Biodegradable poly(vinyl alcohol)‐graft‐ poly(ε‐caprolactone) comb‐like polyester: Microwave synthesis and its characterization

Poly(vinyl alcohol)‐initiated microwave‐assisted ring opening polymerization of ε‐caprolactone in bulk was investigated, and a series of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) copolymers were prepared, with the degree of polymerization (DP) of PCL side chains and the degree of substitution (DS) of PVA by PCL being in the range of 3–24 and 0.35–0.89, respectively. The resultant comb‐like PVA‐g‐PCL copolymers were confirmed by means of FTIR, ¹H NMR, and viscometry measurement. The introduction of hydrophilic backbone resulted in the decrease in both melting point and crystallization property of the PVA‐g‐PCL copolymers comparing with linear PCL. With higher microwave power, the DP of PCL side chains and DS of PVA backbone were higher, and the polymerization reaction proceeded more rapidly. Both the DP and monomer conversion increased with irradiation time, while the DS increased first and then remained constant. With initiator in low concentration, the DP and DS were higher, while the monomer was converted more slowly. Microwaves dramatically improved the polymerization reaction in comparison of conventional heating method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3973–3979, 2007     

Effect of recovery methods and conditions on the yield,solubility, molecular weight,and creep compliance of regenerated chitosan

The objective of this study is to explore the effect of using different recovery methods and conditions on the yield, solubility, molecular weight, and creep compliance of the regenerated chitosan. The results show that yields obtained by dialysis were higher than those using recovery medium of alkali solutions, organic solvents, or alkali–alcohol–water mixtures. For those chitosans employing alkali solutions as the recovery medium, the higher the alkali concentration used, the higher the yields obtained, although the total quantity of alkali in the solution were the same. Solubilities of regenerated chitosans were similar and independent at the methods of using alkali solution, organic solvent or alkali–alcohol–water mixture or at different concentrations of alkali solution. The molecular weight of regenerated chitosan decreased from 2.37 × 10⁷ to 1.68 × 10⁷ Da proportionally with the concentration of the alkali solution of the recovery medium from 1N to 8N. Creep compliance of regenerated chitosan gel obtained from 65% degree of deacetylation (DD) chitosan was lower than that of either 72 or 89% DD chitosan gel. Of the same DD chitosan, compliance of regenerated chitosan gels obtained by using a higher concentration of alkali solution was lower than that of a lower concentration ones. Hydrogels regenerated from different DD chitosans and/or different recovery mediums have different structure and tactile properties. Therefore, they can be used as wound dressings suited to different applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 193–202, 2002; DOI 10.1002/app.10296     

A new approach for the preparation of chitosan from γ‐irradiation of prawn shell: effects of radiation on the characteristics of chitosan

Chitosan is a biodegradable polymer composed of randomly distributed β‐(1,4)‐linked D ‐glucosamine (deacetylated unit) and N‐acetyl‐D ‐glucosamine (acetylated unit). It is produced commercially by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans (such as crabs and shrimps) and the cell walls of fungi. In the work reported, we developed a facile technique for the preparation of chitosan by irradiating prawn shell at various intensities from 2 to 50 kGy. It was observed that γ‐irradiation of prawn shell increased the degree of deacetylation (DD) of chitin at a relatively low alkali concentration during the deacetylation process. Among the various irradiation doses applied to prawn shell, a dose of 50 kGy and 4 h heating in 50% NaOH solution yielded 84.56% DD while the chitosan obtained from non‐irradiated prawn shell with the same reaction conditions had only 74.70% DD. In order to evaluate the effect of γ‐irradiation on the various physicochemical, thermomechanical and morphological properties, the chitosan samples were again irradiated (2–100 kGy) with γ‐radiation. Molecular weight, DD, thermal properties with differential scanning calorimetry and thermogravimetric analysis, particle morphology by scanning electron microscopy, water binding capacity (WBC), fat binding capacity (FBC) and antimicrobial activity were determined and the effects of various γ‐radiation doses were assessed. The DD, WBC, FBC and antimicrobial activity of the chitosan were found to improve on irradiation. It was obvious that irradiation caused a decrease of molecular weight from 187 128 to 64 972 g mol^?1 after applying a radiation dose of 100 kGy which occurred due to the chain scission of chitosan molecules at glycosidic linkages. The decrease of molecular weight increased the water solubility of the chitosan, the extent of which was explored for biomedical applications. Copyright © 2012 Society of Chemical Industry     

