Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.     

Influence of solvent on the poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and the performance of quasi-solid-state dye-sensitized solar cells

The influence of solvents on the property of poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and photovoltaic performance of quasi-solid-state dye-sensitized solar cells (DSSCs) were investigated. Solvents or mixed solvents with large donor number enhance the liquid electrolyte absorbency, which further influences the ionic conductivity of polymer gel electrolyte. A polymer gel electrolyte with ionic conductivity of 4.45 mS cm⁻¹ was obtained by using poly (acrylic acid)-oligo-(ethylene glycol) as polymer matrix, and absorbing 30 vol.% N-methyl pyrrolidone and 70 vol.% γ-butyrolactone with 0.5 M NaI and 0.05 M I₂. By using this polymer gel electrolyte coupling with 0.4 M pyridine additive, a quasi-solid-state dye-sensitized solar cell with conversion efficiency of 4.74% was obtained under irradiation of 100 mW cm⁻² (AM 1.5).     

Coarse-grained modelling of self-assembling poly(ethylene glycol)/poly(lactic acid) diblock copolymers

An implicit-solvent coarse-grained model for poly(ethylene glycol)/poly(lactic acid) (PEG/PLA) diblock copolymer is derived using the iterative Boltzmann inversion technique. The model is shown to be effective in reproducing the micellar core-shell structure of PEG/PLA diblock copolymer recently reported in experiments. Influence of block architecture on the aggregate morphology is investigated. Upon increasing the length of PLA block, the model predicts a morphological change from conventional spherical to anisotropic (e.g., lamellar or cylindrical) structure, in agreement with experimental findings. The current model is also noted to provide very rapid aggregation of the block copolymers, allowing observation of copolymer micelles in their equilibrium structures in a short simulation time.     

Self-association of double-hydrophilic copolymers of acrylic acid and poly(ethylene oxide) macromonomer

Poly(ethylene oxide) (PEO) end-capped by a methacrylate unsaturation was copolymerized with acrylic acid by RAFT with dibenzyltrithiocarbonate as a chain transfer agent. Tapered triblock copolymers consisting of a poly(acrylic acid) (PAA) inner block and comb-like outer blocks of PEO macromomers were formed as result of the comonomers reactivity ratios. Composition of these copolymers and length of the PEO branches were varied. Dynamic light scattering (DLS) was used to characterize the aggregates formed in water and to investigate their response to stimuli, such as pH, temperature and ionic strength. In parallel, the morphology of the aggregates was directly observed by transmission electron microscopy (TEM). Well-defined aggregates were formed in the 5<pH<8 range, with a morphology strongly depending on the copolymer composition. At pH<5, the copolymers were poorly soluble and no well-defined structure was observed, whereas free chains were formed at pH>8 as consequence of the complete ionization of the PAA block.     

Synthesis of nylon 6-g-poly(ethylene glycol) copolymer and its compatibilizing effect in nylon 6/poly(ethylene glycol) blends

Summary A graft copolymer of poly(ethylene glycol) onto nylon 6 was prepared by two-step reactions; poly(ethylene glycol) (PEG) was chlorinated with thionyl chloride in carbon tetrachloride and the chlorinated PEG was then grafted onto nylon 6 by reacting each other with triethylamine and tin chloride in o-chlorophenol. Blends were also prepared from the graft copolymer with nylon 6 or PEG. The thermal properties and crystalline structure of the graft copolymer and the blends were studied using differential scanning calorimeter and X-ray diffractometer. It was found that the grafting of PEG onto nylon 6 changed the crystal structure of nylon 6. It was observed that compatibilization of the nylon 6/PEG blend of 50/50 composition by weight was achieved in the presence of the graft copolymer.     

Synthesis of hydroxyl-capped comb-like poly(ethylene glycol) to develop shell cross-linkable micelles

A novel hydroxyl-capped comb-like poly[poly(ethylene glycol) methacrylate] (PPEGMA) was prepared via atom transfer radical polymerization (ATRP) of α-methylacryloyl-ω-hydroxyl-poly(ethylene glycol) at ambient temperature. The polymerization kinetics of the block copolymer was studied by gel permeation chromatography (GPC) and ¹H NMR. It is of interest to find the well-defined comb-like PEG can associate into micelles, which have hydrophilic PEG shell end-capped by hydroxyl groups. The hydroxyl in the shell were further cross-linked by divinyl sulfone (DVS), which could couple with two capped-end hydroxyl groups. The XPS, TEM, AFM and laser scattering particle size distribution analyzer results revealed that reactive micelles could be cross-linked by DVS. The reactive, cross-linkable micelles with PEG shell may have great potential as new drug carrier and nanoreactor, etc.     

