微波加热和常规加热下功能化离子液体催化合成丁二酸二辛酯

分别在微波辐射和常规加热下,以具有丙烷磺酸基功能基团的离子液体为催化剂催化丁二酸和正辛醇 合成丁二酸二辛酯,考察了其阴、阳离子对催化剂活性的影响.相比常规加热,微波加热提高了反应效率,缩短了反应时间.以[ PyPS]HSO4为催化剂,研究了催化剂用量、醇酸比和反应时间对酯化率的影响.结果表明:当催化剂用量为丁二酸的3wt％,酸醇比(丁二酸∶正辛醇)1∶4,反应温度150℃,反应时间15 min,功率400W时,酯化率达到95.74％.此外,微波辐射下[PyPS]HSO4催化剂重复使用6次后活性没有明显降低,酯化率仍有93.58％.     

聚碳酸1,2-丙二酯/聚琥珀酸丁二酯/邻苯二甲酸二烯丙酯共混体系的研究

采用熔融共混的方法制备了聚碳酸1,2-丙二酯(PPC)/聚琥珀酸丁二酯(PBS)共混物和PPC/PBS/DAOP(邻苯二甲酸二烯丙酯)增塑共混物,对共混物的相容性、热性能、结晶性和物理机械性能进行了初步研究.研究结果表明PPC/PBS共混物为不相容体系,PPC对PBS的结晶度影响很小;PBS的加入提高了共混物的起始热分解温度(Td-5%),当共混物中PBS含量从10%增加到90%时,共混物的Td-5%可分别增加15℃到59℃.DAOP对PPC/PBS共混物有增塑作用,当PPC/PBS/DAOP的比例从30/70/0变化到30/70/30时,共混物玻璃化转变温度(Tg)下降了36.9℃.与PPC/PBS共混物相比,组成优化的DAOP增塑共混物PPC/PBS/DAOP(PPC/PBS/DAOP=30/70/5)的断裂伸长率和断裂能最大可提高31倍和34倍,分别达到655.1%和3.4 J/mm2,因此引入DAOP尽管使共混材料的热稳定性有所下降,但拓宽了PPC/PBS共混材料的使用温度窗口.     

Development of poly(butylene succinate)/calcium phosphate composites for bone engineering

Bone tissue engineering offers the prospect of alternative therapies for clinically relevant skeletal defects. Poly(butylene succinate) (PBSu) is a biodegradable and biocompatible polyester which possesses some unfavorable biomaterial properties. In order to improve this limitation, we developed PBSu/hydroxyapatite (HA) and PBSu/β-tricalcium phosphate (TCP) composites to support the growth and osteogenic differentiation of human mesenchymal stem cells (hMSCs). The results showed that phase separation morphology of the composites were detected in both PBSu/HA and PBSu/TCP films where calcium phosphate (HA and TCP) dispersed thoroughly into PBSu. The addition of either HA or TCP increased the hydrophilicity of the resulting composites. All the materials appeared to be biocompatible and supported in vitro growth and osteoblast differentiation of hMSCs. In conclusion, the currently developed composite materials possess good biocompatibility and allow the growth and osteogenic differentiation of hMSCs in vitro, suggesting their potential application in stem cell-based bone engineering.     

Enhanced nonisothermal crystallization of a series of poly(butylene succinate‐co‐terephthalate) biopolyesters by poly(vinyl butyral)

Enhanced nonisothermal crystallization of a series of poly(butylene succinate‐co‐terephthalate) (PBST) by poly(vinyl butyral) (PVB) as a macromolecular nucleating agent has been examined systematically with various techniques and theoretical modeling. The role of PVB depends strongly on the butylene terephthalate content, PVB content, and cooling rate. The (0.3–0.7 wt %) PVB reduces the spherulitic size, but considerably increases the peak temperature of crystallization, for example, by 28 °C for the PBST with 50 mol % terephthalic acid. The effects of PVB are believed to stem from its unique molecular structure. Both the hydroxyl and butyral groups of PVB may synergistically participate in nucleating PBSTs for crystallization because of favorable secondary interaction and affinity of butyral groups with butylene succinate units of PBSTs. Only the Tobin model suffices to describe the nonisothermal crystallization kinetics, while the modified Avrami model is suitable for limited crystallinity. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 658–672     

Morphology and properties of nanostructured materials based on polypropylene/poly(butylene succinate) blend and organoclay

Nanostructured materials based on organically modified montmorillonite (OMMT) and polypropylene (PP)/poly(butylene succinate) (PBS) blend were prepared via melt-mixing of PP, PBS, and OMMT in a batch mixer. The weight ratio of PP and PBS was 70:30, and the OMMT loading varied from 0.5 to 5 wt%. The surface morphologies of unmodified and OMMT-modified blend were studied by field-emission scanning electron microscopy. Results showed that the particle size of the dispersed PBS phase was significantly reduced with the addition of a small amount of OMMT (1.5 wt%). Upon the addition of 5 wt% of OMMT, the domain size of the dispersed PBS phase changed significantly from the unmodified blend, and a homogeneous dispersion of very fine particles of PBS was observed. The degree of dispersion of silicate layers in the blend matrix was characterized by X-ray diffraction and transmission electron microscopy. The improved adhesion between the phases and the fine morphology of the dispersed phase contributed to the significant improvement in the properties and thermal stability of the final nanocomposite materials. On the basis of these results, we describe a general understanding of how the morphology is related to the final properties of OMMT-incorporated PP/PBS blend.     

