Methoxy poly(ethylene glycol)‐b‐poly(L‐lactic acid) copolymer nanoparticles as delivery vehicles for paclitaxel

Methoxy poly(ethylene glycol)‐b‐poly(L ‐lactic acid) (MPELLA) was prepared by the melt polycondensation of methoxy poly(ethylene glycol) and L ‐lactic acid. The structure and properties of MPELLA were characterized by IR, ¹H‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. To estimate its feasibility as a vehicle for paclitaxel, MPELLA nanoparticles were prepared by a self‐emulsification/solvent evaporation method. The paclitaxel‐loaded nanoparticles (PMTs) showed a spherical morphology with an inner core and an outer shell. The size, size distribution, and loading capacity of PMTs were also measured. The release kinetics of paclitaxel from PMTs in vitro was studied. The results show that paclitaxel can be effectively incorporated into MPELLA nanoparticles, which provide a delivery system for paclitaxel and other hydrophobic or toxic compounds. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2116–2122, 2005     

Structure and properties of aromatic poly(benzimidazole‐imide) copolymer fibers

A series of co‐polyimide fibers were prepared by thermal imidization of copolyamic acids derived from 3,3′,4,4′‐biphenyltertracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) in various molar ratios with 2‐(4‐aminophenyl)?5‐aminobenzimidazole (BIA). The dynamic mechanical behaviors of these polyimide (PI) fibers revealed that the glass transition temperature (T_g) was significantly improved upon increasing PMDA content. Heat‐drawing process led to dramatic change on the glass transition behavior of BPDA/BIA system, but had a small impact on BPDA/PMDA/BIA co‐polyimide fibers. This difference for PI fibers is attributed to the different degree of ordered structure of the fibers affected by heat‐drawing. The incorporation of PMDA obviously improved the dimensional stability against high temperature, due to the restricted movement of polymer chains. In addition, the obtained fibers show excellent mechanical and thermal properties because of the strong hydrogen bonding due to the incorporation of benzimidazole moieties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41474.     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Formation of honeycomb‐patterned microporous films based on a fluorinated poly(siloxane imide) segmented copolymer

The preparation of honeycomb‐patterned microporous films from a soluble fluorinated poly(siloxane imide) segmented copolymer (PSI) by means of water‐droplet templating is reported first in this article. The fluorinated PSI was synthesized from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, and diamine‐terminated poly(dimethyl siloxane) by condensation polymerization. The obtained copolymer had good solubility in chlorinated solvents (chloroform, dichloromethane, and 1,2‐dichloroethane), good thermal stability, and a microphase‐separated amorphous structure. The effects of the copolymer concentration, atmospheric humidity, and solvent properties on the pattern formation were investigated. The results show that the film fabricated from the copolymer solution with chloroform as the solvent at a humidity of 90% and a concentration of 0.5 g/L had the most regular honeycomb‐patterned micropores. We could tailor the pore shape and size by changing the copolymer concentration or the atmospheric humidity. The prepared regular honeycomb‐patterned microporous PSI films have potential applications in cell culture and tissue engineering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Amphiphilic diblock copolymers poly(2‐hydroxyethylmethacrylate)‐b‐(N‐phenylmaleimide) and poly(2‐hydroxyethylmethacrylate)‐b‐(styrene) using the macroinitiator poly(HEMA)‐Cl by ATRP: Preparation,characterization, and thermal properties

In recent years, much attention has been given to the development of specialty polymers from useful materials. In this context, amphiphilic block copolymers were prepared by atom transfer radical polymerization (ATRP) of N‐phenylmaleimide (N‐PhMI) or styrene using a poly(2‐hydroxyethylmethacrylate)‐Cl macroinitiator/CuBr/bipyridine initiating system. The macroinitiator P(HEMA)‐Cl was directly prepared in toluene by reverse ATRP using BPO/FeCl₃ 6 H₂O/PPh₃ as initiating system. The microstructure of the block copolymers were characterized using FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopic techniques and scanning electron microscopy (SEM). The thermal behavior was studied by differential scanning calorimetry (DSC), and thermogravimetry (TG). The theoretical number average molecular weight (M_n,th) was calculated from the feed capacity. The microphotographs of the film's surfaces show that the film's top surfaces were generally smooth. The TDT of the block copolymer P(HEMA)₈₀‐b‐P(N‐PhMI)₂₀ and P(HEMA)₉₀‐b‐P(St)₁₀ of about 290°C was also lower than that found for the macroi′nitiator poly(HEMA)‐Cl. The block copolymers exhibited only one T_g before thermal decomposition, which could be attributed to the low molar content of the N‐PhMI or St blocks respectively. This result also indicates that the phase behavior of the copolymers is predominately determined by the HEMA block. The curves reveal that the polymers show phase transition behavior of amorphous polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhancement of the high‐temperature utility of a polystyrene‐b‐poly(ethylene‐co‐butylene)‐b‐polystyrene block copolymer by friedel–crafts naphthoylation

