the rigid granular starch retained their shape in the composites, thermoplastic starch that is surrounded by microvoids is easily deformed due to plasticization.     

Synthesis and characterization of crystallizable aliphatic thermoplastic poly(ester urethane) elastomers through a non-isocyanate route

A simple non-isocyanate route is developed for synthesizing crystallizable aliphatic thermoplastic poly(ester urethane) elastomers(TPEURs) with good thermal and mechanical properties. Three prepolymers of1,6-bis(hydroxyethyloxycarbonylamino) hexane(BHCH), i.e. Pre PBHCHs, were prepared through the self-transurethane polycondensation of BHCH. A poly(butylene adipate) prepolymer(Pre PBA) with terminal HO― groups was prepared and used as a polyester glycol. A series of TPEURs were prepared by the co-polycondensation of the Pre PBHCHs with Pre PBA at 170 ℃ under a reduced pressure of 399 Pa. The TPEURs were characterized by gel permeation chromatography, FTIR,1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy, and tensile test. The TPEURs exhibited M_n up to 23300 g/mol, M_w up to 51100 g/mol, Tg ranging from-33.8 ℃ to-3.1 ℃, T_m from 94.3 ℃ to 111.9 ℃, initial decomposition temperature over 274.7 ℃, tensile strength up to18.8 MPa with a strain at break of 450.0%, and resilience up to 77.5%. TPU elastomers with good crystallization and mechanical properties were obtained through a non-isocyanate route.     

Synthesis and characterization of biodegradable aliphatic polyesters using dibutylmagnesium as initiator

Aliphatic polyesters were synthesized via the ring opening polymerization of the corresponding lactones initiated with dibutylmagnesium both in bulk and in solution. The resulting polymers were characterized by 1H, 13C NMR, GPC and XRD. The results indicated that dibutylmagnesium is an effective initiator for the ring opening polymerization of lactones.     

Synthesis and properties of novel aliphatic polycarbonate from carbon dioxide with 1,2-butylene oxide and ε-caprolactone

A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR,1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.     

Thermoplastic starch and glutaraldehyde modified thermoplastic starch foams prepared using supercritical carbon dioxide fluid as a blowing agent

Supercritical carbon dioxide (scCO₂) processed thermoplastic starch (scCO₂^aTPS), cellulose nanofiber (CNF) modified scCO₂^aTPS (scCO₂^aTPS₁₀₀CNF_0.02) and glutaraldehyde (GA) modified scCO₂^aTPS₁₀₀CNF_0.02 (scCO₂^aTPS₁₀₀CNF_0.02GA_x) foams were prepared for the first time using scCO₂ as a blowing agent during their foaming processes. The expansion ratio, cell density, moisture resistance, and compressive strength (σ_c) retention properties of each foam series were considerably improved with increasing scCO₂ pressure during the foaming processes. The expansion ratios and cell densities of each scCO₂^aTPS₁₀₀CNF_0.02GA_x foam series were increased considerably to a maximum value, as the GA content approached an optimum value. The optimal scCO₂¹¹TPS₁₀₀CNF_0.02GA_1.6 foam material exhibited a high expansion ratio and cell density at approximately 50 and approximately 8 × 10⁸ cells/cm³, respectively. Compared with corresponding aged scCO₂^aTPS and scCO₂^aTPS₁₀₀CNF_0.02 foam specimens, considerably better moisture resistance and σ_c retention properties were observed for scCO₂^aTPS₁₀₀CNF_0.02GA_x foam specimens, when they were modified with the corresponding optimum GA content. The moisture resistance and σ_c retention for optimal prepared scCO₂⁷TPS₁₀₀CNF_0.02GA_0.4, scCO₂⁹TPS₁₀₀CNF_0.02GA_0.8 and scCO₂¹¹TPS₁₀₀CNF_0.02GA_1.6 foam materials improved further with increasing scCO₂ pressure. Possible reasons accounting for the highly expansion ratio, moisture resistance, and σ_c retention properties for scCO₂^aTPS₁₀₀CNF_0.02GA_x foams are presented.     

