Biodegradable polycaprolactone–polyanhydrides blends

Biodegradable polymers based on a blend of polycaprolactone (PCL) and aliphatic polyanhydrides with various monomer lengths were prepared to obtain desired polymer blends for use as drug carriers. The physicochemical, mechanical, and drug‐release properties of these blends were investigated by various techniques to evaluate the uniformity degree of the polymer blends to establish their potential applications in drug delivery. The results demonstrated that the heat of fusion (ΔH) of the polyanhydride or the blend is increased in relation to the length of the aliphatic chain. However, the blends had different properties than pure polyanhydride, and the crystallization degree of the blends, as expressed by the ΔH, decreased in relation to the ΔH of the pure polyanhydride. Drug‐release studies from blends of PCL and aliphatic polyanhydrides demonstrated first‐order kinetics of the release rate. Polymer degradation was independent at the polyanhydride monomer length. On the basis of theoretical calculation of the interaction factor, a blend of PCL and poly(dodecanedeoic anhydride) was chosen for further elucidation of its thermal, mechanical, and degradation properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3781–3787, 2003     

Complete miscibility of ternary aryl polyesters demonstrating a new criterion and horizon for miscibility characterization

A ternary miscible blend system comprising only crystallizable aryl polyesters [poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(butylene terephthalate)] was characterized with the criteria of thermal analyses, microscopy, and X‐ray characterizations. The reported ternary miscibility (in the quenched amorphous state of blends of the three aryl polyesters) was truly physical and under the condition of no chemical transesterifications; this justified that transesterification was not a necessary condition for miscibility in polyester blends in this case. This study further proposed and tested a novel concept of a new criterion for miscibility characterization for polymer blends of only crystallizable polymers. A single composition‐dependent cold‐crystallization‐temperature (T_cc) peak in blends of only semicrystalline polymers was taken as an indication of an intimate mixing state of miscibility. The theoretical background for establishing the single composition‐dependent T_cc peak as a valid miscibility criterion for crystallizable polymer blends was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2394–2404, 2003     

Synthesis and characterization of biocompatible and biodegradable polymers

New polyesters were synthesized using Krebs cycle acids. Poly(1, 4-butanediol dilactate succinate)(PBDS) and poly(1, 4-butanediol dilactate 2-acetoxy succinate)(PBDAS) were prepared by the polycondensation of 1, 4-butanediol dilactate with succinic anhydride and 2-acetoxy succinic acid, respectively. Poly(1, 4-butanediol succinate)(PBS) was also synthesized from 1, 4-butanediol and succinic anhydride. PBS/PBDS and PBS/PBDAS blends were prepared by the method of solvent casting. The effects of crystallization time and temperature onto melting behavior of PBS/PBDS and PBS/PBDAS blends were investigated by differential scanning calorimetry. The compatibility of each blend system was discussed using equilibrium melting point depressions. The biodegradation behavior was studied using PBS, PBDS, and PBDAS as the sole carbon source by Aspergillus niger. The molecular weights of the polymers which were obtained from GPC analysis decreased after degradation in five weeks.     

Synthesis and Characterization of a Branched Poly(Methacrylamide): Thermal Stability and Molecular Simulation Studies of Their Blends With Vinylic Polymers

The synthesis of a poly(diethylaminoethyl methacrylamide) (BP), based on a lineal methacrylamide with diethylaminoethyl branches was carried out. Thermal behavior was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Relatively high thermal stability is found. Blends with poly(methylmethacrylate) (PMMA), poly(acrylic acid) (PAA) and poly(monomethyl itaconate) (PMMI) were prepared. Their thermal properties in blends were studied together with miscibility, in order to improve thermal properties of vinylic polymer blends. An increase of thermal stability was found for certain blend compositions. By FTIR analysis, higher band displacements were found for low BP compositions. AFM and molecular simulation analysis were carried out in order to elucidate the structural origin leading to thermal stability and miscibility increases. Hydrophobic interactions among methyl end groups of BP and methylene groups of vinylic polymers should be the responsible of miscibility and thermal stability increases.     

