脂肪族聚酯的合成及降解性能研究

通过熔融和溶液结合法合成了脂肪族聚酯—聚丁二酸丁二醇酯(PBS)、丁二酸丁二醇酯-己二酸丁二醇酯共聚物(P(BS-co-BA))和丁二酸丁二醇酯-癸二酸丁二醇酯共聚物(P(BS-co-BSe)),并对其进行了生物降解实验。采用GPC测定了脂肪族聚酯的分子量及其分布,并采用熔点仪测定了聚酯的熔点。得到脂肪族聚酯分子量、熔点以及分子结构对称性和降解之间的关系。     

脂肪族聚酯降解材料的研究进展

本文对脂肪族聚酯类生物降解材料聚乳酸(PLA)、聚己内酯(PCL)、聚羟基烷酸酯(PHAs)、聚丁二酸丁二醇酯(PBS)等进行了简单的综述,简要地介绍了其主要应用领域及存在的主要问题。     

溶液与熔融相结合合成脂肪族聚酯

采用溶液与熔融结合法合成了聚丁二酸丁二醇酯(PBS)、聚己二酸丁二醇酯(PBA)、聚癸二酸丁二醇酯(PBSe).采用1H NMR对聚合物结构进行表征,采用凝胶渗透色谱、热重分析和万能实验机测定PBS的相对分子质量及分布、热稳定性和力学性能.实验结果表明:聚酯的数均分子量都在5万以上,热分解起始温度均在300℃以上,断裂伸长率都大于300%,其中PBA更是超过了400%;结构对称性是熔点和生物降解性的主要影响因素,碳链的长短是热分解的主要影响因素.     

一种脂肪-芳香族共聚酯的降解性能

以1,4-丁二醇、己二酸和对苯二甲酸二甲酯为原料,采用稀土催化剂,合成了不同组成的聚己二酸丁二酯和对苯二甲酸丁二酯的共聚酯。采用堆肥法,以堆肥过程中试样的失重率、单位面积失重和相对分子质量变化作为指标,考察了芳香组分摩尔分数为40%～60%共聚酯的生物降解性,利用核磁共振氢谱测试了降解前后共聚酯组成和序列结构的变化,简述了生物降解行为的作用方式。结果表明:通过在脂肪族聚酯中引入摩尔分数为40%～60%的芳香组分,所制共聚酯既具有优异的力学性能,又具有生物降解性;且随着所含芳香组分的增多,共聚酯的生物降解性变差,降解后试样的对苯二甲酸丁二酯组分增加且芳香链段的长度增加。     

聚丁二酸丁二醇酯(PBS)在不同pH条件下的降解

对聚丁二酸丁二醇酯(PBS)薄膜在不同pH值水溶液中的降解进行对比研究.用失重率及薄膜表面形貌观察等时降解结果进行表征,结果表明:PBS薄膜在不同pH值水溶液中的降解速度为:碱性溶液>酸性溶液>中性溶液.降解过程中不同降解溶液的pH值均有一定程度的下降.     

可生物降解聚酯复合材料吹膜湿热老化性能研究

采用GB/T12000—2003方法,在温度50℃和相对湿度95%条件下利用恒温恒湿箱对聚丁二酸己二酸丁二酯与聚乳酸共混改性材料的吹塑薄膜进行检测,研究了湿热老化时间对力学性能与热封性能变化的影响,总结了简单水解降解和酶解降解反应在PBSA/PLA体系薄膜降解过程中的作用过程。     

线性PBS基脂肪族聚酯的合成和降解研究

为了探讨线性PBS基脂肪族共聚酯的结构和降解之间的关系,首先合成了线性PBS基脂肪族共聚酯,即聚丁二酸丁二醇酯-共-聚己二酸丁二醇酯P(BS-co-BA),聚丁二酸丁二醇酯-共-癸二酸丁二醇酯P(BS-co-BSe),并将线性PBS基脂肪族共聚酯及PBS在土壤悬浮液中进行降解,通过GPC、熔点测定仪对线性PBS基脂肪族共聚酯的分子量和熔点进行了测定;通过测定降解过程中失重率和降解前后聚酯薄膜表面形貌来对共聚酯降解程度进行表征。结果表明:随着二元酸碳链的增长,分子对称性降低,降解性能增大。通过观察分子量,熔点及降解失重率的测定结果,得出分子量越大,降解越不容易进行;熔点越小,降解性能越好。     

可生物降解脂肪族-芳香族共聚酯的研究进展

介绍了脂肪-芳香族共聚酯(CPEs)的合成及其生物降解机理,综述了影响CPEs生物降解的三大因素,分别为化学结构、形态结构、分子量及其分布。并阐述了脂肪-芳香族共聚酯(CPEs)的开发与应用。     

