聚(3-羟基丁酸酯-co-4-羟基丁酸酯)的性能

采用毛细管流变仪、差示扫描量热仪、热失重分析仪及偏光显微镜(POM)研究了聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]的流变性能、热性能及结晶性能.P(3HB-co-4HB)熔体属于典型的假塑性流体,剪切应力与剪切速率关系符合Ostwald-de Wale幂率定律,熔体表观黏度与温度的关系符合Arrhenius方程;P(3HB-co-4HB)的玻璃化转变温度约为-10℃,熔点在100～120℃,降解温度约为205℃;POM观察发现,P(3HB-co-4HB)在约78℃时球晶半径径向生长速率最大.     

生物塑料聚(3-羟基丁酸酯-co-4-羟基丁酸酯)改性研究

文章介绍了生物塑料聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P3/4HB)的性能;综述了针对P3/4HB加工成型温度窄、产品脆性大、应用成本高等缺点而进行的物理改性、化学改性等技术进展;提出了对P3/4HB发展过程中需要解决的问题;同时指出P3/4HB的研究将集中在其材料结晶性能、加工流动性改善的发展方向。     

柠檬酸三乙酯改性聚(3-羟基丁酸酯-co-4-羟基丁酸酯)的性能研究

用熔融模压法制备了柠檬酸三乙酯（TEC）增塑的4HB含量不同的聚（3-羟基丁酸酯-co-4-羟基丁酸酯）[P（3HB-co-4HB）]共混物,用差示扫描量热仪（DSC）、广角X射线衍射仪（WAXI））和拉伸试验对共混物的热性能、结晶结构和力学性能进行了表征,考察了增塑剂TEC的用量和4HB含量对共聚酯性能的影响。结果表明：随着TEC用量的增大,P（3HB—co-17％4HB）共聚酯体系的结晶度减小,其熔融温度、玻璃化温度和结晶温度降低,屈服强度、断裂强度及模量也降低,屈服伸长率增大;随4HB含量的增大,相同用量的TEC共混体系的熔点、玻璃化温度和结晶温度降低,屈服强度、断裂强度和模量减小。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/纳米氮化钛共混体系研究

采用熔融共混方法制备了聚(3-羟基丁酸酯-co-4-羟基丁酸酯) [P(3HB-co-4HB)]和纳米氮化钛(TiN)的复合体系,并通过万能材料试验机、差示扫描量热仪(DSC)、偏光显微镜(POM)、X射线衍射仪(XRD),热失重分析仪(TG)等测试手段考察了不同含量TiN对P(3HB-co-4HB)基体的力学、热力学及结晶性能的影响.结果表明:纳米氮化钛在共混体系中起到成核剂作用,可有效改善P(3HB-co-4HB)结品性能,提高其韧性.     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)的扩链改性

采用环氧丙烯酸型扩链剂改性聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)],考察了扩链剂对熔体黏弹性、力学性能和成型发泡的影响.用流变仪测试熔体稳态黏度与剪切速率、动态黏弹模量与角频率、模量与时间的关系,用扫描电子显微镜观察改性前后P(3HB-co-4HB)的断面形貌.结果表明,扩链剂的加入提高...     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/酰胺成核剂共混体系

采用熔融共混方法制备了聚(3-羟基丁酸酯-co-4 -羟基丁酸酯)[P( 3HB-co-4HB)]和酰胺成核剂的复合体系,并通过万能材料试验机、差示扫描量热仪( DSC)、偏光显微镜(POM)和X射线衍射仪(XRD)等测试手段考察了不同含量酰胺成核剂对P( 3HB-co-4HB)基体的力学、热力学及结晶性能的影响.结果表明:酰胺成核剂在共混体系中起到成核剂作用,可有效改善P(3 HB-co-4HB)结晶性能,提高其韧性.     

聚乳酸/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/改性高岭土纳米复合材料的结晶、动态力学及流变行为

为提高聚乳酸(PLA)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P(3HB-co-4HB))基体的综合性能,采用熔融共混法制备聚乳酸/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/改性高岭土(modified kaolin)纳米复合材料。利用DSC、DMA、旋转流变仪、扫描电镜(SEM)等对复合体系的结晶、动态力学性能、流变行为、表面结构等进行了研究。结果表明:复合体系的冷结晶温度逐渐变小,降低了12.5℃,结晶能力有所提高。此外,结晶度由21.65%增加到35.22%,提高了62.68%。DMA结果显示,随着改性高岭土添加量的增多,复合体系的储能模量E′和玻璃化转变温度出现先增大后减小的变化。熔融态下,复合体系的黏度随剪切速率的增大而减小,属假塑性流体。当体系中改性高岭土添加量为4%时,材料的缺口冲击强度有明显的改善。利用SEM发现,少量改性高岭土可以均匀地分散在PLA/P(3HB-co-4HB)基体中并能显著提高复合体系的韧性。     