Fatty acid terminated polyanhydrides

A systematic study on the synthesis, characterization, degradation, and drug release of fatty acid terminated poly(sebacic acid) (PSA) is reported. Fatty acid terminated sebacic acid polymers were synthesized by melt condensation of acetate anhydrides of linear fatty acids (C8–C18) and sebacic anhydride oligomers to yield waxy off-white materials. Polymers with molecular weights (M_w) in the range of 9,000 and 5,000 were obtained for the 10% and 30% (weight ratio) containing fatty terminals, respectively. Up to about 30% of fatty acid terminals, the final product is mainly fatty terminated polymer with up to about 5% w/w of the symmetric fatty anhydride. Increasing amounts of fatty acid acetate anhydride in the polymerization mixture had little effect on the polymer molecular weight up to a ratio of 40 : 60 (fatty acid acetate : sebacic acid oligomer) which remains in the range of 5,000–8,000. Above this ratio the molecular weight dropped to a level of 2,000–3,000 and the percent of the symmetric anhydride increased to 10–40%. The fatty terminals had little effect on PSA melting point and crystallinity. However, the fatty terminals had a significant effect on the polymer degradation and drug release rate. PSA with 30% w/w of C14–C18 terminals degraded and released the incorporated drug for more than 4 weeks as compared with 10 days for the acetate-terminated PSA. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3337–3344, 1999     

Spontaneous thinning/thickening deformation observed for plastic blend films and some factors affecting film deformation

The fully amorphous films of highly syndiotactic poly[(R,S)‐3‐hydroxybutyrate] (s‐PHB)/atactic poly(4‐vinylphenol) (PVPh) blends show reversible thinning/thickening phenomena at 37 °C in aqueous medium. On the other hand, isotactic poly[(R)‐3‐hydroxybutyrate] (i‐PHB)/PVPh blend film, in which i‐PHB blend component was partially crystalline, did not show any thinning/thickening phenomena under the same conditions. To elucidate the factors influencing these phenomena, the structure and molecular interaction in these blends were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry, and wide‐angle X‐ray diffraction. The FTIR spectra indicated that the ester carbonyl of PHB and the phenolic hydroxyl of PVPh formed hydrogen bonds in both the thinned and thickened s‐PHB/PVPh blend films. The blend composition, intermolecular hydrogen‐bonding interaction, crystallization behavior, miscibility, and the glass‐transition temperature of the blends affected the thinning/thickening phenomena. Some other polyesters such as poly(?‐caprolactone), poly (L‐lactic acid), atactic poly(D,L‐lactic acid), and poly(ethylene terephthalate) had no ability to exhibit thinning/thickening phenomena in water at 37 °C when they were blended with PVPh. This result implies that s‐PHB/PVPh is the rare example with the ability to show reversible thinning/thickening phenomena. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2736–2743, 2002     

Ionic miscibility enhancement via microion elimination in sulfonated polystyrene/poly(ethyl-acrylate-co-4-vinyl pyridine) ionomer blends

Miscibility enhancement of ionomer/ionomer and ionomer/polymeric acid systems is studied on the polymer pairs of poly(styrene-co-tetramethyl ammonium styrenesulfonate)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide) and poly(styrene-co-styrenesulfonic acid)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide). NMR and dynamic mechanical results show that in these blends direct macroion–macroion interaction can be achieved with the elimination of microcounterions from the polymer chains. Ion-ion attraction leads to a miscibility enhancement comparable to that of the previously reported proton transfer blends; a miscible blend is obtained with ca. 5 mol% of ions in the polymers.     

