聚(丁二酸丁二醇酯癸二酸丁二醇酯)的合成与表征

用熔融缩聚法合成了一系列聚(丁二酸丁二醇酯癸二酸丁二醇酯)的无规共聚物(PBSu-co-PBSe)。通过核磁共振(1H-NMR),差示扫描量热(DSC),热重分析(TGA),X射线衍射(XRD)和酶降解测试等方法表征了材料的结构与性能。XRD测试结果表明,共聚酯的晶体结构随着癸二酸含量的增加发生了改变,并产生了共结晶行为;DSC分析得出,随着PBSe组分在共聚酯中含量的增大,产物的熔点(Tm)由84.8℃降低至46.7℃,然后升高至55.9℃,玻璃化温度(Tg)单调降低至-58.7℃;TGA分析表明,癸二酸的引入提高了聚酯的热稳定性;酶降解测试得出产物具有良好的生物降解性,当PBSe占共聚酯含量的40%时,产物具有最快的降解速率。     

聚丁二酸丁二醇酯作为生物材料的应用及研究进展

聚丁二酸丁二醇酯(PBS)作为新型可降解的生物材料,可通过新型催化剂、表面改性、共聚及共混等方法,来调控生物降解速率、提升生物相容性,拓宽在生物材料领域的应用范围。目前,以PBS为基础的生物材料的研究主要集中在药物载体、组织工程支架两个方面,相关结果表明其有很好的实用效果,在进一步开发应用上有广泛市场前景。     

聚丁二酸丁二醇酯的研究进展

对聚丁二酸丁二醇酯(PBS)的合成、改性及应用进行了综述,讨论了合成过程中的影响因素以及合成工艺对材料性能的影响.     

聚(丁二酸丁二醇酯丁二酸环己烷二甲醇酯)的合成与表征

用熔融缩聚法合成了一系列聚(丁二酸丁二醇酯丁二酸环己烷二甲醇酯)的无规共聚物。用FT-IR,1H-NMR,DSC,TGA,XRD及水降解测试等方法表征了材料的结构与性能。通过DSC和TGA分析得到产物的熔点虽然较聚丁二酸丁二醇酯(PBS)有所降低,但是热分解温度却得到了提高;XRD测试结果表明,共聚物的晶体结构并没有发生改变;水降解测试结果表明,共聚物较PBS的降解速率有所提高。     

聚丁二酸丁二醇酯及聚丁二酸/己二酸-丁二醇酯在微生物作用下的降解行为

研究了聚丁二酸丁二醇酯(PBS)及其共聚物聚丁二酸/己二酸-丁二醇酯(PBSA)薄膜在可控堆肥条件下的宏观生物降解行为,结果显示,PBS和PBSA薄膜具有良好的生物降解性能,降解过程经历三个阶段:诱导期、加速期和平坦期。对堆肥中的微生物进行分离和筛选,发现杂色曲霉菌对PBS和PBSA的生物降解能力最强。进一步研究PBS和PBSA薄膜在杂色曲霉菌作用下的微观生物降解行为,结果表明,PBSA薄膜比PBS薄膜具有更快的生物降解速率。     

聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯的合成及性能

以4,4-二苯醚二甲酸(OBBA)、丁二酸(SA)和1,4-丁二醇(BDO)为原料,以钛酸四丁酯(TBOT)为催化剂,采用先酯化后缩聚的两步聚合法制备了一系列聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯(PBSO),研究了二元酸单体SA与OBBA的摩尔比(10∶0、9∶1、7∶3、5∶5、3∶7、1∶9、0∶10)对聚酯的结构、热性能、流变性能和力学性能的影响。红外光谱和核磁共振氢谱分析表明成功地制备了脂肪族-芳香族共聚酯,M_w在22070～43530之间,多分散性指数(PDI)在2.0左右。差示扫描量热分析和X射线衍射结果表明PBS和PBSO(9∶1)为结晶聚合物,结晶度分别为43%和24%,其它共聚酯均为无定形聚合物。随着共聚酯中OBBA单体含量的增加,共聚酯的T_g逐渐升高。热重分析结果表明共聚酯初始分解温度均高于275℃。流变性能分析表明,共聚酯均属于典型的假塑性流体,其中,PBSO(5∶5)的黏度对剪切具有较高的敏感性。拉伸测试结果表明,随着OBBA单体含量增加,聚酯拉伸强度先下降后上升,断裂伸长率先增加后降低。其中,PBSO(5∶5)的拉伸强度为1.2 MPa,断裂伸长率最大为1523.2%,表现出良好的韧性,且循环拉伸测试表明PBSO(5∶5)的拉伸永久变形在10～30℃内对温度具有敏感性。     