Biocomposites based on poly(butylene succinate) and curaua: Mechanical and morphological properties

Biocomposites based on poly(butylene succinate) (PBS) and curaua fibers have been produced by compression molding, and investigated as a function of fiber length and amount. Mechanical tests, water uptake and morphology studies were carried out in order to assess the composite features according to the characteristics of the reinforcing agents. It turns out that the impact and flexural strengths increase with fiber content. Moreover, the fiber length, varying from 1 to 4 cm for the composite reinforced with 20 wt% of fiber, influences impact strength, which is higher for shorter than for longer fibers. However, flexural strength is not greatly influenced by the length of the fibers. Water uptake studies reveal a higher sensitivity of the material to fiber content rather than fiber size. Biocomposites, which are characterized by enhanced mechanical properties as compared to PBS, can have different applications, for example in rigid packaging or interior car parts.     

The crystallization behavior of biodegradable poly(butylene succinate) in the presence of organically modified clay with a wide range of loadings

The crystallization behavior of poly(butylene succinate)(PBS) nanocomposites with a wide range of contents of clays was revealed. It was of interest to find that the crystallization rate of PBS was accelerated obviously at relatively low contents of clays; while a retarded crystallization kinetics and a decreased crystallinity of PBS were found in the nanocomposites with higher clay contents. Two interplaying effects existed in the nanocomposites, i.e., a suppression effect of clays on nucleation and a templating effect of clays on crystal growth, were clarified to contribute to this intriguing crystallization behavior.     

Morphology and thermal properties of poly(L‐lactide)/poly(butylene succinate‐co‐butylene adipate) compounded with twice functionalized clay

Poly(L ‐lactide) (PLLA)/poly(butylene succinate‐co‐butylene adipate) (PBSA) blends were compounded with Cloisite 25A® (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Twice Functionalized Organoclay (TFC). Variation of morphology and properties of PLLA/PBSA/C25A composites was investigated before and after the treatment with GPS. The morphological structure of the composites was analyzed by using X‐ray diffractometry (XRD) and transmission electron microscopy (TEM). The silicate layers of PLLA/PBSA/TFC were exfoliated to a larger extent than PLLA/PBSA/C25A. Incorporation of the epoxy groups on C25A improved significantly elongation at break as well as tensile modulus and tensile strength of PLLA/PBSA/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PBSA/TFC as compared with that in PLLA/PBSA/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that both T_5%, which was the temperature corresponding to 5% weight loss, and activation energy of thermal decomposition of PLLA/PBSA/TFC were far superior to those of PLLA/PBSA/C25A as well as to those of PLLA/PBSA, indicating that the composites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 478–487, 2005     

Multiple melting behavior of poly(butylene succinate). I. Thermal analysis of melt‐crystallized samples

The multiple melting behavior of poly(butylene succinate) (PBSu) was studied with differential scanning calorimetry (DSC). Three different PBSu resins, with molecular weights of 1.1 × 10⁵, 1.8 × 10⁵, and 2.5 × 10⁵, were cooled from the melt (150 °C) at various cooling rates (CRs) ranging from 0.2 to 50 K min^?1. The peak crystallization temperature (T_c) of the DSC curve in the cooling process decreased almost linearly with the logarithm of the CR. DSC melting curves for the melt‐crystallized samples were obtained at 10 K min^?1. Double endothermic peaks, a high‐temperature peak H and a low‐temperature peak L, and an exothermic peak located between them appeared. Peak L decreased with increasing CR, whereas peak H increased. An endothermic shoulder peak appeared at the lower temperature of peak H. The CR dependence of the peak melting temperatures [T_m(L) and T_m(H)], recrystallization temperature (T_re), and heat of fusion (ΔH) was obtained. Their fitting curves were obtained as functions of log(CR). T_m(L), T_re, and ΔH decreased almost linearly with log(CR), whereas T_m(H) was almost constant. Peak H decreased with the molecular weight, whereas peak L increased. It was suggested that the rate of the recrystallization decreased with the molecular weight. T_m(L), T_m(H), T_re, and T_c for the lowest molecular weight sample were lower than those for the others. In contrast, ΔH for the highest molecular weight sample was lower than that for the others. If the molecular weight dependence of the melting temperature for PBSu is similar to that for polyethylene, the results for the molecular weight dependence of PBSu can be explained. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2411–2420, 2002     

Shape memory effects of poly(ethylene terephthalate-co-ethylene succinate) random copolymers

Random copolymers based on terephthalate acid, succinic acid and ethylene glycol, with thermally induced shape memory, were synthesized via melt polycondensation. The chemical structures of these poly(ethylene terephthalate-co-ethylene succinate) copolymers (PET-co-ES) were ascertained by ¹H NMR spectroscopy. The thermal and viscoelastic characteristics of these copolymers were studied in terms of the succinic acid content using differential scanning calorimetry and dynamic mechanical analysis. The shape memory effects of the copolymers were examined using the strain test. The experimental results suggested that all copolymers exhibited shape memory above the glass transition temperature and that the highest shape recovery rate was 90%. The shape recovery rates of all test samples declined with the number of cycles. This decrease in the shape recovery rate may result from the change in the degree of polymer orientation and/or crystallinity during repeated testing.