Thermal analysis on phase behavior of poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactic acid) interacting with aliphatic polyesters

Abstract  

Thermal behavior, miscibility, and crystalline morphology in blends of low-molecular-weight poly(l-lactic acid) (LM_w-PLLA) or high-molecular-weight PLLA (HM_w-PLLA) with various polyesters such as poly(butylene adipate) (PBA), poly(ethylene adipate) (PEA), poly(trimethylene adipate) (PTA), or poly(ethylene succinate) (PESu), respectively, were explored using differential scanning calorimeter (DSC), and polarized-light optical microscopy (POM). Phase behavior in blends of PLLA with other polyesters has been intriguing and not straight forward. Using a low- and high molecular weight PLLA, this study aimed at mainly using thermal analyses for probing the phase behavior, phase diagrams, and temperature dependence of blends systems composed of PLLA of two different molecular weights (low and high) with a series of aliphatic polyesters of different structures varying in the (CH₂/CO) ratio in main chains. The blends of LM_w-PLLA/PEA and LM_w-PLLA/PTA show miscibility in melt and amorphous glassy states. Meanwhile, the LM_w-PLLA/PESu blend is immiscible with an asymmetry-shaped upper critical solution temperature (UCST) at 220–240 °C depending on the blend composition. In contrast to miscibility in LM_w-PLLA/PTA and LM_w-PLLA/PEA blends, HM_w-PLLA with polyesters are mostly immiscible; and HM_w-PLLA/PTA blend is the only one showing an asymmetry-shaped UCST phase diagram with clarity points at 195–235 °C (depending on composition). Reversibility of UCST behavior, with no chemical transreactions, in these blends was proven by solvent recasting, gel permeation chromatography, and Fourier transform infrared spectroscopy (FT-IR). Crystalline morphology behavior of the LM_w-PLLA/PEA and LM_w-PLLA/PTA blends furnishes addition evidence for miscibility in the amorphous phase between LM_w-PLLA and PTA or PEA.     

Miscibility and enzymatic degradation studies of poly(ε-caprolactone)/poly(propylene succinate) blends

In the present study the miscibility behaviour and the biodegradability of poly(ε-caprolactone)/poly(propylene succinate) (PCL/PPSu) blends were investigated. Both of these aliphatic polyesters were laboratory synthesized. For the polymer characterization DSC, ¹H NMR, WAXD and molecular weight measurements were performed. Blends of the polymers with compositions 90/10, 80/20, 70/30 and 60/40 w/w were prepared by solution-casting. DSC analysis of the prepared blends indicated only a very limited miscibility in the melt phase since the polymer-polymer interaction parameter χ₁₂ was −0.11. In the case of crystallized specimens two distinct phases existed in all studied compositions as it was found by SEM micrographs and the particle size distribution of PPSu dispersed phase increased with increasing PPSu content. Enzymatic hydrolysis for several days of the prepared blends was performed using Rhizopus delemar lipase at pH 7.2 and 30 °C. SEM micrographs of thin film surfaces revealed that hydrolysis affected mainly the PPSu polymer as well as the amorphous phase of PCL. For all polymer blends an increase of the melting temperatures and the heat of fusions was recorded after the hydrolysis. The biodegradation rates as expressed in terms of weight loss were faster for the blends with higher PPSu content. Finally, a simple theoretical kinetic model was developed to describe the enzymatic hydrolysis of the blends and the Michaelis-Menten parameters were estimated.     

Evaluation of compatibility and properties of biodegradable polyester blends

Three different biodegradable polyesters, namely, polycaprolactone (PCL), polybutylene succinate (BIONOLLE), and a copolyester of adipic acid, terephthalic acid, and 1,4‐butanediol (EASTAR) were melt‐blended using a twin‐screw extruder. The percentage composition of each of the aforementioned polymers was varied to obtain different blends, and the mechanical properties were evaluated. Selected blends showed significant improvement in tensile strength as compared with the individual polymers used to prepare the blend. The compatibility between the polymer phases was examined via Fourier transform infrared (FTIR) and nuclear magnetic resonace (NMR) spectroscopy as well as dynamic mechanical analysis. FTIR and NMR data confirmed the occurrence of hydrogen‐bonding and ester‐interchange reactions. Thermal properties and changes in crystallinity of the blends were examined with differential scanning calorimetry and X‐ray diffraction. A considerable increase in crystallinity was shown by the blend system containing BIONOLLE/PCL. The morphology of the blends was observed and correlated to the improved mechanical properties of the blend system. Results revealed an intermediate multiphase system in which a significant degree of mixing was achieved through the chemical interaction of the functional groups present, while using the twin‐screw extruder. Significant improvement in mechanical properties of some blends was observed, and information about the miscibility of these polyesters is provided. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2003–2014, 2002     

