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.     

生物可降解共聚物聚丁二酸/对苯二甲酸丁二醇酯(PBST)的序列结构及结晶性研究

制备了高分子量的聚丁二酸丁二醇酯,并通过与对苯二甲酸二甲酯的无规共聚调节其生物可降解性及力学性能,得到了具有优良机械性能和不同生物降解速度的一系列共聚物,并对共聚物序列结构、热力学性能、结晶性进行了研究.结果表明,该共聚物为无规共聚物,PBS和PBT分别结晶.共聚物的结晶熔点符合无规共聚物的Flory方程.     

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. Hoffman-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-co-丁二酸丙二酯)的等温结晶行为研究

以1,4-丁二酸、1,4-丁二醇和1,3-丙二醇为原料通过直接熔融缩聚法合成了聚丁二酸丁二酯(PBS),聚丁二酸丙二酯(PPS)和聚(丁二酸丁二酯-co-丁二酸丙二酯)(PBSPS)等脂肪族聚酯.利用1H-NMR,WAXD,DSC和POM等研究了聚酯的结晶结构和结晶动力学过程等结晶行为.PBSPS的结晶晶型与PBS一致,说明只有丁二酸丁二酯(BS)单元结晶而丁二酸丙二酯(PS)单元处于无定形区.聚酯等温结晶后,在升温熔融过程中出现了多重熔融峰.分析表明多重熔融峰主要来自于聚酯升温过程中的熔融-重结晶行为.利用Avrami方程分析了聚酯的等温结晶动力学,Avrami指数n为2.2~2.8,说明聚酯等温结晶时主要以异相成核的三维生长方式进行;随着PS单元的增多,聚酯的表观结晶活化能升高,也就是说BS单元的结晶变得困难.POM观察到聚酯等温结晶时都出现了环带球晶现象,球晶形态会随着结晶温度和化学结构差异而改变.     

结合分子模拟探讨不同醚键PBS基共聚物的性能与酶催化降解

以硫二甘醇取代二甘醇,在聚(丁二酸丁二醇酯)(PBS)分子主链上分别引入硫醚和氧醚基团,得到聚(丁二酸丁二醇酯-丁二酸硫代二乙二醇酯)[P(BS-co-TDGS)]和聚(丁二酸丁二醇酯-丁二酸二乙二醇酯)[P(BS-co-DEGS)],通过热重分析(TG)和X射线衍射(XRD)测试比较了二者的结晶性能和热性能.采用南极假丝酵母脂肪酶N435(CALB)为催化剂,在水相中研究了P(BS-co-TDGS)和P(BS-co-DEGS)的降解规律及差异性.采用分子模拟方法研究了共聚物可能存在的聚集态以及N435酶与底物的结合,模拟结果验证了共聚物P(BS-co-TDGS)的结晶度下降及热稳定性降低的结论.分子对接模拟结果表明,N435酶与DEGSDEG单元的结合能更大,即含有丁二酸硫代二乙二醇酯键型底物P(BS-co-DEGS)与N435酶活性位点的对接更为稳定.     

离子液体增塑改性玉米淀粉/聚丁二酸丁二醇酯共混材料的结构与性能

为考察离子液体对淀粉/聚丁二酸丁二醇酯(PBS)的作用效果,降低淀粉/PBS的脆性,以离子液体(1-丁基-3-甲基咪唑氯盐[BMIM]Cl)作为增塑改性剂通过熔融共混法制备了玉米淀粉/聚丁二酸丁二醇酯(PBS)共混材料,采用红外光谱(FTIR)、扫描电镜(SEM)、热重分析(TGA)、X射线衍射分析(XRD)及力学性能测试方法研究了[BMIM]Cl对淀粉/PBS共混材料结构和性能的影响.结果表明,[BMIM]Cl能与淀粉/PBS分子发生强相互作用,破坏淀粉/PBS共混物中原有的氢键与结晶结构,增强界面相互作用,改善相容性,进而改变淀粉/PBS共混材料的结构与性能;[BMIM]Cl的加入不影响淀粉/PBS的热稳定性,可使材料玻璃化转变温度(Tg)、结晶温度(Tc)、冷结晶温度(Tcc)及结晶度(Xc)降低.[BMIM]Cl具有显著降低淀粉/PBS脆性的作用,使其断裂伸长率大幅度增加,拉伸强度和弹性模量降低.     

