Hydrierung von Diethylsuccinat zu γ‐Butyrolacton, 1,4‐Butandiol und Tetrahydrofuran

The shortage of fossil resources necessitates the search for alternative sources for the production of important bulk chemicals. Diethyl succinate derived from biobased succinic acid can be used as a renewable alternative to fossil resources for the production of γ‐butyrolactone, 1,4‐butanediol and tetrahydrofuran. Commercially available ZnO‐free copper catalysts in a fixed‐bed reactor show promising selectivity to C4 products, but 1,4‐butanediol dehydration to tetrahydrofuran occurs over acidic sites, like alumina and zirconia.     

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。     

纳米氧化锌填充PBS复合材料性能的研究

采用硅烷偶联剂(KH-550)对纳米氧化锌进行了表面改性,通过熔融共混法制备了聚丁二酸丁二醇酯(PBS)/纳米氧化锌复合材料,利用扫描电子显微镜、热重分析仪、差示扫描量热仪等对复合材料的力学性能、热性能和非等温结晶性能进行了研究分析,并通过Ozawa-Flynn-Wall方法分析了复合材料的热降解行为。结果表明,纳米氧化锌能提高PBS的拉伸强度和弯曲强度,但降低了其冲击强度;改性后的纳米氧化锌可以提高其与PBS的界面相容性,并提高其在PBS基体中的分散性能,不同程度地提高了复合材料的力学性能;纳米氧化锌提高了PBS的结晶速率,降低了其热解反应活化能。     

Reviewing Rare Earth Succinate Frameworks from the Reticular Chemistry Point of View: Structures,Nets, Catalytic and Photoluminescence Applications

The intense development that Metal-Organic Frameworks have experienced along the last two decades, reflects the interest on these compounds as a new generation of multifunctional materials with diverse applications. The first works of Prof. Omar Yaghi devoted to obtain open frameworks by combining rigid aromatic linkers and a variety of metal centers, encouraged the creativity of the scientific community to designcoordination polymers employing aliphatic ligands as multitopic building blocks . Here, a revision of the literature dedicated to rare earth coordination networks mainly based in succinate ligand and derivatives is performed. A structural analysis of 2D and 3D frameworks based on rare earth elements and succinate, was carried out considering their inner connectivities and topologies with focus on those compounds with potential photoluminescent and catalytic technological applications. Thus, a variety of optical behaviours regarding the emission mechanisms, colours, lifetimes, quantum yields as well as chemical/thermal sensing properties are presented and compared with related phases found in literature. The catalytic performance of several rare earth-succinates in three important reactions is discussed in terms of their acidity, dimensionality and available active centers towards the formation of the desired products analysing parameters such as selectivity, yields and TOFs.     

聚丁二酸丁二醇酯的合成及工艺研究

以丁二酸(SA),1,4-丁二醇(BDO)为原料,通过熔融聚合法合成聚丁二酸丁二醇酯(PBS)。通过对催化剂筛选及用量、缩聚反应温度、总反应时间和酸醇比等因素对产品粘均分子量影响的探讨,优化出了熔融法合成PBS的最佳工艺条件:选择SnCl2做催化剂,用量在2%(以催化剂加入SA的质量比表示),缩聚反应温度在230℃,总反应时间5h,在酸醇配比为1∶1.1时,反应得到的PBS产品的粘均分子量最大,粘均分子量为5.14×104g/mol,产品颜色为白色。用IR、TG、1H-NMR等表征证明产品合成成功。     

亲水性PBS/虎杖提取物复合材料的相容性及性能

从天然植物虎杖中提取染色抗菌有效成分获得虎杖提取物(PCSZ),将其与聚丁二酸丁二酯(PBS)亲水改性聚合物PBS–OH和PBS–COOH通过混炼复合,研究了PCSZ与两种亲水性PBS复合后的相容性,测试了不同PCSZ用量下PBS–OH/PCSZ和PBS–COOH/PCSZ复合材料的结晶性能、亲疏水性、热稳定性、拉伸性能和抗菌性能。结果表明,PCSZ中的—OH均可与PBS–OH或PBS–COOH中的酯基产生氢键作用,同时还与改性端基形成H—O…H—O,充分改善了复合材料的相容性。PCSZ的添加对复合材料的结晶形貌不产生影响,但复合材料结晶度随其用量的增加而增大,且水接触角在PCSZ高用量下有所减少,亲水性有所增强;PCSZ可使复合材料的热稳定性和抗菌能力得到提高,当PCSZ用量较高时,PBS–OH/PCSZ复合材料的热稳定性高于PBS–COOH/PCSZ复合材料。与PBS–COOH/PCSZ复合材料相比,PBS–OH/PCSZ复合材料力学性能总体较优,但抗菌能力略差。综合比较两种亲水性PBS/PCSZ复合材料,PBS–OH/PCSZ复合材料的相容性更强。     