生物降解脂肪族聚酯合成技术进展

介绍了生物降解脂肪族聚酯的合成方法,重点讨论了聚羟基脂肪酸酯、聚乳酸的合成工艺路线、工艺条件和聚合机理,指出生物降解脂肪族聚酯具有广阔的发展前景。     

脂肪族聚酯可降解材料的研究进展

综述了脂肪族聚酯的合成方式,介绍了脂肪族聚酯的亲水改性和共聚改性,并对脂肪族聚酯的发展方向进行了展望。     

Performance and biodegradability of a maleated polyester bioplastic/recycled sugarcane bagasse system

The biodegradability, morphology, and mechanical properties of composite materials made of poly(butylene succinate adipate) (PBSA) and sugarcane bagasse (SCB) were evaluated. Composites containing maleic anhydride (MA)‐grafted PBSA (PBSA‐g‐MA/SCB) exhibited noticeably superior mechanical properties because of greater compatibility between the two components. The dispersion of SCB in the PBSA‐g‐MA matrix was highly homogeneous as a result of ester formation between the carboxyl groups of PBSA‐g‐MA and hydroxyl groups in SCB and the consequent creation of branched and crosslinked macromolecules. Each composite was subjected to biodegradation tests in a Rhizopus oryzae compost. Morphological observations indicated severe disruption of film structure after 60 days of incubation, and both the PBSA and the PBSA‐g‐MA/SCB composite films were eventually completely degraded. The PBSA‐g‐MA/SCB films were more biodegradable than those made of PBSA and exhibited a higher intrinsic viscosity, implying a strong connection between these characteristics and biodegradability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of evolved interactions in poly(butylene succinate)/fumed silica biodegradable in situ prepared nanocomposites on molecular weight,material properties,and biodegradability

Poly(butylene succinate) (PBSu)/fumed silica nanocomposites were prepared in situ by condensation polymerization. TEM micrographs verified that the dispersion of the nanoparticles was homogeneous in the PBSu matrix, while some small agglomerates were also formed at a higher SiO₂ content. ¹³C NMR spectra affirmed that the hydroxyl end groups of PBSu could form covalent bonds with the surface silanol groups of SiO₂. These interactions affected the molecular weight of the prepared nanocomposites. At low concentrations the SiO₂ nanoparticles acted as chain extenders, increasing the molecular weight of PBSu, while at higher loadings they resulted in extended branching and crosslinking reactions, leading to gradually decreased molecular weights. Silica nanoparticles acted as nucleating agents, increasing the crystallization rate of PBSu. However, the degree of crystallinity was slightly reduced. Tensile strength and Young's modulus were significantly increased with increasing SiO₂ content. The presence of the nanoparticles resulted in reduced enzymatic hydrolysis rates compared to pure PBSu, attributed to the smaller available organic surface, due to the incorporation of SiO₂, and to the existence of branched and crosslinked macromolecules. Dynamic mechanical and rheological properties were also extensively studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Foaming of aliphatic polyester using chemical blowing agent

Poly(butylene adipate‐co‐succinate) (PBAS), a saturated aliphatic polyester cured by dicumyl peroxide (DCP), was prepared and the viscoelastic property was investigated. The viscosity of crosslinked PBAS increased, and it exhibited rubbery behavior as the content of curing agent was increased. The results suggested that the viscosity and elasticity of PBAS could be regulated by adding a small amount of DCP; hence, the processibility could be improved. Prior to foaming, a proper formulation of blowing agent (blowing agent/urea activator = 100:8 phr) was examined to prepare expanded PBAS foam. Low‐density PBAS expanded foams were prepared using a chemical blowing agent and DCP. The effect of the foaming temperature, additive content, and curing agent content on the blowing ratio and morphology of expanded PBAS foams was investigated. A closed‐cell structure PBAS foam of high blowing ratio (density about 0.05 g/cm³) could be obtained by adding 3 phr DCP. To manufacture expanded PBAS foam under 0.1 g/cm³ using a chemical blowing agent, the storage modulus of the matrix polymer should exceed the loss modulus by enough to stabilize growing bubbles. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2443–2454, 2001     

吹膜级PBS/PLA复合材料的制备与性能研究

利用熔融共混法制备了综合性能优良的吹膜级聚丁二酸丁二酯/聚乳酸(PBS/PLA)复合材料,并通过万能试验机、差示扫描量热分析仪、热重分析仪、透气透湿分析仪分别测试了PBS/PLA复合材料及其薄膜的力学性能、热性能、阻隔性能。结果表明,制备的PBS/PLA复合材料较纯PBS树脂具有更好的刚性,且所吹塑的薄膜与包装用低密度聚乙烯膜各项性能相当。     