聚3-羟基丁酸酯4-羟基丁酸酯性能研究

概述了聚羟基脂肪酸酯(PHA)类生物塑料的发展过程,分析了聚3-羟基丁酸酯4-羟基丁酸酯(P34HB)的结构、综合性能、加工特性,详细介绍了P34HB的改性方法。结果表明:P34HB是新一代优异的生物塑料,通过改性,其力学性能与聚丙烯和聚乙烯相近,可以在传统塑料加工设备上加工成型。但对P34HB的研发及应用还需做大量工作。     

聚（3-羟基丁酸和4-羟基丁酸酯）共聚物性能研究

对生物可降解聚（3-羟基丁酸和4-羟基丁酸酯）共聚物[Poly（3HB-co-4HB）]进行研究。3-羟基丁酸和4-羟基丁酸酯共聚物大大改变了聚3-羟基丁酸酯（PHB）均聚物的缺点，通过一系列物理实验方法证明，随着4-羟基丁酯酯（4HB）含量增加，熔体流动速率由20．7g／10min降低至8．9g／10min，而黏度增加1．8倍，熔融温区增宽20℃，结晶度由11．57%减小到50%，球晶消失。拉伸强度由13．5MPa降低至7．9MPa，断裂伸长率由796％增加至1020％不断裂，柔韧性增加。玻璃化转变温度由-7．29℃升高至-3．17℃。对原料下游制品的开发有广泛的应用价值。     

聚(3-羟基丁酸酯)的化学改性研究进展

评述了降解塑料聚(3 羟基丁酸酯)(PHB)近年来在化学改性方面的研究进展情况,特别就PHB化学改性的方法和产物的性能进行了总结和评述。PHB化学改性的方法包括辐射聚合、大单体反应改性、反应性共混等。PHB化学改性可通过分子设计合成特定结构的PHB共聚物,具有物理共混无法比拟的优势,特别是在组织工程领域有着广泛的应用前景。     

Microbial synthesis and properties of poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Microbial synthesis of copolymers of [R]-3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB), P(3HB-co-4HB), by Alcaligenes eutrophus, Alcaligenes latus, and Comamonas acidovorans from various carbon sources has been studied. The copolyester compositions varied from 0 to 100 mol% 4HB, depending on the microorganism and the combination of carbon substrates supplied. The thermal and physical properties of compositions with 0–100 mol% 4HB were investigated. The copolyesters represented a wide variety of polymeric materials, from hard crystalline plastic to very elastic rubbers, depending on composition. The copolyester films with high 4HB fractions (64–100 mol% 4HB) exhibited the characteristics of a thermoplastic elastomer, and the tensile strength increased from 17 to 104 MPa as the 4HB fraction increased. The enzymatic degradation of P(3HB-co-4HB) films was studied in an aqueous solution of extracellular polyhydroxybutyrate (PHB) depolymerase from Alcaligenes faecalis or lipase from Rhizopus delemer. The erosion rate of P(3HB-co-4HB) films was strongly dependent on the copolymer composition. In addition, environmental degradation of P(3HB-co-4HB) films in sea water was investigated.     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001     

聚3–羟基丁酸与4–羟基丁酸共聚物薄膜的微生物降解

以门多萨假单胞菌为降解菌株,研究了聚3–羟基丁酸与4–羟基丁酸共聚物[poly(3HB-co-4HB)]薄膜的微生物降降过程。门多萨假单胞菌对poly(3HB-co-4HB)薄膜的降解可分为慢速降解阶段和快速降解阶段。经10 d的降解,薄膜的降解率可达到94.7%。扫描电子显微镜观察发现,经微生物降解的薄膜表面因降解而形成的孔洞及蚀痕,这些孔洞及蚀痕随着降解时间的增加有着加大和加深的情况。差示扫描量热法分析发现,随微生物降解时间的增加,薄膜的熔点上升,而相对结晶度降低。X射线衍射分析结果也进一步证实了薄膜经微生物降解后相对结晶度的降低。热重分析法也证明薄膜的热稳定性随降解时间增加而下降。     

