Synthesis and Characterization of Xylan Grafted with Polyethylene Glycol in Ionic Liquid and Their Use as Moisture‐Absorption/Retention Biomaterials

The objective of this study is to broaden the application of xylan as moisture‐absorption/retention biomaterials by grafting polyethylene glycol (PEG) on xylan backbone. Ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([Amim]Cl) and 4,4‐diphenylmethane diisocyanate are used as reaction media and coupling reagent, respectively. FT‐IR, ¹H‐NMR, and gel permeation chromatography analyses indicate the successful occurrence of the grafting reaction. Thermogravimetric analysis/derivative thermogravimetry indicates that the thermal stability of xylan increases after the grafting of the PEG side chains. With an increase of the degree of substitution of xylan‐g‐PEG, the molecular weight (M_w) of PEG side chains (1000 and 5000 g mol^?1), and the relative humidity of environment, the moisture‐absorption/retention ratio of xylan‐g‐PEG increases. To evaluate the biodegradability/biocompatibility of this promising material, the ratio of biochemical oxygen demand to chemical oxygen demand of xylan‐g‐PEG and the cytotoxicity are tested on the samples. The results indicate that PEG‐modified xylan has great potential as moisture‐absorption/retention biomaterials.

     

Preparation of hairy particles by grafting PEG onto the poly(styrene‐co‐maleic anhydride) surface and PEG effect on SiO2 nanoparticles adsorption

Hairy particles were prepared by immobilization of poly(ethylene glycol) (PEG) on the surface of poly(styrene‐co‐maleic anhydride) (poly(S‐co‐MA)) spheres. It was found that the carbonyl groups on the poly(S‐co‐MA) surface can be conveniently esterified with the hydroxyl groups of PEG. Chemical and morphological changes were analyzed by FT‐IR, TEM, and water contact angle. Results revealed that, with the immobilization of PEG, the morphology of poly(S‐co‐MA) turned from a smooth surface to a hairy‐like structure and the hydrophilicity of the polymer particles improved. In addition, berry‐like polymer/silica particles can be obtained by using the hairy particles as template. The PEG hairy chains show steric repulsion during the deposition of silica nanoparticles by in situ sol‐gel process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

Synthesis and characterization of anionic graft copolymers containing poly(ethylene oxide) grafts

Graft copolymers containing poly(ethylene oxide) side chain attached to maleic anhydride‐alt‐vinyl methyl ether (MA‐VME) copolymer were prepared by coupling MA‐VME and poly(ethylene glycol) monomethyl ether (MPEG) by esterification in DMF at 90°C. MPEG and dodecyl alcohol (DA) were grafted onto MA‐VME copolymer in o‐xylene at 140°C in the presence of p‐toluene sulfonic acid as catalyst. The molecular weights of MPEG were found to influence the rate of the grafting reaction and the final degree of conversion. The graft copolymers were characterized by IR, GPC, and ¹H‐NMR. DSC was used to examine thermal properties of the graft copolymers. The analysis indicates that grafts have phase‐separated morphology with the backbone and the MPEG grafts forming separate phases. The properties in aqueous solutions of these grafts were studied with respect to aggregation behavior and viscometric properties. In aqueous solution, the polymers exhibited polyelectrolyte behavior (i.e., a dramatic increase of the viscosity upon neutralization). Graft copolymers with DA have lower viscosities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1138–1148, 2002     

Polyurethanes from 4,4′‐diphenylmethane diisocyanate and poly(ethylene glycol)s. II. Crystallographic data,heats of melting and crystallization,thermal stability,crystallinity and density

Wide‐angle X‐ray scattering analysis, heats of melting, crystallization and re‐melting, thermogravimetric analysis and density measurements have been used to study the crystallographic data and degree of crystallinity of linear polyurethanes (PUs) prepared by the polymerization of 4,4′‐diphenylmethane diisocyanate (MDI) with poly(ethylene glycol)s (PEGs) of various number‐average molecular weights (M_ns) (106, 200, 400, 1000, 2000 and 4000 g mol^?1) in equivalent molar ratios. The crystallinities of polyurethanes PU1000 to PU4000 are shown to be due to the polyoxyethylene segments of the PEGs, while PU400 and PU200 appeared to be amorphous. However, PU106, similarly prepared from diethylene glycol (PEG106), is highly crystalline with a different crystal structure. Thermogravimetric analysis of PU106, PU400 and PU1000 exhibited high thermal stabilities up to 260 °C for these materials under the conditions of measurement (10 °C min^?1). The heat of melting for the 100 % crystalline structure of PU106 has been indirectly obtained. Copyright © 2004 Society of Chemical Industry     

