乳酸/聚乙二醇嵌段共聚物的合成与表征

利用直接缩聚法制备了乳酸与聚乙二醇的嵌段共聚物(PLEG)。采用正交试验法考察了乳酸与聚乙二醇质量比、催化剂种类、催化剂含量、反应温度和反应时间对PLEG性能的影响。结果显示优化的反应条件:乳酸与聚乙二醇质量比为8.5∶1.5,采用自制的复合催化剂,催化剂质量分数0.6%,聚合温度160℃,聚合时间5h。另外还考察了扩链剂对PLEG性能的影响,结果表明扩链剂能够显著提高PLEG的相对分子质量。对合成的PLEG通过红外光谱、核磁共振、热分析进行了表征。     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

电子束辐照聚乳酸-聚乙二醇共聚物的结构及热性能研究

本文首先通过直接熔融缩聚法制备了聚乳酸-聚乙二醇共聚物(PLEG),并采用FTIR和1 H NMR对其结构进行表征。然后在辐射剂量0～100kGy范围下,利用衰减全反射红外(ATR-FTIR)、差示扫描量热(DSC)和热失重分析(TGA)研究了电子束辐照对PLEG结构及热性能的影响。结果表明:加入3%的三聚氰酸三烯丙酯(敏化剂TAC)后,由于交联结构的形成,PLEG的凝胶率、玻璃化转变温度(Tg)和热稳定性均随辐射剂量的增加而有所提高,且其热转变行为也发生变化。     

Hierarchical self-assembly of fluorine-containing diblock copolymer:From onion-like nanospheres to superstructured microspheres

Superstructured microspheres were prepared via a two-tier hierarchical assembly of a fluorine-containing diblock copolymer, poly(tert-butyl acrylate)-b-poly(2-[(perfluorononenyl)oxy]ethyl methacrylate) (PtBA-b-PFNEMA) with well controlled block lengths. At tier 1, water induced self-assembly of the diblock copolymer produced nanospheres of low dispersity with onion-like multilayer inside structures, which were the consequence of the gradual aggregation of the fluorinated segments by accessing the super-strong segregation regime. And both the size and inner structure could be tuned by changing the water addition rate. At tier 2, nanospheres with different sizes were chosen as the building blocks for the formation of closely packed superstructural microspheres through an evaporation assisted process. The packing rules were governed by the volatility distinction between THF and water, the dispersity of nanospheres, and other various forces, such as the capillary force.     

Formation of honeycomb films from poly(L‐lactide)‐block‐poly(ethylene glycol) via water‐droplet templating

The fabrication of honeycomb‐patterned films from amphiphilic poly(L ‐lactide)‐block‐poly(ethylene glycol) (PLEG) in a high‐humidity atmosphere is reported. The influence of the solution concentration on pattern formation was investigated. Moreover, by comparing the different conditions of fabricating regular structures between PLEG and poly(phenylene oxide), the mechanism of the regular pattern formation was studied. Finally, by adding sodium dodecylsulfate to a concentrated solution of 1 g L^?1 PLEG? CHCl₃ which otherwise could not form regular pores, we found that regular pores could be obtained. The PLEG honeycomb films are expected to be of use in cell culture, tissue engineering and many other areas. Copyright © 2007 Society of Chemical Industry     

Reaction Factors Influencing the Synthesis of Polystyrene-Polyurethane-Polystyrene Triblock Copolymer

Polystyrene-polyurethane-polystyrene (PS-PU-PS) triblock copolymer was synthesized by two-step polymerization. The first step, polyurethane (PU) prepolymers based on 2,4-toluene diisocyanate (TDI), hydrophilic poly(ethylene glycol) (PEG), hydroxyethyl acrylate (HEA), and ethylene glycol (EG), were prepared with ethylene glycol as a chain extender, dibutyltin dilaurate as a catalyst, and toluene as a solvent. The next step, polystyrene-polyurethane-polystyrene (PS-PU-PS) triblock copolymers, were prepared by free radical copolymerization between PU prepolymer and styrene (ST) monomer. Toluene and 2,2′-azobisisobutyronitrile (AIBN) were used as solvent and initiator, respectively. Fourier transform infrared spectroscopy (FT-IR) spectroscopy was used to characterize the structure of the copolymer. Influences of reaction temperature, reaction time, catalyst sorts, isocyanate monomer sorts, solvent sorts, and the concentration of initiator on the synthesis of the triblock copolymer were studied.     

