聚丁二酸丁二醇酯/聚羟基烷酸酯熔融共混物的结晶及流变力学行为

用熔融共混法制备聚丁二酸丁二醇酯(PBS)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[Poly(3HB-co-4HB)]复合降解材料,利用差示扫描量热(DSC)、旋转流变仪及万能拉力机对其结晶、流变行为及力学性能进行研究。结果表明,在PBS中加入Poly(3HB-co-4HB)后,发现结晶起始温度(To,c)、结晶峰温度(Tp,c)以及结晶结束温度(Te,c)有所提高,结晶度随着Poly(3HB-co-4HB)的增加呈先增大后下降的趋势;PBS/Poly(3HB-co-4HB)复合降解材料随着Poly(3HB-co-4HB)添加量的增大,断裂伸长率和拉伸强度却呈下降趋势;同时剪切储能模量(G′)、剪切损耗模量(G″)呈现出单增趋势。因此,在复合降解材料中添加适量的Poly(3HB-co-4HB)能改善PBS的结晶、流变及力学行为。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/二氧化钛纤维的成纤性能

用不同含量的二氧化钛(TiO2)改性聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)],并进行了纺丝研究。采用毛细管流变仪、热重分析仪、单丝强力仪测试了P(3HB-co-4HB)/TiO2复合材料的流变性能、热性能、单丝力学性能和回弹性。实验结果表明,P(3HB-co-4HB)和P(3HB-co-4HB)/TiO2为假塑性流体,TiO2可以有效改善材料的加工流动性;提高材料的热稳定性;TiO2的加入使纤维的断裂强度降低;但纤维的弹性恢复率可达100%,退绕性有所改善。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/POSS共混体系的性能

采用熔融模压法分别制备了聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]和两种多面体笼型硅氧烷(POSS)[八异丁基倍半硅氧烷(OIBS)和八氨基苯基倍半硅氧烷(OAPS)]的共混物,考察了不同含量的OIBS,OAPS对共混体系性能的影响。结果表明,两种POSS都起到成核剂的作用。OIBS,OAPS的质量分数小于1%时,可以提高体系结晶温度,力学性能;随着OIBS,OAPS质量分数的提高,成核性有所增加,但因分散性变差,体系热稳定性和力学性能变差。由于OAPS的活泼氨基可与P(3HB-co-4HB)发生化学反应,改性效果较OIBS优。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/酶解木质素共混材料的制备及性能

双螺杆熔融共混制备了全生物降解的聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P3HB4HB)/纤维素酶解木质素(CEL)共混物,分别用热重分析、拉伸弯曲试验、冲击试验、扫描电镜(SEM)考察了CEL含量对共混物热学、力学性能及微观形貌的影响。研究发现,CEL的加入增强了材料的热稳定性,也提高了材料的模量,但断裂伸长率、拉伸强度、弯曲强度和冲击强度平缓降低,当CEL的质量分数为20%CEL,拉伸、弯曲、冲击三种强度的保持率都大于93%;SEM显示,P3HB4HB和CEL相容很好。CEL填充P3HB4HB不仅能降低材料成本,还能对材料的热学、力学性能保持较好或起改善作用,CEL最宜添加的质量分数为20%。     

聚(3-羟基丁酸酯-co-4羟基丁酸酯)熔融接枝马来酸酐的研究

采用熔融接枝法制备P(3HB-co-4HB)-g-MAH.通过接触角测定仪、偏光显微镜、扫描电子显微镜和电子万能试验机等研究了MAH和BPO的用量对共聚物接枝率的影响,考察了P(3HB-co-4HB)接枝前后接触角、结晶形态、力学性能的变化,P(3HB-co-4HB)及其接枝物与木粉共混物的力学性能等.结果表明:随着M...     

改性纳米二氧化硅/聚己内酯/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)的结构与性能研究

利用异丙基三(二辛基焦磷酸酰氧基)钛酸酯偶联剂改性纳米二氧化硅,采用熔融共混挤出法制备聚己内酯(PCL)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P(3HB-co-4HB))/改性纳米二氧化硅(nano-SiO2)复合降解材料;利用红外光谱(FIIR)、万能拉力机、扫描电镜(SEM)、动态力学分析仪(DMA)等研究了改性nano-SiO2对复合材料的表面结构、力学性能等性能的影响。结果表明:改性nano-SiO2含量为4%时,复合降解材料的力学性能有明显的改善;少量添加的改性nano-SiO2可以均匀分散在PCL/P(3HB-co-4HB)基体树脂中,但当加入量过大时,容易发生团聚现象。     