Poly(lactic acid)/coplasticized thermoplastic starch blend: Effect of plasticizer migration on rheological and mechanical properties

Polylactic acid (PLA) and thermoplastic starch (TPS) are known as bio‐based and biodegradable thermoplastic polymers that can be used in different applications owing to their inherent physical and mechanical properties. In order to reduce the higher costs of PLA and tuning its physical and mechanical properties suitable for short life packaging applications, blending of PLA with the TPS, more economical biodegradable polymer, has been considered in academic and industrial researches. However, melt blending of PLA with TPS without compatibilization process caused some drawbacks such as coarsening morphology and declining mechanical properties and ductility because of thermodynamic immiscibility, which may restrict its usage in packaging applications. Subsequently, our approach in this research is compatibilization of PLA/TPS blends by utilization of primary well tuning of TPS formulation with a combination of sorbitol and glycerol plasticizers. In this work, the wide composition range of melt mixed PLA/TPS blends was prepared using a laboratory twin screw extruder. The effects of microstructure on the rheological and mechanical properties of PLA/TPS blends were studied using different methods such as scanning electron microscopy (SEM) images, contact angle, oscillatory shear rheological measurements, and tensile and impact strength mechanical tests. The rheological and mechanical properties were interpreted according to the morphological features and considering the possibility of plasticizer migration from TPS to PLA phase during melt blending. Reduction in complex viscosity and storage modulus of PLA matrix samples indicates the improved melt processability of blends. Finally, in comparison with mechanical results reported in literature, our simple approach yielded the blends with elastic modulus and ductility comparable with those of chemically compatibilized PLA/TPS blends.     

N-Hydroxysuccinimidyl phenylacetate as a novel derivatizing reagent for aliphatic amines in gas chromatography

A new succinimidyl ester amine-reactive reagent, N-hydroxysuccinimidyl phenylacetate (SIPA), has been synthesized for analytical derivatization of aliphatic amines, such as methylamine, ethylamine, propylamine, butylamine and pentylamine in gas chromatography (GC). The derivatiation conditions were investigated in detail. The experimental results showed that SIPA was a useful reagent with the advantages including mild derivatization condition, rapid reaction time and selectivity to amino group. In a pH 8.5 H₃BO₃-Na₂B₄O₇ buffer solution and dichloromethane, the derivatization and extraction can be accomplished at the same time and excess reagent need not be removed before analysis, which greatly simplified the sample preparation. The derivatives were analyzed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography/flame ionization detector (GC/FID). The detection limits (S/N=3) were in the range of pmol level.     

Polypropylene ionic thermoplastic elastomers: Synthesis and properties

Polypropylene ionic thermoplastic elastomers have been prepared by melt radical grafting of maleic anhydride onto polypropylene in the presence of N-bromosuccinimide followed by neutralization of the resulting elastomeric grafted polypropylene using sodium salts. Sodium hydroxide and sodium acetate were compared in aqueous solution, as anhydrous or hydrated powders. The neutralization reaction was followed by Fourier transform infrared spectroscopy, allowing the development of a method to determine the effective neutralization degree. Important physical changes were recorded upon neutralization. Especially thermal stability, shear storage modulus and complex viscosity in the flow region were largely increased as a function of the neutralization degree.     

Preparation,characterization and performances of biodegradable thermoplastic starch

A biodegradable thermoplastic starch (TPS) was successfully prepared from plasticizer ethanolamine and native cornstarch. The hydrogen bonding interaction between starch and ethanolamine was investigated using Fourier transform infrared (FT‐IR). When the ethanolamine mass content was 30%, after the ethanolamine‐plasticized thermoplastic starch (ETPS) was stored at RH 50% for 14 days, the mechanical testing showed that the maximum tensile stress of the ETPS reached 5.98 MPa, the tensile strain reached 106.52%, Young's modulus increased from 38.14 MPa of glycerol‐plasticized thermoplastic starch (GTPS) to 75.32 MPa of ETPS, and the breaking energy increased from 1.921 N·m to 2.305 N·m, which indicated that the mechanical properties of ETPS evidently excelled those of the GTPS. The effects of water contents on the mechanical properties of ETPS and GTPS were studied. A differential scanning calorimetry (DSC) analysis revealed that the low‐temperature transition and the glass transition temperature (T_g) of the ETPS were ?58 and 22°C respectively, which were lower than that of the GTPS. The ETPS effectively restrained the re‐crystallization of traditional GTPS, which was proved by the X‐ray diffraction (XRD). The scanning electron microscopy (SEM) images presented that ethanolamine made starch uniform. Copyright © 2007 John Wiley & Sons, Ltd.     

