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 °）。     

苹果酸对聚乳酸/热塑性淀粉共混物结构与性能的影响

将天然淀粉用甘油改性后制得了热塑性淀粉(TPS),再通过熔融共混法制备了聚乳酸(PLA)/TPS共混物。通过SEM、TG、DSC分析和拉伸性能、吸水性能、流变性能测试,研究了苹果酸对TPS和PLA/TPS共混物结构和性能的影响。结果表明:苹果酸能促进淀粉酸解,使TPS分散相尺寸减小,在PLA基体中的分布更加均匀;苹果酸能提高PLA/TPS共混物的拉伸性能;苹果酸对PLA/TPS共混物的玻璃化转变温度、熔融温度及冷结晶温度影响较小;少量的苹果酸可降低PLA/TPS共混物的吸水率。     

Study of the Plasticizer Effect and Characterization on Diverse Pseudo-Thermoplastic Starch Biodegradable Films

Recently, pseudo-thermoplastic starch (PTS) has been developed to replace industrial plastics because of its advantage in biodegradability. In this study, potato, corn, and wheat starches, which have been modified into PTS biodegradable films by glycerol plasticization, were investigated. For the evaluation of the suitable compositions on PTS, we focus on analysis of the plasticizer effect and characterization. As the results show that the strength and modulus of pseudo-thermoplastic potato starch (PTP) film were respectively, 12.7 and 59.6 MPa, with lower gelatinization temperature (60°C), and the thermal processibility was better than other starches. It is beneficial for the production and application of biodegradable materials.     

Comparison of sorbitol and glycerol as plasticizers for thermoplastic starch in TPS/PLA blends

This article investigates the structure and properties of thermoplastic starch/PLA blends where the TPS phase is plasticized by sorbitol, glycerol, and glycerol/sorbitol mixtures. The blends were prepared using a twin‐screw extruder where starch gelatinization, water removal, and dispersion of TPS into a PLA matrix were carried out sequentially. The plasticizers were added to starch in the first stage of the extruder to allow complete starch gelatinization. The PLA was added at mid‐extruder and thoroughly mixed with the TPS. The plasticizer concentration was varied from 30 to 42% and the TPS content was varied from 27 to 60% on a weight basis. In all investigated blends, the PLA formed the continuous phase and the TPS was the dispersed phase. The viscosity, blend morphology, tensile mechanical properties as well as the thermal properties of the materials were measured. It was found that the glycerol/sorbitol ratio has an important effect on the blend properties. Finer blend morphologies, higher tensile strength and modulus but lower crystallization rate were found for the sorbitol plasticized blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乳酸/羟丙基淀粉复合降解型材料的制备和表征

羟丙基改性淀粉作为填充剂,在偶联剂作用下与聚乳酸共混、挤出制备聚乳酸/羟丙基淀粉复合降解型材料。随着羟丙基改性淀粉含量的增加,共混材料的硬度略有增加、拉伸强度和断裂伸长率都先减小后增大,材料的吸水率和降解速率增加,且改性淀粉取代度的增加有利于提高材料的韧性。     

Biodegradable Composition Based on Low Density Polyethylene

ABSTRACT

Sodium salt of partially carboxymethylated starch (Na-PCMS) with degree of substitution DS 0.58 and starch acetate with DS 1.7 were synthesized from starch. These starch ethers and acetates along with starch, poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA) were blended with low density polyethylene (LDPE) in various proportion using Brabender mixer. Addition of 5% stearic acid as a plasticizer improves the blend compatibility. Change in mechanical properties were monitored and optimum composition of blend were prepared. This blend was studied for growth of Bacillus species (BS) and degradation by means of weight loss and change in mechanical properties viz., tensile strength and % elongation, and total cellular protein. Degradation of pure polymers within one month period was also examined.     

Preparation and application of potato flour with low gelatinization degree using flash drying

A novel processing method of potato flour with a low starch gelatinization degree was realized by flash drying technique. Starch gelatinization degree, pasting properties, thermal characteristics, and morphological features between commercial potato flours (commercial potato flake and commercial potato granule) and flash-dried potato flour were analyzed and compared. Results showed that the gelatinization degree of flash-dried potato flour (14.52%) was reduced by nearly 80% than the commercial potato flours (about 95%). Typical viscosity profile, enthalpy value, and morphology features of flash-dried potato flour were retained maximally through an optimized processing of flash drying. The gelatinization temperature and pasting viscosity of flash-dried potato flour were increased significantly than the commercial potato flour. Besides, the intact morphological structure of flash-dried potato flour granules were kept due to the processing of flash drying. By utilizing the low gelatinization degree of flash-dried potato flour, desirable potato noodles were prepared with the ratio of potato flour up to 50%. Textural characteristics and cooking performance such as broken rate and cooking loss of flash-dried potato noodles were superior to these of the commercial potato flours (in the same amount) added noodles.     

Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch

In this study binary and ternary blends of polylactide (PLA), polycaprolactone (PCL) and thermoplastic starch (TPS) are prepared using a one-step extrusion process and the morphology, rheology and physical properties are examined. The morphology and quantitative image analysis of the 50/50 PLA/TPS blend transverse phase size demonstrate a bimodal distribution and the addition of PCL to form a ternary blend results in a substantial number of fine dispersed particles present in the system. Focused ion beam irradiation, followed by atomic force microscopy (AFM) shows that dispersed PCL forms particles with a size of 370 nm in PLA. The TPS phase in the ternary blends shows some low level coalescence after a subsequent shaping operation. Dynamic mechanical analysis indicates that the temperature of the tan δ peak for the PLA is independent of TPS blend composition and that the addition of PCL in the ternary blend has little influence on the blend transitions. Both the α and β transitions for the thermoplastic starch are highly sensitive to glycerol content. When TPS of high glycerol content is blended with PLA, an increase in the ductility of the samples is achieved and this effect increases with increasing volume fraction of TPS. The ternary blend results in an even greater ductility with an elongation at break of 55% as compared to 5% for the pure PLA. A substantial increase in the notched Izod impact energy is also observed with some blends demonstrating three times the impact energy of pure PLA. The mechanical properties for the ternary blend clearly indicate a synergistic effect that exceeds the results obtained for any of the binary pairs. Overall, the ternary blend approach with PLA/TPS/PCL is an interesting technique to expand the property range of PLA materials.     

Effect of PEG molecular weight on the tensile toughness of starch/PCL/PEG blends

The blend of a gelatinized starch and poly(ε‐caprolactone) (PCL) was prepared and the effect of starch gelatinization on the mechanical properties of the blend was studied. The gelatinization of starch resulted in good dispersion of the starch in the PCL matrix and a higher modulus and strength of the blend. The mechanical properties of the starch/PCL/poly(ethylene glycol) (PEG) blends were also investigated. From the change of the toughness of the blends with the PEG molecular weight, it was found that the blend containing PEG of molecular weight 3400 shows the highest tensile toughness. It was also found from the SEM images that the blend containing PEG of molecular weight 3400 had the smallest domain size of the starch dispersion phases, which implies that PEG of the proper molecular weight could effectively stabilize the interface of the starch/PCL blend. The PEG of the proper molecular weight seems to locate mainly at the interface between the starch and PCL phases and to interact with both the starch phase and the PCL phase. The interactions between starch and PEG and between PCL and PEG in the blend were studied using DSC and FTIR techniques. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2049–2056, 2000     

Preparation and properties of biodegradable poly(butylene succinate)/starch blends

The vital differences between the use of untreated starch and gelatinized starch in blends with poly(butylene succinate) (Bionolle) were thoroughly examined in this study. The melting temperature decreased slightly with increasing dosages of untreated and gelatinized starch. The added starch perhaps tended to disrupt the intermolecular hydrogen bonding within the Bionolle matrix. On the other hand, a large increase in the crystallinity was seen with the addition of starch. Starch appeared to play a nucleating role in the blends. The trend of the glass‐transition temperature decreasing with the starch level was similar to the trend of the melting temperature. For the same starch content, the glass‐transition temperature showed some variations. For blends containing a certain amount of gelatinized starch, the thermal stability remained to a certain degree but continued to decrease. This was ascribed to the relatively low heat stability of starch. As for the mechanical properties, a significant increase in the tensile strength (up to 2 times) was observed when untreated starch was replaced with gelatinized starch in the blends. Similarly, the tear strength increased up to 1.5 times if gelatinized starch was employed. Apparently, the gelatinization of starch was efficiently achieved for promoting its compatibility with Bionolle. In all cases, the mechanical properties of Bionolle blended with gelatinized starch were better than those of Bionolle blended with untreated starch. A morphological investigation provided evidence in support of these findings. This relatively low‐cost gelatinization approach provides an alternative to a high‐cost compatibilizer approach for improving the performance of biodegradable blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 257–264, 2005     

冷法H_2O_2氧化制备马铃薯淀粉粘合剂及改性研究

在室温下,以马铃薯淀粉为原料,双氧水为氧化剂,制备出了马铃薯淀粉粘合剂.探讨了氧化剂用量、催化剂用量、糊化剂用量、氧化时间、糊化时间、粉水比、络合剂用量对粘合剂性能的影响,以粘度和初粘力为评价指标,通过L18(37)正交试验确定制备淀粉粘合剂的最佳条件为:m(水)∶m(马铃薯淀粉)=5∶1,双氧水1.3 mL,硫酸亚铁0.2 g,NaOH为3.0 g,氧化时间90 min,糊化时间30 min,硼砂0.3 g.并以添加聚乙烯醇进行接枝改性,提高其干燥时间和初粘力,实验得到添加量为5%时效果最好.     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

淀粉/WPUR生物可降解塑料的制备与性能

以玉米淀粉与水性聚氨酯(WPUR)为主要原料,以甘油为增塑剂,采用熔融共混工艺制备了生物可降解热塑性淀粉塑料(TPS)/WPUR共混物。考察了TPS/WPUR共混物的微观结构、成型加工性能、力学性能和耐水性能等。结果表明,WPUR不仅有利于TPS的塑化和改善其熔体流动性,而且也有利于提高其拉伸性能和耐水性。     

