Mechanical, thermal and degradation properties of poly(d,l-lactide)/poly(hydroxybutyrate-co-hydroxyvalerate)/poly(ethylene glycol) blend

The mechanical, thermal and biodegradable properties of poly(d,l-lactide) (PDLLA), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ethylene glycol) (PEG) blends were studied. The influence of PEG on the tensile and impact strengths of the blends was investigated. The results showed that the toughness and elongation at break of the PDLLA/PHBV (70/30) blends were greatly improved by the addition of PEG, and the notched Izod impact strength increased about 400% and the elongation at break increased from 2.1% to 237.0%. The thermal and degradation properties of the blends were investigated by differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA), it was found that the thermal stability of PHBV in the presence of PDLLA was improved. The degradation test showed that the addition of PEG could notably accelerate the biodegradation of the blends in the soil at room temperature, and the mass loss is about 20% after 30 days of the storage.     

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     

Influence of poly (ethylene glycol) on the thermal, mechanical, morphological, physical-chemical and biodegradation properties of poly (3-hydroxybutyrate)

Blends of poly (3-hydroxybutyrate) (PHB) with poly (ethylene glycol) (PEG), (PHB/PEG), in different proportions of 100/0, 98/2, 95/5, 90/10, 80/20 and 60/40 wt%, respectively, were investigated for their thermal properties (using differential scanning calorimetry and thermogravimetric analysis), tensile properties, water vapor transmission rate, enzymatic biodegradation (using light microscopy) and mass retention. The addition of plasticizer did not alter the thermal stability of the blends, although an increase in the PEG content reduced the tensile strength and increased the elongation at break of pure PHB.     

Design of Blends with an Extremely Low Viscosity Ratio between the Dispersed and Continuous Phases. Dependence of the Dispersed Phase Size on the Processing Parameters

Summary: This work deals with the development of the dispersed phase morphology in immiscible blends of poly(ethylene glycol)/polyamide 66 (PEG/PA) with an extremely low viscosity ratio. The blends were obtained, under different operating conditions, by melt blending in an internal mixer. The objective was to examine the influence of the main processing parameters on the particles size of the minor phase (PEG). A model was elaborated to describe the dependence of the particle size on interfacial tension, PEG concentration, shear rate and viscosity ratio between the two blend components.     

Use of Natural Monomer in the Synthesis of Nano- and Microparticles of Polyurethane by Suspension-Polyaddition Technique

Summary: Polyurethane nano- and microparticles were synthesized by suspension-polyaddition technique, using aqueous polymerization medium. Castor oil, a vegetable triglyceride possessing hydroxyl groups was used as natural polyol and methylene diphenyl diisocyanate (MDI) as isocyanate. The levofloxacin, an antibacterial drug was used as model drug to measure the particles encapsulation efficiency. The effect of the addition of a second polyol, the poly(ethylene glycol) (PEG), and the stirring rate on the mean diameter and morphology of particles was also investigated. The poly(ethylene glycol) has an important effect in the reduction of particles size and their porosity. On the other hand, the poly(ethylene glycol) reduced the yield of encapsulation from 70% for the formulation without PEG to 20% for formulations with PEG. FTIR analysis confirmed the polyurethane formation. Dynamic light scattering study, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to determine the nanoparticles size and shape. Spectrofluorimetric analysis was used to detect the levofloxacin.     

Sodium Alginate and Poly(ethylene glycol) Blends: Thermal and Morphological Behaviors

Sodium alginate (SA) was blended with varying amounts of poly(ethylene glycol) (PEG) viz., 10, 20, 30, 40 and 50 wt % by using water as a solvent. The obtained SA/PEG blends have been characterized for thermal behavior by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) and surface morphology by scanning electron microscopic (SEM) methods. DSC analysis indicates the increase in glass transition temperature (T_g) of the blends with an increase in PEG content in the blend, which is due to chain entanglement. TGA results reveal the enhancement of thermal stability of SA/PEG blends in terms of the onset of degradation and percentage of weight loss. SEM photomicrographs shows the two phase morphology. This result indicates the immiscible nature of the SA/PEG blends.     

Miscibility-structure-property correlation in blends of ethylene vinyl alcohol copolymer and polyamide 6/66

Blends of ethylene vinyl alcohol (EVOH; 44 mol% ethylene) and polyamide 6/66 (PA; 75 mol% PA 6) random copolymers were studied in the entire composition range. Specific interaction between the components was analyzed by IR spectroscopy; furthermore, coefficients related to the Flory-Huggins interaction parameter were derived from equilibrium water uptake and tensile strength. Morphology of the blends was investigated by thermal analysis (DSC), density measurements, and SEM micrographs. The two polymers form heterogeneous blends in each composition. Although the components crystallize in separate phases, the morphology and the mechanical properties are greatly affected by the association of OH and NH groups. Crystallization is restricted in the blends, and the increase of the amorphous fraction, as well as specific interaction between the components, results in essential improvement in the mechanical properties.     

