Fractionated Crystallization Kinetics and Polymorphic Homocrystalline Structure of Poly(L-lactic acid)/Poly(D-lactic acid) Blends: Effect of Blend Ratio

Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(_L-lactic acid)/poly(_D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (f_D=0.01–0.5) as the model system and investigate the effects of f_D and crystallization temperature (T_c) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both f_D and T_c. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high f_D (≥0.2) at a low T_c (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.

     

制备聚(L-乳酸-co-乙醇酸）/聚D-乳酸共混物立构复合物的新方法

首次以高分子量的聚(L-乳酸-co-乙醇酸）(PLLGA）和D-聚乳酸（PDLA)［m(PLLGA) : m(PDLA)=3:1, c 50 mL·g^-1］为原料,氯仿为溶剂,等体积的甲醇为沉淀剂,于50 ℃蒸发4 h形成了PLLGA和PDLA的立构复合物（sc-PLA）,其结构和性能经XRD, DSC和TGA表征。结果表明：sc-PLA的结晶度达96.2%,热失重5%温度为342 ℃（PLLGA为304 ℃）。     

PPDO/PLLA共混物的制备及其相容性

通过溶液共沉淀法制备了一系列不同组份比例的PPDO/PLLA共混物(Pw)。通过溶度参数、扫描电镜及差式扫描量热仪(DSC)研究了Pw的相容性。结果表明:PPDO与PLLA相容性差;Pw的脆断面扫描电镜图片显示,在不同共混比例下,PLLA在基体PPDO中成典型"海-岛"式分布,且当PLLA含量超过30%时,Pw中出现部分PLLA连续相。     

An AFM Study of Poly(L-lactic acid) and Poly(D-lactic acid) Macromolecules and Their Stereocomplexes at the Solid-Air Interface

The self assembly of PLA enantiomers have been studied at the nanometer scale using atomic force microscopy. At first, the conformation of D and L PLA macromolecules in dilute regime and the initial state of aggregation of both enantiomers were successively observed and compared with the aggregation of PLLA/PDLA blends. Our results points out differences in the aggregates structure between the homo-aggregates of each enantiomers and the 3 Dimensional stereocomplexes formed with racemic mixture of D and L entities. On the one hand, D or L PLA chains, which adopt a rigid conformation in dilute regime, form gradually aggregates that tend to grow from a nucleation center. On the other hand, stereocomplexes have a non-compact structure and are elongated with height variations within the fibrils that support the side by side aggregation of D and L helical structures to form thicker fibrils.     

Stereocomplex Formation of Atactic Poly(methyl methacrylate)

Stereocomplexes formed in atactic poly(methyl methacrylate) (a-PMMA) films cast form different solvents were studied by means of Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The growth of stereocomplex was a function of annealing temperature and annealing time, respectively.     

Stereocomplex Formation of Atactic Poly(methyl mcthacrylate)

Ithasbeenknownthatmixingofsyndiotacticandisotacticpoly(methylmethacrylate)(PMMA)hopolymersinsomesuitablesolventscanformstereocomplexesbytheverderWaalforcebetweenthesyndiotacticandisotacticsegments',butwhetherstereocomplexcouldbeformedina-PMMAhasbeenstillapuzzle'-'.Inthispaper,wewishtofindoutwhethera-PMMAcouldformstereocomplexes,andtherelationshipbetweenstereocomplexationandannealingconditionswasalsodiscussed.FTIRspectraofthea-PMMAfilms,preparedbycastfromacetone,benzeneandchloroformsolu…     

右旋聚乳酸薄膜的结晶形态

利用旋涂法制备一系列右旋聚乳酸(PDLA)均聚物薄膜, 在不同溶液浓度、结晶温度、结晶时间、溶剂和基底条件下对其进行等温结晶处理, 得到直径和长度大小不等的短棒和纤维束球状等形态, 利用原子力显微镜(AFM)研究了不同条件下所得到的PDLA薄膜的结晶形态. 提出了可能的结晶演变过程和生长模型. 通过控制不同的结晶条件, 可以得到PDLA均聚物薄膜的不同结晶形态.     