Nanocomposite polymer electrolytes containing silica nanoparticles: Comparison between poly(ethylene glycol) and poly(ethylene oxide) dimethyl ether

Nanocomposite polymer electrolytes consisting of low molecular weight poly(ethylene oxide) (PEO), iodine salt MI (M = K⁺, imidazolium⁺), and fumed silica nanoparticles have been prepared and characterized. The effect of terminal group in PEO, i.e., hydroxyl (? OH) and methyl (CH₃) using poly(ethylene glycol) (PEG) and PEO dimethyl ether (PEODME), respectively, was investigated on the interactions, structures, and ionic conductivities of polymer electrolytes. Wide angle X‐ray scattering (WAXS), differential scanning calorimetry (DSC), and complex viscositymeasurements clearly showed that the gelation of PEG electrolytes occurred more effectively than that of PEODME electrolytes. It was attributed to the fact that the hydroxyl groups of PEG participated in the hydrogen‐bonding interaction between silica nanoparticles, and consequently helped to accelerate the gelation reaction, as confirmed by FTIR spectroscopy. Because of its interaction, the ionic conductivities of PEG electrolytes (maximum value ～ 6.9 × 10^?4 S/cm) were lower than that of PEODME electrolytes (2.3 × 10^?3 S/cm). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Photo‐induced grafting of poly(ethylene glycol) onto polyamide thin film composite membranes

In this study, the surface grafting of poly(ethylene glycol) (PEG) onto commercial polyamide thin film composite (TFC‐PA) membranes was carried out, using ultraviolet photo‐induced graft polymerization method. The attenuated total reflection Fourier transform infrared spectra verify a successful grafting of PEG onto the TFC‐PA membrane surface. The scanning electron microscope and atomic force microscope analyses demonstrate the changes of the membrane surface morphology due to the formation of the PEG‐grafted layer on the top. The contact angle measurements illustrate the increased hydrophilicity of the TFC‐PA‐g‐PEG membrane surfaces, with a significantly reduced water contact angles compared to the unmodified one. Consequently, the separation performance of the PEG‐grafted membranes is highly improved, with a significant enhancement of flux at a great retention for removal of the different objects in aqueous feed solutions. In addition, the antifouling property of the modified membranes is also clearly improved, with the higher maintained flux ratios and the lower irreversible fouling factors compared to the unmodified membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45454.     

Hybrid poly(ethylene terephthalate)/silica nanocomposites prepared by in‐situ polymerization

The nanocomposites, based on hybrid poly(ethylene terephthalate) (PET)/silica nanoparticles, were prepared via in‐situ condensation polymerization of terephthalic acid and ethylene glycol in the presence of silica nanoparticles pretreated with a silane coupling agent. Such a polymerization process ensured that the silica nanoparticles were well dispersed in PET matrix with the size ranging from 40 to 60 nm, which was confirmed by transmission electron microscope (TEM) observation. Attributed to the unique bonding between SiO₂ nanoparticle and PET, the crystallization behavior of PET was improved significantly, at a low temperature in particular. To further explore the effects of silica nanoparticles on crystallization, extensive differential scanning calorimeter (DSC) measurements were performed in an attempt to reveal the impact of the morphology of the dispersed silica nanoparticle (i.e., sphere or gel‐like) on the peak temperature during melting as well as the amount of heat involved in crystallization. The influences of the structure of polyether glycol (PEG) used for PET preparation as well as the addition of glass fibres (GF) were also investigated using DSC. It was concluded that the synergy among silica nanoparticles, modified PEG, and GFs lowers both T_g and T_m of PET, thus facilitating the injection processes in application. POLYM. COMPOS. 28:42–46, 2007. © 2007 Society of Plastics Engineers     

Particle size and distribution of biodegradable poly‐D,L‐lactide‐co‐poly(ethylene glycol) block polymer nanoparticles prepared by nanoprecipitation

