PBS基三元共聚物的合成及性能研究

在PBS主链中同时引入己内酯(CL)和1,4-环己烷二甲醇(1,4-CHDM),或CL和二乙醇酸(DGA)得到了PBS-co-PCL-co-CHDM和PBS-co-PCL-co-DGA三元共聚物。通过1H-NMR、FTIR对三元共聚物的结构进行了表征,并采用热分析、广角X射线衍射分析和拉力试验比较了三元共聚物的性能。结果表明:随着CL、1,4-CHDM、DGA的引入,三元共聚物的结晶尺寸有所减小,结晶度降低,与PBS相比晶型略有变化;并且tanδ均增大,而储能模量均降低;在CL同时存在的条件下,1,4-CHDM的加入使共聚物的的玻璃化温度(Tg)上升为-30℃,DGA的加入却使Tg下降为-36℃,但二者的热分解温度仍在300℃以上;改性后三元共聚物的柔韧性增强断,裂伸长率显著提高。     

新型车用材料聚（丁二酸-co-己二酸丁二醇）共聚酯酶促降解性能研究

通过酯化和缩聚反应制备聚丁二酸丁二醇酯（PBS）、聚己二酸丁二醇酯（PBA）和聚（丁二酸-co-己二酸丁二醇）共聚酯（P(BS-co-BA)）,对PBS、PBA和P(BS-co-BA)进行酶促降解研究。结果表明：与PBS和PBA相比,共聚酯具有良好的生物降解性能。6种聚酯酶水解速率依次为P(BS-co-40%BA)>P(BS-co-60%BA)>P(BS-co-80%BA)>P(BS-co-20%BA)>PBA>PBS。P(BS-co-40%BA)在10 h内基本完全降解,比PBS快26 h。与PBA相比,共聚酯的热稳定性得到提高,P(BS-co-40%BA)热分解50%的温度比PBA高22.3℃。随着降解时间的增加,共聚酯的化学结构、晶体结构和热稳定性基本不变,有利于其在新能源汽车设计中的应用。     

生物可降解PBS/PBT共聚酯的性能研究

以对苯二甲酸、丁二酸、丁二醇为原料,合成了一系列不同丁二酸含量的共聚酯(PBTS),利用氢核磁(1H NMR)、凝胶渗透色谱(GPC)、差示扫描量热仪(DSC)对共聚物的化学结构、相对分子量及热性能进行了研究。结果表明,将SA引入PBT主链,得到一系列数均分子量在35000~40000的无规PBTS共聚物;在相同动力粘度条件下,共聚酯的特性粘数随SA含量增加而逐渐升高;共聚酯的熔点、熔融热焓、热结晶温度及热结晶热焓等随SA含量增加而下降。     

不同端基PBS的合成与降解性研究

利用熔融溶液相结合的方法,调节反应物比例得到了不同端基的聚丁二酸丁二醇酯(PBS).利用滴定法测定不同样品的羧基值,用乌氏黏度计测定不同样品的特性黏度,降解实验测定降解率随时间的变化情况.结果显示,特性黏度大小的顺序是:等物质的量比>羧基封端>羟基封端,羧值大小的顺序是:羧基封端>等物质的量比>羟基封端,降解率大小的顺序是:羟基封端>羧基封端>等物质的量比.     

PBS不同化学结构共聚物的性能

采用改变原料的组分合成不同化学结构的聚丁二酸丁二醇酯(PBS)改性共聚物:聚丁二酸丁二醇/己二酸丁二醇酯(PBS-co-BA)、聚丁二酸丁二醇酯/聚丁二酸乙二醇酯(PBS-co-ES)、聚丁二酸丁二醇酯/聚丁二酸己二醇酯(PBS-co-HS),利用FT-IR和1H-NMR表征共聚物的化学结构,并对共聚物的结构与物理性能、降解性能的关系进行对比.研究结果表明:所有共聚物的结晶度、熔点较其均聚物有所降低;但所有共聚物的断裂伸长率都有所提高.热分析结果表明:PBS-co-HS热性能有所提高,PBS-co-BA和PBS-co-ES有所下降.堆肥降解实验表明:所有共聚物的降解性都比均聚物有显著提高,其降解速度大小顺序为:PBS-co-BA>PBS-co-HS>PBS-co-ES>PBS,PBS-co-HS是综合性能最优良的材料.     

