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。     

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。     

固相接枝法功能化改性聚1-丁烯

马来酸酐(MAH)和苯乙烯(St)双单体固相接枝聚1-丁烯(1-PB),制备功能化MAH与St双单体接枝的1-PB,研究了反应条件对接枝产物的影响。结果表明:当反应温度为100 ℃,MAH单体用量(即占1-PB质量的百分数。下同)为6%,过氧化苯甲酰用量为0.6%,n(St)∶n(MAH)=2∶1时,MAH与St双单体接枝1-PB展现出较高的熔体强度,达4.87 kPa·s。在接枝体系中,St的存在既提高了MAH的接枝效率,也抑制了1-PB大分子自由基的降解,MAH与St接枝链改变了1-PB分子的支链结构与相对分子质量分布,同时一定程度上提高了接枝产物的熔融温度与结晶温度,结晶速率有所提高,球晶形貌较为完善。     

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。     

聚羟基丁酸-羟基戊酸共混干纺初生纤维的研究

将不同羟基戊酸(HV)含量的聚羟基丁酸-羟基戊酸共聚酯(PHBV)进行溶液共混,采用干法纺丝工艺获得PHBV共混纤维。通过SEM、DSC、XRD等仪器对所得纤维表面形态、热性能及力学性能随时间变化等进行了研究。结果表明,所得PHBV共混纤维表面有凹槽;随着共混HV含量的增高,PHBV共混纤维的熔点逐渐降低,结晶度逐渐减小;对于未经后处理的初生纤维,纺后4h内纤维的断裂伸长可达300%以上,断裂强度及断裂伸长也随着共混物中HV含量的增大而有所提高。通过共混降低了纤维脆性转变速率,为后续加工提供了性能良好的初生纤维。     

聚丙烯固相接枝的研究及应用进展

综述了聚丙烯(PP)固相接枝技术的研究进展,重点介绍了固相接枝的机理及分类,讨论了一些主要因素如引发剂,辐射或预辐射剂量,光敏剂和光照时间对接枝率的影响,并简要介绍了聚丙烯接枝物的应用前景和固相接枝设备的发展。     

聚羟基丁酸戊酸酯溶液共混改性研究

采用溶液共混方法来制备聚羟基丁酸戊酸酯(PHBV)生物降解薄膜,通过与不同材料共混,实现对PHBV薄膜的增韧改性.通过对共混膜力学性能、透光率的测定、红外光谱分析、扫描电镜观察,得出实验结果Ecoflex含量达到50%时,PHBV/Ecoflex薄膜韧性得到明显改善;PHBV/双酚A(BPA)溶液共混体系之间有氢键形成;PHBV/羟丙基交联改性淀粉体系,为不相容体系,其力学、光学性能明显下降.     

扩链剂TMP-6000对聚乳酸/聚（3-羟基丁酸-co-3 -羟基戊酸酯）共混物性能的影响

以扩链剂TMP-6000为增容剂,采用熔融共混制备了聚乳酸（PLA）和聚（3羟基丁酸co3羟基戊酸酯）（PHBV）复合材料,研究了TMP-6000对PLA/PHBV复合材料的结晶行为、微观结构、力学性能的影响。结果表明,无定形PLA的加入抑制了PHBV的结晶,TMP-6000的加入使得PLA/PHBV复合材料的结晶能力变弱,提高了PLA的冷结晶温度,且当TMP-6000含量为0.5 %（质量分数,下同）时,PLA的冷结晶峰开始消失,且适量的TMP-6000使得PHBV的玻璃化转变温度（Tg）升高;TMP-6000的加入使得PHBV均匀分散于PLA基体中,且当TMP-6000含量为0.7 %时,PLA与PHBV的相容性最好;TMP-6000的加入显著提高了PLA/PHBV复合材料的分子量;TMP-6000提高了PLA与PHBV之间的结合力,提高了复合材料的拉伸强度,但断裂伸长率有稍微地降低。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)研究进展

介绍了生物可降解材料聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P(3HB-co-4HB))的性能及特点;综述了针对P(3HB-co-4HB)加工温度窄、脆性大、成本高等缺点而进行的增塑改性、扩链改性、共混改性的技术进展以及P(3HB-co-4HB)纺丝成纤技术;阐述了利用P(3HB-co-4HB)可塑性、生物降解性和生物相容性等在医疗领域的应用情况及发展前景;指出P(3HB-co-4HB)的研究将集中在其材料加工流动性、结晶性能的改善及其纤维加工技术与纤维表面整理技术等方面。     

