The effect of epoxide content on compatibility of poly(lactic acid)/epoxidized natural rubber blends

The objective of this work was to determine the effect of the epoxide content in epoxidized natural rubber (ENR) on the miscibility and compatibility with poly(lactic acid) (PLA) in prepared PLA/ENR blends. PLA was blended with 10 wt% of ENRs (epoxidized at 10, 15, 20, and 25 mol%). The presented study showed that the in situ graft copolymer, PLA-g-ENR, was formed during melt blending in the blends containing 10 and 15 mol% ENR. This work is the initial study showing the presence of PLA-g-ENR in the blends by ¹H-NMR and ¹³C-NMR. PLA-g-ENR acted as a compatibilizer, producing a partially miscible blend, indicated by an inward shift of the α-transition temperatures of PLA and ENR in the blends. PLA-g-ENR also greatly reduced the particle size of ENR and increased the impact strength, tensile strength, and elongation at break of the blends. The epoxide content of ENR changed deformation mechanisms of the blends.     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚乳酸/聚己二酸对苯二甲酸丁二酯合共混体系发泡行为研究

采用多环氧基团增容剂制备了聚乳酸/聚己二酸对苯二甲酸丁二酯(PLA/PBAT)共混物,研究了增容剂含量对于PLA/PBAT共混体系的结晶和流变性能的影响。并采用高压釜发泡的方法进行PLA/PBAT共混物的间歇发泡,研究增容剂对发泡材料泡体结构的影响。结果表明,增容剂加入后会降低其绝对结晶度,以及显著改善PLA/PBAT共混体系的熔体弹性,提高其可发性;增容剂可以有效地改善共混体系的泡体结构,降低共混物发泡密度,提高其发泡倍率。     

聚乳酸/聚丁二酸丁二醇酯共混物的研究

通过熔融共混制备了聚乳酸(PLA)/聚丁二酸丁二醇酯(PBS)共混物,采用扫描电子显微镜、差示扫描量热仪、旋转流变仪对其相容性、热性能和黏度等进行了研究,并研究了PBS的加入对PLA力学性能的影响。结果表明,PLA和PBS之间是部分相容的,PBS的少量添加并不影响PLA的拉伸强度,且其冲击强度随着PBS含量的增加呈先上升后下降的趋势,当PBS含量为10份时,共混物的冲击强度最好;与纯PLA相比,共混物的黏度有所增加,且随着PBS含量的增加,共混物的黏度逐渐增大;PBS的添加起到异相成核作用,促进了PLA的结晶。     

环氧化天然橡胶在全钢子午线轮胎胎面配方中的应用

研究了环氧化天然橡胶(ENR-40)在全钢子午线轮胎胎面配方中的应用效果。试验表明,ENR-40部分取代NR应用到轮胎配方中具有一定的优异性,对胎面配方硫化特性影响不大,胎面胶配方的物理机械性能提高,压缩疲劳生热降低。     

橡胶加工分析仪研究环氧化天然橡胶的性能

用橡胶加工分析仪对环氧化天然橡胶进行了温度扫描、频率扫描和应变扫描，并和天然橡胶的响应曲线进行了对比。     

The Curing Behavior and Adhesion Strength of the Epoxidized Natural Rubber Modified Epoxy/Dicyandiamide System

The curing properties and adhesive strengths of the epoxidized natural rubber (ENR, 25 mole percent epoxidation) modified epoxy systems are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and lap shear strength (LSS) measurement. The results of DSC analyses indicate that the curing exotherm, the curing rate, the reaction order, and the glass transition temperature of the epoxy system are affected by the presence of reactive ENR. From SEM micrographs, it is obtained that a second spherical rubber phase is formed during cure and the particle size of the rubber phase is increased by increasing the curing temperature and the ENR content. The changes of the volume fraction of the rubber phase and the T_g of the cured systems indicate that the mutual dissolution between epoxy resin and ENR happens and which changes with the curing temperature and the ENR content. The LSS of adhesive joints prepared with the ENR modified adhesives are all lower than those of the unmodified epoxy system, and decrease with increasing the amount of ENR added because of the limited compatibility of the ENR with the epoxy matrix.     

Extrusion Foaming of Poly (lactic acid)/Soy Protein Concentrate Blends

Poly(lactic acid) (PLA) and soy protein concentrate (SPC) were compounded using poly(2‐ethyl‐2‐oxazoline) as compatibilizer by twin‐screw extrusion, and the resulting blends were foamed by a chemical blowing agent (CBA) using the same extruder. Effects of foaming temperature and CBA content on cell density and foam density were investigated. Polymeric methylene diphenyl diisocyanate (pMDI) as a co‐compatibilizer was added prior to foaming extrusion and its effects on foam morphology and properties were also studied. The results showed that cell density and foam density were greatly influenced by foaming temperature and CBA content. Using the strong interfacial modifier pMDI in PLA/SPC blends resulted in high‐cell density and low‐foam density when CBA concentration was low.