钛酸酯偶联剂对聚乳酸/3-羟基丁酸同4-羟基丁酸共聚酯/纳米羟基磷灰石共混体系流变行为的影响

采用异丙基三(二辛基焦磷酸酰氧基)钛酸酯偶联剂对纳米羟基磷灰石(HA)改性,再与聚乳酸(PLA)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(PHA)熔融共混法制备PLA/PHA/HA纳米复合降解材料。利用流变仪对其流变行为进行了研究。结果表明,PLA/PHA基体在没有添加钛酸酯偶联剂和纳米HA时,基体储存模量G′和复数黏度η*随温度升高而逐渐降低;纯的纳米HA的加入可以提高PLA/PHA基体的储存模量G′和损耗模量G″,然而,PLA/PHA/HA纳米复合降解材料引入钛酸酯偶联剂反而会使储存模量G′和损耗模量G″降低。当过量引入钛酸酯偶联剂会明显降低体系线性-非线性转变的临界应变。在190℃,PLA/PHA基体加入纯的纳米HA时,储存模量G′升高,引入钛酸酯偶联剂后,基体储存模量G′反而有一定降低,但所有样品至少在30min内能保持较稳定的线性粘弹行为。     

SiO2/聚（3-羟基丁酸酯-co-4-羟基丁酸酯）薄膜研究

目的研究纳米SiO2对可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P34HB)包装膜结晶行为和力学性能的影响。方法采用溶液浇铸法制备SiO_2/P34HB纳米复合薄膜,利用红外光谱仪(FTIR)、扫描电镜(SEM)、正置热台显微镜(POM)、差示扫描量热仪(DSC)和万能力学试验机等研究纳米SiO_2对P34HB结构、结晶性和力学性能等的影响。结果纳米SiO_2在P34HB中起到异相成核的作用,SiO2/P34HB复合膜的结晶速率和结晶度得到明显改善。相比P34HB包装膜,当纳米SiO_2质量分数为2%时,SiO_2/P34HB复合膜的弹性模量和拉伸强度分别提高了72.7%和60.9%。结论获得了纳米SiO2改善可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)包装膜结晶度和力学性能的最佳掺杂比例参数。     

成核剂对聚(3-羟基丁酸酯-co-4羟基丁酸酯)性能的影响

分别以氮化硼(BN)、BRUGGOLENP250、CaCO3和Tm-3为成核剂,用熔融模压法制备了聚(3-羟基丁酸酯-co-4羟基丁酸酯)[P(3HB-co-4HB)]样品,借用偏光显微镜(POM)、差示扫描量热(DSC)、热重分析(TGA)和扫描电镜(SEM)等考察了成核剂种类及用量对P(3HB-co-4HB)结晶形态、熔点、热分解温度、力学性能及断面形态的影响。结果表明,各种成核剂均能有效细化P(3HB-co-4HB)的球晶尺寸,提高其熔点及热分解温度;当成核剂BN的质量分数为5‰~8‰时,P(3HB-co-4HB)的综合性能最好。     

扩链改性对聚(3-羟基丁酸酯-co-4-羟基丁酸酯)性能的影响EI北大核心CSCD

以多苯基多亚甲基多异氰酸酯(PAPI)为扩链剂,采用熔融共混法扩链改性聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]。使用凝胶渗透色谱、热失重分析仪、电子拉力机、毛细管流变仪、旋转流变仪等研究了PAPI添加量对P(3HB-co-4HB)的相对分子质量、热稳定性、力学性能以及流变性能的影响。结果表明,PAPI的使用能够提高P(3HB-co-4HB)的相对分子质量和熔体黏度,并能有效改善P(3HB-co-4HB)的热稳定性和力学性能,成功实现了对P(3HB-co-4HB)的扩链改性。PAPI的添加量为2.0phr时,体系综合性能最佳,其起始分解温度和最大分解温度分别比纯P(3HB-co-4HB)提高了16.7℃和11.4℃,其拉伸强度和断裂伸长率分别比纯P(3HB-co-4HB)提高了21%和218%。     

聚(3-羟基丁酸-co-4-羟基丁酸酯)/碳纳米管复合微孔发泡薄膜研究

用红外(FT-IR)谱、X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和差示扫描量热仪(DSC),研究了多壁碳纳米管(MWCNT)分别在强酸和偶氮二异丁腈(AIBN)+过氧化二苯甲酰物(BPO)中的表面修饰过程,并将其与聚(3-羟基丁酸-co-4-羟基丁酸酯)/碳纳米管复合,制备了微孔发泡薄膜,孔径最大50μm,最小10μm。结果表明,在相同溶剂条件下,偶氮二异丁腈+过氧化二苯甲酰可以成功地实现碳纳米管的表面修饰,修饰后的碳管浓度为1%(质量分数)与聚合物较好相容,当其比例为1∶2、1∶1时分别获得"莲蓬型"和"蜂窝型"微孔发泡结构薄膜,并具有较好的导电性。     

PBS的降解及其机理研究

通过配制碱、酸、水及土壤的培养液对聚丁二酸丁二醇酯(PBS)薄膜进行不同环境条件下的降解,对其降解机理进行研究。采用失重率及表面观察等手段对降解结果进行表征,结果表明:降解速率按照下列顺序递减:碱性降解土壤悬浮液降解酸性降解水降解。在降解的过程中,pH值呈逐渐减小的趋势。     

Tensile properties and impact behaviour of poly(D(−)3-hydroxybutyrate)/rubber blends

A random ethylene-propylene rubber copolymer with functional ester or anhydride groups and an ethylene vinilacetate copolymer modified by a partial transformation of acetate groups in alcoholic groups were used as minor components to obtain binary poly(D(-)3-hydroxy-butyrate) blends by melt-mixing. The influence of the rubbery impact modifier on the morphology and on the tensile and high-speed fracture behaviour of such blends was investigated. Better properties were found when anhydride groups were present on the rubbery component. This was attributed to chemical interactions occurring between the dispersed phase and the matrix during the blending process.     