不同相对分子质量聚丁二酸丁二酯的合成及表征

以丁二酸、1,4–丁二醇为原料,采用溶液–熔融法合成了不同相对分子质量的聚丁二酸丁二酯(PBS),并研究了4种不同催化剂合成PBS反应的催化性能。采用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H–NMR)、差示扫描量热(DSC)、热重(TG)分析和力学拉伸仪对产物的结构、热稳定性、相对分子质量、力学性能等进行表征。结果表明,不同催化剂催化合成的PBS相对分子质量大小顺序为:对甲苯磺酸钛酸异丙酯氯化亚锡醋酸锌无催化剂。相对数均分子质量最大值为5.57×10~4,最小值为2.54×10~4。所有合成的PBS的热分解温度均大于250℃,都具有较好的热稳定性。其中以钛酸异丙酯和氯化亚锡为催化剂时,得到的PBS具有良好的力学性能。综上结果,钛酸异丙酯为催化剂时合成的PBS最优,相对分子质量为5.50×10~4,拉伸强度为34.5 MPa,断裂伸长率高达201%。     

聚丁二酸丁二醇酯/纤维素纳米晶复合纤维增强机制

采用熔融纺丝法制备了聚丁二酸丁二醇酯(PBS)/纤维素纳米晶(CNC)复合纤维,重点研究了CNC的分散性、PBS与CNC间氢键作用、PBS分子取向、CNC沿轴向排布以及PBS相结晶度对复合纤维强度的影响。通过光学显微镜和场发射扫描电镜观察发现:高牵伸倍率下的复合纤维较低牵伸倍率下的复合纤维侧面更加平整、光滑,且高牵伸倍率下CNC列。红外光谱图证实了PBS与CNC用力。此外,在提高牵伸倍率时,PBS复合纤维结晶度增大,并且其声速值也明显提高。多因素协同导致PBS/CNC(质量比99/1)复合纤维经4倍牵伸后断裂强度达3.59 cN/dtex,远高于相同处理条件下的纯PBS纤维。     

生物可降解聚丁二酸乙二醇酯的合成与降解性能研究

以丁二酸和乙二醇为原料,直接熔融聚合,合成了高相对分子量的聚丁二酸乙二醇酯(PES),用FTIR,1H-NMR表征其结构;考察了不同聚酯反应催化剂对其聚合反应的影响,结果表明:三氧化二锑的催化效果是最佳的。同时,利用酶降解和体外水解的方法,对聚合物降解性能进行研究,结果表明:PES是一种可生物降解的聚合物,且在体外具有一定的降解性。     

Effects of polymer concentration and zone drawing on the structure and properties of biodegradable poly(butylene succinate) film

To produce various biodegradable poly(butylene succinate) (PBS) films for particular use, the effects of initial polymer concentration and zone drawing on the structure, physical properties, and hydrolytic degradation of PBS film were investigated. PBS films were prepared from chloroform solutions with different initial concentrations of 8, 11, 14, 17 and 20 g/dl. In order to investigate the drawing behavior of the PBS films with different solution concentrations, the films were drawn under various zone drawing conditions. Through a series of experiments, it turned out that the initial concentration of PBS solution in chloroform caused significant changes in the draw ratio of the PBS film. That is, the zone draw ratios of the film at initial concentration of 14 g/dl exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was concluded that the initial concentration of 14 g/dl is the optimum polymer concentration to produce maximum draw ratio in this work. In addition, the crystal and amorphous orientations and tensile properties of PBS film having similar draw ratio and similar crystallinity were highest at 14 g/dl and surface crystal morphologies of these films were absolutely different. The hydrolytic degradation rate of the film at 14 g/dl was lowest, but with similar draw ratio, film dimension, and crystallinity, indicating that the degradation behaviors were greatly affected by the initial polymer concentration, orientation, and crystal morphology.