可生物降解聚酯P(ES-co-DGA)和P(BS-co-DGA)的合成及性能比较

通过改变二乙醇酸(DGA)的含量,将其与乙二醇、1,4-丁二醇进行缩聚反应,得到了P(ES-co-DGA)和P(BS-co-DGA)共聚物,采用1H-NMR表征化学结构,并对共聚物的相对分子质量(Mn)、热性能、力学性能、降解性等进行比较研究。结果表明:随着DGA的增加,两种共聚物的熔点(Tm)均呈下降趋势,但P(ES-co-DGA)的玻璃化转变温度(Tg)逐渐升高,P(BS-co-DGA)的Tg却变化不大;所有共聚物的热分解温度(Td)(失重2%)均在300℃左右。当DGA含量为50%时,P(BS-co-DGA)的最大断裂伸长率可达到921%;当DGA含量为20%时,P(ES-co-DGA)的最大断裂伸长率可达到853%。随着DGA的增加,P(BS-co-DGA)的降解速率增大;当DGA含量为10%以上时,P(BS-co-DGA)的降解性能逐渐降低。     

PHBV/PBS共混物的性能研究

通过熔融共混的方法制备了聚β-羟基丁酸戊酸酯/聚丁二酸丁二醇酯(PHBV/PBS)共混材料。研究了PHBV/PBS共混物的力学性能、相形态、结晶性能、热性能及晶胞结构。结果表明,将PHBV和PBS共混后,PHBV的韧性会有明显改善。当PHBV/PBS/TEC质量比为20/80/5时,PHBV的断裂伸长率由原来的5.7%增至124%、冲击强度由1.7 kJ/m2增加到4.3 kJ/m2,分别为PHBV的21.7倍和2.5倍。DSC研究表明,PBS的加入抑制了PHBV的结晶,但当PHBV/PBS/TEC质量比为20/80/5时,共混物出现了共晶现象。XRD显示PBS的加入在一定程度上影响了PHBV的晶型,复合材料的晶面特征峰发生了明显偏移。     

淀粉／PBS共混材料的制备与性能研究

将聚丁二酸丁二醇酯（PBS）加入到淀粉体系中，制备了淀粉基共混材料，并对共混体系的性能进行了研究。结果表明：在淀粉中加入PBS可有效增加体系的硬度并提高其维卡软化点，100份淀粉中加入40份PBS体系硬度达到最大值；加入10份PBS时，体系的维卡软化点达到最大值；100份淀粉中加入40份PBS时体系拉伸性能最优，再增加时反而下降；PBS的加入对淀粉材料的防水性有一定改善，与纯淀粉体系相比，样品溶于水的质量下降了近50％。此外，加入10份的PBS可使淀粉注射成型的冷却定型时间缩短3／4，使挤出成型的牵引速度提高两倍，有利于淀粉的成型加工。     

不同酶对PBS基共聚酯/淀粉复合材料降解性能的影响

采用L_9(3~3)正交试验对α–淀粉酶降解聚丁二酸丁二酯(PBS)基共聚酯/热塑性淀粉(TPS)复合材料的条件进行了优化,得出α–淀粉酶的最优降解条件为:温度65℃,磷酸盐缓冲液p H=6.8,α–淀粉酶浓度3.5 g/L。利用α–淀粉酶和南极假丝酵母脂肪酶N435对PBS/TPS、聚(丁二酸丁二醇-co-丁二酸二甘醇)酯(PBS-co-DEG)/TPS、聚(丁二酸丁二醇-co-丁二酸乙二醇-co-丁二酸聚乙二醇200)酯(PBES-co-PEG200)/TPS、聚(丁二酸丁二醇-co-丁二酸乙二醇-co-丁二酸聚乙二醇400)酯(PBES-co-PEG400)/TPS复合材料分别进行降解实验,研究了两种酶对这4种复合材料降解性能的影响。结果表明,α–淀粉酶和N435脂肪酶对复合材料均有较好的降解能力,当降解时间较短(6 h)时,α–淀粉酶对复合材料的降解效果优于脂肪酶N435,但当降解时间超过60 h后,后者的降解效果略优于前者;(PBES-co-PEG200)/TPS和(PBES-co-PEG400)/TPS复合材料的降解性能总体上优于(PBS-coDEG)/TPS及PBS/TPS复合材料;随PEG200和PEG400在共聚酯中的含量增加,即醚链含量的增加,相应复合材料的质量损失率呈升高趋势,但当醚链含量较高时,复合材料的质量损失率反而有所下降。     

MPO改性PBS共聚酯的合成及其热性能研究

采用直接酯化-熔融缩聚的方法合成聚丁二酸丁二醇酯(PBS)和2-甲基-1,3-丙二醇(MPO)改性的PBS共聚酯(PBMS).通过傅里叶红外光谱仪(FTIR)、核磁共振谱仪(NMR)和凝胶渗透色谱仪(GPC)分别对其化学结构和分子量进行了表征;通过差示扫描量热仪(DSC)、同步热分析仪(STA)和熔体流动速率测定仪(M...     