Thermal and spectroscopy studies on ternary miscibility and phase behavior in blends comprising poly(4‐vinyl phenol) and two aryl polyesters

Thermal analysis and Fourier transform infrared spectroscopy characterizations were performed on three ternary blend systems that comprise poly(4‐vinyl phenol) (PVPh) and any two of the three homologous aryl polyesters [poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT)]. Although PVPh is miscible with any one of the polyesters in forming a binary blend system, miscibility in ternary systems by introducing one more polymer of different structures to the blend system is not always expected. However, this study concludes that miscibility does exist in all these three ternary blends of all compositions investigated. Reasons and factors for such behavior were probed. Quantitative interactions in the ternary blend system were also estimated. The overall interaction energy density (B) by analysis of melting point depression for the PBT/PVPh/PET ternary blend system led to a negative value (B = −5.74 cal/cm³). Similarly, T_g‐composition analyses were performed on two other ternary blend systems, PET/PVPh/PTT and PTT/PVPh/PBT. Comparison of the qualitative results showed that the interaction energy densities in the other two ternary blend systems are similarly negative and comparable to the PBT/PVPh/PET ternary blend system. The Fourier transform infrared spectroscopy results also support the qualitative findings among these three ternary blend systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1339–1350, 2006     

Blends of a novel high-temperature poly(oxy-1,4′-diphenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) with poly(ether imide): structure, interaction, and miscibility

 Polymer miscibility has been discovered in a blend system comprising poly(ether imide) (PEI) and a new poly(ether diphenyl ether ketone) (PEDEK). The miscibility of the PEDEK/PEI polymer system (quenched from the molten state) was investigated in this study using differential scanning calorimetry and Fourier transform (FT-IR) spectroscopy. A composition-dependent single glass-transition temperature (T _g) in the PEDEK/PEI blends over a full composition range was observed; the sharp transition width and the T _g–composition relationship both suggest that the scale of mixing is fine and uniform. Evidence based on observation of the cold-crystallization peak and suppression of the blend crystallinity and melting peak also indicated intimate intermolecular mixing. The FT-IR result yielded further evidence that the physical interactions leading to miscibility were weak, with no apparent specific interactions between the constituent polymers. Relationships between structures and interactions responsible for the miscibility in PEI and several ether-ketone-type polymers are briefly discussed. Received: 8 July 1999 Accepted in revised form: 21 October 1999     

Poly(ester anhydride)s prepared by the insertion of ricinoleic acid into poly(sebacic acid)

New degradable poly(ester anhydride)s were prepared by the melt polycondensation of diacid oligomers of poly(sebacic acid) (PSA) transesterified with ricinoleic acid. The transesterification of PSA with ricinoleic acid to form oligomers was conducted via a melt bulk reaction between a high molecular weight PSA and ricinoleic acid. A systematic study on the synthesis, characterization, degradation in vitro, drug release, and stability of these polymers was performed. Polymers with weight‐average molecular weights of 2000–60,000 and melting temperatures of 24–77 °C were obtained for PSA containing 20–90% (w/w) ricinoleic acid. NMR and IR analyses indicated the formation of ester bonds along the polyanhydride backbone. These new degradable copolymers have potential use as drug carriers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1059–1069, 2003     

Phase behavior,crystallization, and morphology in thermosetting blends of a biodegradable poly(ethylene glycol)‐type epoxy resin and poly(ϵ‐caprolactone)