聚乙烯/聚乙二醇共混物中极性组分的表面富集

采用衰减全反射傅立叶变换红外光谱(FTIR-ATR)和扫描电子显微镜研究了极性组分聚乙二醇在聚乙烯／聚乙二醇共混物中的表面富集特性。研究结果认为不同组分表面自由能的差异以及聚乙烯基体的结晶异相排斥作用是导致聚乙二醇组分向共混物表面富集的主要驱动力，而极性组分相区的大小和分布则是影响其选择性迁移过程的重要因素。因此，可以通过添加合适相容剂的办法对聚乙二醇组分的表面富集程度进行有效的调控。     

Synthesis of polyvinyltrimethylsilane-graft-poly(ethylene glycol) copolymers and properties of gas-separating membranes formed on their basis

A method is developed for the synthesis of the graft copolymer polyvinyltrimethylsilane-graft-poly(ethylene glycol) via the interaction of a brominated polymer with the methyl ether of a low-molecular-mass poly(ethylene glycol). Graft copolymer samples containing up to 79 wt % poly(ethylene glycol) are synthesized through this method. The properties of the graft copolymers and blends formed on their basis with a specially synthesized low-molecular-mass PEG derivative with a terminal trimethylsilyl group are investigated. Physical blends are prepared in order to increase the content of ethylene oxide groups while the film-forming properties of the composite materials are preserved. As shown by structural studies, the graft copolymers are amorphous single-phase systems, while the related blends are two-phase disperse systems, in which one phase is enriched in polytrimethylvinylsilane and the other is enriched in PEG. Studies of the gas-transport behavior of the samples reveal that the introduction of PEG, in contrast to the nonselective initial polymer, results in the formation of PVTMS-based materials that are selective for CO₂ in mixtures with H₂.     

Binary blends based on poly(vinyl chloride) and multi-block copolymers containing poly(ϵ-caprolactone) and poly(ethylene glycol) segments

Binary blends based on poly(vinyl chloride) (PVC) were prepared both by casting from tetrahydrofuran (THF) and by mixing in the melt form, in a discontinuous mixer, PVC and multi-block copolymers containing poly(ϵ-caprolactone) (PCDT) and poly(ethylene glycol) (PEG) segments. PCDT-PEG copolymers were synthesized using a polycondensation reaction where the α,ω-bis-chloroformate of an oligomeric poly(ϵ-caprolactone) diol terminated (PCDT) and oligomeric PEG were employed as macromonomers. For comparison purposes, blends PVC with starting oligomers as well as with mixtures containing a typical low molecular plasticizer, dioctylphthalate (DOP), were also prepared. The copolymer miscibility was studied by differential scanning calorimetry (DSC) and FT-IR spectroscopy. The blend morphology was investigated by polarized light microscopy (PLM). A higher miscibility with PVC was observed for copolymers compared to PEG.     

尼龙6与半芳香性非晶尼龙原位共混物的结构与性能

一种半芳香的非晶尼龙共聚物溶解于熔融的己内酰胺中,引发后者负离子开环聚合原位制备尼龙6与非晶尼龙的共混物.与纯尼龙6相比较,此原位共混物的强度与模量显著提高.非晶区呈现单一的玻璃化转变,表明共混物为均相体系,其组分的相容性源于负离子聚合过程中链交换反应引起的共聚.与纯尼龙6相比较,此共混物的熔点与结晶度显著降低.此外,与纯尼龙6只存在α晶不同,共混物中伴生有大量的γ晶.当非晶尼龙含量为20 wt%时,绝大部分晶体为γ晶.然而,共混物中球晶仅有一定程度细化.共混物强度和模量的提高被认为主要源于非晶区分子活动能力降低以及γ晶相对含量的提高.     

Functionalization of Poly[Ethylene Terephthalate) by Means of Glow-Discharge-Initiated Polymerization of Acrylic Acid

Glow-discharge-initiated polymerization of acrylic acid incorporated in poly(ethylene terephthalate) (PET) films was investigated. An increase in polymerization yield with plasma treatment duration and power was found. Polymerization was not confined to the film surface. At high power and long treatment time, polymerization in the bulk of the PET also took place. Water regain and contact angle of the PET-treated films were affected by the presence of poly(acrylic acid) (PAA). The carboxyl groups of the PAA chains incorporated in the PET matrix were utilized for further chemical modification of the PET film. Poly(ethylene glycol) (PEG) was grafted onto PAA by esterification. DSC studies showed the presence of both PAA and PEG in the PET matrix and shed light on the morphology of the multicomponent polymeric system. Free isocyanate groups were introduced into the PET matrix by reacting PAA carboxyl groups with hexamethylene diisocyanate.     

