直接熔融缩聚法合成聚L-乳酸

以L-乳酸为原料,通过直接缩聚法合成了聚L-乳酸(PLLA)。探讨了反应历程中包括聚合温度及时间、催化剂种类及用量对PLLA黏均分子量和光学纯度的影响。采用红外光谱确定聚合物结构,用乌氏黏度计测定黏均分子量,通过旋光仪测定比旋光度,并通过其值计算PLLA的光学纯度。研究表明:合适的聚合温度为150℃,聚合时间为20 h,真空度0.1 MPa,催化剂氯化亚锡和对甲苯磺酸(TSA)组成的复合催化剂效果好于辛酸亚锡、氧化锌;得到的PLLA最高黏均分子量达到41 320,最高光学纯度达到86.4%,可以作为增塑剂使用。     

生物降解材料聚乳酸的直接法合成与表征

分别以外消旋乳酸(D,L-LA)和左旋乳酸(L-LA)为原料,通过熔融聚合法直接合成了生物降解材料聚外消旋乳酸(PDLLA)和聚左旋乳酸(PLLA),并用特性粘度[η]、凝胶渗透色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振氢谱(1H NMR)、差热分析(DSC)、X-射线衍射等手段.对PLLA、PDLLA的相对分子质量、结构、性能等进行了系统的表征与比较,发现相同合成条件下PLLA的相对分子质量、熔融温度、熔融热、结晶度等明显比PDLLA高。     

直接熔融聚合合成聚L-乳酸

以L-乳酸为原料,采用正交试验方法,研究了直接熔融聚合工艺对聚L-乳酸(PLLA)粘均相对分子质量的影响,并对PLLA的热性能进行了表征。结果表明:以氯化亚锡和分子筛为催化剂,其质量分数为0．5%,聚合温度170℃,聚合时间5 h,PLLA的相对分子质量可达到15 000,其玻璃化转变温度为57．03℃,熔点为148．5℃。     

聚左旋乳酸/聚氧化乙烯共混物的结构和性能

通过熔融共混法制备了一系列不同比例的聚左旋乳酸(PLLA)/聚氧化乙烯(PEO)共混试样,系统研究了PEO含量对PLLA共混物相形态、结晶性能、拉伸性能和冲击性能的影响。结果表明:PLLA/PEO共混物为非均相体系,且随着PEO含量的增加,相分离程度增大。PEO可有效提高PLLA的结晶性能;随着PEO含量的增加,共混物的断裂伸长率逐渐增大。共混物冲击强度值也随着PEO含量的增加而增大,表明PEO的加入显著增加了PLLA的韧性。     

萘钾及乙醇钾引发L-丙交酯开环聚合研究

分别以萘钾和乙醇钾为引发剂成功地引发了L-丙交酯的开环聚合,考查了不同的单体/引发剂(M/I,物质的量比)在不同的反应时间下对聚L-乳酸(PLLA)相对分子质量及其分布的影响。以FT-IR1、H-NMR、GPC和粘均相对分子质量测试等对所得PLLA进行了表征,结果表明,通过改变M/I,2种引发剂都能够有效地控制PLLA的相对分子质量;PLLA的相对分子质量分布随反应时间的增加而变宽,其中乙醇钾的引发活性比萘钾的高,得到PLLA的相对分子质量比萘钾引发时大,相对分子质量分布也较窄。     

气体发泡法制备PLLA/BCP多孔复合支架及其性能研究

用气体发泡法制备的聚乳酸(PLLA)多孔支架,力学性能通常随着孔隙率的增加而降低,且支架表面的疏水性限制着其在骨支架中的应用。通过共混PLLA与双相磷酸钙(BCP)陶瓷粉末,以碳酸氢铵(AB)作为致孔剂,采用气体发泡法制备了PLLA/BCP多孔复合支架,分析了AB粒径对支架孔径的影响以及AB和BCP的含量对PLLA支架力学性能及亲水性能的影响。结果表明,随着AB粒径的增大,支架的孔径尺寸也相应增大;随着AB含量的增加,PLLA/BCP复合支架的孔隙率相应增大、力学性能呈下降趋势;BCP的加入对PLLA支架的孔隙率影响不大,随着BCP含量的增加,支架的力学性能和亲水性能整体上升。通过调节AB的粒径和含量、BCP的含量,控制支架材料的孔隙率(52.2%~82.1%)、力学性能(压缩强度0.52~1.24MPa)以及亲水性能,制备的PLLA/BCP多孔复合支架能更好地满足骨组织工程的要求。     