Alkanolamide as an accelerator,filler-dispersant and a plasticizer in silica-filled natural rubber compounds

A feasibility study was carried out on the utilization of Alkanolamide (ALK) on silica reinforcement of natural rubber (NR) by using a semi-efficient cure system. The ALK was incorporated into the NR compound at 1.0, 3.0, 5.0, 7.0 and 9.0 phr. An investigation was carried out to examine the effect of ALK on the cure characteristics and properties of NR compounds. It was found that ALK gave shorter scorch and cure times for silica-filled NR compounds. ALK also exhibited higher torque differences, tensile modulus, tensile strength, hardness and crosslink density of up to 5.0 phr of ALK loading, and then decreased with further increases of ALK loading. The resilience increased with increased ALK loading. Scanning electron microscopy (SEM) micrographs proved that 5.0 phr of ALK in the silica-filled NR compound exhibited the greatest matrix tearing line and surface roughness due to higher reinforcement level of the silica, as well as better dispersion and cure enhancement.     

Biodegradable polymers by reactive blending trans-esterification of thermoplastic starch with poly(vinyl acetate) and poly(vinyl acetate-co-butyl acrylate)

Wheat starch was reacted with poly(vinyl acetate) and with poly(vinyl acetate-co-butyl acrylate) in an internal mixer at 150 °C in the absence of catalyst, and in the presence of sodium carbonate, zinc-acetate and titanium(IV) butoxide. The resulted blends were pressed into film and characterized by ¹H NMR-¹³C NMR spectroscopy, differential scanning calorimetry (DSC), mechanical testing, dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), and water absorption. Partial trans-esterification took place between wheat starch and the polymers. The blends appeared as homogenous, translucent films with one glass transition temperature range, between that of starch and of the polymer. The presence of wheat starch in the blends improved the mechanical strength of the polymers, although elongation at break severely decreased, which is disadvantageous for processability. Zinc-acetate improved the tensile strength of the blends of starch with PVAC, while all catalysts resulted in an increase in strength of the blends of starch with poly(vinyl acetate-co-butyl acrylate) compared to the strength of the blends without catalyst. Water absorption of wheat starch/copolymer blends was between 150% and 250%, higher than that of the blends with the homopolymer, which was between 100% and 150% after soaking in water. The onset temperature of thermal decomposition was between 290 and 300 °C for all the blends, although the presence of sodium carbonate resulted in a decrease in the onset temperature of thermal decomposition by about 60 °C.     

Synthesis and mesomorphism of new aliphatic polycarbonates containing side cholesteryl groups

New cholesterol side-functionalised polycarbonate polymers were synthesised by the ring-opening homo- and copolymerisation reaction of the cyclic monomer cholesteryl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate and d,l-lactide using Sn(Oct)₂ as a catalyst. The chemical structures and average molecular weights of the cyclic monomer, homopolymer and block copolymers obtained in this study were characterised using FT-IR, ¹H NMR and gel permeation chromatographic measurement. The mesomorphism and mesophase structure were investigated with polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurement. As a result, the homopolymer and block copolymers showed an enantiotropic smectic A (SmA) phase. With the concentration of the lactide segment increasing, the glass transition temperature and isotropic temperature of the corresponding block copolymer all decreased. In addition, XRD suggested that the homopolymer and two block copolymers showed the SmA double-layer packing of side chains.     

