生物可降解聚丁二酸/苯基丁二酸丁二醇酯系列共聚物的合成及其结晶行为

合成了一系列聚丁二酸/苯基丁二酸丁二醇共聚酯(PBSBS),利用DSC、1H-NMR和X射线等测试手段对共聚物组成、热力学性能、结晶性能、等温结晶行为进行了表征和研究.结果表明,含苯基的共聚单元的引入显著改变了聚丁二酸丁二醇酯(PBS)的热力学性能4,利用Hoffman-Week曲线得到的共聚物平衡熔点随共聚组分含量的增加显著降低,玻璃化转变温度则明显升高,结晶熔点符合无规共聚物的Flory方程.此外,利用Avrami方程对均聚物PBS以及共聚物PBSBS-10分别进行了等温结晶行为研究,结果表明共聚使结晶速率降低,PBS和PBSBS-10的Avrami指数分别介于2.8~3.0和2.7~2.9之间,结晶方式为三维生长异相成核,X射线测试结果表明共聚不影响晶体结构.     

生物可降解聚丁二酸/甲基丁二酸丁二酯系列共聚物的合成和表征

摘要合成了一系列聚丁二酸/甲基丁二酸丁二醇共聚酯(PBSM), 利用DSC, 1H NMR和X射线衍射等方法对共聚物组成、 热学性能、 结晶性能、 等温结晶行为进行了研究. 结果表明, 引入甲基丁二酸共聚单元较为显著地改变了聚丁二酸丁二酯(PBS)的热学性能, 利用Hoffman\|Weeks方程得到的共聚物平衡熔点随共聚物的组分含量增加而降低, 玻璃化转变温度亦有所降低, 熔点则符合无规共聚物的Flory方程. 此外, 利用Avrami方程分别研究了均聚物PBS及共聚物PBSM-20的等温结晶行为, 结果表明， 在所研究的温度范围内, 聚酯结晶速率随温度升高而降低, PBS和PBSM\-20的Avrami指数分别介于2.8~3.0和2.7~3.0之间,  结晶方式为三维生长异相成核, 而X射线衍射测试结果表明晶体结构几乎不变.     

1，4-环己烷二甲醇改性生物可降解聚酯PBS的合成与性能表征

用熔融缩聚法合成了一系列聚（丁二酸丁二醇酯丁二酸-1,4-环己烷二甲醇酯）无规共聚物。通过。H—NMR、FT—IR、DSC、TGA、XRD、酶降解测试等方法表征了材料的结构与性能。结果表明：合成得到的共聚酯为预期产物;共聚酯的晶体结构发生了改变,并产生了共晶行为;随着1,4-环己烷二甲醇（CHDM）含量的增加,产物的熔点由113．7℃降至64．6℃,然后升至114．2℃,玻璃化转变温度由-33．8℃单调升高至5．4℃;CHDM的引入增强了共聚酯的热稳定性;酶降解测试得出产物P51、P31具有良好的生物降解性,且P51降解最快。     

胆甾液晶／聚合物多组分体系的结构与性质的研究 Ⅱ．壬酸胆甾酯／聚（甲基丙烯酸甲酯－甲基丙烯酸丁酯）混合体系的结晶动力学研究

研究了壬酸胆甾酯与甲基丙烯酸甲酯－甲基丙烯酸丁酯无规共聚物共混体系的等温结晶动力学．讨论了共聚物组成及分子链刚性对体系中胆甾液晶组分结晶速度及成核方式的影响     

POM/PBSA合金的分子间作用力与相容性及结晶行为研究

采用熔融共混的方法制备了聚甲醛(POM)/丁二酸丁二醇酯-己二酸丁二醇酯共聚物(PBSA)合金.利用FTIR、DMA、DSC、PLM及WAXD研究了POM与PBSA分子间相互作用、相容性及结晶行为.结果表明PBSA的羰基和POM的端羟基之间形成了氢键,这使得PBSA和POM具有一定的相容性,同时使POM的熔融与结晶温度降低;当POM含量为15%时对PBSA起到成核剂的作用,促进了PBSA的结晶,使其晶体结构变得致密.另外,POM与PBSA之间的相容性依赖于PBSA含量,随着PBSA含量的增大,两者的相容性变好,但是PBSA的加入并没有改变POM的晶型.     