熔融缩聚法合成高分子量聚L-乳酸

以L-乳酸为原料,采用分步除水、丙交酯回流、优选催化剂等工艺,通过熔融缩聚法制备了高分子量聚L-乳酸(PLLA),研究了脱水产物、反应装置、催化剂、聚合工艺等对产物分子量、产率及色泽的影响,并对产物分子结构进行了表征。在加装丙交酯回流装置后,以Sn(Ot)2/SnC l2.2H2O/TSA为催化剂,在170℃,反应12h所得PLLA黏均分子量(Mη)可达10.6万,产率为76%。     

聚乳酸的化学合成与应用

简述了近年来聚乳酸(PLA)尤其是聚左旋乳酸(PLLA)的化学合成方法(缩合聚合和开环聚合)及其结构与性能,并对这类材料的应用和发展作了展望。     

聚乳酸/可反应性纳米SiO2复合材料的等温结晶动力学

采用熔融共混法制备了聚乳酸/可反应性纳米二氧化硅(PLLA/RNS)复合材料。利用差示扫描量热仪研究了RNS对PLLA等温结晶行为的影响;用Avrami 方程研究了PLLA及其复合材料的等温结晶动力学。结果表明,加入RNS对PLLA结晶起到了异相成核作用,随着RNS含量的增加,PLLA的结晶速率(K)提高,半结晶时间(t1/2)减小,而Avrami指数(n)变化不大,说明RNS没有改变PLLA结晶的成核机理;利用Arrhenius方程和Lauritzen-Hoffman理论分别对PLLA及其复合材料的结晶活化能(ΔE)、成核参数(Kg)和折叠链端表面自由能(σe)进行计算后发现,复合材料的ΔE比纯聚乳酸的小,Kg 、σe略有增加。这表明加入RNS降低了复合材料的ΔE,从而有效地促进了PLLA基体的结晶。     

聚羟基丁酸己酸酯对聚乳酸结晶性能的影响

通过溶液共混法制备了生物可降解左旋聚乳酸(PLLA)和聚羟基丁酸己酸酯(PHBHHx)复合材料,用差示扫描量热仪和偏光显微镜研究了PHBHHx对PLLA热性能与结晶性能的影响。结果表明,PLLA与PHBHHx存在一定的相容性和相互作用,PLLA的玻璃化转变和冷结晶行为随着共混组成而变化。PLLA的相对分子质量越大,球晶形貌的规整性越差。当PHBHHx含量达到30%(质量分数,下同)时,其能加快PLLA的链段运动,提高结晶的成核密度,加快结晶速率。     

Preparation and Characterization of Poly L-Lactide/Triclosan Nanoparticles for Specific Antibacterial and Medical Applications

This work aims at preparation of poly-L-lactide (PLLA)/triclosan nanoparticles as antibacterial products used in some specific medical applications. PLLA was synthesized by the reaction extrusion via the ring opening polymerization of L-lactide using a continuous single-stage process, which is a fast and easy method. The PLLA triclosan nanoparticles were prepared by the emulsification–diffusion process with few modifications. Chloroform was used for the surface reaction of triclosan without any chemical shifts. The resulting nanoparticles with various triclosan quantities were fully characterized. The release as well as its kinetics was studied using the UV-visible spectroscopy. All the results confirmed the high stability and process efficiency of molecular dispersion and attachment of triclosan to PLLA. The sample containing 30% triclosan showed the best form among the others with the highest encapsulation efficiency. The synthesized nanoparticles with the controlled antibacterial activity could be considered as an appropriate alternative for application as antibacterial agent in the implantable surgical products as well as the drug delivery and wound-dressing applications.     

Synthesis and characterization of biodegradable poly(l-lactide)/layered double hydroxide nanocomposites

The effects of layered double hydroxide (LDH) composed by calcium/aluminum and magnesium/iron as divalent/trivalent cations and intercalated with dodecyl sulfate anion in the properties of poly(l-lactide) (PLLA) were analyzed. Two PLLA nanocomposites were produced by in situ intercalative bulk polymerization using 1 and 2 wt% of LDH. The PLLA nanocomposites were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and ultraviolet–visible spectroscopy (UV–VIS). XRD results demonstrated that PLLA nanocomposites showed a good dispersion of LDH in the polymeric matrix, which may have caused an increase in thermal stability indicated by thermogravimetric analysis. UV–VIS analyses showed that PLLA nanocomposites presented lower transmittance values when compared to the neat PLLA, which is an interesting characteristic for plastics used in food packaging. This enhancement in the properties of PLLA nanocomposites can enlarge the range of applications of this material in several areas.     