Grafting of the acrylic acid on poly(ethylene terephthalate)

A study has been made of the effect of solvent nature, concentrations of monomer, initiator and homopolymerization inhibitors, and initial polymer structure on the modification of poly(ethylene terephthalate) (PET) films and fibers by grafting the acrylic acid (AA). AA grafting initiated by radicals formed from thermal decomposition of benzoyl peroxide. It has been established that preswelling of PET in dichloroethane leads to changes in its sorption–diffusion properties and favors an increase in the degree of grafting. Addition of the Fe(II), Ni(II), and Cu(II) salts to AA solution decreased homopolymer yield. The studied process of grafting can be described by equations of diffusion kinetics. Distribution of the poly(acrylic acid) (PAA) over the cross section of samples and a number of physical and chemical properties depend also on conditions of performing the graft polymerization.     

Inhibition of bovine serum albumin adsorption by poly(ethylene glycol) soft segment in biodegradable poly(ethylene glycol)/poly(L-lactide) copolymers

The objective of this study was to investigate the effects of the incorporation of ether linkages into polylactide (PLLA) chains and the time of biodegradation on the behavior of protein adsorption. The content of poly(ethylene glycol) (PEG) in PLLA/PEG copolymers is from 4.4 to 18.3 wt %, and the length of the PEG soft segment is 1000, 2000, and 6000 daltons. The bovine serum albumin (BSA) adsorption onto the biodegradable PLLA/PEG copolymers was carried out using ultraviolet spectroscopy. The surface tension of PLLA and PLLA/PEG was measured using a contact angle. The data show that the incorporation of PEG segments makes the copolymer more polar and, therefore, leads to a reduction of protein adsorption. As the hydrolysis of polymers proceeds, both PLLA and PLLA/PEG turn out to be more polar. However, the initial compositions of degraded PLLA/PEG have a weak influence on the protein adsorption onto its hydrolyzed surface with a substantially long duration of hydrolysis. This phenomenon is attributed to the hydrophobic interaction between polar PLLA/PEG and BSA. © 1993 John Wiley & Sons, Inc.     

Effect of various types of interaction on the stability of some ternary interpolymer complexes involving poly(ethylene imine), poly(acrylic acid) and poly(ethylene glycol)

The effect of various types of interaction on the stability of multi‐component interpolymer complexes was studied for some three‐component interpolymer complexes involving poly(ethylene imine), poly(acrylic acid) and poly(ethylene glycol). The degree of linkage (θ), stability constant (K) and related thermodynamic parameters (e.g. ΔH⁰ and ΔS⁰) of these complexes were determined at several temperatures and compared for various complexation systems. The comparative study indicated considerable difference in the values of these parameters, which is explained in terms of various modes of interaction between the components. Copyright © 2010 Society of Chemical Industry     

Synthesis of monomethoxy poly(ethylene glycol) without diol poly(ethylene glycol)

Since monomethoxy poly(ethylene glycol) (mPEG) inevitably contains diol PEG and is difficult to get high molecular weight through traditional synthesis at high temperature under high pressure, a novel synthetic technique via anionic solution polymerization was reported in this study. With a new initiating system, potassium naphthalene and methanol, was introduced, the polymerization proceeded at ambient temperature and side reactions were well restrained. Furthermore, a slight excess of potassium naphthalene can effectively remove the trace of water and oxygen in the reaction system. Under this condition, mPEG was nearly quantitatively obtained without containing diol PEG. Its Mn ranged from 1 to 30 kDa and the polydispersity was kept lower than 1.07. Characterization of the mPEG obtained was carried out using GPC to determine the content of diol PEG and ¹H‐NMR and MALDI‐ToF MS spectroscopic analysis to confirm the exact structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and properties of poly(ethylene glycol)-block-poly(acrylic acid)-coated cobalt nanocrystals

Reported in this paper are the preparation and properties of ?-Co nanocrystals coated by poly(ethylene glycol)-block-poly(acrylic acid) (PEG-b-PAA). These particles were prepared via the thermal decomposition of Co₂(CO)₈ at 185 °C in 1,2-dichlorobenzene, in the presence of the surfactant PEG-b-PAA and the co-surfactant trioctylphosphine oxide. At a given initial Co₂(CO)₈ concentration, the size of the particles increased with increasing Co₂(CO)₈-to-PEG-b-PAA molar ratio, and could be tuned between ∼5 and ∼20 nm. The size distribution of the particles narrowed as the Co₂(CO)₈ concentrations increased. The resultant particles were dispersible in a wide range of solvents, including chloroform, N,N-dimethylforamide, and water, which solubilized PEG. Magnetic measurements revealed that the particles possessed saturation magnetization close to that of bulk Co, suggesting high purity of the particles.     