聚(3-羟基丁酸和4-羟基丁酸酯)共聚物与聚乳酸共混体系性能研究

研究了可完全生物降解的聚(3-羟基丁酸-co-4-羟基丁酸醋)与聚乳酸(PLA)共混体系,利用偏光显微镜、动态和静态剪切流变、X射线衍射和差示扫描量热仪,分析共混体系的结晶性能、流变性能和热稳定性。结果表明:随着PLA添加量增加,熔融温度由156.05℃降低到130. 32 C,结晶温度由102. 09℃降低62. 33 C,结晶度下降。而玻璃化转变温度由一5 . 69℃上升3. 42 C,体系的热稳定性和豁弹性提高。     

P3/4HB/PBS共混物的物理性能及微生物降解

将不同比例的聚(3-羟基丁酸-co-4-羟基丁酸)共聚酯(P3/4HB)和聚丁二酸丁二酯(PBS)进行物理共混,通过FTIR、DSC、TG和SEM研究了复合材料的力学性能、亲水性能、热稳定性和结晶性。当PBS的添加量为10%时,复合材料的力学性能较好。与纯P3/4HB相比,拉伸强度增加了154%,达到了18.6 MPa;断裂伸长率增加了82%,为638%;弹性模量约下降94 MPa。复合物水溶解性能较小,只有0.34%,抗水性增强。DSC分析表明,2种聚合物的相容性较好。PBS的添加降低了材料的熔点,增加了结晶性能,同时减缓了材料的结晶速率。TG分析结果表明,复合材料稳定性增强,加工窗口拓宽了32℃。采用Pseudomonas.mendocina DS04-T菌株降解复合材料,当降解时间为120 h时,复合材料降解率为92.5%。     

聚羟基丁酸己酸酯对聚羟基丁酸戊酸酯结晶性能的影响

采用溶液浇铸法制备了生物可降解聚羟基丁酸戊酸酯（PHBV）和聚羟基丁酸己酸酯（PHBHHx）共混物,用差示扫描量热仪和偏光显微镜研究了PHBHHx对PHBV热性能与结晶性能的影响。结果表明,PHBV和PHBHHx之间存在一定的相互作用,PHBV的冷结晶温度随PHBHHx含量的增加向高温方向移动;PHBV/PHBHHx共混物的结晶呈环带球晶现象,随PHBHHx含量的提高,环带球晶逐渐变得规整、清晰,且带宽逐渐减小。     

Some properties of poly(3-hydroxybutyrate)–poly(3-hydroxyvalerate) blends

The melting, crystallization and dynamic mechanical behaviour of blends of bacterially produced poly[D (–)-3-hydroxybutyrate] (PHB) and poly[D (–)-3-hydroxyvalerate] (PHV) have been investigated. Results showed that melt-pressed PHB–PHV blends contained phase-separated domains in the melt which subsequently crystallized as PHB and PHV type spherulites respectively. The two melting regions detected by DTA related to separate melting of PHB and PHV crystallites, which were almost unaffected by the blend composition. The mechanical behaviour of a random copolymer of PHB/HV was compared with that of a blend of almost the same composition, and found to be markedly different.     

P(3,4HB)/PHBV共混改性及微生物降解研究

将聚(3羟基丁酸共聚4羟基丁酸酯)［P(3,4HB)］与聚(3羟基丁酸共聚3羟基戊酸酯)(PHBV)通过溶剂共混的方式进行共混改性,研究了改性后材料力学性能的变化情况,并进一步利用差示扫描量热法和热重法进行了表征,最后利用Pseudomonas mendocina DS04-T菌株对共混材料的降解性能进行了考查,并利用扫描电子显微镜观察了薄片降解后的微观形貌。结果表明,当P(3,4HB)与PHBV的混合比例为80/20时复合材料有较好的力学性能,断裂伸长率和拉伸强度均达到最大值;当PHBV组分的含量小于60 %时,共混物均形成了稳定的晶体结构,且两组分具有较强的相互作用和较好的相容性;Pseudomonas mendocina DS04-T对共混材料的完全降解时间大大低于单独降解P(3,4HB)所需的时间。     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

邻苯二甲酸二辛酯与PHB共混改性的研究

采用邻苯二甲酸二辛酯(DOP)对聚3-羟基丁酸酯(PHB)进行共混改性,并对共混物的流变行为、结晶行为和力学行为进行了研究。结果表明,DOP与PHB具有良好的相容性,能降低PHB的结晶行为,降低熔融温度,加宽熔融温区,改善加工条件,提高韧性。