pH-Sensitive Micelles Based on Double-Hydrophilic Poly(methylacrylic acid)-Poly(ethylene glycol)-Poly(methylacrylic acid) Triblock Copolymer

pH-sensitive micelles with hydrophilic core and hydrophilic corona were fabricated by self-assembling of triblock copolymer of poly(methylacrylic acid)-poly(ethylene glycol)-poly(methylacrylic acid) at lower solution pH. Transmission electron microscopy and laser light scattering studies showed micelles were in nano-scale with narrow size distribution. Solution pH value and the micelles concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible mechanism for the formation of micelles was proposed. The obtained polymeric micelle should be useful for biomedical materials such as carrier of hydrophilic drug.     

Synthesis and characterization of a poly(methyl methacrylate-acrylic acid) copolymer for bioimplant applications

This paper describes the development of a new crosslinked poly(methyl methacrylate-acrylic acid) copolymer for potential applications in bone implants. This copolymer, comprising hydrophobic and hydrophilic components, has been designed to provide small amounts of controllable swelling strains at saturation when exposed to an aqueous saline environment. The volume fraction of the hydrophobic methyl methacrylate monomer to the hydrophilic acrylic acid monomer strongly influenced the swelling behavior of the copolymer. Two different cross-linking agents, allyl methacrylate and diethylene glycol dimethacrylate, were evaluated for their effectiveness in cross-linking and limiting the saturated swelling levels. The influences of the amounts of cross-linking agents and other processing parameters on the swelling behavior of the copolymer were studied using differential scanning calorimetry measurements, solubility tests, and swelling measurements in saline solutions. These measurements provided a good understanding of the structure of the copolymer, the effectiveness of the cross-linkers, the swelling mechanisms in this system, and the factors that strongly affect the swelling weight gain levels in this copolymer. © 1997 John Wiley & Sons, Inc.     

Synthesis and evaluation of a star amphiphilic block copolymer from poly(ε‐caprolactone) and poly(ethylene oxide) as load and release carriers for guest molecules

The use of polymeric materials as the carrier in the controlled release of guest molecules has become an important research area in the polymeric materials science, because of their advantages of the safety, efficacy and patient convenience. One of them, star amphiphilic polymer can self‐assemble into supermolecular structure (polymer micelles) by the balance of hydrophilic and hydrophobic interaction. In this study, star amphiphilic copolymer consisting of hydrophobic and biodegradable poly(ε‐caprolactone) (PCL) and hydrophilic poly(ethylene oxide) (PEO) blocks were synthesized by two‐step ring‐opening polymerization. The resultant polymer was characterizated by FTIR, ¹H‐NMR, and DSC to determine its chemical structure. The morpholoy of the polymer micelles was analyzed by TEM. Using star‐PCL‐b‐PEO as carriers and congo red as model guest molecules, the encapsulation and release properties were investigated by UV–visable analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymeric nanoparticles with tunable architecture formed by biocompatible star shaped block copolymer

An amphiphilic star shaped block copolymer, based on well known biocompatible components, was synthesized using branched poly(ε-caprolactone) as hydrophobic core and branched poly(ethyleneglycol) as hydrophilic corona. The composition of this macromolecule, based on two well differentiated blocks, conferred amphiphilic behavior to the whole system that acted as driving force for its self-assembling in aqueous media. Depending on the polymer concentration it was possible to obtain different architectures. The TEM micrographs permitted to follow the evolution of the system from single vesicles toward necklace entanglements. In this work, we discuss the mechanism that would be involved in the evolution of the system's morphology as a function of the block copolymer concentration. In addition, the proposed star shaped block copolymer presented good solubilizing properties that were used to disperse in water, poorly soluble molecules such as chlorine-carbazoles, which were used to investigate the suitability of the self-assembled nanostructures as drug nano-carriers.     