Influence of water and degree of sulfonation on the structure and dynamics of SPEEK studied by solid-state C and H NMR

The molecular motions of sulfonated poly(ether-ether ketone) (SPEEK), synthesized by conventional method with a range of degree of sulfonation (DS) between 42 and 70%, as a function of DS and hydration were studied by ¹H-¹³C dipolar recoupling by rotor-encoded longitudinal magnetization (RELM) and ¹³C spin-lattice relaxations. The proton conductivity increased linearly with increasing DS from 52% and was comparable to that of Nafion 115 measured in the same condition for DS higher than 65%. The RELM dipolar patterns analyzed by the SIMPSON simulation program indicated that the population of phenyl rings in large amplitude motions such as 180°-flips was reduced with increasing DS. On the other hand, T_1ρ (¹³C) and T₁ (¹³C) results suggested that the dynamic chains in both 66 kHz and 100 MHz regimes were more populated with increasing DS, possibly in small-amplitude oscillations.     

Effect of preparation method and characteristics of chitosan on the mechanical and release properties of the prepared capsule

The objective of this study is to elucidate the effect of preparation method and the characteristics of chitosan used on the mechanical and release properties of the prepared capsule. The characteristics of the chitosan explored include molecular weight (1.8, 5.6, 20.2, and 31.8 × 10⁵ Dalton) and chain flexibility parameter (B), which was manipulated by a varying degree of deacetylation (DD, 67.9, 81.3, 90.5, and 92.2%), and sodium chloride concentration (0 or 0.3%). The orifice method was used to encapsulate hemoglobin, whereas complex coacervation was used to encapsulate the bovine serum albumin (BSA). The axial ratio was measured to characterize the appearance of the capsule. Break strength was used as an index of mechanical strength. Release percent of protein was used as a pore size indicator. The results show axial ratio and hemoglobin release percent of the capsule prepared by the orifice method increased with the increase of the chain flexibility parameter (B), but decreased with the increase of the chitosan molecular weight. However, break force behaved just opposite from that of the axial ratio and release percent of hemoglobin. The capsule cannot be prepared from 92.2% DD chitosan. Break strength and BSA release percent of the capsule prepared by complex coacervation did not vary with different DD, molecular weight of chitosan, and sodium chloride concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 161–169, 1997     

Relationships between the molecular structure and moisture-absorption and moisture-retention abilities of succinyl chitosan

Summary N-Succinyl chitosan (NSC) with various degrees of deacetylation (DD 6–94%) and substitution (DS 0.14–0.79) were successfully prepared from N-acetylchitosans in varying reaction time. Infrared spectroscopy (IR), ¹H NMR and gel-permeation chromatographic (GPC) techniques were used to characterize their molecular structures. The moisture-absorption (R_a) and -retention (R_h) abilities of NSC are closely related to the DD and DS values. Under conditions of high relative humidity, the maximum R_a and R_h were obtained at DD values of about 50%, and when the DD value deviated from 50%, R_a and R_h decreased. Under dry conditions, when the DD value was 50%, the R_h was the lowest. The NSC with DS 0.65 to 0.79 exhibited better R_h than that of HA, and has the potential to prepare HA-like substances in pharmaceutical and cosmetics industries.     