甲基丙烯酸固相接枝聚丙烯及增容研究

本文系统研究了甲基丙烯酸 (MAA)接枝聚丙烯的固相反应工艺 ,探讨了各因素对枝率的影响。在氮气保护下 ,于 10 5～ 12 0℃范围内 ,MAA和PP进行固相接枝反应 ,最佳反应条件为PP 2 0g ,MAA2 5mL ,BPO占单体量 1 5 % ,反应时间 2 5hr,反应温度 115℃。所制备的PP -g-MAA能改善PP与高岭土两相相容性及其复合材料的性能     

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     

Lamellar Morphology of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(methyl methacrylate) Blends Probed by Small Angle X-ray Scattering

The lamellar morphology of a melt-miscible blend consisting of random poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) copolymer containing 10 mol% HV units and poly(methyl methacrylate) (PMMA) prepared by solution casting films have been investigated by means of small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and polarized optical microscope (POM). The composition dependence of the amorphous layer thickness (l_a), and the volume fraction of the P(HB-co-HV) lamellar stack (φ_s) revealed that the interfibrillar segregation morphology was generated, where the extent of interfibrillar segregation of PMMA increased with increasing PMMA content. The Lorentz-corrected SAXS profiles of the blends crystallized at T_c=40 ^○C has observed “zero-angle scattering”, attributed to the electron density contrast between the lamellar stack domains consisting of alternating crystalline/amorphous layers and the PMMA-rich domains located outside the lamellar stack domains.     

Influence of Processing Parameters on the Mass Crystallinity of Poly(3-hydroxybutyrate- co-3-hydroxyvalerate)

It is proposed that melt-extrusion of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) at varying processing temperatures and screw speeds causes changes in the atomic positioning of the oxygen atoms in the helix structure due to torsion of the main chain bonds. By wide angle X-ray scattering it was observed that an increase of the processing temperature has a pronounced effect on the intensity of the two sharp Bragg reflections (020) and (110). The unit cell dimensions remain, however, unchanged. The observed repositioning did not change during conditioning for two weeks at 60°C, although the degree of crystallinity increased by approximately 10%. The degree of crystallinity is largely unaffected by the processing conditions. Model differential scanning calorimetry experiments indicate that the observed shoulders or double melting peaks with different relative size are due to recrystallization phenomena governed by morphology changes induced by the processing. This study has served as a test case for a flexible dialogue computer program, designed to be used as a routine tool for determination of the degree of mass crystallinity of polymers from X-ray diffraction data. The change in atomic position of oxygen, as indicated in this work, may be one explanation for the varying enzymatic degradability of the polymers from renewable resources. © 1997 SCI.     

Microscopy and microbeam X-ray analyses in poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with amorphous poly(vinyl acetate)

Double ring-banded spherulites of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV with 12 wt% 3HV) blending with 30 wt% amorphous poly(vinyl acetate) (PVAc) were examined using polarized light optical microscopy (POM), scanning electron microscopy (SEM), atomic-force microscopy (AFM) and micro-beam X-ray diffraction. A ring-banded spherulite of PHBV/PVAc 70/30 blend was linearly scanned across the bands in 5 μm steps by means of micro-beam X-ray diffraction. Solvent-etching and fracturing were utilized for probing the interior lamellar textures of the blend samples. Detail interior lamellar orientations in bulk film of PHBV three-dimensional ring-banded spherulites were revealed. SEM and micro-beam X-ray diffraction results suggest that the PHBV lamellar orientation gradually change along the radial growth direction with right-handed rotation sense. The blending effect in band pattern (width and regularity) of PHBV/PVAc blend was discussed.     

Additive Manufacturing of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(D,L-lactide-co-glycolide) Biphasic Scaffolds for Bone Tissue Regeneration

Polyhydroxyalkanoates are biopolyesters whose biocompatibility, biodegradability, environmental sustainability, processing versatility, and mechanical properties make them unique scaffolding polymer candidates for tissue engineering. The development of innovative biomaterials suitable for advanced Additive Manufacturing (AM) offers new opportunities for the fabrication of customizable tissue engineering scaffolds. In particular, the blending of polymers represents a useful strategy to develop AM scaffolding materials tailored to bone tissue engineering. In this study, scaffolds from polymeric blends consisting of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(D,L-lactide-co-glycolide) (PLGA) were fabricated employing a solution-extrusion AM technique, referred to as Computer-Aided Wet-Spinning (CAWS). The scaffold fibers were constituted by a biphasic system composed of a continuous PHBV matrix and a dispersed PLGA phase which established a microfibrillar morphology. The influence of the blend composition on the scaffold morphological, physicochemical, and biological properties was demonstrated by means of different characterization techniques. In particular, increasing the content of PLGA in the starting solution resulted in an increase in the pore size, the wettability, and the thermal stability of the scaffolds. Overall, in vitro biological experiments indicated the suitability of the scaffolds to support murine preosteoblast cell colonization and differentiation towards an osteoblastic phenotype, highlighting higher proliferation for scaffolds richer in PLGA.     

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。     

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%。