Production of double‐walled nanoparticles containing meloxicam

Double‐walled nanospheres, containing meloxicam, were fabricated with poly‐(D,L ‐lactide‐co‐glycolide) (PLGA) and poly(L ‐lactide) (PLLA) using the solvent evaporation technique. This article discusses the effect of formulation variables [sonication power, sonication time, concentration of poly(vinyl alcohol), organic/aqueous volume ratio in the first emulsion] on the production of double‐walled nanospheres. The involved phase separation of these two polymers was investigated using differential scanning calorimetry. Double‐walled microspheres containing meloxicam were also produced to determine the composition of the shell and core polymer, based on different solubilities of polymers in ethyl acetate, and to examine the inner morphology and drug distribution using optical and fluorescence microscopy. The produced microparticles have shown a double‐walled structure with meloxicam solubilized in the PLGA‐rich phase. Therefore, adjusting the selected formulation variables and using a mass ratio of 1:1 PLLA/PLGA, double‐walled nanospheres where meloxicam is dispersed within the core can be produced. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Stereocomplex‐induced gelation properties of polylactide/poly(ethylene glycol) diblock and triblock copolymers

The ring‐opening polymerization of L ‐ or D ‐lactide was realized in the presence of dihydroxyl or monomethoxy poly(ethylene glycol) (PEG) with a number‐average molecular weight of 2000. The resulting low‐molar‐mass poly(L ‐lactide) (PLLA)/PEG and poly(D ‐lactide) (PDLA)/PEG triblock and diblock copolymers were characterized with nuclear magnetic resonance (NMR), differential scanning calorimetry, size‐exclusion chromatography, and X‐ray diffractometric analysis. Bioresorbable hydrogels were successfully prepared from aqueous solutions containing both copolymers because of interactions and stereocomplexation between the PLLA and PDLA blocks. Gelation was evaluated with the tube inverting method and rheological measurements. A phase diagram was realized with gel–sol transitions as a function of concentration. The rheological properties of the hydrogels were investigated under various conditions through changes in the copolymer concentration, temperature, time, and frequency. It was concluded that the hydrogels constituted a dynamic and evolutive system because of the continuous formation/destruction of crosslinks and degradation. Further studies are underway to elucidate the degradation behavior and the potential of these substances as drug carriers or cell culture scaffolds. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface characterization of biocompatible polysulfone membranes modified with poly(ethylene glycol) derivatives

Self-transformable and blood compatible devices of sulfonated poly(ethylene glycol) acrylate diblock copolymer (PEG-SO₃A/OA) with hydrophilic and hydrophobic block entrapped to polysulfone membrane surface were investigated in terms of the degree of hydrophilicity. The asymmetric membrane was formed by phase inversion process, and the induced hydrophilicity by reorientation of diblock copolymer at interface was verified with contact angle measurement, electron spectroscopy for chemical analysis (ESCA) depth profiling with ion sputtering and platelet adhesion test. Molecular dynamics (MD) simulations for the interface of hydration layer were also performed with various hydrophilic copolymer densities to gain optimum interfacial structure in information. The dependency of water clustering behavior around diblock copolymers as a hydrophilicity parameter was described in terms of atom-atom radial distribution function (RDF). The results showed that the diblock copolymer entrapped surfaces demonstrated less platelet adhesion than control or copolymers having no hydrophobic blocks. In addition, oxygen composition significantly began to decrease deeper into the membrane, indicating the reorientation of diblock chains. Copolymer entrapped surfaces significantly induced the degree of water clustering, and the resulting equilibrium rearrangement of interfacial structures was distinctly dependent upon the density of copolymer. Taken together, the results show that the novel concept ofin situ self-transformable surface modification strategy was successfully developed for biocompatible ultrathin biomedical membrane device.     