Sulfonation of poly(phthalazinone ether sulfone ketone) by heterogeneous method and its potential application on proton exchange membrane (PEM)

A series of sulfonated PPESK (SPPESKs) were synthesized through a heterogeneous sulfonation process with fuming sulfuric acid as sulfonating agent in a chloroform solvent. Membranes prepared from SPPESKs were investigated and proved to be candidates of proton exchange membrane in fuel cell operating at high temperature and low humidity. The heterogeneous sulfonation reaction is verified to first occur on the interface of the acid phase and the chloroform phase, then went on in the acid phase. SPPESKs with sulfonation degree (DS) up to 2.0 are obtained through a new reprecipitation method. Effects of reaction temperature, reaction time, acid/polymer ratio, and chloroform/polymer ratio on the sulfonation reaction are reported in details. An increase in sulfonation degree results in the increase of hydrophilicity, bringing about a substantial gain in proton conductivity. SPPESK membranes exhibit high water uptake of about 105.4% with DS of 1.01, almost two times higher than that of Nafion® with similar dimensional variation. Conductivity values at 35°C, 60% R.H. ranging from 10^?3 to 10^?2 S/cm were measured, which are comparable to or higher than that of Nafion® 112 (1.635 × 10^?2 S/cm) under the same test condition. Thermogravimetric analysis shows that SPPESK membranes are stable up to 290°C in N₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1002–1009, 2007     

Effects of chitosan characteristics on the physicochemical properties,antibacterial activity,and cytotoxicity of chitosan/2‐glycerophosphate/nanosilver hydrogels

The effects of molecular weight (MW) and the degree of deacetylation (DD) of chitosan (CS) on the physicochemical properties, antibacterial activity, and cytotoxicity of CS/2‐glycerophosphate (GP)/nanosilver hydrogel in the development of a thermosensitive in situ formed wound dressing are examined herein. The gelation temperatures for the hydrogels were measured in the range of 32–37°C by manipulating the MW and DD of CS and the GP concentration. The structure of 88% DD CS hydrogel was more porous, uniform, and connective than that of the 80% DD CS hydrogel. The superior water vapor transmission rates of hydrogels with 80% and 88% DD CS were 7150 ± 52 and 9044 ± 221 gm^?2 d^?1, respectively. The skin permeations of nanosilver by the 80% and 88% DD CS hydrogels were 3.82 and 4.99 μg cm^?2, respectively, in 24 h tests. Both the hydrogels with 6 and 12 ppm nanosilver showed cytotoxicity for HS68 cells. The diameters of the hydrogel's inhibition zones for Pseudomonas aeruginosa and Staphylococcus aureus increased when the concentration of nanosilver increased and the MW of the CS decreased. Therefore, the hydrogel could be prepared with lower MW CS and lower concentration of nanosilver in order to reduce the cytotoxicity of nanosilver, while maintaining similar antibacterial activity for a hydrogel prepared with higher concentration nanosilver and higher MW CS. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of O‐carboxymethyl chitosans and their effect on color yield of acid dyes on silk

O‐Carboxymethyl chitosans with a low degree of substitution (DS) and a high degree of deacetylation (DD) were prepared directly from chitin and characterized by using ¹H‐NMR, ¹³C‐NMR, and elemental analysis methods. In our study, O‐carboxymethyl chitosans could increase the color yield of Acid Red 44 and Acid Green 25 on silk fabrics without lowering the corresponding washing fastness property. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2500–2502, 2003     

Molecular weight determination of 83% degree of decetylation chitosan with non‐Gaussian and wide range distribution by high‐performance size exclusion chromatography and capillary viscometry

Molecular weight determination of 83% degree of deacetylation (DD) chitosan with non‐Gaussian and broad molecular weight distribution by high‐performance size exclusion chromatography (HPSEC) and by capillary viscometry were proposed. The relationships between weight average retention volumes (RVw) of HPSEC and intrinsic viscosities ([η]) measured by capillary viscometer and the weight average molecular weight (Mw) measured by static light scattering were established for routine molecular weight determination of chitosans either by HPSEC or by the capillary viscometry method, respectively. These results showed: relationships of RVw and Mw for different Mw of 83.0% DD chitosans can be expressed by the equation Log Mw = −0.433 RVw + 11.66. The RVw of other DD chitosans do not correlate well with this equation. It indicated that DD of chitosan affected the relationship of RVw and Mw of chitosans studied. The Mark–Houwink constant a decreased from 0.715 to 0.521, as the solution ionic strength increased from 0.01M to 0.30M, whereas constant k increased from 5.48 × 10⁻⁴ to 2.04 × 10⁻³ over the same range of ionic strength solutions. The established RVw and Mw equation and [η] and Mw equation (Mark–Houwink equation) can be routinely used to determine the molecular weight from RVw or [η] of chitosan by HPSEC or by capillary viscometer, respectively, without the need of expensive instrumentation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1905–1913, 1999     

