An efficient solid‐state polycondensation method for synthesizing stereocomplexed poly(lactic acid)s with high molecular weight

Simultaneous solid‐state polycondensation (SSP) of the powdery prepolymers of poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) can produce entire stereocomplexed poly(lactic acid)s (sc‐PLA) with high molecular weight and can be an alternative synthetic route to sc‐PLA. Ordinary melt polycondensations of L ‐ and D ‐lactic acids gave the PLLA and PDLA prepolymers having medium molecular weight which were pulverized for blending in 1:1 ratio. The resultant powder blends were then subjected to SSP at 130–160 °C for 30 h under a reduced pressure of 0.5 Torr. Some of the products thus obtained attained a molecular weight (M_w) as high as 200 kDa, consisting of stereoblock copolymer of PLLA and PDLA. A small amount of the stereocomplex should be formed in the boundaries of the partially melted PLLA and PDLA where the hetero‐chain connection is induced to generate the blocky components. The resultant SSP products showed predominant stereocomplexation after their melt‐processing in the presence of the stereoblock components in spite of containing a small amount of racemic sequences in the homo‐chiral PLLA and PDLA chains. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3714–3722, 2008     

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 ℃）。     

Poly(lactic acid) Synthesis in Solution Polymerization

The step-growth polymerization of L-lactic acid in solution was studied in this work. In order to attain a polymer with high molecular weight, the water formed during the polymerization must be continuously removed. The use of organic solvents with high boiling point, drying agents and reduced pressure led to poly(lactic acid) (PLA) with high molecular weight, directly from the monomer. Tin (II) chloride dihydrate, SnCl₂.2H₂O, was the best of the catalysts tested as it allowed achieving PLA with a molecular weight close to 80 000 g.mol⁻¹. However, the stereoregurarity control is a severe problem in PLA synthesis by step-growth due to transesterification reactions, which lead to an inversion of the conformation and a decrease of the optical purity of the polymer. Specific rotation measurements were used in this work and showed to be a powerful technique to evaluate the racemization extent. The thermal stability of the PLA samples was evaluated by DSC which exhibits a thermal behaviour similar to the commercial Polylactide.     

Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid)

Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.     

开环聚合-固相缩聚法制备立体嵌段聚乳酸

首先,采用乳酸为引发剂,辛酸亚锡为催化剂,引发丙交酯开环聚合制得具有缩聚活性的L-聚乳酸和D-聚乳酸;然后,将两者熔融共混后进行固相缩聚,合成了一系列立体嵌段聚乳酸。采用核磁共振(NMR)、凝胶渗透色谱(GPC)及差示扫描量热仪(DSC)分析了产物的链结构、重均分子量、热性能,并探讨了均相晶体和立体复合晶体共存情况下的固相缩聚机理。结果表明,固相缩聚产物分子量增长的适宜反应条件为:反应时间30h,较低的催化剂含量,L-聚乳酸质量分数为80%。L-聚乳酸和D-聚乳酸共混物较低的初始立体复合晶体结晶度有利于后续固相缩聚过程中产物分子量的增长;固相缩聚不仅发生在异链之间,而且也发生在同链之间。     

Melt polycondensation of L‐lactic acid with Sn(II) catalysts activated by various proton acids: A direct manufacturing route to high molecular weight Poly(L‐lactic acid)

Poly(L ‐lactic acid) (PLLA) was produced by the melt polycondensation of L ‐lactic acid. For the optimization of the reaction conditions, various catalyst systems were examined at different temperature and reaction times. It was discovered that Sn(II) catalysts activated by various proton acids can produce high molecular weight PLLA [weight‐average molecular weight (M_w ) ≥ 100,000] in a relatively short reaction time (≤15 h) compared with simple Sn(II)‐based catalysts (SnO, SnCl₂ · 2H₂O), which produce PLLA with an M_w of less than 30,000 after 20 h. The new catalyst system is also superior to the conventional systems in regard to racemization and discoloration of the resultant polymer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1673–1679, 2000     

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.     

聚丁二酸丁二醇酯与氯醚弹性体协同增韧改性聚乳酸多元共混体系

以来源于可再生资源聚丁二酸丁二醇酯(PBS)和氯醚橡胶(ECO)作为聚乳酸(PLA)的增韧改性剂,通过熔融共混的方法制备了PLA/PBS/ECO三元共混体系。动态力学分析和扫描电子显微镜结果表明,ECO促进了PBS和PLA之间的相容性。力学性能测试表明,ECO与PBS可实现对聚乳酸基体的协同增韧: PLA/PBS/ECO(70/20/10)显示出最优的拉伸性能,断裂伸长率高达270%;PLA/PBS/ECO(70/10/20)的冲击强度提高至23.7 kJ/m²,是纯聚乳酸的12倍。结合形态结构和冲击断面形貌分析表明ECO的存在可起到增容/增韧双重作用, 与柔性PBS产生良好的协同效应,有效改善聚乳酸材料的韧性。我们的研究表明,构造PLA-柔性生物聚酯和生物基弹性体多元共混体系是一种获得高性能生物基材料简单高效的手段。     

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.     