Syntheses of poly(lactic acid)‐poly(ethylene glycol) serial biodegradable polymer materials via direct melt polycondensation and their characterization

Directly starting from lactic acid (LA) and poly(ethylene glycol) (PEG), biodegradable material polylactic acid‐polyethylene glycol (PLEG) was synthesized via melt copolycondensation. The optimal synthetic conditions, including prepolymerization method, catalyst kinds and quantity, copolymerization temperature and time, LA stereochemical configuration, feed weight ratio m_LA/m_PEG and M_n of PEG, were all discussed in detail. When D ,L ‐LA and PEG (M_n = 1000 Da) prepolymerized together as feed weight ratio m_{D ,l‐LA}/m_PEG = 90/10, 15 h copolycondensation under 165°C and 70 Pa, and 0.5 wt % SnO as catalyst, gave D ,L ‐PLEG1000 with the highest [η] of 0.40 dL/g, and the corresponding MW was 41,700 Da. Using L ‐LA instead of D ,L ‐LA, 10 h polymerization under 165°C and 70 Pa, and 0.5 wt % SnO as catalyst, gave L ‐PLEG1000 with the highest [η] of 0.21 dL/g and MW of 15,600 Da. Serial D ,L ‐PLEG with different feed weight ratio and M_n of PEG were synthesized via the simple and practical direct melt copolycondensation, and characterized with FTIR, ¹H NMR, GPC, DSC, XRD, and contact angle testing. D ,L ‐PELG not only had higher MW than PDLLA, PLLA and L ‐PELG, but also better hydrophilicity than PDLLA. The novel one‐step method could be an alternative route to the synthesis of hydrophilic drug delivery carrier PLEG instead of the traditional two‐step method using lactide as intermediate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 577–587, 2006     

Properties of Block Copolymers of Poly(Butylene Terephthalate) and Polyoxytetramethylene Glycol

Synthesis of polyester thermoelastoplasts, block copolymers of polyoxytetramethylene glycol and poly(butylene terephthalate) of the polyblock type, was developed and implemented in pilot industrial conditions. POTM blocks act as flexible molecular decouplings that give the copolymer elasticity, while PBT blocks form physical linkages and are responsible for the mechanical strength and hardness of the material. The composition of the reaction systems, process stage sequence, and synthesis parameters are optimized for block copolymers with a concentration of the flexible POTM block of 65-10 wt. % and a molecular weight of 1000. The structure is investigated, and the physicochemical and mechanical properties of the material obtained are determined. It was found that the concentration of flexible blocks has a determining effect on the physicochemical structure and properties of the block copolymers. For a 40% concentration of the flexible block, the character of the concentration curves of the physicomechanical indexes changes significantly due to phase-structural transformations in the block copolymers.     

Studies on syntheses and permeabilities of special polymer membranes. XVI. Permeation and separation characteristics of aqueous polymer solutions for acrylonitrile-styrene copolymer membranes

The permeation and separation characteristics of aqueous polymer solutions using acrylonitrile-styrene copolymer membranes were investigated under various conditions. The membranes obtained from dimethyl sulfoxide solution of acrylonitrile-styrene copolymer have not a sufficient reproducibility and stability of permeation. These lacks were improved by adding ethylene glycol or glycerol to the casting solution and treating the membranes with pressure. The permeation and separation characteristics were influenced significantly by the additional amount of above additives, the heat treatment temperature, and the operating pressure. It was found that the concentration polarization of poly(vinyl alcohol) molecules onto the surface of the acrylonitrile-styrene copolymer membranes is smaller than that onto hydrophilic polymer membranes such as membranes of cellulose acetate, cellulose nitrate, and nylon 12, etc. Moreover, the acrylonitrile-styrene copolymer membranes show better performance for separation and concentrating of aqueous polymer solutions than hydrophilic membranes.     