Effect of degree of deacetylation of chitosan on the kinetics of ultrasonic degradation of chitosan

The objective of the study was to explore the effect of the degree of deacetylation (DD) of the chitosan used on the degradation rate and rate constant during ultrasonic degradation. Chitin was extracted from red shrimp process waste. Four different DD chitosans were prepared from chitin by alkali deacetylation. Those chitosans were degraded by ultrasonic radiation to different molecular weights. Changes of the molecular weight were determined by light scattering, and data of molecular weight changes were used to calculate the degradation rate and rate constant. The results were as follows: The molecular weight of chitosans decreased with an increasing ultrasonication time. The curves of the molecular weight versus the ultrasonication time were broken at 1‐h treatment. The degradation rate and rate constant of sonolysis decreased with an increasing ultrasonication time. This may be because the chances of being attacked by the cavitation energy increased with an increasing molecular weight species and may be because smaller molecular weight species have shorter relaxation times and, thus, can alleviate the sonication stress easier. However, the degradation rate and rate constant of sonolysis increased with an increasing DD of the chitosan used. This may be because the flexibilitier molecules of higher DD chitosans are more susceptible to the shear force of elongation flow generated by the cavitation field or due to the bond energy difference of acetamido and β‐1,4‐glucoside linkage or hydrogen bonds. Breakage of the β‐1,4‐glucoside linkage will result in lower molecular weight and an increasing reaction rate and rate constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3526–3531, 2003     

Influence of wood pulp quality on the structure of carboxymethyl cellulose

The quality of carboxymethyl cellulose (CMC) prepared from different wood-derived market pulps is examined. The pulps represent kraft and sulfite qualities with different levels of hemicellulose (1.5–22.8 wt %), intrinsic viscosity (391–780 mL g⁻¹), and content of extractives (0.04–0.13 wt %). The pulps are carboxymethylated in aqueous medium at three different levels of sodium hydroxide concentration, resulting in three levels of degree of substitution (DS), 0.3, 0.7–0.8, and 1.3–1.4 (according to nuclear magnetic resonance spectroscopy and high-performance liquid chromatography). CMC with DS 0.7–0.8 is found to be near the limit for water solubility and the resulting ranking for that solubility is shown to be correlated to DS. The DS is found to be impaired by a high content of impurities and high degree of Cellulose II in the pulp. The sulfite pulps yield CMC with the best solubility in water. A high level of extractives does not interfere with reactivity. Moreover, it is found that impurities, such as lignin and xylan, inhibit thickening behavior even at high DS, and that the ratio of substitution on Position 3 is a measure of the xylan content, which suggests that this position in xylan has extremely high reactivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47862.     

Effect of deacetylation on sorption of dyes and chromium on chitin

Deacetylated chitins (10.7–67.2%) were prepared by alkaline hydrolysis to determine an optimal degree of deacetylation (DD) which can effectively remove four dyes and chromium ions from textile effluent. Sorption isotherms were carried by varying the treatment time, pH, and initial concentration of dyes or chromium ions. Experimental results were analyzed in three ways: (1) equilibrium sorption capacity and sorption rate constant, (2) Langmuir isotherms, and (3) separation factor. Results indicated that except for the chitin with a 67.2% DD, rate and capacity of the dye sorption on the chitin increased with the increase of the DD in chitin for each pH but decreased with the increase of pH for each deacetylated chitin. This was mainly due to the increase of—NH⁺₃ groups in chitin with a high DD and the low pH of the system. On the contrary, dye desorption from the deacetylated chitin was highly effective at 80° and pH ≥ 10, which could facilitate the reduction of—NH⁺₃ ions and the increase of electrostatic repulsion. The number of chromium ions sorbed on the chitin also increased with the increase of the DD at a specific time. Therefore, by controlling the DD of the deacetylated chitin maximum efficiency can be achieved in the removal of dyes and metal ions from textile effluent.     

