全生物降解PBS的扩链改性研究

采用新型扩链剂2,2′-双(2-噁唑啉)(BOZ)对聚丁二酸丁二醇酯(PBS)进行扩链,研究了BOZ加入量、稳定剂加入量、时间、温度对扩链反应的影响。结果表明,选择最佳条件,扩链后的PBS的相对分子质量较未扩链PBS的相对分子质量大为增加,而且扩链PBS相对分子质量分布与未扩链PBS基本一致,说明PBS扩链后的线性度与起始PBS相同,没有支化或交联反应发生。     

Compositional analysis of biodegradable polyphosphoester copolymers using nmr spectroscopic methods

The chemical composition and quantitative molar ratios among all components of biodegradable polyphosphoester copolymers of DL ‐lactide and ethylphosphate were determined by a comprehensive set of NMR spectroscopic methods. The polyphosphoester copolymers studied were synthesized using condensation polymerization of oligomeric DL ‐lactide prepolymers and ethyl dichlorophosphate. Conclusive identification of the chemical shift patterns of all functional groups in the copolymers required additional NMR methods such as ³¹P‐NMR and two‐dimensional ¹H–¹H COSY NMR, in addition to the synthesis and comparative NMR analysis of model compounds possessing identical phosphoester linkages in the polyphosphoester copolymers. For the polymers synthesized using the bulk polycondensation process, ¹H–¹H COSY NMR analysis revealed the presence of a small amount of side products that were undetected by ¹H‐NMR alone. These side reactions most likely occurred between the pendant ethoxy group of the phosphoesters and the hydrogen chloride gas generated in the bulk polycondensation process. ³¹P‐NMR spectra of the copolymers revealed a consistent triple‐peak pattern characteristic of phosphoesters linked to a racemic mixture of D,L ‐lactides. These results offered new insight into the side reactions occurring in bulk polymerization of polyphosphoesters and provided a powerful tool of characterizing complex biodegradable polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4021–4031, 2003     

Kinetics of microwave‐assisted polymerization of ϵ‐caprolactone

The kinetics of polymerization of ?‐caprolactone (CL) in bulk was studied by irradiating with microwave of 350 W and frequency of 2.45 GHz with different cycle‐heating periods (30–50 s). The molecular weight distributions were determined as a function of reaction time by gel permeation chromatography. Because the temperature of the system continuously varied with reaction time, a model based on continuous distribution kinetics with time/temperature‐dependent rate coefficients was proposed. To quantify the effect of microwave on polymerization, experiments were conducted under thermal heating. The polymerization was also investigated with thermal and microwave heating in the presence of zinc catalyst. The activation energies determined from temperature‐dependent rate coefficients for pure thermal heating, thermally aided catalytic polymerization, and microwave‐aided catalytic polymerization were 24.3, 13.4, and 5.7 kcal/mol, respectively. This indicates that microwaves increase the polymerization rate by lowering the activation energy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1450–1456, 2004     

医用可生物降解聚氨酯材料研究进展

可生物降解聚氨酯材料具有良好的生物相容性、机械强度好、易加工等特点,在医学中应用十分广泛。本文综述了可生物降解聚氨酯材料在医学上的应用、研究进展并对聚氨酯的组织相容性、血液相容性及降解性能进行了讨论,展望了其在医学中的发展前景。     

Effect of coal filler on the properties of soy protein plastics

The influence of ultrafine coal filler (UFC) content on tensile properties, water absorption, and biodegradability of soy protein plastics were investigated. The addition of UFC in the soy protein plastics, with different content of glycerol as a plasticizer, was at different ratio varying from 10:0 to 6:4. Blend sheets of the soy protein composites were prepared by the compression molding processing. The results show that, with 23.08 wt % glycerol, the tensile strength and elongation at break for the soy protein sheet with coal filler (range from 5 to 30 parts) can be enhanced as compared with nonfilled soy protein plastics. Water resistance of the soy protein plastics improves with the increase in UFC content. The derivative thermogravimetry (DTG) curves indicate a double‐stage degradation process for defatted soy flour (SPF), while three‐stage degradation process for soy plastics and the soy protein composites. FT‐IR, XPS, and SEM were applied to study the interfacial interaction between coal macromolecules and soy protein molecules in UFC filled soy protein plastics. The results demonstrated that there is strong interfacial interaction in the soy protein plastics caused by the compression molding processing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3134–3143, 2006     

组织工程多孔支架制备技术进展

综述了天然或合成生物降解材料为原料的组织工程多孔支架的几种制备方法，包括无纺织物／纤维粘结法、溶液浇铸／粒子洗出法、相分离／冻干法、气体成孔法和三维“印刷”等方法。特别评述了近期组织工程多孔支架研究进展及其在骨、软骨和皮肤等组织修复中的应用。     

Ways of strengthening biodegradable soy‐dreg plastics

Biodegradable plastics (GSD) based on soy dreg (SD) were prepared by compression‐molding, with glycerol as the plasticizer and glutaraldehyde (GA) as the cross‐linker. The structure and properties of the GSD sheets were investigated by Fourier‐transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), scanning electron microscope (SEM), and tensile test methods. The results indicate that when GA content was 6.8%, the tensile strength (σ_b) of the sheet reached the maximum value of 14.5 MPa. Moreover, the strength and water resistance of the sheets coated with castor‐oil‐based polyurethane/nitrochitosan interpenetrating network (IPN) coating were significantly enhanced to 24.6 MPa in the dry state and 9.8 MPa in the wet state. Simultaneously, the test of biodegradability of the GSD sheet in a mineral salts medium containing microorganisms and agar proved that GSD could be fully biodegradable. This work has provided a novel way to utilize low‐cost SD to prepare biodegradable plastics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 422–427, 2003     

Enzymatic degradation of thermoresponsive poly(N‐isopropylacrylamide) grafted to carboxymethylcellulose copolymers

The enzymatic degradation of poly(N‐isopropyl acrylamide) (PNIPAM) grafted to carboxymethylcellulose (CMC) copolymers with a cellulasic preparation (Trichoderma viride) was studied. The enzymatic activity of the cellulasic preparation against CMC and the grafted copolymers was determined by the Petterson–Porath method, while their reduced viscosity variation in the presence of the same preparation was also followed. It has been shown that the enzymatic degradation behavior depends on the copolymer composition and the reaction temperature. Reducing sugars analysis showed that the experimental values for the grafted copolymers were higher than the calculated ones. At 50°C, the enzymatic reaction is completed in about 20 min for the copolymers, whereas for CMC it takes more than 40 min. It can be concluded that their enzymatic degradation is facilitated by the presence of the PNIPAM grafts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1383–1386, 2003     

聚乳酸的改性及应用进展

综述了近几年聚乳酸生物降解材料的改性进展。改性方法分为化学改性和物理改性。化学改性包括共聚、交联、表面修饰等，主要是通过改变聚合物大分子或表面结构改善其脆性、疏水性及降解速率等；物理改性主要是通过共混、增塑及纤维复合等方法实现对聚乳酸的改进。     

聚乳酸的直接合成研究(Ⅱ)

研究了以乳酸单体为原料的直接熔融缩聚的工艺条件,包括工艺路线、原料含水率、催化剂种类、温度及余压对合成的影响。结果表明:采用适当的工艺能通过熔融缩聚法制备出高分子质量的聚乳酸,且具有良好的生物降解性能。