Fractional crystallization behavior of PCL and PEG in blends

The crystallization behavior of poly(e-caprolactone)/poly(ethylene glycol) (PCL/PEG) blend was investigated by differential scanning calorimetry (DSC) and polarized microscopy (POM). Individual phase transition peaks in the DSC curves for both PEG and PCL in all the polymer blends with different PCL contents were observed. The crystallization and melting peak temperatures of PEG were at 41 and 65°C, respectively; while the crystallization and melting temperatures of PCL located at 28 and 56°C, respectively. In-situ POM results demonstrated that spherulites crystalline morphology was formed for both PCL and PEG homopolymers. In PEG/PCL blend, however, both the phase separation morphology and spherulitic morphology can be observed. In blends with 30 or 50 wt % PCL, the PCL component formed dispersed phase and crystallized at lower temperature. However, in blends with 70% PCL, the phase inversion behavior occurred. The continuous PCL phase crystallized at 35°C, while the PEG dispersed phase crystallized at a lower temperature. Fractional crystallization behavior of PEG and PCL was controlled by temperature. The spherulites growth rate of PEG was greatly influenced by temperature, instead of the content of PCL component in the PCL/PEG blends.     

MMA/BA/双官能团单体无皂共聚乳液的稳定性

用马来酸酐和(聚)乙二醇合成了一系列双官能团共单体,将其用于MMA/BA无皂乳液共聚合.研究了共单体的空间效应、用量、加料方式对其无皂乳液稳定性的影响.用适当的共单体和半连续加料方式,可得到较稳定的乳液,粒径分布接近单分散.凝聚物的生成机理主要是失稳凝聚和架桥凝聚.     

Preparation of core‐shell structured particle and its application in toughening PA6/PBT blends

Combining the excellent mechanical strengths of polyamide 6 (PA6) with the low water absorption of poly(butylene terephthalate) (PBT) was supposed to be a feasible way to prepare a high comprehensive performance material. However, the poor compatibility between PA6 and PBT resulted in low‐notched impact strength of PA6/PBT blends. Poly(n‐butyl acrylate)/poly(methyl methacrylate‐co‐methacrylic acid) (PBMMA), a core‐shell structured modifier with controlled particle sizes, was prepared by seed emulsion polymerization and confirmed by Transmission electron microscope (TEM). The PBMMA particles as toughening modifier and compatilizer were employed to toughen PA6/PBT blends. The notched impact strength of the PA6/PBT blends was significantly increased and the water absorption was reduced with the addition of PBMMA particles. With 23.0 wt% modifier loading, the notched impact strength of the blends was 25.66 kJ/m², which was 4.04 times higher than that of pure PA6/PBT. Meanwhile, the water absorption of the blends was only 1.3%, dropping 53.6% compared with pure PA6 and reducing by 26.6% than PA6/PBT. Scanning electron microscope results showed that the PBMMA particles were dispersed in the PA6/PBT blends homogeneously, and the toughening mechanism was the cavitation of rubber particles and shear yielding of the matrix. Thermo‐gravimetric analysis analysis demonstrated that the compatibility between PA6 and PBT was improved with the addition of core‐shell PBMMA particles. The core‐shell particles could be used as an effective modifier to achieve the high toughness and low water absorption for PA6/PBT blends. Copyright © 2016 John Wiley & Sons, Ltd.     

Poly (caprolactone)/poly (ethylene glycol) pervaporation blend membranes: Synthesis,characterization, and performance

Poly (caprolactone) membranes with addition of different poly (ethylene glycol) concentrations were prepared for separation of water/isopropanol azeotropic mixture by pervaporation process. Different characterization tests including Fourier transform infrared, scanning electron microscopy, water contact angle, and thermogravimetric analysis were carried out on the prepared membranes. In addition, the effect of poly (ethylene glycol) PEG content on the swelling degree and the performance of the prepared membranes in pervaporation process were investigated. According to the obtained results, all the membranes were water selective and the blend membrane containing 3 wt% PEG exhibited the best pervaporation performance with a water flux of 0.517 kg/m² hour and separation factor of 1642 at the ambient temperature. Hydrophilicity improvement of the blend membranes was confirmed by constant decrease in water contact angle of the membranes as PEG content increased in the casting solution. Scanning electron microscopy cross‐sectional images indicated that the blend membranes containing PEG had a closed cellular structure. Furthermore, mechanical and thermal properties of the membranes decreased by adding PEG.     