聚丁二酸丁二醇酯的自成核结晶行为

利用差示扫描量热仪(DSC)研究了自成核对聚丁二酸丁二醇酯(PBS)的结晶行为的影响.研究结果表明,PBS的有效自成核温度处理区间为118～120℃.PBS经自成核处理后结晶温度提高,可以在100～118℃温度区间内迅速结晶.同时,研究了自成核处理后样品在100～104℃范围内的等温结晶行为、动力学过程及熔融行为.结果表明,随着等温结晶温度的升高,结晶速率变慢,熔融曲线出现多重熔融峰.Hoff-man-Weeks方程分析结果表明,自成核处理对PBS的平衡熔点没有影响.Avrami等温结晶动力学方程适合分析自成核处理样品的等温结晶动力学过程,获得其动力学参数K与n,其中n值偏大的原因在于自成核的样品结晶生长点增多.根据Arrhenius方程,计算获得PBS自成核处理后等温结晶活化能为-286 kJ/mol.     

聚丁二酸丁二酯的合成、共聚改性及功能化研究进展

聚丁二酸丁二酯(PBS)因具备良好的物理性能和加工性能而备受关注,是最具有前途的生物降解材料之一。本文总结了PBS材料合成、共聚改性及其功能化方面的研究进展。无规共聚、嵌段共聚等方法可以调节材料的力学性能、生物降解性能、热性能和结晶行为。通过与聚富马酸丁二酯无规共聚或者嵌段共聚,可以利用分子链上的双键高效引入磺酸根、羧酸、氨基等基团,提高材料的亲水性和生物相容性能,并制备PH响应性的电荷翻转胶束,拓展PBS在生物医药领域的应用。     

甲基取代的新型聚醚醚酮及其共聚物的合成、表征和性能研究

设计合成了一种甲基侧基取代的可溶性聚芳醚酮均聚物PETMDEK，同时合成了一系列不同比例的无规共聚物PETMDEK—PEDEK，考察了共聚组成对聚合物性能的影响．随着共聚物中可溶性PETMDEK组分的不断增加，其聚集态结构也发生变化，出现从结晶一液晶一结晶一无定形固体的转变，同时溶解性也由可溶向不溶转变．本文还侧重研究了PETMDEK组分摩尔分数为20％的无规共聚物的热致液晶行为．     

侧基为磺酸根基团的聚丁二酸丁二醇酯共聚物的合成及应用研究

以丁二酸,富马酸和1,4-丁二醇为原料,通过溶液聚合的方法合成了一系列主链含有碳碳双键的不饱和脂肪族聚酯,聚(丁二酸丁二醇酯-共-富马酸丁二醇酯)P(BS-co-BF)s.以过量的Na HSO3为磺化试剂,合成了侧基为磺酸根基团的聚丁二酸丁二醇酯PBS共聚物P(BS-co-SBS)s.运用核磁共振氢谱(1HNMR),红外光谱(IR)和凝胶渗透色谱(GPC)表征了共聚物的化学结构及分子量.结合溶剂挥发和透析法研究了系列共聚物P(BS-co-SBS)s在水中的自组装行为.动态光散射(DLS)和透射电镜(TEM)的研究发现,系列共聚物P(BS-co-SBS)s均可自组装形成稳定的、具有核壳结构,表面带有负电荷的胶束(尺寸:103~165nm,PDI:0.187~0.264,zeta电位-35~-51 m V).载药和释药的结果显示,胶束对疏水药物阿霉素具有一定的缓释效果.     

HDI作为扩链剂合成含PLLA和PBS链段的聚酯氨酯

以数均分子量为6350g/mol端羟基聚L-乳酸(PLLA-OH)与10500g/mol端羟基聚丁二酸丁二酯(PBS-OH)为预聚物,六亚甲基二异氰酸酯(HDI)为扩链剂,通过熔融反应制备了分子量高达30×104g/mol的可完全生物降解聚酯氨酯(PEU).研究了异氰酸根(NCO)与羟基比例对扩链反应的影响.结果表明,当[NCO]/[OH]=1∶1时,扩链效果最好,PEU分子量最大;PEU分子量随着预聚物中PBS含量增大而提高.通过核磁共振谱(1H-NMR)确定了PEU的结构与组成,并对聚酯氨酯进行了凝胶渗透色谱(GPC)、差示扫描量热(DSC)、热重分析(TGA)以及拉伸性能测试.DSC结果显示,扩链后PEU的结晶主要由PBS链段产生,而PLLA链段几乎不结晶;TGA结果表明,PEU的热降解分两步进行,第一步为PEU中PLLA链段的热降解,第二段为其中PBS链段的降解;拉伸测试结果表明,PBS与PLLA的共聚能够制备拉伸强度与断裂伸长率优异的聚合物材料.     

