Fully biodegradable blends of poly(butylene succinate) and poly(butylene carbonate): Miscibility, thermal properties, crystallization behavior and mechanical properties

Fully biodegradable poly(butylene succinate) (PBS) and poly(butylene carbonate) (PBC) blends were prepared by melt blending. Miscibility, thermal properties, crystallization behavior and mechanical properties of PBS/PBC blends were investigated by scanning electron microscopy (SEM), phase contrast optical microscopy (PCOM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and mechanical properties tests. The SEM and PCOM results indicated that PBS was immiscible with PBC. The WAXD results showed that the crystal structures of both PBS and PBC were not changed by blending and the two components crystallized separately in the blends. The isothermal crystallization data showed that the crystallization rate of PBS increased with the increase of PBC content in the blends. The impact strength of PBS was improved significantly by blending with PBC. When the PBC content was 40%, the impact strength of PBS was increased by nearly 9 times.     

生物基超韧聚乳酸复合材料的制备与性能

采用来源于可再生资源的聚醚酰胺弹性体（PEBA）增韧聚乳酸（PLA）制备超韧聚乳酸（PLA/PEBA-GMA）复合材料.为了提高PEBA与PLA之间的相容性,选择极性单体甲基丙烯酸缩水甘油酯（GMA）、共接枝单体乙烯基吡咯烷酮（NVP）及引发剂过氧化二异丙苯（DCP）对PEBA进行接枝改性制备PEBA-GMA.研究了接枝单体组分的用量（m/g）对PLA/PEBA-GMA复合材料性能的影响.研究发现,随着接枝单体组分用量的提高,复合材料的缺口冲击强度逐渐增大,当接枝单体组分GMA,NVP和DCP的用量分别为2.5,2.5和0.25 g时,复合材料的冲击强度高达88.6 kJ/m²,断裂伸长率为164.1%.研究表明,在熔融共混过程中,聚乳酸的端基（—OH和—COOH）与PEBA-GMA上环氧基团发生反应,有效改善两相间的界面相容性,随着接枝单体组分比例的提高,分散相PEBA-GMA的粒子尺寸逐渐减小且分布均匀.     

The influence of core-shell structured modifiers on the toughness of poly (vinyl chloride)

The core-shell structured grafted copolymer particles of polybutadiene grafted polymethyl methacrylate (PB-g-PMMA, MB) were prepared by emulsion polymerization. The MB particles were used to modify poly (vinyl chloride) (PVC) by melt blending. The mechanical properties of the PVC blends were investigated. The micro-morphology of the PVC blends was observed by scanning electron microscopy (SEM). The results indicated that the samples with the best impact strength could be obtained when the core-shell weight ratio of PB to PMMA is lower than 93:7, the mechanical properties correlated well with SEM morphologies, the addition of modifier with the ratio core to shell of 93:7 could reduce the domain size of the dispersed phase. Furthermore, the compatibility and properties of the blends were greatly enhanced and improved. The modifier particles could be well dispersed in the PVC matrix.     

苯乙烯—丙烯酸钠共聚物改性PET结晶行为的研究

本文用DSC和FT-IR方法研究了PET/苯乙烯-丙烯酸钠共聚物共混体系的相溶性、等温结晶动力学、组成、温度等因素对结晶速率、结晶度等结晶行为的影响,并初步探讨了离聚物对PET的作用。     

线性聚酯酰胺对聚碳酸亚丙酯的改性

通过己内酯和氨基己酸开环、缩合反应制备了酯段含量为81%的线性聚酯酰胺（PEA）,并用熔融共混的方法制备了PEA/聚碳酸亚丙酯（PPC）共混物,考察了PEA的引入对共混体系相容性、热力学稳定性和机械性能的影响。 结果表明,PEA与PPC之间有较好的相容性,共混物的热力学稳定性比PPC有显著提高,当PEA质量分数为3%时,共混体系的起始分解温度（T-5%）和最大分解速率时的温度（Tmax）比PPC分别提高了52.7%和46.4%。 通过调节PEA的含量可以使共混体系同时达到增强和增韧的效果。     

Thermal,morphological, mechanical and aging properties of polylactide blends with poly(ether urethane) based on chain-extension reaction of poly(ethylene glycol) using diisocyanate