Mixed micelles from methoxy poly(ethylene glycol)–polylactide and methoxy poly(ethylene glycol)–poly(sebacic anhydride) copolymers as drug carriers

mPEG–PLLA (poly l-lactic acid) is synthesized by ring-opening polymerization of lactide and conjugation with mPEG. Sebacic acid is modified with acetic anhydride and condensed with mPEG to form mPEG–PSA (poly sebacic anhydride). The micelles formed by mPEG–PLLA are characterized by slow degradation and low drug encapsulation efficiency; on the contrary, mPEG–PSA micelles are characterized by rapid degradation but high encapsulation efficiency. They can merge into spherical micelles (Φ = 140 nm) by self-assembly in water. The mixed micelles can successfully encapsulate a typical hydrophobic drug (curcumin), and significantly improve its solubility. Experimental results show that the mixed micelles have the features of high encapsulation efficiency and slow degradation.     

Novel poly(vinyl alcohol)-g-poly(hydroxy acid) copolymers: Synthesis and characterization

Poly(vinyl alcohol) (PVA) was reacted with three hydroxy acids (HA), namely D,L-lactic acid (LA), glycolic acid (GA) and D,L-3-hydroxybutyric acid (HB). The graft copolymers obtained were thoroughly characterized by ¹H and ¹³C NMR, FTIR, and DSC. Copolymer compositions were in the range 14–45 mol% HA with average lateral chain lengths in the range 1.1–1.3. The CO stretching band, arising from the lateral polyester chains, presents significant differences from that of pure polyesters. In case of the VALA and VAGA copolymers, carbonyl groups are almost completely interassociated with hydroxyl groups and as a result the carbonyl band presents a single contribution; however, splitting appears in VAHB. The band at about 1735 cm^?1 already observed for Poly(3-hydroxybutyrate) P3HB was reexamined in the light of molecular models for VAHB and the splitting observed was attributed to C–H???OC and to O–H???OC hydrogen bonding. The thermal analysis of copolymers demonstrates that esterification suppresses crystallinity and increases free volume, both accounting for a Tg reduction with regard to PVA. The stronger intermolecular hydrogen bonding interactions found in PVA with the chemically modified PVAs opens an interesting way towards miscibility with polyesters and other polymer systems containing carbonyl groups.     

Interpolymer complexation between poly(ethylene oxide) and poly(acrylic acid)

Summary Solution and solid state properties of the interaction between poly(acrylic acid) and poly(ethylene oxide) have been studied in the presence and absence of CaSO₄ in water or in methanol systems. The association in solution has been investigated by viscosity measurements and NMR spectroscopy. The solid state of the systems has been studied using DSC, IR, X-RAY and 13-C-CPMAS-NMS. Complex formation is also clearly indicated.     

Influence of ionic charge placement on performance of poly(ethylene glycol)-based sulfonated polyurethanes

Poly(ethylene glycol) (PEG)-based sulfonated polyurethanes bearing either sulfonated soft segments (SSSPU) or sulfonated hard segments (SHSPU) were synthesized using sulfonated monomers. Differential scanning calorimetry (DSC) revealed that sulfonate anions either in the soft segments or hard segments both increased the glass transition temperatures (T_g’s) of the soft segments and suppressed their crystallization. Moreover, dynamic mechanical analysis (DMA) and tensile analysis demonstrated that SSSPU possessed a higher modulus and tensile strength relative to SHSPU. Fourier transform infrared (FTIR) spectroscopy revealed that hydrogen bonding interactions in SHSPU were suppressed compared to SSSPU and noncharged PU. This observation suggested a high level of phase-mixing for SHSPU. In addition, atomic force microscopy (AFM) phase images revealed that both SSSPU and noncharged PU formed well-defined microphase-separated morphologies, where the hard segments phase-separated into needle-like hard domains at the nanoscale. However, SHSPU showed a phase-mixed morphology, which was attributed to increased compatibility of polar PEG soft segments with sulfonated ionic hard segments and disruption of hydrogen bonds in the hard segment. The phase-mixed morphology of SHSPU was further demonstrated using small angle X-ray scattering (SAXS), which showed a featureless X-ray scattering profile. In contrast, SAXS profiles of SSSPU and noncharged PU demonstrated microphase-separated morphologies. Moreover, SSSPU also displayed a broad ionomer peak ranging in q = 1–2 nm^?1, which resulted from the sodium sulfonate ion pair association in the polar PEG soft phase. Morphologies of sulfonated polyurethanes correlated well with thermal and mechanical properties.     