A biodegradable block copolymer, poly‐D ,L ‐lactide (PLA)‐co‐poly(ethylene glycol) (PEG), was prepared by the ring‐opening polymerization of lactide with stannous caprylate [Sn(Oct₂)] as a catalyst; then, the PLA–PEG copolymer was made into nanoparticles by nanoprecipitation under different conditions. The average molecular weight and structure of PLA–PEG were detected by ¹H‐NMR and gel permeation chromatography. The sizes and distributions of the nanoparticles were investigated with a laser particle‐size analyzer. The morphologies of the nanoparticles were examined by transmission electron microscopy. The effects of the solvent–nonsolvent system, operation conditions, and dosage of span‐80 on the sizes and distributions of the nanoparticles are discussed. The results show that acetone–water was a suitable solvent–nonsolvent system and the volume ratio of the nonsolvent phase to the solvent phase (O/W) (v/v), the concentration of PLA–PEG in the solvent phase, and the dosage of span‐80 had important effects on the particle sizes and distributions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1884–1890, 2005     

Preparation of superhydrophobic silica‐based films by using polyethylene glycol and tetraethoxysilane

Preparation of superhydrophobic silica‐based films via sol‐gel process by adding polyethylene glycol (PEG4000) in the silica sol precursor solution has been developed. The casting films were prepared by casting the above solution on the glass and adding poor solvent on it or not. Surface roughness of the films was obtained by removing polymer from the films at high temperature. Then, the hydrophobic group on the surfaces was obtained by reaction with hexamethyldisilazane (HMDS). Characteristic properties of the as‐prepared surface of the films were analyzed by contact angle measurement, scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared (FT‐IR) spectrophotometer, and X‐ray photoelectron spectrometer (XPS). The results showed that the contact angles of the films were varied with the PEG weight fraction of the films, the solvent for the PEG solution, the reaction temperature and time, and adding poor solvent (n‐hexane) or not. However, the surface roughness has been controlled by adjusting the experimental parameters during the early period. The contact angle of the film that prepared by spraying the poor solvent (n‐hexane) onto each coating layer for four times after casting process was greater than 150°. It was difficult to obtain superhydrophobic surface without adding n‐hexane onto any coating layer in this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of Nonionic Rosin Surfactants on Surface Activity of Silica Particles and Stability of Oil in Water Emulsions

Rosin as a natural product has become a source for production of less toxic bio-surfactants to produce emulsions which are widely used in various agriculture and food products, cosmetic, and pharmaceutical industries. In this respect, a nonionic surfactant was prepared from reaction of rosin acids and rosin maleic anhydride adduct with poly(ethylene glycol) monomethyl ether 750 (MPEG 750) to produce a rosin ester (RMPEG 750). The surface activity parameters of the prepared surfactants, such as surface excess concentration (Γ _max), the area per molecule at interface (A _min), and the effectiveness of surface tension reduction, were measured to determine the micellization and adsorption characteristics of the prepared surfactants at the water/air interface. The adsorption of the prepared surfactants on the surface of either hydrophilic or hydrophobic silica particles was determined using a spectrophotometric method. Interfacial tension between water and toluene were measured to select the best condition to obtain toluene/water emulsion in the presence of modified solid silica particles. The effects of silica particle hydrophilicity and the surfactant concentrations on the surface, interfacial activity, and on the emulsion drop size were also investigated.     

Synthesis and phase separation of poly(N‐isopropyl acrylamide‐co‐methoxy polyethyleneglycol monomethacrylate)

The poly(N‐isopropyl acrylamide‐co‐methoxy polyethyleneglycol monomethacrylate, NIPAM‐co‐MPEG) with different length of ethylene oxide (EO) were synthesized from their monomers, NIPAM and MPEGs. The numbers of repeating units of EO were 6, 10, 24, and 46. The chemical structure and mole ratio of the monomers was determined by Fourier transform infrared (FTIR), ¹H‐NMR, and ¹³C‐NMR spectroscopy. The d‐spacing increased with the number of EO and the values of the copolymers were in the range of 0.437–0.452 nm. The lower critical solution temperature of the poly(NIPAM‐co‐MPEG) shifted to higher temperature as the number of EO and the amount of MPEG increased. The change of chemical shift for methoxy proton in MPEG exhibited a larger than those of the other protons of the poly(NIPAM‐co10?2MPEG). Activation energy (E_a) for methoxy proton in MPEG showed a larger value than that of the methyl proton in NIPAM. These NMR results indicate the fact that more significant conformational transformations occur in the methoxy group through the phase separation than in the methyl group in NIPAM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1833–1841, 2006     