Preparation and studying properties of polybutene‐1/thermoplastic starch blends

Starch as an inexpensive and renewable source has been used as a filler for environmental friendly plastics for about two decades. In this study, glycerol was used as a plasticizer for starch to enhance the dispersion and the interfacial affinity in thermoplastic starch (TPS)/polybutene‐1(PB‐1) blend. PB‐1 was melt blended with TPS using a single screw extrusion process and molded using injection molding process to investigate the rheological and mechanical properties of these blends. Rheological properties were studied using a capillary rheometer, and the Bagley's correction was performed. Mechanical analysis (stress–strain curves) was performed using Testometric M350‐10 kN. The rheological properties showed that the melt viscosity of the blend is less than that of PB‐1, and the flow activation energy at a constant shear stress of the blend increases with increasing glycerol content in the blend. The mechanical experiments showed that both stress and strain at break of the blends are less than that of PB‐1, whereas the Young's modulus of the most blends is higher than that of PB‐1 which confirms the filling role of TPS in the blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of polyhydroxybutyrate blended with different types of starch

This study examines the properties of polyhydroxybutyrate (PHB) when blended with two types of maize starch, Starch 1 (containing 70% amylose) and Starch 2 (containing 72% amylopectin). The PHB/starch blends were prepared by melt compounding at a ratio of 70/30 by weight and characterized in terms of their morphology, structure, thermal, rheological, and mechanical properties. The results show that starch granules act as a filler in PHB/starch blends and also act as a nucleating agent causing a very significant reduction in the size of the PHB spherulites. There were found to be significant improvements in thermal, rheological, and mechanical properties, and these were greater for blends containing Starch 1 than those containing Starch 2. These improvements are attributed to enhanced hydrogen bonding between PHB and Starch 1 with high‐amylose content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Blending of poly(lactic acid) and starches containing varying amylose content

Four dry corn starches with different amylose content were blended at 185°C with poly(lactic acid) (PLA) at various starch:PLA ratios using a lab‐scale twin‐screw extruder. Starch with 30% moisture content also was blended with PLA at a 1:1 ratio. Each extrudate was ground and dried. The powder was mixed with about 7.5% plasticizer, and injection molded (175°C) into test tensile bars. These were characterized for morphology, mechanical properties, and water absorption. Starch performed as a filler in the PLA continuous matrix phase, but the PLA phase became discontinuous as starch content increased beyond 60%. Tensile strength and elongation of the blends decreased as starch content increased, but no significant difference was observed among the four starches at the same ratio of starch:PLA. The rate and extent of water absorption of starch/PLA blends increased with increasing starch. Blends made with high‐amylose starches had lower water absorption than the blends with normal and waxy corn starches. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3639–3646, 2003     

Properties of blends of starch and synthetic polymers containing anhydride groups. II. Effect of amylopectin to amylose ratio in starch

Corn starch with different amylopectin to amylose ratios was blended with styrene maleic anhydride copolymer (SMA) and ethylene–propylene-g-maleic anhydride copolymer (EPMA). The starch had an amylose content of approximately 0, 50, and 70%. The concentration of starch in the blend was kept constant at 60% by weight. The samples were melt blended in a corotating twin screw extruder. Scanning electron micrographs showed that the amount of starch granules remaining in the samples varied with the torque. Optical micrograph showed that starch/EPMA blends formed a cocontinuous phase in all blends irrespective of starch variety. For starch/SMA blends, the starch granules remained dispersed in the SMA phase. The torque during blending, tensile strength, water absorption, storage and loss modulus, and data on biodegradability of the blends are presented. Tensile strength and water absorption correlated well with the torque generated during blending: the higher the torque, the lower the tensile strength and the higher the water absorption. The tensile strength of blends containing SMA decreased when the humidity increased. Fractured surfaces of starch/SMA blends exhibited brittle failure; for the ductile starch/EPMA blends, shear tearing appeared to be the major failure mechanism. For blends containing EPMA, the percentage elongation increased with increased humidity. Dynamic mechanical analysis of the blends showed two sharp peaks for tan δ vs. temperature plot for starch/EPMA plots, but showed a single peak for starch/SMA blends. Starch/EPMA blends had a higher percentage of water aborption that became constant after 20 days. Using the ASTM test method D5902, the starch content in the samples was found to degrade. © 1995 John Wiley & Sons, Inc.     

乙酰化淀粉/聚己内酯共混物的制备和性能研究

分别采用淀粉(TPS)、乙酰化淀粉(TPAS)与聚己内酯(PCL)进行熔融共混,制备了可生物降解的塑料,探讨了淀粉乙酰化改性后对共混物力学性能、耐水性、熔融流动性、相容性及生物降解性的影响。共混物的拉伸强度均随PCL用量的增加而增大,TPAS／PCL体系的拉伸强度低于TPS／PCL体系,而断裂伸长率高于TPS／PCL体系。PCL可以明显改善淀粉基材料的耐水性,淀粉乙酰化后共混体系的相容性及熔体流动性得到一定的改善,生物降解性略微下降。     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

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