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

Short‐segmented block copolymers of poly(butylene succinate‐co‐butylene fumarate) were synthesized and their crystallinity and crosslinking behavior were investigated. ¹H NMR was used to characterize the microstructure and composition of the copolyesters. Molecular weight determination was performed using gel permeation chromatography. Based on the DSC results all copolyesters were crystalline and the degree of crystallinity of the copolymers did not change with butylene fumarate mole fraction due to co‐crystallization of the butylene succinate and butylene fumarate groups. Crosslinked copolyesters showed a lower crystallization rate and degree of crystallinity while the crystallization temperature shifted to higher temperatures compared with uncrosslinked copolyesters due to the formation of nucleating agents by crosslinkages. Photo‐DSC was used to investigate the crosslinking kinetics for UV‐initiated photo‐curing. Three kinetics parameters including the rate constant (k) and the orders of the initiation and propagation reactions (m and n, respectively) were determined for the quenched and unquenched copolymers. © 2016 Society of Chemical Industry     

聚丁二酸丁二醇酯的研究进展

综述了脂肪族聚酯类可降解生物材料聚丁二酸丁二醇酯(PBS)的研究进展,重点对PBS的制备方法、改性、产业化等方面进行了探讨,指出PBS产业存在的问题及今后的研究重点。     

生物基共聚酯PBSeT制备与性能

采用单釜酯化缩聚法合成了聚癸二酸-对苯二甲酸丁二酯(PBSeT),研究了对苯二甲酸和癸二酸配比对共聚酯PBSeT热性能和拉伸性能的影响.结果表明,共聚酯PBSeT的热性能和性能性能可以通过控制共聚单体的物质的量之比来调整.采用傅立叶变换红外光谱(FTIR)和核磁共振氢谱(1H NMR)表征了PBSeT的化学结构和组成,...     

The effect of 60Co γ‐rays on the crystal structure,melting and crystallization behavior of poly(butylene succinate)

The results obtained for poly(butylene succinate) (PBS) after ⁶⁰Co γ‐ray irradiation, studied by wide‐angle X‐ray diffraction (WAXD), differential scanning calorimeter (DSC) and polarizing optical microscopy (POM), revealed that the degree of crystallinity, melting temperature and enthalpy decreased with increasing irradiation dose, but that the crystal structure of PBS did not vary when compared to non‐irradiated PBS. By using Scherrer equation, small changes occurred in the crystal sizes of L₀₂₀, L₁₁₀ and L₁₁₁. The spherulitic morphology of PBS was strongly dependent on irradiation dose and changed significantly at higher irradiation dosages. The crystallization kinetics of PBS indicated that the Avrami exponent (n) for irradiated PBS was reduced to 2.3, when compared to non‐irradiated PBS (3.3). Copyright © 2004 Society of Chemical Industry     

Synthesis of novel biodegradable poly(butylene succinate) copolyesters composing of isosorbide and poly(ethylene glycol)

A series of biodegradable isosorbide‐based copolyesters poly(butylene succinate‐co‐isosorbide succinate‐co‐polyethyleneoxide succinate) (PB_xI_yE_zS) were synthesized via bulk polycondensation in the presence of dimethyl succinate (DMS), 1,4‐butanediol (BDO), poly(ethylene glycol) (PEG) and isosorbide (ISO). The crystallization behaviors, crystal structure and spherulite morphology of the copolyesters were analyzed by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarizing optical microscopy (POM), respectively. The results indicate that the crystallization behavior of the copolyesters was influenced by the content of isosorbide succinate (IS) and polyethyleneoxide succinate (PEOS) units, which further tuned the mechanical and biodegradable properties of the copolyesters. The PB_xI_yE_zS copolyesters, compared to pure poly(butylene succinate), showed lower crystallization temperature, melting temperature, degree of crystallinity and degradation rate while a significant increase in glass transition temperature with increasing isosorbide content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丁二酸丁二酯的结晶动力学研究