Poly(methyl methacrylate)-induced Microstructure and Hydrolysis Behavior Changes of Poly(L-lactic acid)/Carbon Nanotubes Composites

Poly(L-lactic acid)(PLLA)-based composites exhibit wide applications in many fields.However,most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA,which is unfavorable for the prolonging of the service life of the articles.In this work,a small quantity of poly(methyl methacrylate)(PMMA)(2 wt%-10 wt%)was incorporated into the PLLA/carbon nanotubes(CNTs)composites.The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated.The results showed that PMMA promoted the dispersion of CNTs in the composites.Amorphous PLLA was obtained in all the composites.Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA,especially at relatively high PMMA content.Incorporating 10 wt%PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19%/h of the PLLA/CNT composite sample to 0.059%/h of the PLLA/PMMA-10/CNT composite sample.The microstructure evolution of the composites was also detected,and the results showed that no crystallization occurred in the PLLA matrix.Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs,which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs.This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.     

A Mini Review on the Functional Biomaterials Based on Poly(lactic acid) Stereocomplex

Poly(lactic acid) stereocomplex (sc-PLA) prevails over homo-poly(lactic acid)s in many aspects and showed great potential as biomaterials depending on its extraordinary biological, thermal, and mechanical properties. In the past few years, sc-PLA has gained tremendous attention as a new approach to the development of new types of functional biomaterials. This paper summarizes recent progress in the application of the concept of sc-PLA in the design and fabrication of stabilized nanoparticles and in situ gelling hydrogels for biomedical applications.     

聚左旋乳酸/聚氧化乙烯共混物的拉伸行为及结构转变

采用熔融共混方法制备了聚左旋乳酸(PLLA)和超高分子量聚氧化乙烯(PEO)共混物, 通过差示扫描量热(DSC)、 扫描电子显微镜(SEM)和二维广角X射线散射(2D-WAXS)等方法系统研究了PEO的加入对不同温度下PLLA拉伸行为及拉伸过程中微观结构变化的影响. 结果表明, PLLA/PEO共混物为非均相体系, PEO粒子均匀分布在PLLA中形成两相结构. PEO的加入能够显著降低PLLA的玻璃化转变温度(T_g), 在25～60 ℃范围内显著提高PLLA的拉伸性能. 在60 ℃拉伸时, PEO的加入提高了PLLA在拉伸过程中的结晶和形变能力. 在80 ℃拉伸时, 共混物的拉伸断裂伸长率下降, 但共混物的结晶速度仍高于纯PLLA样品.     

Enhanced stereocomplex formation of poly(L-lactic acid) and poly(D-lactic acid) in the presence of stereoblock poly(lactic acid)

Stereoblock poly(lactic acid) (sb-PLA) is incorporated into a 1:1 polymer blend system of poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA) that has a high molecular weight to study its addition effect on the stereocomplex (sc) formation of PLLA and PDLA. The ternary polymer blend films are first prepared by casting polymer solutions of sb-PLA, PLLA, and PDLA with different compositions. Upon increasing the content of sb-PLA in the blend films the sc crystallization is driven to a higher degree, while the formation of homo-chiral (hc) crystals is decreased. Lowering the molecular weight of the incorporated sb-PLA effectively increases the sc formation. Consequently, it is revealed that sb-PLA can work as a compatibilizer to improve the poor sc formation in the polymer blend of PLLA and PDLA.     

聚乳酸立构复合物的研究最新进展与应用展望

立构复合型聚乳酸(SC-PLA)由于聚左旋乳酸(PLLA)与聚右旋乳酸(PDLA)分子链之间强烈的相互作用,可以使熔点提高约50℃,改善了聚乳酸在耐热性上的不足,同时这种立构复合结构使聚乳酸的力学性能、结晶性能、耐水解性等也得到提升.立构复合型聚乳酸的合成新进展主要集中在嵌段型SC-PLA的制备,同时广泛采用X射线衍射...     