Poly(ether urethane)s(PEU), including PEUI15 and PEUH15, were prepared through chain-extension reaction of poly(ethylene glycol)(PEG-1500) using diisocyanate as a chain extender, including isophorone diisocyanate(IPDI) and hexamethylene diisocyanate(HDI). These PEUs were used to toughen polylactide(PLA) by physical and reactive blending.Thermal, morphological, mechanical and aging properties of the blends were investigated in detail. These PEUs were partially compatible with PLA. The elongation at break of the reactive blends in the presence of triphenyl phosphate(TPP)for PLA with PEUH15 or PEUI15 was much higher than that of the physical blends. The aging test was carried out at-20 °C for 50 h in order to accelerate the crystallization of PEUs. The PEUs in the PLA/PEU blends produced crystallization and formed new phase separation with PLA, resulting in the declined toughness of blends. Fortunately, under the aging condition,although PEUH15 in blends could also form crystallization, the reactive blend of PLA/PEUH15/TPP(80/20/2) had higher toughness than the other blends. The elongation at break of PLA/PEUH15/TPP(80/20/2) dropped to 287% for the aging blend from 350% for the original blend. The tensile strength and modulus of PLA/PEUH15/TPP blend did not change obviously because of the crystallization of PEUH15.     

Compatible blends of biorelated polyesters through catalytic transesterification in the melt

The transesterification during the melt blending of polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) was investigated in presence of Ti(OBu)₄ as a catalyst. Both the effect of catalyst concentration and reaction duration was considered. The process was studied by analyzing the molecular weight of the polyesters by size exclusion chromatography (SEC). The rheological, thermal and morphological properties of the blends were investigated by melt flow rate, DSC and SEM analyses, respectively. Evidences about the formation of PBAT-PLA copolymers were obtained and discussed. The tensile properties of compression moulded films were also determined and correlated to the structure and phase morphology development of the blends. In particular, the use of Ti(OBu)₄ resulted in the improvement of compatibility. Moreover, the decrease in stiffness and the increase in elongation at break with the increase of mixing time was observed, in good agreement with the improved compatibility of the modified blend.     

Mechanical,aging, optical and rheological properties of toughening polylactide by melt blending with poly(ethylene glycol) based copolymers

Two novel biodegradable copolymers, including poly(ethylene glycol)-succinate copolymer (PES) and poly(ethylene glycol)-succinate-l-lactide copolymer (PESL), have been successfully synthesized via melt polycondensation using SnCl₂ as a catalyst. The copolymers were used to toughen PLA by melt blending. The DSC and SEM results indicated that the two copolymers were compatible well with PLA, and the compatibility of PESL was superior to that of PES. The results of tensile testing showed that the extensibility of PLA was largely improved by blending with PES or PESL. At same blending ratios, the elongation at break of PLA/PESL blends was far higher than that of PLA/PES ones. The elongation maintained stable through aging for 3 months. The moisture absorption of the blends enhanced due to the strong moisture absorption of PEG segments in PES or PESL molecules, which did not directly lead to enhance the hydrolytic degradation rate of the PLA. The PLA blends containing 20–30 wt% PES or PESL were high transparent materials with high light scattering. The toughening PLA materials could potentially be used as a soft biodegradable packaging material or a special optical material.     

Miscibility and crystallization kinetics in blends of poly(ethylene terephtalate) and thermotropic liquid crystal polyesters

Binary blends of poly(ethylene terephtalate) (PET) and thermotropic liquid crystal polyester (TLCP) have been prepared by both solution and melt blending methods. The TLCPs utilized were Vectra (Hoechst Celanese), TR-4, a TLCP synthesized in our laboratory, and a block copolymer consisting of three TR-4 units followed by three PET units. The phase behavior of the blends was studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and optical microscopy. The results show that none of the blends is miscible, but significant interactions exist between the PET phase and the TLCP phase in the case of TR-4 and TR-4 block copolymer blends. These interactions lead to a different nucleation mechanism in these blends compared to that in PET/Vectra.     