Poly(allyl glycidyl ether)‐block‐poly(ethylene oxide): A novel promising polymeric intermediate for the preparation of micellar drug delivery systems

Novel diblock copolymers designed for the preparation of micellar drug delivery systems, consisting of hydrophobic poly(allyl glycidyl ether) (PAGE) and hydrophilic poly(ethylene oxide) (PEO), were prepared, and their self‐assembly into micellar structures was studied. Copolymers differing in the length of the polymer blocks were purified and characterized. These amphiphilic copolymers with narrow molecular weight distributions were prepared through the anionic polymerization of allyl glycidyl ether with PEO monomethyl ether sodium salt as the macroinitiator. The PAGE–PEO copolymer readily formed small micelles with narrow size distributions via simple dissolution in water. The addition of pendant double bonds to the hydrophobic part of the chain was intended for further covalent modifications. Catalytic hydrogenation, the radical crosslinking of the micelle core, and the addition of thiol to double bonds of the copolymer were examples of such modifications that were proved to proceed with a quantitative yield for this copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 201–211, 2005     

Preparation and properties of a biodegradable polymer as a novel drug delivery system

Poly (DL ‐lactic acid‐co‐glycolic acid)‐co‐poly(ethylene glycol) was synthesized by bulk ring‐opening polymerization of DL ‐lactide/glycolide/poly(ethylene glycol) using stannous chloride as an initiator. The molecular structure of the copolymer was analyzed by IR, ¹H NMR, and DSC. The degradation behavior of copolymer was assayed by the reduction of molecular weight, the loss‐in‐mass, and the changes of pH value for degradation medium. The different contents of PGA and PEG in the molecules of the copolymer could control the degradation rate of polymer. Human Serum Albumin (HSA) was chosen as the model hydrophilic drug and encapsulated in the copolymer. The HA‐loaded copolymer microspheres were characterized by the diameter, diameter distribution of the microspheres, and the loading efficiency. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3150–3156, 2003     

马来酸酐改性端羟基乳酸预聚体的合成及性能研究

采用聚乙二醇（PEG）与乳酸反应,合成了端羟基乳酸预聚体（PLEG）。然后将PLEG与马来酸酐进行直接熔融缩聚得到改性聚乳酸（MPLA）。采用正交分析法探讨了原料比、反应温度、反应时间等工艺条件对MPLA相对分子质量的影响,并研究了MPLA的亲水性能、力学性能和在体外模拟生物环境中的降解特性。结果表明：马来酸酐与PLEG的质量比为1:15,在130 ℃反应15 h,MPLA的黏均相对分子质量最大为61564。相较于PLEG,MPLA的拉伸强度、弹性模量和断裂伸长率明显提高,亲水性得到改善。MPLA在体外模拟生物环境中的降解性能较好,其降解速率与马来酸酐含量有关。     

Preparation of liquid‐filled micelles based on an amphiphilic triblock copolymer

A series of novel amphiphilic triblock poly(ethylene glycol)‐b‐poly(2‐aminoethyl methacrylate hydrochloride)‐b‐poly(heptadeca‐fluorodecyl acrylate) (PEG‐b‐PAEMA‐b‐PHFDA) comprised of two hydrophilic PEG and PAEMA segments and one hydrophobic PHFDA segment was designed and synthesized. The structure of the triblock copolymer was characterized by ¹H‐NMR and GPC analysis. The amphiphilic triblock copolymer was capable of self‐assembling into liquid‐filled micelles that consisted of PHFDA and liquid perfluorocarbons (PFCs) as the core and PEG as outer shell. PAEMA can be used as cross‐linking sites to increase the stability of the liquid‐filled micelles. The shape, size, and Acoustic properties of the obtained liquid‐filled micelles were investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009