Synthesis of poly(ethylene glycol)/polypeptide/poly(D,L‐lactide) copolymers and their nanoparticles

Core‐shell structured nanoparticles of poly(ethylene glycol) (PEG)/polypeptide/poly(D ,L ‐lactide) (PLA) copolymers were prepared and their properties were investigated. The copolymers had a poly(L ‐serine) or poly(L ‐phenylalanine) block as a linker between a hydrophilic PEG and a hydrophobic PLA unit. They formed core‐shell structured nanoparticles, where the polypeptide block resided at the interface between a hydrophilic PEG shell and a hydrophobic PLA core. In the synthesis, poly(ethylene glycol)‐b‐poly(L ‐serine) (PEG‐PSER) was prepared by ring opening polymerization of N‐carboxyanhydride of O‐(tert‐butyl)‐L ‐serine and subsequent removal of tert‐butyl groups. Poly(ethylene glycol)‐b‐poly(L ‐phenylalanine) (PEG‐PPA) was obtained by ring opening polymerization of N‐carboxyanhydride of L ‐phenylalanine. Methoxy‐poly(ethylene glycol)‐amine with a MW of 5000 was used as an initiator for both polymerizations. The polymerization of D ,L ‐lactide by initiation with PEG‐PSER and PEG‐PPA produced a comb‐like copolymer, poly(ethylene glycol)‐b‐[poly(L ‐serine)‐g‐poly(D ,L ‐lactide)] (PEG‐PSER‐PLA) and a linear copolymer, poly(ethylene glycol)‐b‐poly(L ‐phenylalanine)‐b‐poly(D ,L ‐lactide) (PEG‐PPA‐PLA), respectively. The nanoparticles obtained from PEG‐PPA‐PLA showed a negative zeta potential value of ?16.6 mV, while those of PEG‐PSER‐PLA exhibited a positive value of about 19.3 mV. In pH 7.0 phosphate buffer solution at 36 °C, the nanoparticles of PEG/polypeptide/PLA copolymers showed much better stability than those of a linear PEG‐PLA copolymer having a comparable molecular weight. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(ethylene glycol)-based shape-memory polymers

Poly(ethylene glycol) (PEG) blends photo-curable and thermal activated shape-memory polymers (SMPs), with different activation temperature (T_switch), have been synthesized and characterized. PEG blends with different molecular weights were chain-end functionalized with isocyanate ethyl methacrylate and photo-cured with UV lamp. Degree of cross-linking of the blend network, determined by gel content measurement, resulted as higher than 95%. The thermal and thermomechanical properties of these SMPs PEG blends were characterized by differential scanning calorimetry and dynamic mechanical analysis. The shape-memory properties of the networks were quantified using thermomechanical three-point bending experiments and showed strain fixity rates higher than 99% and a minimum strain recovery ratio of 82%.     

The self‐diffusion of macromolecules in binary blends of poly(ethylene glycol)

The concentration and molecular mass dependencies of the self‐diffusion coefficients were obtained for higher molecular mass component in binary blends of the homopolymer poly(ethylene glycol) (PEG) by a nuclear magnetic resonance method with pulsed magnetic field gradient. The shape of the diffusion decay and its dependence on the diffusion observation time in binary PEG blends have been investigated. The experimental results were explained by hypothesizing the existence of cluster formation in polymer melts and polymer blends and the possibility of molecular exchange between clusters. The entanglement time in such systems was evaluated. Copyright © 1999 John Wiley & Sons, Ltd.     

Preparation of Polyamide‐6 Submicrometer‐Sized Spheres by In Situ Polymerization

Polyamide‐6 (PA6) submicron‐sized spheres are prepared by two steps: (1) anionic ring‐opening polymerization of ε‐caprolactam in the presence of poly(ethylene glycol)‐block‐poly‐(propylene glycol)‐block‐poly(ethylene glycol)(PEG‐b‐PPG‐b‐PEG) and (2) separation of PA6 spheres by dissolving PEG‐b‐PPG‐b‐PEG from the prepared blends. The PA6 microspheres obtained are regular spherical, with diameter ranging from 200 nm to 2 μm and narrow size distribution, as confirmed by scanning electron microscopy. By comparison with PA6/PS and PA6/PEG systems, it is denominated that the PEG blocks in PEG‐b‐PPG‐b‐PEG can effectively reduce the surface tension of PA6 droplets and further decrease the diameter of the PA6 microspheres. The PPG block in PEG‐b‐PPG‐b‐PEG can prevent the PA6 droplets coalescing with each other, and isolated spherical particles can be obtained finally. The phase inversion of the PA6/PEG‐b‐PPG‐b‐PEG blends occurs at very low PEG‐b‐PPG‐b‐PEG content; the PEG‐b‐PPG‐b‐PEG phase can be removed by water easily. The whole experiment can be finished in a short time (approximately in half an hour) without using any organic solvents; it is an efficient strategy for the preparation of submicron‐sized PA6 microspheres.