Synthesis and characterization of carboxymethylated red angico (Anadenanthera macrocarpa) exudate polysaccharide

Red angico is a heteropolysaccharide (arabinogalactan) obtained from Anadenanthera macrocarpa trees. Carboxymethylation of angico gum (AG) with monochloroacetic acid (MCA) in alkaline aqueous medium resulted in samples which were characterized by ¹³C nuclear magnetic resonance spectroscopy and gel permeation chromatography. The effects of reaction parameters, such as alkali concentration, MCA/AG ratio and temperature on the reaction yield and degree of substitution (DS) were investigated. The DS and MCA total efficiency values increase up to 2 h reaction time and then decrease. The DS varied from 0.11 to 1.10 depending on NaOH/MCA/AG ratio and temperature. The highest MCA total efficiency (0.57) was obtained for NaOH/MCA/AG molar ratio equal to 3:1:1, at 70°C. (DS = 0.63, yield = 91.0%). Nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) analysis shows that polymer degradation was observed in all samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2985–2991, 2007     

Cationic polyelectrolytes from natural building blocks of chitosan and inulin

Novel chitosan-N-inulin graft copolymers with different degree of substitution (DS) of chitosan were synthesized via water-soluble 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide mediated reaction. Chemical structure and composition of the chitosan derivatives was confirmed by chemical analysis, FT-IR, XPS, ¹H and ¹³C NMR spectroscopy, and potentiometry. Chitosan–inulin copolymers were high-molecular-weight hydrophilic products soluble in water in a wide pH range forming extraordinary viscous solutions. Intrinsic viscosity of N-modified chitosans was sharply suppressed by added electrolyte and had tendency to decrease at higher DS of chitosan. pK_α values of the chitosan–inulin copolymers determined from potentiometric titration data using Henderson–Hasselbalch equation were in the range 6–7 slightly increasing at higher DS. Novel water-soluble chitosan copolymers retained cationic properties of chitosan and could be used as surface conditioners.     

Deacetylation of β‐chitin. I. Influence of the deacetylation conditions

The influences of the deacetylation temperature, deacetylation time, and NaOH concentration on the degree of deacetylation (DD) of deacetylated products prepared from β‐chitin are discussed. The DD values of deacetylated products are related to the ratio of the signal intensities of methyl on acetyl groups and the first anomeric carbon, which are obtained from ¹³C‐NMR spectra. The results show that the DD values of deacetylated product increase as the NaOH concentration, deacetylation time, or deacetylation temperature increases. The thermal properties, chemical structures, and crystalline characteristic of deacetylated products are significantly related to their DD values. Differential scanning calorimetry shows that the peak temperature is slightly increased as the DD values of deacetylated products of β‐chitin increase. Thermogravimetric analysis shows that the thermal degradation onset temperature of deacetylated products decreases as the DD values increase. Fourier transform infrared spectra show that the intensity of a specific absorption peak of ? NH₂ in deacetylated products significantly increases as DD increases. X‐ray diffraction patterns of deacetylated products with DD values of 17.5 and 44.7% have three significant diffraction peaks. However, there are only two diffraction peaks found in products with higher DD values of 76.5 and 94.7%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2416–2422, 2004     

Liquid‐crystalline behavior of chitosan in malic acid

This report describes how the degree of deacetylation and molecular weight of chitosan and the concentrations of sodium chloride and malic acid affect the formation of lyotropic chitosan liquid crystals. Chitosan samples of various degrees of deacetylation were prepared from β‐chitin that was isolated from squid pens. They were degraded by ultrasonic irradiation to various molecular weights. The critical concentrations forming chitosan liquid crystals were determined with a polarized microscope. A chitosan sample with a degree of deacetylation of 67.2–83.6% formed cholesteric lyotropic liquid crystals when it was dissolved in 0.37–2.59M malic acid. The critical concentrations increased with increasing degrees of deacetylation of chitosan. They decreased with increasing molecular weights or increasing concentrations of sodium chloride and malic acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The effect of reaction time and temperature during heterogenous alkali deacetylation on degree of deacetylation and molecular weight of resulting chitosan