Thermosetting blends of a biodegradable poly(ethylene glycol)‐type epoxy resin (PEG‐ER) and poly(?‐caprolactone) (PCL) were prepared via an in situ curing reaction of poly(ethylene glycol) diglycidyl ether (PEGDGE) and maleic anhydride (MAH) in the presence of PCL. The miscibility, phase behavior, crystallization, and morphology of these blends were investigated. The uncured PCL/PEGDGE blends were miscible, mainly because of the entropic contribution, as the molecular weight of PEGDGE was very low. The crystallization and melting behavior of both PCL and the poly(ethylene glycol) (PEG) segment of PEGDGE were less affected in the uncured PCL/PEGDGE blends because of the very close glass‐transition temperatures of PCL and PEGDGE. However, the cured PCL/PEG‐ER blends were immiscible and exhibited two separate glass transitions, as revealed by differential scanning calorimetry and dynamic mechanical analysis. There existed two phases in the cured PCL/PEG‐ER blends, that is, a PCL‐rich phase and a PEG‐ER crosslinked phase composed of an MAH‐cured PEGDGE network. The crystallization of PCL was slightly enhanced in the cured blends because of the phase‐separated nature; meanwhile, the PEG segment was highly restricted in the crosslinked network and was noncrystallizable in the cured blends. The phase structure and morphology of the cured PCL/PEG‐ER blends were examined with scanning electron microscopy; a variety of phase morphologies were observed that depended on the blend composition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2833–2843, 2004     

PPEKK/PEI共混物的相容性及拉伸性能

作为相容体系 ,聚芳醚酮与聚醚酰亚胺 (ＰＥＩ)共混物体系的研究受到了研究者的重视[1～ 4] .由于现在已商品化的聚芳醚酮基本上都是半结晶型聚合物 ,所以有有关无定型聚芳醚酮与聚醚酰亚胺共混物的研究鲜见报道 .含二氮杂萘酮结构聚芳醚酮酮 (ＰＰＥＫＫ)是一种新型耐高温聚合物 ,相比于已经商品化的各种聚芳醚酮 ,ＰＰＥＫＫ除具有优异的综合性能外 ,它最大的特点表现在以下两方面 ,ＰＰＥＫＫ耐热性突出 ,玻璃化转变温度 (Ｔｇ)为 2 4 5℃左右 ,远高于各种商品化的聚芳醚酮 ;ＰＰＥＫＫ为无定型聚合物 ,易溶于多种有机极性溶剂 ,大大的扩…     

Synthesis of Poly(Adipic Anhydride) by Use of Ketene

Polyadipic anhydrides were prepared (a) from the mixed anhydride of adipic acid and acetic acid, (b) from the mixed anhydride of adipic acid and ketene in tetrahydrofurane solution (0°C), (c) by melt polycondensation of adipic acid with ketene, and (d) from the seven-membered ring adipic anhydride. The polymers were characterized by means of NMR, IR, DSC, and GPC. The polymer with the highest melting temperature was obtained by melt polycondensation of adipic acid with ketene (T _peak 76°C). The heat of fusion was approximately 40 J/g in all four methods. The number-average and weight-average molecular weights of the polyanhydrides were 2000 and 3000, respectively.     

聚合物共混物相容性的研究进展

相容性聚合物共混物由于其优异的复合性能已成为新材料的主要研究方向。但许多共混物是互不相容的 ,因此必须改善它们的相容性。文章综述了聚合物共混物相容性研究的现状与发展 ,介绍了各种增容方法及其应用     

Solvent effects on phase behavior with false UCST in blends of PVPh with aliphatic polyesters

Solvent effects on phase behavior in blends were examined. Misinterpretation might be resulted if effects of solvent were not properly evaluated and avoided. Solvent effects were found to influence to widely different levels on blend systems comprised of poly(4-vinyl phenol) (PVPh) and a homologous series of polyesters of different CH₂/CO ratios. Confusion and misinterpretation in phase behavior between miscibility and immiscibility with upper-critical-solution-temperature (UCST) could be resulted if solvent effects were not fully excluded from true thermodynamic phase behavior in the blends. However, apparent solvent effects on interfering true phase behavior were found in the blends of PVPh with several polyesters whose structures led to borderline miscibility. Superficially, the blends prepared by solvent casting behaved similarly to phase-separated blends with UCST. By comparison, regardless of methods of blend preparation, the miscibility was straightforwardly proven for the blends of PVPh with poly(hexamethylene adipate) (PHA) that possesses an average CH₂/CO ratio = 5.0 located on the center of window, and the phase behavior of PVPh/PHA blends is largely free of solvent interference. Care must be exercised in interpretation of phase behavior by excluding the solvent effects, especially for those blends with borderline miscibility with weak interactions.