PLA/PBAT共混物的降解性能研究

通过双螺杆挤出机和吹膜机组制备不同比例的聚乳酸/聚对苯二甲酸己二酸丁二酯（PLA/PBAT）共混物薄膜,测量共混物的热性能、力学性能,并观察其相形貌,计算共混物在堆肥条件下的生物降解率,研究共混物降解前后的结构、热力学行为和元素的变化。结果表明,PLA与PBAT是不相容体系,加入PBAT后PLA的韧性得到改善;PLA的生物降解率高于PBAT,共混物的生物降解率随着PBAT含量的增加而降低,且在降解初期,PLA的降解产物会促进PBAT的水解;PLA、PBAT及其共混物在堆肥降解前期只是大分子链水解为小分子链的过程,不发生分子链的结构变化;PLA及PBAT的降解会先发生在无定形区,共混物中PLA在无定形区的降解速度受到PBAT的影响而变慢,且共混物中PLA、PBAT的降解行为发生变化,无定形区与结晶区的降解同时发生;共混物在堆肥试验初期的降解以水解为主。     

Effect of orientation on the biodegradability of uniaxially stretched aliphatic copolyester films

The effects of uniaxial drawing conditions on the orientation of aliphatic copolyester films were investigated by using both Fourier transform infrared-attenuated total reflection (FTIR-ATR) dichroism and wide angle X-ray diffraction (WAXD) methods. The results showed that orientation in uniaxially drawn films was determined by the drawing rate and drawing temperature. At higher drawing rates and higher drawing temperatures, higher orientation was obtained due to a large deformation of spherulites. The WAXD patterns of drawn films exhibited the preferential orientation of lamellar crystallites. The results of microbial degradation indicated that development of crystalline orientation evidently depressed biodegradability of samples. Video microscopy observations revealed that the degree of orientation played a dominant role in determining the rate of surface erosion. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1999–2006, 1997     

Morphology,biodegradability, mechanical,and thermal properties of nanocomposite films based on PLA and plasticized PLA

In this study, melt intercalation method is applied to prepare poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG)‐plasticized PLA nanocomposite films including 0, 3, and 5% organoclay (Cloisite 30B) using a laboratory scale compounder, which is connected to a microcast film device. To evaluate the nanomorphology and the dispersion state of the clays, X‐ray diffraction (XRD) and transmission electron microscopy (TEM) are conducted. Tensile tests are performed to characterize the mechanical behavior of the films. Biodegradation rate is determined by degradation tests in composting medium. Differential scanning calorimeter (DSC) is applied to observe the thermal behavior of the films. XRD and TEM show that the exfoliation predominantly occurrs in plasticized PLA nanocomposites, whereas unexfoliated agglomerates together with exfoliated clays are observed in the nonplasticized PLA. Tensile tests indicate that the addition of 3% clay to the neat‐PLA does not affect the strength; however, it enhances the modulus of the nanocomposites in comparison to neat‐PLA. Incorporation of 3% clay to the plasticized PLA improves the modulus with respect to PLA/PEG; on the other hand, the strain at break value is lowered ～ 40%. The increase in the rate of biodegradation in composting medium is found as in the order of PLA > PLA/PEG > 3% Clay/PLA/PEG > 5% Clay/PLA/PEG > 3% Clay/PLA. DSC analysis shows that the addition of 3% clay to the neat PLA results in an increase in T_g. The addition of 20% PEG as a plasticizer to the neat‐PLA decreases T_g about 30°C, however incorporation of clays increases T_g by 4°C for the plasticized PLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PLA/PBS共混物的动态流变性能

研究聚丁二酸丁二酯(PBS)对聚乳酸(PLA)流变性能的影响。通过熔融挤出的方法在双螺杆挤出机上制备PLA/PBS共混物,采用旋转流变仪研究PLA/PBS共混物的动态流变性能。结果表明,当应变为6%时,PLA/PBS共混物的储能模量和损耗模量随着角频率的增加而增大,而PLA/PBS共混物的损耗因子和复数黏度随着角频率的增加而降低,共混物熔体表现出剪切变稀现象。用Han方法分析表明,共混物没有发生明显的相分离现象。动态时间扫描表明,时间对于纯PLA的储能模量没有影响,但是对于PLA/PBS共混物的储能模量有较大的影响。     

Evaluating The Extent of Bio-Polyester Polymerization in Solid Wood by Thermogravimetric Analysis

In this study, the thermogravimetric analysis (TGA) technique has been applied to determine the extent of in situ polymerization achievable in solid wood on treating with bio-polyester oligomers. Low-molecular-weight oligomers of poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(butylene succinate) (PBS), and poly(butylene adipate) (PBA) were impregnated and then thermally polymerized within solid wood to enhance the physical properties of wood. TGA revealed a similar degree of oligomer polymerization was achieved either with pure oligomers or within the wood structure. The influence of relatively acidic treatments, such as low-molecular-weight PGA oligomers, was observed to lead to degradation of the hemicellulose wood component. Polymerization of PLA and PGA oligomer treatments which penetrate the wood cell wall gave relatively lower wood thermal stability. Treatment and polymerization of lumen filling PBS and PBA oligomers contributed to increased wood thermal stability.