New approach on the development of plasticized polylactide (PLA): Grafting of poly(ethylene glycol) (PEG) via reactive extrusion

In this work, new ways of plasticizing polylactide (PLA) with low molecular poly(ethylene glycol) (PEG) were developed to improve the ductility of PLA while maintaining the plasticizer content at maximum 20 wt.% PLA. To this end, a reactive blending of anhydride-grafted PLA (MAG-PLA) copolymer with PEG, with chains terminated with hydroxyl groups, was performed. During the melt-processing, a fraction of PEG was grafted into the anhydride-functionalized PLA chains. The role of the grafted fraction was to improve the compatibility between PLA and PEG. Reactive extrusion and melt-blending of neat and modified PLA with PEG did not induce any dramatic drop of PLA molecular weight. The in situ reactive grafting of PEG into the modified PLA in PLA/PEG blends showed a clear effect on the thermal properties of PLA. It was demonstrated by DSC that the mobility gained by PLA chains in the plasticized blends yielded crystallization. The grafting of a fraction of PEG into PLA did not affect this process. However, DSC results obtained after the second heating showed an interesting effect on the T_g when 20 wt.% PEG were melt blended with neat PLA or 10 wt.% MAG-PLA. In the latter case, the T_g displayed by the reactive blend was shifted to even lower temperatures at around 14 °C, while the T_g of neat PLA and PLA blended with 20 wt.% PEG was around 60 and 23 °C, respectively. Regarding viscoelastic and viscoplastic properties, the presence of MAG-PLA does not significantly influence the behavior of plasticized PLA. Indeed, with or without MAG-PLA, elastic modulus and yield stress decrease, while ultimate strain increases with the addition of PEG into PLA.     

Crystallization behavior and hydrophilicity of poly (vinylidene fluoride) (PVDF)/poly (styrene-<Emphasis Type="Italic">co</Emphasis>-acrylonitrile) (SAN) blends

Poly (styrene-co-acrylonitrile) (SAN) is a hydrophilic non-crystalline copolymer, which is initially used in this paper to improve the hydrophilicity of poly (vinylidene fluoride) (PVDF). Investigation of the crystallization behavior of PVDF/SAN blends showed that the samples presented only α phase regardless of SAN content as cooling from the melt. A double-melting phenomenon was related to the perfection or crystal size of PVDF crystals. As the SAN content is increasing, crystallization of PVDF was limited, leading to a decreased crystallinity and lamellar growth. Besides, the hydrophilicity of PVDF was improved by blending with SAN. The sample containing 70 wt.% SAN performed a similar surface property of the neat SAN owing to the besieging of the PVDF phase by SAN. Observed from the cross section of the blends, PVDF/SAN blends were partially miscible with less than 50 wt.% SAN addition. As the SAN content was more than 50 wt.%, the crystalline PVDF particles clearly dispersed in the amorphous matrix.     

氨酯化合物对聚碳酸1,2-丙二酯的同时增韧和增强研究

采用非异氰酸酯路线合成了1,6-六亚甲基二氨基甲酸羟异丙酯(BPU),分子量为320.利用熔融共混方法制备了聚碳酸1,2-丙二酯(PPC)/BPU共混物.研究发现BPU与PPC间有较好的相容性,随着BPU含量的增加,共混体系的起始热分解温度(Td.5％)可分别增加24～33℃,共混物韧性也显著提高,断裂伸长率最大可增至...     

Improvement in toughness of poly(l-lactide) (PLLA) through reactive blending with acrylonitrile-butadiene-styrene copolymer (ABS): Morphology and properties

Poly(l-lactide) (PLLA) was melt-blended with acrylonitrile-butadiene-styrene copolymer (ABS) with the aim of enhancing impact strength and elongation at break of PLLA, but not sacrificing its modulus and stiffness significantly. However, PLLA and ABS were found to be thermodynamically immiscible by simply melt blending and the formed blends show deteriorated mechanical properties. The reactive styrene/acrylonitrile/glycidyl methacrylate copolymer (SAN-GMA) by incorporating with ethyltriphenyl phosphonium bromide (ETPB) as the catalyst was used as the in situ compatibilizer for PLLA/ABS blends to improve the compatibility between PLLA and ABS. The reactive process during melt blending was investigated by Fourier transformed infra-red (FTIR). It showed that the epoxide group of SAN-GMA reacted with PLLA end groups under the mixing conditions and that the addition of ETPB accelerated the reaction. Phase structure and physical properties of the compatibilized blends were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), tensile tests and impact property measurements. It was found that the size of ABS domains in PLLA matrix is significantly decreased by addition of the reactive compatibilizer. The dynamic mechanical analysis revealed markedly shifted glass transition temperatures for both PLLA and ABS, indicating the improved compatibility between PLLA and ABS. The mechanical tests showed the compatibilized PLLA/ABS blends had a very nice stiffness-toughness balance, i.e., the improved impact strength and the elongation at break with a slightly loss in the modulus.     