β-环糊精与聚丁二酸丁二醇酯(PBS)包合物对PBS结晶性的影响

与不同传统成核剂进行比较,研究了β-环糊精(β-CD)与聚丁二酸丁二醇酯(PBS)包合物存在时PBS的结晶行为。采用偏光显微镜观察了复合物球晶形态的变化,采用差示扫描量热法(DSC)和X射线衍射法(WAXD)研究了不同成核剂对PBS结晶性的影响,并且研究了成核剂改性后PBS复合物的力学性能和亲/疏水性。研究结果表明,β-CD与PBS包合物(PBSIC)与PBS复合后,球晶变化不明显,其球晶直径为150μm。PBSIC可以显著提高PBS的结晶能力,其结晶温度、结晶度较纯PBS分别提高3.86℃、6.45%,结晶速度明显增加,力学性能有所改善,并具有与传统聚酯类成核剂相当的成核能力。     

聚丁二酸丁二醇酯和聚辛二酸丁二醇酯及聚(丁二酸-co-辛二酸丁二醇)共聚酯的酶促降解

以1,4-丁二醇与不同链长二元酸单体为原料,合成了聚丁二酸丁二醇酯（PBS）和聚辛二酸丁二醇酯（PBSub）2种均聚酯和4种不同比例聚(丁二酸-co-辛二酸丁二醇)共聚酯。以上述6种聚酯为降解底物,利用角质酶对其进行降解研究。通过衰减全反射傅里叶变换红外光谱、核磁共振波谱仪、差示扫描量热仪、X射线衍射仪和热重分析仪等对聚酯及其降解产物进行表征分析。6种聚酯的晶体结构、熔点、结晶度和热稳定性变化不大。研究表明,聚酯的结晶度和熔点温度是影响其酶降解的重要因素。角质酶降解共聚酯的结晶区和非结晶区,但优先降解非结晶区。丁二酸/辛二酸投料摩尔比为4/6和6/4的降解效果最好,但摩尔比为6/4的样品熔点较高,为最佳比例。     

聚(丁二酸丁二醇-co-二聚酸丁二醇)酯的合成及等温结晶行为

以1,4-丁二醇(BDO)、丁二酸(SA)和二聚酸(DA)为原料,采用先酯化后缩聚的两步法合成一系列聚(丁二酸丁二醇-co-二聚酸丁二醇)酯(PBSBDA)。采用核磁共振谱仪、凝胶渗透色谱仪、X射线衍射仪、热台偏光显微镜、差示扫描量热仪等分析聚酯结构组成及结晶行为。研究发现,聚丁二酸丁二醇酯(PBS)与PBSBDA同为单斜α晶系,无晶型变化;球晶形貌呈环带状,球晶形态随化学结构和结晶温度改变。利用Avrami方程分析聚酯等温结晶动力学,结果表明Avrami指数(n)均在2.2~2.8之间,聚酯主要表现为异相成核的三维球晶生长,DA单体的引入没有改变其成核方式和生长方式。聚酯的熔融-重结晶行为使其在等温结晶后的升温过程中呈现熔融双峰。     

聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯/聚对苯二甲酸丁二醇酯复合材料的制备及性能

聚对苯二甲酸丁二醇酯(PBT)是半结晶热塑性聚合物,具有出色的尺寸稳定性、高的刚度和硬度、良好的耐化学性、力学性能和可加工性等优良特点。但其抗冲击性较低、韧性较差。采用将PBT与具有优异韧性的聚(丁二酸丁二醇-co-二苯醚二甲酸丁二醇)酯(PBSO)进行熔融共混以改善PBT的韧性。首先以二苯醚二甲酸(OBBA)、丁二酸(SA)和丁二醇(BDO)为单体,以钛酸四丁酯为催化剂,采用先酯化后缩聚的两步法合成了PBSO。然后将不同质量比的PBSO与PBT进行熔融挤出共混,研究复合材料的力学韧性、PBSO与PBT的相容性、结晶行为、热稳定性以及流变性能等。FT-IR、1H NMR、GPC测试分析了所合成PBSO的结构。力学性能测试表明,20wt%PBSO/PBT复合材料的拉伸强度为40.3 MPa,断裂伸长率达到82.1%,断裂能增加到24.7 MPa,冲击强度达到较大值23.2 kJ/m²,具有较高的拉伸强度和良好的韧性。动态热机械分析(DMA)和SEM结果发现,PBSO对PBT具有增容效果,PBSO/PBT是部分相容共混体系。差示扫描量热(DSC)和广角X射线衍射(WA...     