     

超支化聚酰胺酯对聚乳酸增韧改性的研究

采用熔融共混的方法,用生物可降解的超支化聚酰胺酯(HBP)对聚乳酸(PLA)进行增韧改性,制备出具有良好韧性的PLA复合材料。对不同HBP含量的共混物的红外光谱、热性能和力学性能进行了测试和分析。红外光谱显示PLA和HBP间存在氢键作用。HBP的加入使PLA的结晶度从30.99%降低到18.58%。当HBP含量增加到10%时,PLA共混物的拉伸强度略有提高,且断裂伸长达到43.06%。结果表明:HBP的加入对PLA起到了很好的增韧作用。     

环氧化天然橡胶及其应用研究进展

介绍环氧化天然橡胶(ENR)的制备方法、性能及其对聚合物基复合材料的改性效果.ENR在保留天然橡胶(NR)的结构和性能的基础上,可进一步提高NR的气密性能和耐油性能等.不同硫化体系硫化ENR的性能不同,ENR的环氧度越高,其玻璃化温度越高,气密性能和耐溶剂性能越好.ENR可作为相容剂对NR和其他橡胶及白炭黑进行改性,提高胶料的性能和白炭黑在胶料中的分散性.     

Biocomposites of poly(lactic acid) and lactic acid oligomer-grafted bacterial cellulose: It's preparation and characterization

This work demonstrates the synthesis of lactic acid oligomer-grafted-untreated bacterial cellulose (OLLA-g-BC) by in situ condensation polymerization which increased compatibilization between hydrophobic poly(lactic acid) (PLA) and hydrophilic BC, thus enhancing various properties of PLA-based bionanocomposites, indispensable for stringent food-packaging applications. During the synthesis of OLLA-g-BC, hydrophilic BC is converted into hydrophobic due to structural grafting of OLLA chains with BC molecules. Subsequently, bionanocomposites films are fabricated using solution casting technique and characterized for structural, thermal, mechanical, optical, and gas-barrier properties. Morphological images showed uniform dispersion of BC nanospheres in the PLA matrix, which shows strong filler–matrix interaction. The degradation temperatures for bionanocomposites films were above PLA processing temperature indicating that bionanocomposite processing can be industrially viable. Bionanocomposites films displayed decrease in glass transition (T_g) and ~20% improvement in elongation with 10 wt % fillers indicating towards plasticization of PLA. PLA/OLLA-g-BC films showed a slight reduction in optical transparency but had excellent UV-blocking characteristics. Moreover, dispersed BC act as blocking agents within PLA matrix, reducing the diffusion through the bionanocomposite films which showed ~40% improvement in water-vapor barrier by 5 wt % filler addition, which is significant. The reduced T_g, improved elongation combined with improved hydrophobicity and water-vapor barrier make them suitable candidate for flexible food-packaging applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47903.     

聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物的非等温结晶动力学

采用熔融挤出法制备了聚乳酸/聚(已二酸-对苯二甲酸丁二酯)共混物。利用差示扫描量热仪研究了聚乳酸及其共混体系的非等温结晶过程。用经Jeziorny修正的Avrami方程和Mo法对其非等温结晶动力学进行了分析。结果表明:Avrami方程和Mo法都适用于处理聚乳酸及其共混体系的非等温结晶过程,共混物的结晶速率大于聚乳酸的结晶速率。此外,用Huffman-Lauritzen理论计算了非等温结晶的结晶活化能,发现共混体系的结晶活化能绝对值小于聚乳酸。     

Compatibilization of poly(lactic acid)/epoxidized natural rubber blend with maleic anhydride

The objective of this work was to determine the compatibilization effect of different concentrations of maleic anhydride (MA) in poly(lactic acid) blended with epoxidized natural rubber (PLA/ENR). ENR-grafted MA [ENR-g-MA] was synthesized using four concentrations of MA: 0.15, 0.30, 0.45, and 0.60 phr. Using an internal mixer, binary (PLA/ENR, PLA/ENR-g-MA) and ternary (PLA/ENR/ENR-g-MA) polymer blends were prepared with a constant rubber content of 10 wt %. ENR impaired the mechanical properties of PLA, perhaps due to the relatively large size of the rubber particles. The compatibilization effect of MA was evaluated from the results of impact strength testing. ENR-g-MA was a toughening agent for PLA when the concentration of MA was in the range of 0.30–0.60 phr. MA increased miscibility between PLA and ENR. This effect was indicated in the blends by reductions in rubber particle size, the glass transition temperature of PLA, and the α-transition temperatures of PLA and ENR. In the binary polymer blends, the MA concentration in ENR-g-MA that produced the optimal mechanical properties of PLA was 0.60 phr. In the ternary blends, mechanical properties of PLA did not improve at any concentration of MA in ENR-g-MA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48297.     