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。     

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.     

含异山梨醇的全生物基PBS嵌段共聚酯的制备及性能

采用熔融扩链法制备了高分子量的全生物基聚丁二酸丁二醇酯(PBS)-聚丁二酸异山梨醇酯嵌段共聚酯.GPC测试结果表明,该嵌段共聚酯在较高的异山梨醇(Is)含量时仍具有较高的分子量,其M_n介于3.5×10~4~7.0×10~4之间.采用TGA和DSC对嵌段共聚酯的热稳定性和结晶性能进行了研究,结果表明嵌段共聚酯保持了PBS优异的热稳定性和结晶性能,即使异山梨醇含量达60 mol%,其熔点较PBS仅下降2 K.采用DMA分析了嵌段共聚酯的玻璃化转变温度T_g,发现随着异山梨醇含量的增加,其T_g随之升高,当Is含量为60mol%时,嵌段共聚酯的T_g高达68℃,并且共聚酯的2个链段具有很好的相容性.力学性能测试结果表明,异山梨醇的引入可使PBS的力学性能得到明显地提高和调控,随着异山梨醇含量的增加,嵌段共聚酯的拉伸强度先增加后降低,断裂伸长率约是PBS的2倍,其中,当异山梨醇含量达60 mol%时,嵌段共聚酯的屈服强度由PBS的35.0 MPa增至43.0 MPa.     

分子间氢键的形成对聚丁二酸丁二酯结晶熔融及动态力学行为的影响

研究了含有酚羟基的小分子添加剂双酚A(BPA)对可生物降解高分子材料聚丁二酸丁二酯(PBS)的结晶、熔融及玻璃化转变的影响.研究表明在PBS中添加BPA,使PBS的结晶能力下降、熔点降低,这源于PBS与BPA通过氢键相互作用形成复合物,破坏了PBS的规整结晶结构.动态力学热分析表明,复合物的玻璃化转变温度随着BPA含量...     

Properties of biodegradable poly(butylene succinate) (PBS) composites with carbon black

Biodegradable poly(butylene succinate)/carbon black (PBS/CB) nanocomposite was prepared by melt compounding and the amount of CB loading was 3 wt %. The PBS/CB nanocomposite exhibited not only a good dispersion of aggregates of CB in the PBS matrix, but also an improvement in mechanical and electrical properties as well. The nonisothermal crystallization behavior and crystal structure of neat PBS and its nanocomposite were also studied by differential scanning calorimetry and wide angle X-ray diffraction in detail. The crystal morphology is observed by polarized optical microscopy. The Avrami equation and the Mo equation were employed to describe the nonisothermal crystallization kinetics. The Mo equation was found to be more suitable to predict the whole nonisothermal crystallization process for both neat PBS and its nanocomposite. It was concluded that the addition of CB retarded the crystallization rate compared with that of neat PBS at the same cooling rate, which can be attributed to restricting effect of CB on the segmental motions of the polymer chains. Moreover, the incorporation of the CB particles does not modify the crystal structure of PBS.     

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.     

Melting behaviors,crystallization kinetics,and spherulitic morphologies of poly(butylene succinate) and its copolyester modified with rosin maleopimaric acid anhydride