生物质基降解塑料PBS的研制

以玉米和小麦秸秆为原料,通过粉碎、闪蒸等化学和物理处理和加工,并进行初步糖化,使其可作为微生物可发酵的糖源。以新的琥珀酸产生菌株-产琥珀酸放线杆菌及重组微生物作为发酵的微生物菌株对生物质基糖源进行厌氧发酵,在液体深层厌氧培养条件下制备琥珀酸。通过正交实验研究了发酵液中葡萄糖、酵母膏、磷酸盐、尿素、K+、Mg2+、Mn2+等因素对琥珀色产量的影响。通过离子色谱柱脱色,分离得到纯度为95%以上琥珀酸,秸秆转化率达到75%。利用生物法制备的琥珀酸在Sn-Ti系纳米催化剂作用下通过一步法合成了重均分子量超过20万降解塑料聚(琥珀酸丁二醇酯)。     

Mechanical properties of poly(butylene succinate) (PBS) biocomposites reinforced with surface modified jute fibre

A biocomposite was originally fabricated with biodegradable polymer PBS and jute fibre, and the effects of fibre surface modification on characteristics of jute fibre and mechanical properties of the biocomposite were evaluated in this paper. The experimental results show that surface modification can remove surface impurities and reduce diameter of jute fibres. Regarding the mechanical properties of biocomposites, it is observed that the biocomposites with jute fibres treated by 2% NaOH, 2 + 5% NaOH or coupling agent, respectively, an optimum in mechanical properties can obtain at fibre content of 20 wt.%, which exhibit an obvious enhancement in mechanical strength and modulus compared to the ones with untreated jute fibre. Furthermore, surface modification also exhibits less effects on flexural properties compared to tensile properties and more on flexural or tensile modulus than on the strength.     

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

Multiblock copolyester (PBS-b-PES) containing poly(butylene succinate) (PBS) and poly(ethylene succinate) (PES) was successfully synthesized by chain-extension of dihydroxyl terminated PBS (HO-PBS-OH) and PES (HO-PES-OH) using 1,6-hexmethylene diisocyanate (HDI) as a chain extender. The chemical structures, molecular weights, crystallization behaviors, thermal and mechanical properties of the copolyesters were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), wide-angle X-ray diffraction (WAXD), tensile testing and hydrolytic degradation. High-molecular-weight copolyesters with M_w more than 2.0 × 10⁵ g mol⁻¹ were easily obtained through chain-extension. The copolyesters showed a single glass transition temperature (T_g) which increased with PES content. The melting point temperature (T_m) and relative degree of crystallinity (X_c) of the copolyesters decreased first and then increased with PES content. The copolyesters manifested excellent mechanical properties, for example, PBS₅-b-PES₅ had fracture stress of 61.8 MPa and fracture strain of 1173%. The chain-extension reaction provided a very effective way to produce high molecular weight multiblock copolyesters.     

高分子量聚丁二酸丁二醇酯的制备及性能研究

以1,4-丁二醇和丁二酸为原料,通过加入少量的扩链剂,利用直接缩聚法在短时间内合成了高分子量的聚丁二酸丁二醇酯(PBS).采用GPC、DSC以及TGA等方法对产物进行了表征,同时研究了扩链剂的加入对聚合物性能的影响.结果表明,当扩链剂加入量为PBS预聚物的2.5％时,扩链产物的性能最佳,重均分子量由3万上升到17万,拉...     

Thermal and thermomechanical properties of poly(butylene succinate) nanocomposites

This article describes the thermal and thermomechanical properties of poly(butylene succinate) (PBS) and its nanocomposites. PBS nanocomposites with three different weight ratios of organically modified synthetic fluorine mica (OMSFM) have been prepared by melt-mixing in a batch mixer at 140 degrees C. The structure and morphology of the nanocomposites were characterized by X-ray diffraction (XRD) analyses and transmission electron microscopy (TEM) observations that reveal the homogeneous dispersion of the intercalated silicate layers into the PBS matrix. The thermal properties of pure PBS and the nanocomposite samples were studied by both conventional and temperature modulated differential scanning calorimetry (DSC) analyses, which show multiple melting behavior of the PBS matrix. The investigation of the thermomechanical properties was performed by dynamic mechanical analysis. Results reveal significant improvement in the storage modulus of neat PBS upon addition of OMSFM. The tensile modulus of neat PBS is also increased substantially with the addition of OMSFM, however, the strength at yield and elongation at break of neat PBS systematically decreases with the loading of OMSFM. The thermal stability of the nanocomposites compared to that of the pure polymer sample was examined under both pyrolytic and thermo-oxidative environments. It is shown that the thermal stability of PBS is increased moderately in the presence of 3 wt% of OMSFM, but there is no significant effect on further silicate loading in the oxidative environment. In the nitrogen environment, however, the thermal stability systematically decreases with increasing clay loading.     