Synthesis of PLLA‐PEOMA comb‐block‐comb type molecular brushes based on AGET ATRP and ring‐opening polymerization

BACKGROUND: Molecular brushes are types of macromolecules with densely grafted side chains on a linear backbone. The synthesis of macromolecular brushes has stimulated much interest due to their great potential in applications in various fields. Poly(L ‐lactide)–poly(ethylene glycol) methyl ether methacrylate (PLLA‐PEOMA) comb‐block‐comb molecular brushes with controlled molecular weights and narrow molecular weight distributions were successfully synthesized based on a combination of activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) and ring‐opening polymerization. The synthetic route is a combination of the ‘grafting through’ method for AGET ATRP of the PEOMA comb block and the ‘grafting from’ method for the synthesis of the PLLA comb block. Poly(2‐hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, and PLLA side chains and PEOMA side chains were grown from the backbones and the terminal sites of PHEMA, respectively. RESULTS: The number‐average degrees of polymerization of PLLA chains and poly[poly(ethylene glycol) methyl ether methacrylate] (PPEOMA) comb blocks were determined using ¹H NMR spectroscopy, and the apparent molecular weights and molecular weight distributions of the brush molecules were measured using gel permeation chromatography. The crystallization of the components in the comb‐block‐comb copolymers was also investigated. The crystallization of PLLA side chains is influenced by PLLA chain length and the content of PPEOMA in the molecular brushes. The comb‐block‐comb copolymer composed of hydrophobic PLLA and hydrophilic PEOMA can self‐assemble into a micellar structure in aqueous solution. CONCLUSION: A combination of AGET ATRP and ring‐opening polymerization is an efficient method to prepare well‐defined comb‐block‐comb molecular brushes. The physical properties of the molecular brushes are closely related to their structures. Copyright © 2009 Society of Chemical Industry     

Surface modification of poly‐L‐lactide by photografting of hydrophilic polymers towards improving its hydrophilicity

Poly‐L ‐lactide (PLLA) has been used to prepare scaffolds to guide tissue regeneration in tissue engineering research. However, one of the limitations to the use of PLLA as an ideal biomaterial is its high hydrophobicity. To improve the hydrophilicity of PLLA, hydrophilic polymers were grafted onto PLLA membrane surfaces through the combination of photooxidization in hydrogen peroxide and subsequent ultraviolet (UV)‐induced grafting copolymerization in the monomer solution. Three kinds of modified PLLA membranes (i.e., PLLA‐g‐polyhydroxyethyl methacrylate, PLLA‐g‐polyacrylamide, and PLLA‐g‐polymethacrylic acid) were obtained, resulting in the more wettable PLLA membranes. The occurrence of the grafting polymerization was confirmed by attenuated total reflectance infrared spectroscopy (ATR‐IR) and X‐ray photoelectron spectroscopy (XPS) analysis. Surface morphology of the modified PLLA membranes was studied by scan electronic microscopy (SEM). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2163–2171, 2002     

Biodegradable Electrospun Poly(lactic acid) Nanofibers for Effective PM 2.5 Removal

In addition to the rapid urbanization and industrialization around the world, air pollution due to particulate matter is a substantial threat to human health. A considerable research effort has been devoted to the development of electrospun polymer nanofibers for air filter applications. Among these new technologies, electrostatic charge‐assisted air filtration is a promising technology for removing small particulate matter (PM). In this investigation, biodegradable electrospun poly(l ‐lactic acid) (PLLA) polymer nanofibers are employed for air filter applications. Electrostatic charges generated from the PLLA nanofiber can significantly enhance air filter applications. Compared with a 3M commercial respirator filter, electrospun PLLA fibrous filters exhibit a high efficiency of 99.3%. Even after 6 h of filtration time, the PLLA filtration membrane still exhibits a 15% improvement in quality factor for PM 2.5 particles than the 3M respirator. This is mainly attributed to the electrostatic force generated from the electrospun PLLA nanofibers, which significantly benefit submicron particle absorption. Due to their biodegradability, ease of fabrication, and relatively high efficiency, electrospun PLLA nanofibers show great promise in applications such as air cleaning systems and personal air purifier applications.     