Temperature-dependent Crystallization and Phase Transition of Poly(L-lactic acid)/CO_2 Complex Crystals

Semicrystalline polymers can crystallize in the unique crystalline polymorph and show different phase behaviors under the highpressure CO_2 treatment. Understanding such unique crystallization and phase transition behavior is of fundamental importance for the CO_2-assisited processing of semicrystalline polymers. Herein, we investigated the polymorphic crystalline structure, phase transition, and structureproperty relationships of poly(L-lactic acid)(PLLA) treated by CO_2 at different pressures(1-13 MPa) and crystallization temperatures(T_c's, 10-110 °C). PLLA crystallized in the PLLA/CO_2 complex crystals under 7-13 MPa CO_2 at T_c≤50 °C but the common α crystals under the high-pressure CO_2 at T_c≥70 °C. Solid-state nuclear magnetic resonance analysis indicated that the PLLA/CO_2 complex crystals possessed weaker interactions between the PLLA chains than the common α crystals. The PLLA/CO_2 complex crystals were metastable and transformed into the thermally stableα crystals via the solid-to-solid route during heating or annealing at the temperature above 50 °C. The complex crystals of PLLA produced at low T_c was more ductile than the α crystals due to the lower crystallinity and the plasticizing effect of CO_2.     

远离临界组成的聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物共混薄膜表面相分离动力学

采用温控原子力显微镜方法,在线跟踪了远离临界组成聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混薄膜的表面相分离行为,并研究了其动力学规律。 结果表明,在SAN含量为70%的样品中观察到了表面相分离行为,其过程可分为早期、中期和晚期3个阶段,分别对应特征化的标度指数:早期结果验证了Cahn线性理论,即标度指数为零;中期相行为主要受“碰撞-扩散”机理控制,因此表现出1/3的标度指数;在相分离后期,流体动力学主导了相区的生长和归并行为,此时标度指数变为2/3。 我们的研究结果对于深刻理解高分子相行为具有积极作用,并将对高分子薄膜加工提供必要的指导。     

Synthesis and Antibacterial Action of Poly(DMAEMA-BC)with Various Molecular Weights

Antibacterial polymers of dimethylaminoethyl methacrylate benzyl ammonium chloride(DMAEMA-BC) with various molecular weights(Mws) were prepared under controlling radical polymerization conditions. The Mws of these polymers were determined by means of static multiangle laser light scattering and viscosity method. A Mark-Houwink equation was established to be [η]=0.154M0.764 for the Mw evaluation of poly(DMAEMA-BC)s. The effects of the Mws of these poly(DMAEMA-BC)s on their antibacterial activities against E. coli and S. aureus were investigated by various methods including viable cell counting, electrical conductivity titration, intracellular constituent leakage tests and electron microscopy. Our results indicate that the antibacterial efficiency of DMAEMA-BC was significantly enhanced after the monomers were polymerized into a polymer and increased obviously with the Mws,as a result of the increase of charge density. Further investigation of the molecular basis underlying the anti-bacterial role of these polymers revealed that poly(DMAEMA-BC) promoted the release of potassium ion from the membrane of bacterial cells and the release increased significantly with the Mws of the polymers used.     

溶剂诱导的聚乳酸/聚乳酸衍生物共结晶行为

通过溶液浇铸法制备不同组分的左旋聚乳酸(PLLA)和聚(L-2-羟基-3-甲基丁酸)(PL-2H3MB)共混物.运用差示扫描量热仪(DSC)、偏光显微镜(POM)、广角X射线衍射(WAXD)和热重分析仪(TGA)分析共混物的结晶、熔融行为和热稳定性.通过观察到DSC加热曲线中新的熔融峰判断PLLA和PL-2H3MB共晶...     