Synthesis of hydroxyethylcellulose‐g‐methoxypoly (ethylene glycol) copolymer and its application for protein separation in CE

Hydroxyethylcellulose‐g‐methoxypoly (ethylene glycol) (HEC‐g‐PEG) graft copolymers were synthesized through the etherification reaction between the hydroxyl group of hydroxyethylcellulose (HEC) and iodinated methoxypoly (ethylene glycol) (PEG‐I), which was prepared on the basis of two‐step reaction. Fourier transforms infrared spectrum (FTIR), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and iodide oxidation method were used to prove the success of synthesis of graft copolymer. Furthermore, the comparative studies of electro‐osmotic flow (EOF) and protein separation in bare‐fused silica, HEC and HEC‐g‐PEG‐coated capillary were performed in capillary electrophoresis (CE). The results showed that HEC‐g‐PEG‐coated capillary presented efficient EOF suppression ability and excellent resisting protein adsorption ability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of bi‐continuous poly(acrylonitrile‐co‐methyl acrylate) microporous membranes by a thermally induced phase separation method

Poly(acrylonitrile‐co‐methyl acrylate) [P(AN‐MA)] flat microfiltration membranes were successfully prepared via the thermally induced phase separation (TIPS) method, by using low polar caprolactam (CPL) and methoxypolyethylene glycol 550 (MPEG 550) as the mixed diluent. In this work, P(AN‐MA) membranes exhibit bi‐continuous networks, porous surfaces, high porosity, and big pore size, when membrane fabricated from a high MPEG 550 content, low P(AN‐MA) concentration, and small cooling rate, it can be dry state preservation and do not need to be impregnated by any solvent. When the ternary system was composed of 15 wt % P(AN‐MA), 12.5 wt % CPL, and 87.5 wt % MPEG 550, formed at 25 °C air bath, membrane has the highest water flux of 4420 L m^?2 h^?1. The obtained P(AN‐AN) membrane displays a high carbonic black ink rejection ranging from 83.7 to 98.5 wt %. Moreover, P(AN‐MA) polymer not only retains the advantages of PAN but also reduces the polar component from 16.2 to 10.77 MPa^0.5. It can be used membrane matrix to obtain pore structure and excellent mechanical property membrane via TIPS. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46173.     

Synthesis and thermal properties of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) copolymers as novel solid–solid phase‐change materials for thermal energy storage

We synthesized a series of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) (PAA‐g‐MPEG) copolymers as novel polymeric solid–solid phase‐change materials by grafting methoxypoly(ethylene glycol) (MPEG) to the main chain of poly(acrylonitrile‐co‐allyl glycidyl ether) (PAA). PAA was the skeleton, and MPEG was a functional side chain, which stored and released heat during its phase‐transition process. Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy analysis were performed to investigate the chemical structures. The crystalline morphology and crystal structures were also measured with polarized optical microscopy and X‐ray diffraction. Moreover, the thermal‐energy‐storage properties, thermal stability, and thermal reliability of the PAA‐g‐MPEG copolymers were characterized by differential scanning calorimetry and thermogravimetric analysis (TGA) methods. These analysis results indicate that the MPEG chains were successfully grafted onto PAA, and we found that the PAA‐g‐MPEG copolymers had typical solid–solid phase‐transition temperatures in the range 11–54 °C and high latent heat enthalpies between 44 and 85 J/g. In addition, the as‐prepared PAA‐g‐MPEG copolymers showed reusability and thermal reliability, as shown by the thermal cycle testing and TGA curves. Therefore, the synthesized PAA‐g‐MPEG copolymers have considerable potential for thermal energy storage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46641.     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.     