Reactively Modified Poly(lactic acid): Properties and Foam Processing

Summary: In order to produce modified poly(lactic acid) (PLA) resins for applications requiring high melt viscosity and elasticity (e.g., low‐density foaming, thermoforming), a commercial PLA product has been reactively modified in melt by sequentially adding 1,4‐butanediol and 1,4‐butane diisocyanate as low‐molecular‐weight chain extenders. By varying amounts of the two chain extenders associated to the end group contents of PLA, three resulted samples were obtained. They were then structurally characterized by FTIR spectroscopy and molecular structure analysis. Their thermal, dynamic mechanical thermal properties and melt viscoelastic properties were investigated and compared along with unmodified PLA. The results indicated that chemical modification may be characterized as chain scission, extension, crosslinking, or any combination of the three depending on the chain extender amounts. The increase of PLA molecular weight could be obtained by properly controlling amounts of two chain extenders. The samples with increased molecular weights showed enhanced melt viscosity and elasticity. Such property improvements promised a successful application for modified PLA in a batch foam processing by producing foams with reduced cell size, increased cell density and lowered bulk foam density in comparison with plain PLA foam.

Cellular morphology of a modified PLA foam.     

聚乳酸结晶的研究进展

综述了自合成以来聚乳酸（PLA）结晶行为研究的主要成果，介绍了PLA的α、β、γ三种晶型结构参数及不同晶型晶体的形成条件，以及PLA球晶、单晶、孪晶、微纤晶和串晶等结晶形态及其形成条件。此外，还介绍了PLA在不同条件下的结晶行为，着重阐述了分子结构、第二组分及温度场、应力场以及辐照等外部因素对其结晶行为的影响。     

环氧化天然橡胶复合材料性能研究

采用新方法制备环氧化天然橡胶(ENR)/白炭黑和天然橡胶(NR)/ENR/白炭黑复合材料,并对其性能进行研究。结果表明:ENR/白炭黑复合材料的热稳定性优于ENR;在NR/ENR并用胶中加入白炭黑和硅烷偶联剂KH-550,NR/ENR/白炭黑复合材料0℃时的损耗因子(tanδ)增大,65℃时的tanδ值减小,复合材料的抗湿滑性能提高,滚动阻力减小。     

马来酸酐接枝细菌纤维素改性聚乳酸研究

制备了马来酸酐接枝细菌纤维素（BC-g-MAH）,然后采用溶液浇铸法将BC-g-MAH与聚乳酸（PLA）制备成复合材料,通过红外光谱、差示扫描量热分析、拉伸实验和热失重分析等测试手段,研究了由PLA与不同含量BC-g-MAH制备成的复合材料的结构和性能。结果表明,MAH对BC进行了成功的接枝,制得的BC-g-MAH与 PLA具有较好的界面相容性;随着BC-g-MAH含量的增加,改性后的复合材料的结晶度、拉伸强度和拉伸模量较纯PLA有较大提高;BC-g-MAH含量为 20 %（质量分数,下同）时,复合材料的结晶度、拉伸强度和拉伸模量较纯PLA分别提高了17.1 %、69.4 %和428.4 %,复合材料热稳定性能也有了显著增强。     

非共价功能化石墨烯改性PLA薄膜的制备

以双十二烷基二甲基溴化胺非共价修饰还原石墨烯(DDAB–RGO)为纳米填料,通过溶液铸膜法制备了聚乳酸/功能化石墨烯(PLA/DDAB–RGO)纳米薄膜。用傅立叶变换红外光谱和扫描电子显微镜对DDAB–RGO及纳米复合薄膜的化学结构及形貌进行了表征,并对纳米薄膜的结晶性能、力学性能、热稳定性等进行了测试分析。结果表明,DDAB–RGO与PLA具有良好的相容性,均匀分散于PLA基体中,在较低DDAB–RGO含量时对PLA膜起到了纳米增强的作用,当其含量为0.2%时,PLA/DDAB–RGO纳米薄膜的拉伸强度、拉伸弹性模量比纯PLA膜分别提高了21%和36%。同时DDAB–RGO的加入还改善了PLA的结晶性、热稳定性。