聚乳酸扩链及热性能研究

采用L-乳酸熔融缩聚,制备了粘均相对分子质量较低的聚乳酸,并以亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚为扩链剂对其扩链。亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚可以有效提高聚乳酸的粘均相对分子质量,但是,扩链产物PLLA-TPPi和PLLA-BDDE的粘均相对分子质量未随亚磷酸三苯酯和1,4-丁二醇二缩水甘油醚的用量呈线性变化,而是表现为一峰值。PLLA-TPPi和PLLA-BDDE的玻璃化温度均随扩链产物的粘均相对分子质量的增大而提高;与PLLA-BDDE相比,PLLA-TPPi链中的TPPi结构更能有效促进PLLA链的结晶。     

The Crystallization and Melting Processes of Poly(L-lactic acid)

A throughout investigation of crystallization and melting behavior of poly(L -lactic acid) is detailed in this contribution. Crystallization analyses, conducted in both isothermal and non-isothermal conditions, revealed the occurrence of a sudden acceleration in phase transition rate in the temperature range between 100 and 118 °C. This unusual increase, due to very high rates of spherulite growth, seems not related to morphological changes of PLLA spherulites, nor to unexpected variations in nucleation rate. DSC analyses disclosed multiple melting behavior of PLLA, depending on crystallization temperature. At low temperatures the very high crystallization rates lead to the achievement of low values of crystalline degree, with formation of small and/or defective crystals, which have a large tendency to reorganize into more stable structures during the heating scan that leads to complete fusion. The multiple melting process of PLLA was also analyzed at different heating rates.     

Sorption and Swelling of Poly(D,L-lactic acid) and Poly(lactic-co-glycolic acid) in Supercritical CO2

Summary: The equilibrium sorption and swelling behavior in supercritical CO₂ of poly(D,L-lactic acid) and poly(lactic-co-glycolic acid) has been studied at a temperature of 35 °C and at pressures up to 200 bar. Sorption was measured through a gravimetric technique and swelling by visualization. From these data, the behavior of the different polymers can be compared. In terms of partial molar volume of CO₂ in the polymer matrix, all the polymers exhibit a behavior typical of rubbery systems. The experimental results have been modeled using the Sanchez-Lacombe equation of state, which is able to represent the actual behavior of the polymer-CO₂ systems with reasonable accuracy.     

静电纺丝法制备胆固醇-g-聚乳酸液晶/ 聚乳酸复合纳米纤维膜

以辛酸亚锡为催化剂, 胆固醇(CHOL)为共引发剂引发D,L-丙交酯开环聚合, 制备了胆固醇-g-聚(D,L-乳酸)(CHOL-g-PDLLA)低聚物, 采用偏光显微镜(POM)和差示扫描量热(DSC)方法考察了其液晶特性. 通过静电纺丝技术制备了CHOL/PDLLA和CHOL-g-PDLLA /PDLLA复合纳米纤维膜, 对其形貌、界面相容性、孔隙率、拉伸性能和细胞相容性进行了研究. 结果表明, CHOL-g-PDLLA为一种热致胆甾型液晶, 液晶温度区间为21.8~74.5 ℃; CHOL-g-PDLLA/PDLLA复合纳米纤维膜的纤维形态良好, 表面均匀光滑, 孔隙率在70%~75%之间, 且其界面相容性优于相应的CHOL/PDLLA. 随着CHOL和CHOL-g-PDLLA含量的增加, 复合纳米纤维膜的拉伸强度逐渐下降, 但CHOL-g-PDLLA/PDLLA复合纳米纤维膜的拉伸强度显著大于CHOL/PDLLA. 体外骨髓间充质干细胞培养结果显示, CHOL-g-PDLLA/PDLLA复合纳米纤维膜具有良好的细胞相容性, 且优于相应的PDLLA和CHOL/PDLLA纳米纤维膜.