Design,Synthesis and Characterization of A Novel Cationic Polymer Poly(lactic acid-b-L-lysine)

A novel biodegradable block copolymer poly(lactic acid-b-lysine) (PLA-b-PLL) has been synthesized and characterized in this study. This product was synthesized via a five-step reaction: Synthesis of hydroxyl-tailed poly(lactic acid) (PLA) by the ring-opening polymerization (ROP) of D,L-lactide in the presence of stannous octoate (Sn(OCt)₂) as initiator; coupling N-t-butoxycarbonyl-L-phenylalanine to hydroxyl-tailed PLA using dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP); the amino-tailed PLA was obtained through de-protection of the Boc-protective group in trifluoroacetic acid (TFA) solution; and then ring-opening polymerization of N ^ε -(Z)-lysine-N-carboxyanhydride (NCA) using the amino-tailed PLA as macro-initiator; finally removal of the Cbz-protective group of PLA-b-poly(N ^ε -(Z)-L-lysine) (PLA-b-PLL(Z) in a mixed hydrobromic acid/acetic acid solution to give the target copolymer. The characterization of this copolymer and its precursors were performed by ¹H-NMR, FTIR and GPC. The block copolymer PLA-b-PLL, combining the characteristics of an aliphatic polyester and poly(amino acids), could be of potential interest in a variety of medical applications, such as the fields of targeted drug delivery and gene delivery systems.     

Poly(lactic acid) Polymerized by Aluminum Triflate

The ring-opening polymerization of L -lactide (LA) has been initiated by aluminum triflate (trifluoromethanesulfonate) in air using a simple glass tube at 100 °C without desiccation steps and stirring. It was found that the molecular weight of poly(lactic acid) (PLA) was increased by the addition of an alcohol as an initiator to the reaction mixture. The highest number averaged molecular weight, molecular weight distribution, and recovery of the obtained PLA at 100 °C for 6 h were 18,200, 1.20, and 73%, respectively. With the addition of a small percentage of alcohol and a long reaction time of the polymerization method with the re-addition of LA, PLA (ca. 80 wt%) with a higher molecular weight (ca. 30,000) initiated by the added alcohol was produced with PLA (ca. 20 wt%) with a lower molecular weight (ca. 2,000) initiated by impurities such as water, which exist in a monomer, initiator, or catalyst.     

Poly(lactic acid)‐based nanocomposites

Classic plastics accumulate in nature causing environmental pollution, yet as a counterbalance they benefit society in many ways. They are versatile, cost‐effective, and can be tailored to have desired properties. The global environment has led to the fabrication of commodity plastics from environmentally degradable polymers. Poly(lactic acid) (PLA) is the most promising among the environmentally friendly polymers available. PLA‐based plastics have mechanical, thermal, and transparency similar to traditional plastics, and they can be molded and fabricated using the same equipment and procedures. Their material properties are enhanced through nanocomposites, compatibilizers, plasticizers, and other fillers (flame retardant, ultraviolet filter, etc.). This review summarizes mass production techniques and property reinforcements (focusing on nanocomposites and plasticizers) for PLA‐based plastics for commodity use. Copyright © 2016 John Wiley & Sons, Ltd.     

聚乳酸热塑性弹性体的研究进展

热塑性弹性体(TPE)是一类应用领域非常广泛且极具发展潜力的高分子材料,然而目前TPE品种所选用的原料(包括单体或聚合物)绝大部分都是源于石油基不可再生资源。作为一种极具潜力替代石油基高分子的生物基脂肪族聚酯材料,聚乳酸(PLA)具有原料来源丰富并可再生、生物降解性良好、强度和模量高等优点,因此聚乳酸TPE的研究吸引了国内外学者广泛的关注。本文综述了PLA嵌段共聚物型TPE和PLA基动态硫化热塑性弹性体(TPV)的最近的研究进展,详细阐述了它们的制备路线以及材料的性能,最后指出了当前PLA热塑性弹性体研究中存在的不足。     

Synthesis and characterization of multiblock copolymers based on L‐lactic acid,citric acid,and poly(ethylene glycol)