Synthesis of a novel polyester-ether copolymer and its derivatives as antistatic additives for thermoplastic films

Development of antistatic thermoplastic elastomer composites is gaining much interest in scientific and industrial aspects. In this contribution, a novel type of polyester-block-ether copolymer (PEBE), PEBE with ionic liquid (PEBE-IL) and quaternized PEBE (PEBE-Q) were synthesized, characterized and compounded with a commercial bottle grade polyester (PET) resin. It was found that the surface resistivity of the PET composite films was around 10⁹–10¹⁰ Ω/sq. The addition of the PEBE copolymers as an antistatic agent into PET matrix resulted in almost 10⁶ times enhancement in surface resistivity compared to neat PET film. Among the PET films with an antistatic agent, it was emphasized that PEBE-IL and ionic liquid doping to PET matrix led to a relatively lower crystallization degree, surface resistivity, contact angle and breaking force with a translucent appearance compared to neat PET film. Furthermore, it was illustrated that antistatic PET films with fine-tune physical, mechanical and morphological properties can be achieved by choosing appropriate antistatic agent type and amount.     

Extrusion foaming of semi-crystalline PLA and PLA/thermoplastic starch blends

Low density open-cell foams were obtained from polylactic acid (PLA) and from blends of PLA with thermoplastic starch (TPS) using CO(2) as a blowing agent. Two unexpected features were found. First, a 2D cavitation process in the fractured cell walls was unveiled. Elliptical cavities with dimensions in the 100-300 nm range were aligned perpendicular to large cell cracks clearly exhibiting 2D crazing prior to macroscopic cell rupture. Secondly, a significant crystallization rate increase associated with the CO(2) foaming of PLA was discovered. While the PLA used in this study crystallized very slowly in isothermal crystallization, the PLA foams exhibited up to 15% crystallinity, providing evidence that CO(2) plasticization and the biaxial stretching upon foam expansion provided conditions that could increase the crystallization rate by several orders of magnitude.     

Synthesis and characterization of new copolymers of ethyl methacrylate grafted on tapioca starch as novel excipients for direct compression matrix tablets

In last years, the introduction of new materials for drug delivery matrix tablets has become more important. This paper evaluates the physicochemical and mechanical properties of new graft copolymers of ethyl methacrylate (EMA) on tapioca starch (TS) and hydroxypropylstarch (THS), synthesized by free radical polymerization and dried in a vacuum oven (OD) or freeze-dried (FD). Infrared and ¹³C NMR spectroscopies confirm the change of chemical structure of the copolymers and X-ray diffraction shows up the higher amorphization of copolymers respect to the carbohydrates. Particle size analysis and SEM indicate that graft copolymerization leads to an increase of particle size and a more irregular shape. Graft copolymerization implies decrease of density and moisture content values. Heckel equation shows that copolymers have less densification by particle rearrangement and fragmentation than carbohydrates. Concerning the drying methods, FD products have larger plasticity and lower elasticity than OD copolymers. Graft copolymerization produces a decrease of the applied pressure necessary to obtain tablets, ejection force and friction work. Furthermore, graft copolymers show longer disintegration time than tablets from raw starches. These qualities suggest that these copolymers could be used as excipients in matrix tablets obtained by direct compression, and with a potential use in controlled release.     

新型热塑性淀粉的制备和性能

以二甲基亚砜(DMSO)为增塑剂, 通过熔融共混法制备了一种新型热塑性淀粉(TPS), 研究不同增塑剂含量对材料结构和性能的影响, 并与甘油及甘油/水复合增塑淀粉体系进行了比较. FTIR结果显示, DMSO能够与淀粉产生强烈而稳定的氢键相互作用. WAXD和SEM的研究结果表明, DMSO的加入破坏了淀粉的有序结构, 实现了淀粉的塑化, 形成均一的非晶连续相. 同甘油及甘油/水增塑体系相比, DMSO与淀粉的羟基形成更为稳定的氢键, 能够有效抑制淀粉的重结晶. 动态力学和拉伸力学性能测试结果表明, 经过DMSO的增塑, 有效降低了淀粉的玻璃化转变温度, 改善了材料的韧性, 增塑效率要好于甘油及甘油/水复合增塑体系.