Recent advances in stereocomplexation of enantiomeric PLA-based copolymers and applications

Poly(lactic acid) or poly(lactide) (PLA) is a biodegradable and biocompatible thermoplastic polymer, being derived from renewable resources such as corn and sugar cane. The building block of PLA, lactic acid is chiral and the polymerization of lactic acids (or lactides) leads to isotatic, syndiotatic and atactic/heterotactic PLA primary structures. The stereoselective interaction between two complementary enantiomeric PLLA and PDLA has led to enhanced physical properties such as mechanical properties, thermal resistance and hydrolytic stability compared with the parent polymers. Progress in controlled and/or living polymerization techniques combined with other new synthetic methodologies has facilitated the preparation of PLA-based copolymers with complex architectures such as diblock, triblock, multiblock, star-shape block, comb-shape block and various PLA-grafted structures. The utilization of stereocomplexation strategy to these newly developed copolymers has opened avenues to access a variety of new materials with unique characteristics, including novel chemical functionalities, bioactivities, and smart (responsive to external stimulus) properties tailored for specific applications. This review presents recent advancements in the synthesis of PLA-based block/graft copolymers having complex architectures, with emphasis on the enhanced material performances induced by PLA stereocomplex formation. The origin of the enhanced thermal mechanical property observed in PLA stereocomplex is first discussed. The strong interaction resulted from stereocomplexation in PLA based copolymers could be exploited not only for fabrication of advanced therapeutic delivery carriers and tissue engineering devices, but also for stabilizing colloidal systems in microparticles, micelles and hydrogels, that further broaden the applications of PLA that could not have been attained with single PLLA or its copolymers. The stereocomplexation could also be used to tailor the interface interactions between fillers and PLA matrix that lead to higher strength and toughness of PLA.     

纳米氧化锌催化丙交酯开环聚合的研究

采用纳米氧化锌为催化剂进行L-丙交酯(L-LA)的开环聚合,研究了催化剂用量、反应温度和反应时间对聚合反应的影响.结果表明,纳米氧化锌在催化聚合转化率和聚合产物分子量上,均显示出较好的催化性能.采用了FTIR、DSC、WAXD等方法对聚乳酸的结构进行了表征,结果表明聚乳酸是L-丙交酯开环聚合产物.     

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L ‐lactide) (PLLA) onto silica nanoparticle surface by ring‐opening polymerization of L‐lactide (LA) was investigated in the presence of an amidine base catalyst. The ring‐opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica‐NH₂) and an amidine base catalyst to give PLLA‐grafted silica, but not in the presence of untreated silica (silica‐OH). In the absence of the amidine base catalyst no ring‐opening polymerization of LA even in the presence of silica‐NH₂ and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring‐opening graft polymerization of LA from the surface of silica‐NH₂. In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA‐grafted silica was smaller than that of silica‐NH₂. Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLA‐grafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface modification of halloysite nanotubes with l‐lactic acid: An effective route to high‐performance poly(l‐lactide) composites

To improve the interfacial bonding between halloysite nanotubes (HNTs) and poly(l ‐lactide) (PLLA), a simple surface modification of HNTs with l ‐lactic acid via direct condensation polymerization has been developed. Two modified HNTs were obtained: HNTs grafting with l ‐lactic acid (l‐HNTs) and HNTs grafting with poly(l ‐lactide) (p‐HNTs). The structures and properties of l‐HNTs and p‐HNTs were investigated. Then, a series of HNTs/PLLA, l‐HNTs/PLLA and p‐HNTs/PLLA composites were prepared using a solution casting method and were characterized by polarized optical microscopy (POM), field scanning electron microscopy, and tensile testing. Results showed that l ‐lactic acid and PLLA could be easily grafted onto the surface of HNTs by forming an Al carboxylate bond and following with condensation polymerization, and the amounts of the l ‐lactic acid and PLLA grafted on the surface of the HNTs were 5.08 and 14.47%, respectively. The surface‐grafted l ‐lactic acid and PLLA played the important role in improving the interfacial bonding between the nanotubes and matrix. The l‐HNTs and p‐HNTs can disperse more uniformly in and show better compatibility with the PLLA matrix than untreated HNTs. As a result, the l‐HNTs/PLLA and p‐HNTs/PLLA composites had better tensile properties than that of the HNTs/PLLA composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41451.