Thermal properties of poly(butylene oxalate) copolymerized with azelaic acid

Poly(butylene oxalate) (PBO) and poly(butylene oxalate/butylene azelate) random copolymers (PBOBAz) of various compositions were synthesized in bulk and characterized in terms of chemical structure and thermal properties. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All copolymers were found to be partially crystalline and thermally stable up to about 290 °C. The main effect of copolymerization was a decrease in melting and glass transition temperatures with respect to PBO homopolymer. The pure crystalline phase characteristic of PBO was evidenced by means of X-ray measurements in all the copolymers under investigation. The fusion temperatures appeared to be well correlated to composition by Baur's equation.Amorphous samples were obtained after melt quenching and showed a monotonic decrease of glass transition temperatures as the content of the flexible butylene azelate units is increased. Fox equation described well the T_g-composition data. Lastly, the overall crystallization rate of PBO was found to decrease regularly with increasing butylene azelate unit content.     

Performance of biodegradable microcapsules of poly(butylene succinate), poly(butylene succinate-co-adipate) and poly(butylene terephthalate-co-adipate) as drug encapsulation systems

Poly(butylene succinate) (PBSu), poly(butylene succinate-co-adipate) (PBSA) and poly(butylene terephthalate-co-adipate) (PBTA) microcapsules were prepared by the double emulsion/solvent evaporation method. The effect of polymer and poly(vinyl alcohol) (PVA) concentration on the microcapsule morphologies, drug encapsulation efficiency (EE) and drug loading (DL) of bovine serum albumin (BSA) and all-trans retinoic acid (atRA) were all investigated. As a result, the sizes of PBSu, PBSA and PBTA microcapsules were increased significantly by varying polymer concentrations from 6 to 9%. atRA was encapsulated into the microcapsules with an high level of approximately 95% EE. The highest EE and DL of BSA were observed at 1% polymer concentration in values of 60 and 37%, respectively. 4% PVA was found as the optimum concentration and resulted in 75% EE and 14% DL of BSA. The BSA release from the capsules of PBSA was the longest, with 10% release in the first day and a steady release of 17% until the end of day 28. The release of atRA from PBSu microcapsules showed a zero-order profile for 2 weeks, keeping a steady release rate during 4 weeks with a 9% cumulative release. Similarly, the PBSA microcapsules showed a prolonged and a steady release of atRA during 6 weeks with 12% release. In the case of PBTA microcapsules, after a burst release of 10% in the first day, showed a parabolic release profile of atRA during 42 days, releasing 36% of atRA.     

Thermal,mechanical and rheological properties of biodegradable poly(propylene carbonate) and poly(butylene carbonate) blends

Poly(propylene carbonate)(PPC) was melt blended in a batch mixer with poly(butylene carbonate)(PBC) in an effort to improve the toughness of the PPC without compromising its biodegradability and biocompatibility. DMA results showed that the PPC/PBC blends were an immiscible two-phase system. With the increase in PBC content, the PPC/PBC blends showed decreased tensile strength, however, the elongation at break was increased to 230% for the 50/50 PPC/PBC blend. From the tensile strength experiments, the Pukanszky model gave credit to the modest interfacial adhesion between PPC and PBC, although PPC/PBC was immscible. The impact strength increased significantly which indicated the toughening effects of the PBC on PPC. SEM examination showed that cavitation and shear yielding were the major toughening mechanisms in the blends subjected the impact tests. TGA measurements showed that the thermal stability of PPC decreased with the incorporation of PBC. Rheological investigation demonstrated that the addition of PBC reduced the value of storage modulus, loss modulus and complex viscosity of the PPC/PBC blends to some extent. Moreover, the addition of PBC was found to increase the processability of PPC in extrusion. The introduction of PBC provided an efficient and novel toughened method to extend the application area of PPC.     