Interaction of lodine with nonionic surfactant and polyethylene glycol in aqueous potassium lodide solution

When a nonionic surfactant, such as hexaoxyethylene glycol dodecyl ethers (6ED) is added to an aqueous iodine solution in the presence of potassium iodide, some spectral changes corresponding to the interaction of iodine-potassium iodide mixture with 6ED are found above the critical micelle concentration (CMC) of 6ED. The absorption maximum bands of complexes formed between 6ED and iodine are significantly different from those formed between 6ED and iodine-potassium iodide mixture in aqueous solution. The complexes of iodic compounds (such as iodine, triiodide ion and polyiodide ion) with 6ED show absorption bands at 390 nm, 370 nm and 385 nm which are assigned to an interaction between iodine-6ED, triiodide ion-6ED and polyiodide ion-6ED, respectively. When the concentration of polyethylene glycol (PEG, MW=200–600) becomes high in aqueous triiodide ion solution, the maximum absorption wavelength of triiodide ion solution also shifts toward 370 nm, similar to that of the triiodide ion-6ED complex. If it is assumed that the absorbance between I₃ ^? and the EO chain in 6ED is the same as that between I₃ ^? and the EO chain of PEG, the concept of effective EO number can be applied to explain the behavior in the absorption spectra among I₃ ^?, 6ED and PEG. Here, the effective EO number is defined as the product of EO chain length and concentration of each 6ED and PEG in the complexes. The effective EO number and concentration of PEG decrease in the triiodide ion-PEG complex as the molecular weight of PEG becomes large. Moreover, the effective EO number and concentration of 6ED are lower than those of PEG at all maximum absorption wavelengths.     

Surface functionalization of rubber latex nanoparticles with sulfidosilane moieties

Polybutadiene latex particles were functionalized with bis[3‐(triethoxysilyl) propyl] tetrasulfide (TESPT) in the presence of zinc oxide as an activator and ethanol as a co‐solvent. The success of this reaction was confirmed both by the peaks attributed to Si‐O groups at 1085 and 1110 cm^?1 and C‐S bond at 630 cm^?1 which appeared after reaction in Attenuated Fourier Transform Infrared (ATR‐FTIR) Spectra and also by increasing in the particle size diameter of latex particles (from 95 to 127 nm) in Dynamic Light Scattering analysis. X‐ray Diffraction results also showed changes in crystalline structure of the modified particles (as a strong decrease in the intensity of peak at 2θ=19.54). The effect of reactant concentration in a constant amount of TESPT (by varying the water and ethanol content), reaction time, activator size (micro and nanoparticles), and pH (≈7, 8.5) were investigated on degree of grafting (obtained from thermogravimetric analysis and ATR‐FTIR spectra), particle size diameter, cross‐link density, and swelling ratio of the samples. The amounts of silane grafting and cross‐link density of polymer particles were increased by an increase in the reaction time. The highest grafting degree was observed at low concentration of TESPT. Silane functionalization was also improved in a slight basic condition (pH=8.5) rather than neutral pH. The grafting reaction took place such as sulfur pre‐vulcanization and the possible mechanism of this reaction was discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43268.     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Amphiphilic triblock copolymer based on poly(p‐dioxanone) and poly(ethylene glycol): Synthesis,characterization, and aqueous dispersion

Amphiphilic triblock copolymers composed of poly(p‐dioxanone) (PPDO) and poly(ethylene glycol) (PEG) were synthesized by ring opening polymerization of PDO initiated through dihydroxyl‐terminated PEG in the presence of stannous 2‐ethylhexanoate [Sn(oct)₂] as a catalyst. Polymeric nanoparticles were prepared in an aqueous medium (triple distilled water and phosphate buffer pH 7.4) by cosolvent evaporation technique at room temperature (25°C). Stability of nanoparticles was significantly enough in triple distilled water when compared with the phosphate buffer. Core‐shell geometry of polymeric nanoparticles was characterized by ¹H‐NMR spectroscopy and further confirmed by spectrophotometric analysis using pyrene as a probe. Variation in physicochemical characteristics of polymeric nanoparticles with the fraction of PPDO was investigated through the analysis of microscopic, spectroscopic, and light scattering techniques. Critical micelle concentration of polymer in triple distilled water decreased from 2.3 × 10^?3 to 4.7 × 10^?3. Atomic force microscopic observation revealed that polymeric nanoparticles were spherical and uniform with smooth textured of around 50–68 nm diameter. Dynamic light scattering and electrophoretic light scattering measurements showed a mono‐disperse size distribution of around 113–171 nm hydrodynamic diameters and negative zeta (ζ)‐potential (?4.00 to ?5.87 mV), respectively. The investigation showed a significant effect of polymeric composition on the physicochemical characteristic of polymeric nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2695–2702, 2007