聚酰亚胺对高性能树脂共混体系界面的反应增强

研究了以5-降冰片烯-2,3-二羧酸单甲酯为端基的PMR型聚酰亚胺(POI)作为界面介质对部分相容的聚醚砜/聚苯硫醚(PES/PPS)、聚醚醚酮/聚醚砜(PEEK/PES)共混体系的界面性质、形态结构及结晶行为的影响.结果表明,POI可以有效地增强两相间的界面粘结,显著降低PPS/PES共混物中PPS分散区的尺寸,改善两组分间的相容性.在熔融共混过程中,POI从本体向界面扩散并同PPS,PES产生交联和/或接枝,POI同PPS的反应活性远高于PES,但POI与PES发生反应.POI是PPS结晶的有效成核剂.     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

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.     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

Electrical conductivity of poly(vinylidene fluoride)/polyaniline blends under oscillatory and steady shear conditions

Blends of poly(vinylidene fluoride) (PVDF) and polyaniline (PAni) were prepared through melt blending in a batch mixer. The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy (TEM) and combined electro-rheological measurements. Through TEM analysis, it was possible to observe that all blends showed typical phase separation with the presence of conductive polymer aggregates. Deformations imposed during a strain sweep caused, not only disturbance of the linear viscoelastic behavior, but also changes in electrical conductivity. The oscillatory shear altered the morphology, breaking the PAni domains into smaller ones. This effect increases the distance between them and, consequently, resulted in a decrease of the electrical conductivity. The measurements under quiescent conditions and steady shear proved that the disturbance in morphology for PVDF/PAni system is non-recoverable. Through combined electrical and rheological measurements, it was possible to achieve good correlation between the electrical and flow behavior of PVDF/PAni blends.     

PREFERENTIAL INTERCALATION BEHAVIOR OF CLAY AND ITS EFFECT ON THE THERMAL DEGRADATION IN IMMISCIBLE PP/PS BLENDS

The typical immiscible PP/PS blend based clay nanocomposites were prepared via melt blending.The dispersion of clay was determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM).Thermal stability and dynamic mechanical properties were measured by thermogravimetrical analysis (TGA) and dynamic mechanical analysis (DMA),respectively.Preferential intercalation behavior of clay in PP/PS blends was found.The dispersion of clay is significantly influenced by the polarity of PP and PS,mea...     

Thermal,mechanical and rheological properties of biodegradable poly(propylene carbonate) and poly(butylene carbonate) blends

Poly(propylene carbonate)(PPC) was melt blended in a batch mixer with poly(butylene carbonate)(PBC) in an effort to improve the toughness of the PPC without compromising its biodegradability and biocompatibility. DMA results showed that the PPC/PBC blends were an immiscible two-phase system. With the increase in PBC content, the PPC/PBC blends showed decreased tensile strength, however, the elongation at break was increased to 230% for the 50/50 PPC/PBC blend. From the tensile strength experiments, the Pukanszky model gave credit to the modest interfacial adhesion between PPC and PBC, although PPC/PBC was immscible. The impact strength increased significantly which indicated the toughening effects of the PBC on PPC. SEM examination showed that cavitation and shear yielding were the major toughening mechanisms in the blends subjected the impact tests. TGA measurements showed that the thermal stability of PPC decreased with the incorporation of PBC. Rheological investigation demonstrated that the addition of PBC reduced the value of storage modulus, loss modulus and complex viscosity of the PPC/PBC blends to some extent. Moreover, the addition of PBC was found to increase the processability of PPC in extrusion. The introduction of PBC provided an efficient and novel toughened method to extend the application area of PPC.