A procedure was developed for the Friedel–Crafts naphthoylation of the polystyrene segments of a polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymer. It was possible to obtain up to 72% 1‐naphthoylation or 100% 2‐naphthoylation of the polystyrene segments in the copolymer. Naphthoylation could also be accomplished using trifluoromethanesulfonic acid as a catalyst. The naphthoylated products were characterized by ¹H‐NMR spectroscopy, size‐exclusion chromatography, and dynamic mechanical thermal analysis. The mechanical properties of the original and naphthoylated polymers were measured from 25 to 125°C. The results obtained indicate that naphthoylation enhances the tensile properties of the polymers at elevated temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1289–1295, 2003     

Synthesis and thermal properties of poly(urethane‐imide)

The synthesis and thermal properties of thermoplastic poly(urethane‐imide) (PUI) resins were studied. Model reaction studies on the reactions of 4,4′‐diphenylcarbamatodiphenylmethane and 4,4′‐diisocyanatodiphenylmethane with phthalic anhydride were performed. We found that the reaction of anhydrides with urethane groups could take place under certain reaction conditions. According to the model reaction studies, N‐2‐methyl‐pyrrolidone was employed as a solvent, and no catalyst was used in the polymerization. To restrain the side reaction of anhydrides with urethane groups, we adopted a two‐step chain‐extending procedure in a chain‐extending reaction. The inherent viscosity of PUI was 0.83–0.99 dL/g. The prepared polymers not only exhibited improved solubility in organic solvents but also formed flexible films. Thermogravimetric analysis showed that PUI exhibited a two‐step thermal weight‐loss pattern. The first step of the thermal degradation of PUI was attributed to the thermooxidizing cleavage of weak and labile linkage, such as urethane groups, isopropylidene, and methylene, except for imide rings. The polymer inherent viscosity decreased sharply during the first step of thermal degradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 773–781, 2001     

Preparation and properties of polystyrene‐g‐poly(butyl acrylate) copolymer emulsions with ultrasonic radiation. I. Preparation technology and coagulum ratio

A stable emulsion of polystyrene‐g‐poly(butyl acrylate) was prepared via the following steps: (1) foam polystyrene waste was dissolved in butyl acrylate; (2) the solution was added to an aqueous solution of sodium dodecyl sulfate, ammonium persulfate, and sodium hydrogen bicarbonate; and (3) the mixture was emulsified and graft‐copolymerized by ultrasonic radiation and agitation. Then, the effects of various factors, such as the strength and time of the ultrasonic radiation, the type and dosage of the emulsifier, the concentrations of the initiator and butyl acrylate, the quantity of acrylic acid, and the reaction temperature, on the coagulum ratio were investigated and analyzed. As a result, a suitable technology for reducing the amount of coagulum could be proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1405–1409, 2005     

Synthesis and characterization of poly(L‐lactide‐co‐ϵ‐caprolactone)‐b‐poly(L‐lactide) biodegradable diblock copolyesters: Effect of the block lengths on their thermal properties

Poly(L ‐lactide‐co‐ε‐caprolactone)‐b‐poly(L ‐lactide) [P(LL‐co‐CL)‐b‐PLL] diblock copolyesters were synthesized in a two‐step process with 1‐dodecanol (DDC) and stannous octoate as the initiating system. In the first‐step reaction, a 50:50 mol % amorphous poly(L ‐lactide‐co‐ε‐caprolactone) [P(LL‐co‐CL)] copolyester was synthesized via the bulk copolymerization of L ‐lactide and ε‐caprolactone, which was followed by the polymerization of the PLL crystalline block at the end chain in the second‐step reaction. The yielded copolyesters were characterized with dilute‐solution viscometry, gel permeation chromatography, ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry methods. The molecular weights of the P(LL‐co‐CL) copolyesters from the first‐step reaction were controlled by the DDC concentrations, whereas in the second‐step reaction, the molecular weights of the P(LL‐co‐CL)‐b‐PLL diblock copolyesters depended on the starting P(LL‐co‐CL) copolyester molecular weights and L ‐lactide/prepolymer molar ratios. The starting P(LL‐co‐CL) copolyester molecular weights and PLL block lengths seemed to be the main factors affecting specific thermal properties, including the melting temperature (T_m), heat of melting (ΔH_m), crystallizing temperature (T_c), and heat of crystallizing (ΔH_c), of the final P(LL‐co‐CL)‐b‐PLL diblock copolyester products. T_m, ΔH_m, T_c, and ΔH_c increased when the PLL block lengths increased. However, these thermal properties of the diblock copolyesters also decreased when the P(LL‐co‐CL) block lengths increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of fluorescent methoxy poly(ethylene glycol)‐b‐Poly(ethyl cyanoacrylate)–2‐(N‐carbazolyl) ethyl methacrylate copolymer via living oxyanion‐initiated polymerization

