Macromolecular design of novel sulfur‐containing copolyesters with promising mechanical properties

The miscibility of poly(butylene succinate) (PBS)/poly(butylene thiodiglycolate) (PBTDG) blends was investigated by DSC technique. PBS and PBTDG were completely immiscible in as blended‐state, as evidenced by the presence of two T_gs at ?34 and ?48°C, respectively. The miscibility changes upon mixing at elevated temperature: the original two phases merged into a single one because of transesterification reactions. Poly(butylene succinate/thiodiglycolate) block copolymers, prepared by reactive blending of the parent homopolymers, were studied to investigate the effects of transesterification reactions on the molecular structure and solid‐state properties. ¹³C‐NMR analysis evidenced the formation of copolymers whose degree of randomness increased with mixing time. Thermal characterization results showed that all the samples were semicrystalline, with a soft rubbery amorphous phase and a rigid crystal phase whose amount decreased by introducing BTDG units into the PBS chain (20 ≤ χ_c ≤ 41). Lastly, the mechanical properties were found strictly related to crystallinity degree (χ_c), the random copolymer, exhibiting the lowest elastic modulus (E = 61 MPa) and the highest deformation at break (ε_b (%) = 713). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Selective Transport of Cu2+ Ions through Bulk Liquid Membrane System Mediated by Erythromycin Ethyl Succinate

The carrier mediated transport of Cu²⁺ ions from an aqueous medium has been examined. The ability of Erythromycin Ethyl Succinate (EES) as a carrier to form a complex with Cu²⁺ ions and transport them to the receiving phase is reported. The fundamental parameters influencing the transport of Cu²⁺ ions such as the pH in the source and receiving phases and concentration of the stripping agent in the receiving phase have been optimized and accordingly, the amount of Cu²⁺ transported across the liquid membrane after 5 h was 94.3 ± 1.8% in the presence of L-histidine as a suitable stripping agent. Moreover, the selectivity and efficiency of Cu²⁺ ions transport from aqueous solution over other cations in ternary and quaternary mixtures have been investigated. The results indicate that our fabricated membrane is very sensitive toward Cu⁺² ions in the presence of heavy metal ions.     

聚(丁二酸丁二酯-co-衣康酸丁二酯)的合成

用含不饱和双键基团的衣康酸作共聚单体,采用直接熔融酯化聚合法制备可生物降解的聚(丁二酸丁二酯-co-衣康酸丁二酯)。共聚物的相对分子质量及其分布、溶解性能、热性能及结晶性能均受分子链中衣康酸含量的影响,当衣康酸摩尔分数达50%时,共聚物成为不溶/熔的交联弹性体。     

十二烯基琥珀酸淀粉酯性质的研究

采用RVA快速粘度测定仪，研究了十二烯基琥珀酸淀粉酯(SSDS)糊的粘度性质。测定了糊的凝沉性质、糊的乳化性质、糊的冻融稳定性、并采用扫描电子显微镜对SSDS的微观结构进行了分析。结果显示：酯化后SSDS的颗粒形貌、糊粘度性质较原玉米淀粉糊有较显著变化、其抗凝沉性、乳化性都明显优于原玉米淀粉，而冻融稳定性比原玉米淀粉差。     

温度对维生素E琥珀酸酯结晶效率的影响

对以天然维生素E和琥珀酸酐为原料制备的维生素E琥珀酸酯的结晶过程进行研究,主要考察结晶初始温度、降温速率、结晶终点温度对维生素E琥珀酸酯含量和收率的影响。结果表明:在结晶初始温度50℃,降温速率2℃/h,结晶终点温度0℃,养晶时间10 h的条件下,维生素E琥珀酸酯的含量达到97.1%,收率为91.4%。     

Effect of Co‐Rotation and Counter‐Rotation Extrusion Processing on the Thermal and Mechanical Properties,and Morphology of Plasticized Soy Protein Isolate and Poly(butylene succinate) Blends