采用氯仿溶解聚丁二酸丁二酯（PBS）,然后利用甲醇逐级沉淀分离获得不同相对分子质量及其分布的PBS级分,分别采用差示扫描量热仪、广角X射线衍射仪、偏光显微镜等对不同级分PBS的等温和非等温结晶动力学、晶体形态及结构进行了系统研究。结果表明,随着相对分子质量的增加和相对分子质量分布的变宽,各级分的半结晶时间逐渐降低,结晶半峰宽逐渐变窄,结晶度逐渐增加;但各级分PBS的晶型和晶貌并未发生明显的转变。     

生物可降解共聚物PBST和PBS的结构与结晶性能

利用核磁共振氢谱和广角X射线衍射法研究了生物可降解共聚物聚对苯二甲酸-共-丁二酸丁二醇酯(PBST)的结构及结晶性能,并与聚丁二酸丁二醇酯(PBS)进行比较。结果表明:PBST为无规共聚物,其晶体结构为三斜晶系,PBS为均聚物,为单斜晶系,PBST的结晶度和结晶尺寸均比PBS的小。     

聚丁二酸丁二醇酯的等温结晶动力学研究

采用差示扫描量热仪(DSC)对聚丁二酸丁二醇酯(PBS)的等温结晶动力学进行了研究,并用Avrami方程对实验数据进行了量化分析。研究结果表明:在等温结晶时,PBS倾向于以均相成核的三维生长方式结晶,并通过偏光显微镜进行了验证;同时,随着结晶温度的升高,PBS的结晶速率常数K值下降,半结晶时间t1/2延长。     

Morphology and hydrogen‐bond restricted crystallization of poly(butylene succinate)/cellulose diacetate blends

Poly(butylene succinate)/cellulose diacetate (PBS/CDA) blends were prepared by the solution blending method from poly(butylene succinate) (PBS) and cellulose diacetate (CDA). The influence of hydrogen bond on the structure, morphology, crystallization, as well as the physical properties of PBS/CDA blends was significantly investigated. The fourier transform infrared spectroscopy (FTIR) results indicated that the carbonyl groups of PBS shifted to higher wavenumbers and disappeared at the content of 60% CDA, due to the formation of hydrogen bond between PBS and CDA. The wide‐angle X‐ray diffractometer (WAXD) and differential scanning calorimeter (DSC) analysis suggest that the crystallization of PBS was significantly restricted by the incorporation of CDA, which is also attributed to the hydrogen bonding. The scanning electron miscroscope (SEM) and polarized optical microscopy (POM) results revealed that PBS and CDA were miscible without appearance of obvious phase separation. The hydrogen bonding interaction led to the change of decomposing mechanism of blends as determined by thermogravimetric analysis (TGA), as well as the increase of the elongation at break due to the reduced crystallinity of PBS. The existence of CDA led to the decrease of water contact angle, showing of the improved hydrophilicity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization of the mechanical properties,crystallization, and enzymatic degradation behavior of poly(butylene succinate‐co‐ethyleneoxide‐co‐DL‐lactide) copolyesters

A series of aliphatic biodegradable poly (butylene succinate‐co‐ethyleneoxide‐co‐DL ‐lactide) copolyesters were synthesized by the polycondensation in the presence of dimethyl succinate, 1,4‐butanediol, poly(ethylene glycol), and DL ‐oligo(lactic acid) (OLA). The composition, as well as the sequential structure of the copolyesters, was carefully investigated by ¹H‐NMR. The crystallization behaviors, crystal structure, and spherulite morphology of the copolyesters were analyzed by differential scanning calorimetry, wide angle X‐ray diffraction, and polarizing optical microscopy, respectively. The results indicate that the sequence length of butylene succinate (BS) decreased as the OLA feed molar ratio increasing. The crystallization behavior of the copolyesters was influenced by the composition and sequence length of BS, which further tuned the mechanical properties of the copolyesters. The copolyesters formed the crystal structures and spherulites similar to those of PBS. The incorporation of more content of ethylene oxide (EO) units into the copolyesters led to the enhanced hydrophilicity. The more content of lactide units in the copolyesters facilitated the degradation in the presence of enzymes. The morphology of the copolyester films after degradation was also studied by the scanning electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012