Because poly(L ‐lactic acid) (PLLA) is a biodegradable polyester with low immunogenicity and good biocompatibility, it is used as a biomaterial. However, hydrophobic PLLA does not have any reactive groups. Thus, its application is limited. To increase the hydrophilicity of PLLA and accelerate its degradation rate, functionalized pendant groups and blocks were introduced through copolymerization with citric acid and poly(ethylene glycol) (PEG), respectively. This article describes the synthesis and characterization of poly(L ‐lactic‐co‐citric acid) (PLCA)‐PLLA and PLCA‐PEG multiblock copolymers. The results indicated that the hydrolysis rate was enhanced, and the hydrophilicity was improved because of the incorporation of carboxyl groups in PLCA‐PLLA. The joining of the PEG block led to improved hydrophilicity of PLCA, and the degradation rate of PLCA‐PEG accelerated as compared with that of PLCA‐PLLA. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2073–2081, 2003     

Synthesis and Characterization of Stereo Multiblock Poly(lactic acid)s with Different Block Lengths by Melt Polycondensation of Poly(L‐lactic acid)/Poly(D‐lactic acid) Blends

Stereo multiblock PLAs with different block lengths are synthesized by melt polycondensation of low‐molecular‐weight poly(L ‐lactic acid)/poly(D ‐lactic acid) blends with a wide variety of $\overline {M} _{{\rm w}} $ in the range of 1.1–5.2 × 10³ g · mol^–1. The average block length (ν_av) of the stereo multiblock PLAs increases with increasing $\overline {M} _{{\rm w}} $ of the blend and with the reaction temperature, whereas $\overline {M} _{{\rm w}} $ and PDI of the stereo multiblock PLAs increases with increasing $\overline {M} _{{\rm w}} $ of the blend, the reaction time, and the temperature. Stereo multiblock PLAs with ν_av > 7 are crystallizable to form stereocomplex crystallites, and the crystallinity and melting temperature of the stereo multiblock PLAs increases with increasing ν_av and $\overline {M} _{{\rm w}} $ of the stereo multiblock PLAs.

     

A Novel Synthetic Procedure for Stereoblock Poly(propylene) with a Living Polymerization System

Summary: Propylene polymerization was conducted at 0 °C in heptane or chlorobenzene (CB) by an ansa‐fluorenylamidodimethyltitanium complex combined with dried, modified methylaluminoxane that had been treated by dilution with heptane and successively repeatedly vacuum dried to remove any free trialkylaluminiums. The post‐polymerizations testified that the living polymerization proceeded irrespective of the solvent used. The heptane system gave the syndiotactic poly(propylene)s (PPs), whereas the CB system gave almost atactic PPs. After the first polymerization in heptane had been completed, the same amounts of propylene and CB were added for the second polymerization. This procedure gave the syndiotactic‐atactic stereoblock PP with narrow molecular‐weight distributions.

Structure of the ansa‐fluorenylamidodimethyltitanium complex and its application to the synthesis of syndiotactic‐atactic stereoblock poly(propylene)s reported here.     

A Thermogravimetric Approach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid)

Summary: An amorphous grade Poly (lactic acid) (PLA) was selected for an accelerated burial in soil test during 450 days. Thermogravimetric analyses were carried out to study the effects of degradation in soil on the thermal stability and the thermal decomposition kinetics. A single stage decomposition process is observed for all degradation times. It is shown that the thermal stability of PLA is slightly affected by degradation in soil. Concerning the study of the thermal decomposition kinetics, Criado master curves were plotted from experimental data to focus the study of the thermodegradation kinetic model.The kinetic methods proposed by Broido and Chang were used to calculate the apparent activation energies (Ea) of the degradation mechanism. These results were compared to the Ea values obtained by the method developed by Coats and Redfern in order to prove the applicability of the former methods to the kinetic study. As expected, non-linear tendency is found out for Ea variation along the degradation times, which can be explained as an evolution by stages.     

Hydrogen bonding assists stereocomplexation in poly(l‐lactic acid)/poly(d‐lactic acid) racemic blends

In this communication, we reported the sequence variation of stereocomplex crystals (SC) and homocrystals (HC) in poly(l ‐lactic acid)/poly(d ‐lactic acid) (PLLA/PDLA) racemic blends melts. It was evidenced that the emerging sequence of the SC and HC depends on the hydrogen bond formation in the melt, and the hydrogen bond is required for the stereocomplexation in PLLA/PDLA racemic blend. First, by combining a commercial fast‐scan chip‐calorimeter (Flash DSC 1) and micro‐FTIR, we found that hydrogen bonds were formed in the melt during cooling at 2.5 K/s, but not at 3000 K/s. Second, annealing the melt without hydrogen bonds at 100 °C led to HC emerging first, while annealing the melt with hydrogen bonds resulted in SC emerging at first. Third, the crystallization kinetics of the racemic blends after cooling to predefined T_c at 2.5 or 3000 K/s further verified that the hydrogen bonding can be inhibited effectively by cooling the racemic blends isotropic melt at fast enough rate. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 83–88