Isothermal crystallization kinetics and morphology of biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Isothermal crystallization kinetics and morphology of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] with different 4-hydroxybutyrate (4HB) molar fraction were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The results show that the crystallization mechanism and crystal structure of P(3HB-co-4HB) copolymers are the similar as those of poly(3-hydroxybutyrate) (PHB). While the equilibrium melting point and crystallization rate decrease with the increase of 4HB molar fraction. Banded spherulites are observed in neat PHB and P(3HB-co-4HB) copolymers, and morphology is influenced apparently by the crystallization temperature and 4HB unit.     

Crystallization,mechanical performance and hydrolytic degradation of poly(butylene succinate)/graphene oxide nanocomposites obtained via in situ polymerization

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were fabricated via in situ polymerization with very low GO content (from 0.03 to 0.5 wt%). The microstructures of the nanocomposites were characterized with Raman spectroscopy, fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), sedimentation experiments and atomic force microscopy (AFM). The results showed that PBS chains have been successfully grafted onto GO sheets during in-situ polymerization, accompanied by the thermo-reduction from GO to graphene. The grafted GO displayed a great nucleating effect on PBS crystallization, resulting in largely improved crystallization temperature and decreased spherules size. A simultaneous enhancement in tensile strength and elongation was achieved for PBS/GO nanocomposites fiber. Meanwhile, increase in hydrolytic degradation rate was also observed for these nanohybrids. Our result indicates that using very low content GO is a simple way to achieve good dispersion yet with remarkable property enhancement for polymer/GO nanocomposites.     

New poly(butylene succinate)/layered silicate nanocomposites: preparation and mechanical properties

New poly(butylene succinate) (PBS)/layered silicate nanocomposites have been successfully prepared by simple melt extrusion of PBS and octadecylammonium modified montmorillonite (C18-mmt) at 150 degrees C. The d-spacing of both C18-mmt and intercalated nanocomposites was investigated by wide-angle X-ray diffraction analysis. Bright-field transmission electron microscopic study showed several stacked silicate layers with random orientation in the PBS matrix. The intercalated nanocomposites exhibited remarkable improvement of mechanical properties in both solid and melt states as compared with that of PBS matrix without clay.     

Thermal degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) in nitrogen and oxygen studied by thermogravimetric-Fourier transform infrared spectroscopy

The thermal degradation behavior of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx), HHx=12 mol%) has been studied under different environmental conditions by thermogravimetric analysis (TGA) Fourier transform infrared (FT-IR) spectroscopy. It is reported that at higher temperature (>400 degrees C) carbon dioxide and propene are formed from the decomposition product crotonic acid in a nitrogen atmosphere, whereas in an oxygen atmosphere propene oxidizes in a further step to carbon dioxide, carbon monoxide and hydrogen. It was also found that PHB and P(HB-co-HHx) have a similar thermal degradation mechanism. The analysis of the FT-IR-spectroscopic data was performed with 2D and perturbation-correlation moving-window 2D (PCMW2D) correlation spectroscopy.     

4-羟基丁酸含量对聚 3-羟基丁酸 与 4-羟基丁酸共聚物性能和结构的影响

目的对3-羟基丁酸4-羟基丁酸共聚酯P(3HB-co-4HB)进行酶解测试。方法通过力学性能测试、失重率分析、热失重分析、X-射线衍射分析、扫描电镜等测试和表征手段对样品的物理性能及生物降解情况进行评价。结果 P(3HB-co-4HB)分子中4HB单体(文中均用摩尔分数表示)的引入提高了材料的柔韧性,材料的脆性下降;失重率方面,4种材料的降解速率从高到低依次为P(3HB)P(3HB-co-5%4HB)(3HB-co-10%4HB)P(3HB-co-15%4HB);酶解前期,材料的热稳定性增强,而酶解后期材料的热稳定性逐渐下降;XRD结果表明材料降解过程中结晶度的变化不明显;P(3HB-co-4HB)分子中随着4HB单体含量的增加,材料表面粗糙度降低,酶解后材料表面被侵蚀,降解速率与失重率结果一致。结论 P(3HB-co-4HB)分子中4HB单体的引入显著影响了材料的机械性能,随着4HB含量的增加,材料的失重率越来越大,热稳定性呈现先上升后下降的趋势,材料表面粗糙度逐渐降低,由于酶解过程属于从表面侵蚀开始,因此酶解过程中样品的结晶度变化不大。