ABA triblock copolymers from poly(p‐dioxanone) and poly(ethylene glycol)

Poly(p‐dioxanone)–poly(ethylene glycol)–poly(p‐dioxanone) ABA triblock copolymers (PEDO) were synthesized by ring‐opening polymerization from p‐dioxanone using poly(ethylene glycol) (PEG) with different molecular weights as macroinitiators in N₂ atmosphere. The copolymer was characterized by ¹H NMR spectroscope. The thermal behavior, crystallization, and thermal stability of these copolymers were investigated by differential scanning calorimetry and thermogravimetric measurements. The water absorption of these copolymers was also measured. The results indicated that the content and length of PEG chain have a greater effect on the properties of copolymers. This kind of biodegradable copolymer will find a potential application in biomedical materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1092–1097, 2006     

Characterization and emulsifying properties of block copolymers prepared from lactic acid and poly(ethylene glycol)

Block copolymers were prepared by the direct polycondensation of an aqueous lactic acid solution on monomethoxy or dihydroxyl poly(ethylene glycol) (PEG) in the absence of a catalyst. The resulting poly(lactic acid) (PLA)–PEG diblock and PLA–PEG–PLA triblock copolymers were characterized by various analytical techniques, including matrix‐assisted laser desorption/ionization time of flight mass spectrometry (MALDI‐TOF MS), gel permeation chromatography, and ¹H‐NMR. The molecular structure between PLA–PEG and PLA–PEG–PLA could be distinguished after the calculation of the repeat unit masses and end‐group masses through the MALDI‐TOF MS spectra. Interestingly, both copolymers could serve as a hydrophilic emulsifier to stabilize the squalene/water interfaces and yield narrowly distributed oil‐in‐water nanoparticles. In contrast, the prepolymer PEG failed to stabilize the squalene/water interface under the same homogenization conditions. These features are of great interest for applications as bioactive agent delivery, especially for candidate vaccine antigens and lipophilic anticancer drugs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shape memory behavior of poly(methyl methacrylate)-graft-poly(ethylene glycol) copolymers

This paper describes a shape memory behavior of graft copolymers poly(methyl methacrylate)-graft-poly(ethylene glycol) (PMMA-g-PEG). In shape memory test, the sample was deformed from its original shape to a temporary shape above glass transition temperature (T_g), cooled below T_g to fix the temporary shape, and subsequently heated above T_g for spontaneous recovery to the original shape. By grafting PEG onto PMMA backbone, shape memory ability was drastically enhanced than PMMA homopolymer. The shape recovery ratio was decreased with the increase in the shape deformation temperature. With considering a good miscibility of backbone and side chain in PMMA-g-PEG, this shape memory ability may be related to a physically cross-linked network structure by chain entanglement of the comb-like graft copolymer. Stress relaxation measurements were investigated in order to confirm the effect of the graft chains on the shape memory behavior.     

pH stimulus response of complex-forming poly[(ethylene glycol-co-propylene glycol)-g-acrylamide]: cr-poly(acrylic acid)

A novel interpenetrating polymer network (IPN) was synthesized on the basis of polyhydroxy-terminated poly(ethylene glycol-co-propylene glycol) chain extended with acrylamide and poly(acrylic acid) crosslinked with N,N-methylene bisacrylamide. The study focused on the IPN's reversible response to pH and intelligent release behavior on pH stimulus.     

A mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poly(ethylene glycol) macromer

A new mucoadhesive polymer complex was prepared by the template polymerization of acrylic acid with poly(ethylene glycol) macromer (PEGM) as a template polymer. Fourier transform infrared results showed that the poly(acrylic acid) (PAA)/PEGM mucoadhesive polymer complex was formed by hydrogen bonding between the carboxyl groups of PAA and the ether groups of PEGM. The glass‐transition temperature of the PAA/PEGM mucoadhesive polymer complexes was shifted to a lower temperature as the repeating unit ratio of PAA/PEGM in the complex decreased. The dissolution rate of the PAA/PEGM mucoadhesive polymer complex was much slower than that of the PAA/poly(ethylene glycol) (PEG) mucoadhesive polymer complex and was dependent on the pH and molecular weight of PEGM. The mucoadhesive force of the PAA/PEGM mucoadhesive polymer complexes was stronger than that of commercial Carbopol 971P NF and almost the same as that of the PAA/PEG mucoadhesive polymer complex. The PAA/PEGM interpolymer complex seemed to be a better mucoadhesive polymer matrix than the PAA/PEG interpolymer complex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1904–1910, 2002