The objective of the study is to elucidate the effect of reaction time and temperature during heterogenous alkali reaction on degree of deacetylation (DD) and molecular weight (MW) of the resulting chitosans, and to establish the reaction conditions to obtain desired DD and MW chitosan products. Chitin was extracted from red shrimp process waste. DDs and MWs were determined by infrared spectroscopy (IR) and static light scattering, respectively. The results are as follow: The DD and MW of chitin obtained were 31.9% and 5637 kDa, respectively. The DD of the resulting chitosan increased along with reaction time and/or reaction temperature. The DDs of the resulting chitosan that were obtained from 140°C were higher than those reacted at 99°C. The highest DD of the resulting chitosans after alkali deacetylation at 99 and 140°C were 92.2 and 95.1%, respectively. The DDs of chitosans increased fast at the beginning of reaction process then slowed over time. The reaction rate and rate constant of the deacetylation reaction decreased with increasing DD of the reactant. The MWs of chitosans decreased along with the deacetylation time. MW of those chitosans reacted at 140°C are smaller than those at 99°C. The rate of chitosan degradation was above 43.6%/h in the initial stage, then decreased to about 20%/h. The degradation rate constants raised substantially in the late stage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2917–2923, 2003     

Variables affecting the methylation reactions of cellulose

Solubility of methyl cellulose (MC) depends on the degree of substitution (DS), the average degree of polymerization (DP), and the distribution of methoxyl groups. Of these, the DS appears to be the most important. The DS of the MC depends on the conditions of preparation. The conditions studied in this work revealed that the DS of the MC increased as the concentration of sodium hydroxide increased from 10 to 50%. This result is attributed to the increase in the extent of formation of alkali cellulose II as a result of the increase in the alkali concentration and hence the increase of the DS of the MC. Decreasing both the ratio of dimethyl sulfate: cellulose and the liquor ratio increased the DS. High DS was achieved within a period of 2 and 3 h. However, the DS increased as the time increased. The decrease of the DS as the liquor ratio increased may be attributed to the sol–gel transition due to the interaction of the hydrophobic methoxyl groups within the polymer chains. To reveal the effect of the thermal sol–gel transition, the reaction was carried out in nonaqueous medium and the results obtained showed an increase of the DS with the increase of the solvent ratio until a maximum. This result may be contributed to the breakdown of the hydrogen bonding in the presence of solvents that transfer the reaction medium to the sol-form and hence more methylating reaction takes place. The degree of the solvation of the methyl groups into the solvents also plays a role. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of biodegradable aliphatic copolyesters with poly(tetramethylene oxide) soft segments

A series of aliphatic poly(ether–ester)s based on flexible poly(tetramethylene oxide) (PTMO) and hard poly (butylene succinate) (PBS) segments were synthesized by the catalyzed two‐step transesterification reaction of dimethyl succinate, 1,4‐butanediol, and α,ω‐hydroxy‐terminated PTMO (M_n = 1000 g/mol) in the bulk. The content of soft PTMO segments in the polymer chains was varied from 10 to 50 mass %. The effect of the introduction of the soft segments on the structure, thermal, and physical properties, as well as on the biodegradation properties was investigated. The composition and structure of the aliphatic segmented copolyesters were determined by ¹H NMR spectroscopy. The molecular weights of the polyesters were verified by viscometry of dilute solutions and polymer melts. The thermal properties were investigated using DSC. The degree of crystallinity was determined by means of DSC and WAXS. Biodegradation of the synthesized copolyesters, estimated in enzymatic degradation tests on polymer films in phosphate buffer solution with Candida rugosa lipase at 37°C, was compared with hydrolytic degradation in the buffer solution. Viscosity measurements confirmed that there was no change in molecular weight of the copolyesters leading to the conclusion that the degradation mechanism of poly(ester–ether)s based on PTMO segments occurs through the surface erosion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007