This article investigated the melting behaviors, crystallization kinetics, and spherulitic morphologies of poly(butylene succinate) (PBS) and its copolyester (PBSR) modified with rosin maleopimaric acid anhydride, using wide‐angle X‐ray diffraction, differential scanning calorimeter (DSC), and polarized optical microscope. Subsequent DSC scans of isothermally crystallized PBS and PBSR exhibited two melting endotherms, respectively, which was due to the melt‐recrystallization process occurring during the DSC scans. The equilibrium melting point of PBSR (125.9 °C) was lower than that of PBS (139 °C). The commonly used Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the model combining Avrami equation and Ozawa equation was employed. The result showed a consistent trend in the crystallization process. The crystallization rate was decreased, the perfection of crystals was decreased, the recrystallization was reduced, and the spherulitic morphologies were changed when the huge hydrogenated phenanthrene ring was added into the chain of PBS. The activation energy (ΔE) for the isothermal crystallization process determined by Arrhenius method was 255.9 kJ/mol for PBS and 345.7 kJ/mol for PBSR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 900–913, 2006     

Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

Synthesis and performances of poly(butylene-succinate) with enhanced viscosity and crystallization rate via introducing a small amount of diacetylene groups

A cross-linkable comonomer containing a diacetylene group, named dimethyl 4,4'-(buta-1,3-diyne-1,4-diyl)dibenzoate (DA) was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a series of slightly cross-linked PBS copolyesters (PBDASx). The chemical structure, crystallization and rheological behaviours of PBDASx were well investigated. Compared to neat PBS, PBDASx showed the greatly increased crystallization rate because of the promoting nucleation of the cross-linking domains, and the XRD results indicated that it had no influence on crystallization structure of PBS. The rheological behaviours indicate that PBDASx possessed higher viscosity than neat PBS even at high shear rate and temperature. PBDAS0.3 exhibited better comprehensive properties than neat PBS, which will widen applications of PBS.     

CRYSTALLIZATION KINETICS OF ETHYLENE-PROPYLENE COPOLYMERS PREPARED BY LIVING COORDINATION POLYMERIZATION

In this paper,crystallization kinetics of a series of ethylene-propylene copolymers prepared by living polymerization coordination catalyzed by a fluorinated bis(phenoxyimine)Ti catalyst(FI-EP copolymers)was studied,and was compared with that of ethylene-propylene copolymers prepared by a conventional Ziegler-Natta catalyst(ZN-EP copolymers).It is found that,the Avrami exponent and the crystallization rate constant of the FI-EP and ZN-EP copolymer show similar dependence on crystallization temperature,bu...     

Isothermal crystallization of propylene-1-decene copolymers

The isothermal crystallization and subsequent melting behavior of one propylene homopolymer and three propylene-1-decene copolymers with different comonomer contents prepared by metallocene catalyst were studied using differential scanning calorimetry (DSC). It is found that the Avrami exponent of the propylene copolymers decreases gradually with the increase of comonomer content, from 3.0 for the propylene homopolymer to 1.4 for the copolymer with 7.83 mol% 1-decene units. Higher comonomer content also weakens the dependence of crystallization rate constant and crystallization halftime on temperature. Double melting peaks, which correspond to α and γ crystal phases, respectively, are observed for all copolymers under isothermal crystallization. The result shows that higher crystallization temperature is favorable to the segregation of α and γ crystal phases, resulting in higher proportion of γ crystal phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Crystallization kinetics and morphology of biodegradable poly(butylene succinate‐co‐propylene succinate)s

The crystallization behavior of biodegradable poly(butylene succinate) and copolyesters poly(butylene succinate‐co‐propylene succinate)s (PBSPS) was investigated by using ¹H NMR, DSC and POM, respectively. Isothermal crystallization kinetics of the polyesters has been analyzed by the Avrami equation. The 2.2‐2.8 range of Avrami exponential n indicated that the crystallization mechanism was a heterogeneous nucleation with spherical growth geometry in the crystallization process of polyesters. Multiple melting peaks were observed during heating process after isothermal crystallization, and it could be explained by the melting and recrystallization model. PBSPS was identified to have the same crystal structure with that of PBS by using wide‐angle X‐ray diffraction (WAXD), suggesting that only BS unit crystallized while the PS unit was in an amorphous state. The crystal structure of polyesters was not affected by the crystallization temperatures, too. Besides the normal extinction crosses under the POM, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. The morphology of spherulites strongly depended on the crystallization temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 420–428, 2007