PBS合成用催化剂的研究概况

选择良好的催化剂对聚丁二酸丁二醇酯(PBS)的合成至关重要.对PBS的各种催化剂进行了归纳和总结,并重点介绍了催化机理,为PBS的催化合成提供了重要的参考.     

Ductility of polylactide composites reinforced with poly(butylene succinate) nanofibers

Sustainable “green nanocomposites” of polylactide (PLA) and poly(1,4-butylene succinate) (PBS) were obtained by slit die extrusion at low temperature. Dispersed PBS inclusions were sheared and longitudinally deformed with simultaneous cooling in a slot capillary and PBS nanofibers were formed. Shearing of PBS increases nonisothermal crystallization temperature by 30 °C. Tensile deformation was investigated by in-situ experiments in SEM chamber. Dominant deformation mechanism of PLA is crazing, however, there are dormant shear bands formed during slit die extrusion. Pre-existing shear bands are inactive in tensile deformation but contribute to ductility by blocking, initiating and diffusing typical craze growth. PBS nanofibers are spanning PLA craze surfaces and bridging craze gaps when PLA nanofibrils broke at large strain. Straight crazes become undulated because either dormant or new shear bands become activated between crazes. Due to interaction of crazes and shear bands the ductility increases while high strength and stiffness are retained.     

聚丁二酸丁二醇酯/水滑石纳米复合材料的制备及性能研究

采用双螺杆挤出机制备了聚丁二酸丁二醇酯/水滑石(PBS/HT)纳米复合材料,并详细研究了复合材料的形貌及分散、结晶和熔融行为,晶体结构和球晶形态以及力学性能。采用SEM、TEM、DSC、XRD、POM和DMA进行了表征测试,结果表明层状水滑石纳米粒子较好地分散在PBS基体中,加入HT具有明显的异相成核能力,显著地提高了PBS的结晶温度。偏光显微镜结果显示,随着HT加入量的增加PBS球晶密度增加,球晶尺寸细化。HT添加量为1%(质量分数)时复合材料的拉伸强度增大,随着HT加入量增加断裂伸长率下降而弹性模量增加。动态机械测试表明复合材料的储能模量显著提高。     

微晶纤维素/聚丁二酸丁二醇酯复合材料的流变行为

采用熔融共混法制备了微晶纤维素/聚丁二酸丁二醇酯(MCC/PBS)复合材料,用高级毛细管流变仪和旋转流变仪分别测定复合材料的稳态流变性能和动态流变性能,研究了不同MCC含量、不同温度对复合材料流变行为的影响。结果表明,复合材料的黏度与剪切速率的流变曲线符合幂律流体的特征,可以用幂律模型对其进行拟合;复合材料的黏度与温度的关系可用Arrhenius方程对其进行描述。在线性黏弹区,复合材料的储能模量(G′)维持恒定,当应变(γ)超过临界值(γ_c)时,复合材料进入非线性黏弹区,出现了"Payne"效应,并且随着MCC含量的增加,γ_c下降。在角频率(ω)扫描范围内,复合材料的储能模量(G′)、损耗模量(G″)和复数黏度|η*|均随着MCC含量的增加而增大。在相同的MCC含量下,G″的值始终大于G′的值,损耗因子(tanδ)均大于1。在低频区,G′出现第二平台。MCC/PBS复合材料加工流变特性的研究,对指导MCC/PBS复合材料的成型加工具有一定的价值。     

New application of poly(butylene succinate) (PBS) based ionomer as biopolymer: a role of ion group for hydroxyapatite (HAp) crystal formation

Sodium sulfonate ionic group bearing PBS ionomer (PBSi) and hydroxyapatite (HAp) composites were prepared by soaking in the simulated body fluid (SBF) solution, which is the biomimetic method, as well as the effects of the ionic group on the HAp crystal formation and growth were investigated. The introduced sodium sulfonate ionic groups operated as the functional groups with negative charge densities, which can bind plentiful Ca²⁺ ions efficiently, consequently serving as active sites allowing HAp crystals to grow on the surfaces of the PBSi matrix. By SEM analysis, it was observed that HAp became growing as the shape with the porous holes. These holes are thought to be very suitable for the ingrowths of the surrounding tissue and the assistance to the bone formation. Based on this finding, it can be clearly concluded that the ionic groups in the PBSi may be decisive factors in growing HAp, and it is anticipated that this novel materials can contribute to excellent biopolymer.