The fluorescent amphiphilic block copolymer methoxy poly(ethylene glycol) (mPEG)‐b‐poly(ethyl cyanoacrylate) (PECA)–2‐(N‐carbazolyl) ethyl methacrylate (CzEMA) was synthesized via living oxyanion‐initiated polymerization. mPEG‐b‐PECA–CzEMA was characterized by gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The results indicate that the polymerization was well controlled with a narrow molecular weight distribution. The mPEG‐b‐PECA–CzEMA nanoparticles prepared by nanoprecipitation techniques showed a narrow size distribution with an average diameter of less than 100 nm. The mPEG‐b‐PECA–CzEMA exhibited a strong carbazole fluorescence. Furthermore, it was found that the fluorescence intensity of mPEG‐b‐PECA–CzEMA was sensitive to a change in solvent. The results indicate that a subtle change in the state of the polymer micellar association may have altered the state of carbazole groups, which was responsible for the fluorescence emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of biodegradable block copolymer pluronic‐b‐poly(L‐lysine)

This study presented the investigations on the synthesis of a novel biodegradable block copolymer of pluronic‐b‐poly(L ‐lysine) (pluronic‐b‐PLL), which combined the characteristics of aliphatic polyester and poly(amino acids). The synthesis work started with end‐capping of pluronic with N‐t‐butoxycarbonyl‐L ‐phenylalanine using dicyclohexylcarbodiimide in the presence of 4‐dimethylaminopyridine, followed by a deprotection process to obtain the amino‐terminated pluronic; the new primary amino group in the modified pluronic initiated ring‐opening polymerization of amino acid N‐carboxyanhydride, which afforded the pluronic‐b‐poly(N^ε‐(Z)‐L ‐lysine) block copolymer. Finally, removal of the side‐chain N^ε‐(carbonybenzoxy) end protecting groups yields the block copolymer of pluronic‐b‐PLL. The products were characterized by ¹H‐NMR, FTIR, DSC, and GPC. The block copolymer micelle containing the anticancer drug paclitaxel was prepared by the double emulsion method. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Application of the biodegradable diblock copolymer poly(L‐lactide)‐block‐poly(L‐cysteine): Drug delivery and protein conjugation

A novel approach to self‐assembled and shell‐crosslinked (SCL) micelles from the diblock copolymer poly(L ‐lactide)‐block‐poly(L ‐cysteine) to be used as drug and protein delivery carriers is described. Rifampicin was used as a model drug. The drug‐loaded SCL micelles were obtained by self‐assembly of the copolymer in the presence of the drug in aqueous media. Their morphology and size were studied with dynamic light scattering and field emission scanning electron microscopy. The rifampicin loading capacity and encapsulation efficiency were studied with ultraviolet–visible spectrophotometry. The drug‐release rate in vitro depended on the oxidizing and reducing environment. Moreover, a straightforward approach to the conjugation of the copolymer with bovine serum albumin (BSA) was developed, and a gel electrophoresis test demonstrated that this conjugated BSA could be reversibly released from the copolymer substrate under reducing conditions. In conclusion, this L ‐cysteine copolymer can be used in drug delivery and in protein fixation and recovery. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of a type of ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone

Combination of the organic–inorganic hybrid such as silsesquioxane with ε‐caprolactone will lead to materials expected to be environmentally friendly and applicable to biomedical usages. A ladder‐like poly(phenyl silsesquioxane) based hybrid star‐shaped copolymer of ε‐caprolactone was prepared by ring opening polymerization of ε‐caprolactone catalyzed by Sn(Oct)₂ with hydroxyl terminated ladder‐like poly(phenyl silsesquioxane) as initiator. The copolymers were characterized by proton nuclear magnetic resonance (¹H‐NMR), silicon nuclear magnetic resonance (²⁹Si‐NMR), Fourier‐transform infrared spectrometer (FT‐IR), size exclusion chromatography (SEC), thermo gravimetric analysis (TGA), and differential scanning calorimetry (DSC) in detail. Furthermore, the enzymatic degradation property of the copolymers was also investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42335.     