PBT／PET共混体系非晶区的相容性

利用ＰＢＴ、ＰＥＴ的特性参数，通过不同组份比ＰＢＴ／ＰＥＴ共混体系的混合自由能△Ｇｍ，从理论上预测其相容性。在一定的条件下△Ｇｍ＜０，ＰＢＴ、ＰＥＴ可以相容。对不同组份比共混体系的玻璃化转变过程从分子链段运动的角度进行分析。     

Miscibility and properties of poly(l-lactic acid)/poly(butylene terephthalate) blends

Binary blends of poly(l-lactide) (PLLA) and poly(butylene terephthalate) (PBT) containing PLLA as major component were prepared by melt mixing. The two polymers are immiscible, but display compatibility, probably due to the establishment of interactions between the functional groups of the two polyesters upon melt mixing. Electron microscopy analysis revealed that in the blends containing up to 20% of poly(butylene terephthalate), PBT particles are finely dispersed within the PLLA matrix, with a good adhesion between the phases. The PLLA/PBT 60/40 blend presents a co-continuous multi-level morphology, where PLLA domains, containing dispersed PBT units, are embedded in a PBT matrix. The varied morphology affects the mechanical properties of the material, as the 60/40 blend displays a largely enhanced resistance to elongation, compared to the blends with lower PBT content.     

结晶性芳香聚酯高压结晶行为研究进展

运用高压极限手段研究聚合物的结构、形态和性能是20世纪60年代以来兴起的一项聚合物前沿课题。本文主要结合作者自己的研究工作，重点叙述聚对苯二甲酸乙二醇酯(PET)的高压结晶行为研究，包括温度、压力、时间及分子量对PET高压结晶行为的影响，高压结晶PET的形态。以及对PET伸直链晶体结晶机理的探讨，同时简要介绍了对其它结晶性芳香聚酯诸如聚对苯二甲酸丁二醇酯(PBT)及聚对萘二甲酸乙二醇酯(PEN)的高压结晶行为研究，反映了该领域的研究概况和最新进展。并对今后的研究提出了展望。     

Inhibited transesterification of PET/PBT blends filled with silica nanoparticles during melt processing

The blends of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) undergo transesterification reactions between PET and PBT during melt processing. In this research, PET/PBT transesterification has been investigated in the presence of nano-fillers, including pure SiO₂ and silane-coupling-agent-modified SiO₂. The results show that the incorporation of SiO₂ nanoparticles inhibits PET/PBT transesterification, and the influence of pure SiO₂ is higher than modified SiO₂. The inhibition of SiO₂ on transesterification is explained by the fact that the hydroxyl end groups of PET and PBT react with the surface hydroxyl groups of SiO₂ before transesterification due to the high activity of surface hydroxyl groups of SiO₂, and the reduction of hydroxyl end groups of PET and PBT leads to the inhibition of transesterification between PET and PBT. This has been demonstrated by the experimental data of TGA, FTIR, and XPS. And the reactivity of hydroxyl end groups of PBT is higher than that of PET.     

Fully biodegradable blends of poly(butylene succinate) and poly(butylene carbonate): Miscibility, thermal properties, crystallization behavior and mechanical properties

Fully biodegradable poly(butylene succinate) (PBS) and poly(butylene carbonate) (PBC) blends were prepared by melt blending. Miscibility, thermal properties, crystallization behavior and mechanical properties of PBS/PBC blends were investigated by scanning electron microscopy (SEM), phase contrast optical microscopy (PCOM), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and mechanical properties tests. The SEM and PCOM results indicated that PBS was immiscible with PBC. The WAXD results showed that the crystal structures of both PBS and PBC were not changed by blending and the two components crystallized separately in the blends. The isothermal crystallization data showed that the crystallization rate of PBS increased with the increase of PBC content in the blends. The impact strength of PBS was improved significantly by blending with PBC. When the PBC content was 40%, the impact strength of PBS was increased by nearly 9 times.     

Discrimination of Thermoplastic Polyesters by MALDI-TOF MS and Py-GC/MS

The aim of this work is to discriminate thermoplastic polyester-polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT), which cannot be easily identified by many methods. Both matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) were applied to identify these polyesters owing to their analytical ability to determining polymers' chemical structure. The three thermoplastic polyesters can be easily distinguished by MALDI-TOF MS according to their different repeated units. Py-GC/MS was used to analyze their specific pyrolyzates. The three polyesters can be identified through their characteristic pyrolysis products as well.