Blends of plasticized soy protein isolate (PSPI) and poly(butylenes succinate) (PBS) were prepared in a 70:30 wt.‐% ratio via co‐rotation (CR) and counter‐rotation (CTR) twin‐screw extrusion. The novelty in this research suggests that CTR extrusion provides enhanced interfacial adhesion, tensile elongation and prolonged onset (T_onset) and end (T_end) thermal degradation temperatures. The average tensile strain at break showed to be ≈40% higher for PSPI‐CTR material and ≈55% higher for PBS:PSPI‐CTR (70:30) blends. Both T_onset and T_end for CTR processed PBS:PSPI(70:30) and PSPI were ≈10 °C greater than those of CR. These results suggest that the enhanced shear rate and radial motion associated with CTR allows for better destructurization and blending of PSPI within the PBS matrix, resulting in enhanced structural integrity due to the formation of possible amide and ester linkages. Scanning electron microscopy (SEM) provides further support based on evidence of reduced voids on the surface of all CTR blends

     

Synthesis of novel biodegradable poly(butylene succinate) copolyesters composing of isosorbide and poly(ethylene glycol)

A series of biodegradable isosorbide‐based copolyesters poly(butylene succinate‐co‐isosorbide succinate‐co‐polyethyleneoxide succinate) (PB_xI_yE_zS) were synthesized via bulk polycondensation in the presence of dimethyl succinate (DMS), 1,4‐butanediol (BDO), poly(ethylene glycol) (PEG) and isosorbide (ISO). The crystallization behaviors, crystal structure and spherulite morphology of the copolyesters were analyzed by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarizing optical microscopy (POM), respectively. The results indicate that the crystallization behavior of the copolyesters was influenced by the content of isosorbide succinate (IS) and polyethyleneoxide succinate (PEOS) units, which further tuned the mechanical and biodegradable properties of the copolyesters. The PB_xI_yE_zS copolyesters, compared to pure poly(butylene succinate), showed lower crystallization temperature, melting temperature, degree of crystallinity and degradation rate while a significant increase in glass transition temperature with increasing isosorbide content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丁二酸丁二醇酯的扩链改性及共混研究

采用扩链剂2,4-甲苯二异氰酸酯（TDI）、2,2′-双（2-恶唑啉）（BOZ）以及新型扩链剂ADR-4370对聚丁二酸丁二醇酯（PBS）进行扩链,对比研究3种扩链剂对PBS性能的影响。采用聚乳酸（PLA）与PBS共混,选择最佳配比以及合适的共混工艺。结果表明,新型扩链剂ADR-4370可以良好的改善PBS的加工性能和机械性能,m（PBS）/m（PLA）最佳配比为70：30,在共混同时进行扩链比扩链后再共混可以更好的提高PBS/PLA的性能。     

化学修饰Novozym-435酶催化合成维生素E琥珀酸酯的研究

Vitamin E succinate was synthesized in organic solvents using a modified Novozym-435 as catalyst.In order to improve the catalytic performance of Novozym-435,the enzyme was modified using acetic anhydride, propionic anhydride and succinic anhydride separately.We found that both the hydrolytic activity and the thermal stability of the modified Novozym-435 were enhanced compared with the unmodified enzyme.The modified Novozym-435 catalysts were used to synthesize the succinate derivative of vitamin E.Compared with the native Novozym-435,the catalytic activity of the modified novozym-435 in promoting the synthesis of vitamin E succinate was dramatically increased,with the novozym-435 modified with succinic anhydride(N435-S)as the most active catalyst.Conditions for the synthesis of vitamin E succinate were also optimized.A mixture of tert-butanol and DMSO(volume ratio of 2︰3)was the most suitable medium for the reaction,whereas the appropriate molar ratio of vitamin E to succinic anhydride and reaction temperature were 1︰5 and 40°C,respectively.Under these reaction conditions,the yield of vitamin E succinate reached 94.4%.N435-S could be reused for five batches.     

PBS基三元共聚物的合成及性能研究

在PBS主链中同时引入己内酯(CL)和1,4-环己烷二甲醇(1,4-CHDM),或CL和二乙醇酸(DGA)得到了PBS-co-PCL-co-CHDM和PBS-co-PCL-co-DGA三元共聚物。通过1H-NMR、FTIR对三元共聚物的结构进行了表征,并采用热分析、广角X射线衍射分析和拉力试验比较了三元共聚物的性能。结果表明:随着CL、1,4-CHDM、DGA的引入,三元共聚物的结晶尺寸有所减小,结晶度降低,与PBS相比晶型略有变化;并且tanδ均增大,而储能模量均降低;在CL同时存在的条件下,1,4-CHDM的加入使共聚物的的玻璃化温度(Tg)上升为-30℃,DGA的加入却使Tg下降为-36℃,但二者的热分解温度仍在300℃以上;改性后三元共聚物的柔韧性增强断,裂伸长率显著提高。