Characterization of polystyrene‐b‐poly(ethylene oxide) diblock copolymer and investigation of its micellization behavior in water

The recent studies deal with a diblock copolymer, polystyrene–poly(ethylene oxide). Infrared spectroscopy, proton resonance spectroscopy (¹H‐NMR), and laser light scattering techniques have been used to characterize the polymer. It has been concluded that the sample investigated is diblock copolymer polystyrene–poly(ethylene oxide) having molecular mass 1.656 × 10⁴ g/mol and blocks ratio 1 : 2. The micellization behavior is explored through ¹H‐NMR, laser light scattering, light absorption, surface tension, and conductance and viscosity measurements. The results conclude that the critical micelles concentration of copolymer is 0.0951 g/dL at 25°C. It has been observed that the surface tension of solution decreases with the temperature and its impact is maxima in dilute concentration region. In addition, new methodologies have been introduced to get accurate critical micelles concentration and critical micelles temperature. © 2010 Wiley Periodicals, Inc., J Appl Polym Sci, 2010     

Influence of the synthesis conditions on the structural and thermal properties of poly(l‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l‐lactide)

The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.     

Compatibilization of the poly(lactic acid)/poly(propylene carbonate) blends through in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) copolymer

The in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) (PLA‐b‐PPC) block copolymers were carried out by the reaction between PLA and PPC in the presence of tetrabutyl titanate via transesterification. Molecular weight measurements and ¹³C nuclear magnetic resonance spectroscopy revealed that PLA‐b‐PPC block copolymers with higher molecular weight were obtained by controlling the reactivity point ratio between PLA chains and PPC chains in PLA/PPC reaction system. The sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % had a more proportionable reactivity point ratio between PLA chains and PPC chains compared with other samples, resulting in a most conspicuous transesterification and inconspicuous chain scission reaction. Therefore, its high molecular weight fraction (M_w > 40.0 × 10⁴) increased 80%. The formation of macromolecular PLA‐b‐PPC copolymer could strengthen the entanglement between PLA and PPC molecular chains, which resulted in an increased viscosity of blends at low shear rate. In addition, the elongation at break of sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % was nearly as twice as which without catalyst because of the improving miscibility of PLA domains and PPC matrix by the compatibilization of PLA‐b‐PPC copolymer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46009.     

Synthesis of polystyrene‐b‐poly(ethylene‐co‐butene) block copolymers by anionic living polymerization and subsequent noncatalytic hydrogenation

A series of polystyrene‐b‐polybutadiene (PSt‐b‐PBd) block copolymers with various chain lengths and compositions were synthesized by sequential living anionic polymerization and then converted into the corresponding polystyrene‐b‐poly(ethylene‐co‐butene) (PSt‐b‐PEB) block copolymers through the selective hydrogenation of unsaturated polybutadiene segments. Noncatalytic hydrogenation was carried out with diimide as the hydrogen source. The microstructures of PSt‐b‐PBd and PSt‐b‐PEB were investigated with gel permeation chromatography, ¹H‐NMR, ¹³C‐NMR, Fourier transform infrared, and differential scanning calorimetry. The results showed that the hydrogenation reaction was conducted successfully and that the chain length and molecular weight distribution were not altered by hydrogenation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2632–2638, 2006     

Preparation,characterization, and properties of crosslinked hydroxylated poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer

Acrylic acid was crosslinked with N,N′‐methylenebisacrylamide and converted to bioactive hydrogels by neutralization with different amino containing compounds. Several amino containing compounds were used such as 2‐aminopyridine, triethanol amine, hexamethylenetetramine (HMTA), pyridine, and imidazole. The best crosslinker ratio was determined in addition to the maximum absorbed water in different mediums. The antibacterial activity of the prepared gels were examined against examples of Gram‐positive (Staphylococcus aureus) and Gram‐negative bacteria (Escherichia coli) using agar plate method. The study was extended by evaluating one of prepared gels in columns as models for water filters. All prepared gels showed antibacterial action in agar plate method against both bacterium and the column method using one of the prepared gels showed excellent filtration and biocidal action. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal decomposition kinetics of poly(nButMA‐b‐St) diblock copolymer synthesized by ATRP

The reaction mechanism of decomposition process and the kinetic parameters of the poly(n‐butyl methacrylate‐b‐styrene), poly(nButMA‐b‐St), diblock copolymer synthesized by atom transfer radical polymerization (ATRP) were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA curves showed that the thermal decomposition occurred in one stage. The apparent activation energies of thermal decomposition for copolymer, as determined by the Kissinger's, Flynn–Wall–Ozawa and Tang methods, which does not require knowledge of the reaction mechanism (RM), were 112.52, 116.54, and 113.41 kJ/mol, respectively. The experimental results were compared with master plots, in the range of the Doyle approximation. Analysis of experimental results suggests that in the conversion range studied, 3–18%, the actual RM is an A₂ sigmoidal type. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009