Synthesis and characterization of poly(carbonate urethane) networks with shape‐memory properties

In this study, a series of shape‐memory polyurethanes were prepared from polycarbonate diol (PCDL) with a molecular weight of 2000, trimethylol propane, and isophorone diisocyanate (IPDI). The properties of crosslinked poly(carbonate urethane) (PCU) networks with various compositions were investigated. The chemical structures and thermal properties were determined with Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. FTIR analysis indicated that PCU had the structures of IPDI and PCDL and the amido formyl ester in polyurethanes. The gel content of PCU showed that PCU could be effectively formed as crosslinked polyurethane networks. The glass‐transition temperatures of the PCU networks increased slightly with decreasing soft‐segment content in the networks. The values of Young's modulus in the networks at 25°C increased with decreasing soft‐segment content, whereas the tensile stress and breaking elongation decreased significantly. PCU showed shape‐memory effects with a high strain fixity rate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A poly(γ‐glutamic acid)‐based hydrogel loaded with superoxide dismutase for wound healing

The purpose of this study was to develop a poly(γ‐glutamic acid) (γ‐PGA)‐based hydrogel loaded with superoxide dismutase (SOD) to accelerate wound healing. First, γ‐PGA was modified with taurine (γ‐PGAS), and then the SOD‐loaded γ‐PGAS/γ‐PGA hydrogel (SOD‐PGAS/PGA‐H) was prepared by cross‐linking of ethylene glycol diglycidyl ether. The swelling behavior and water vapor transmission rate revealed that PGAS/PGA‐H could create a moist environment for wound surface. In vitro kinetics of SOD release showed that SOD released from PGAS/PGA‐H maintained high activity and SOD‐PGAS/PGA‐H effectively scavenged the superoxide anion. The results of our fibroblast proliferation experiments showed that PGAS/PGA‐H had good cytocompatibility. The effects of SOD‐PGAS/PGA‐H on wound healing were examined in a Type I diabetic rat model with full‐thickness wounds. Twenty‐one days after grafted to wounds, SOD‐PGAS/PGA‐H exhibited a higher rate of wound healing than control group and showed increased collagen deposition and epithelialization. SOD‐PGAS/PGA‐H seems to promote better wound healing and thus might be a promising candidate for wound healing management. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42033.     

Influence of absorbing materials on the functionalization of poly(tetrafluoroethylene) during γ‐irradiation

This contribution describes the effect of absorbing materials on the functionalization and the concentration of radicals of poly(tetrafluoroethylene) (PTFE) during the γ‐irradiation compared to the results without absorbing materials. Different absorbing calcium‐based materials were used to study their efficiency to avoid the release of fluorinated gases that occur within the irradiation procedure in the environment. It was found, that the type of the absorbing material had a significant effect on the formation and concentration of functional groups (carbonyl fluoride, carboxylic acid) and persistent radicals within the radiation‐treated PTFE samples. In addition, by means of wide angle X‐ray scattering (WAXS) the quantitative determination of fluorine (F^?) concentration after irradiation in the absorbing materials could be followed. It may be used for scientific investigations of radiation induced PTFE chain scission mechanisms as well as for the monitoring of industrial γ‐irradiation processes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1787–1793, 2013     

Flexible aliphatic poly(isocyanurate–oxazolidone) resins based on poly(ethylene glycol) diglycidyl ether and 4,4′‐methylene dicyclohexyl diisocyanate

New flexible aliphatic oxazolidone‐isocyanurate networks (AISOX) are obtained by reacting a low molecular weight diisocyanate (4,4′‐methylene dicyclohexyl diisocyanate, H₁₂MDI) and a macro‐diepoxyde (poly(ethylene glycol) diglycidyl ether, M_n = 526, PEGDGE) in different molar ratio. The curing reaction, carried out from 25 °C to 200 °C, is studied by using DSC and FTIR. The effect of the molar ratio of the two monomers on thermal and mechanical properties of AISOX resins is investigated by DSC, thermogravimetric analysis, stress?strain measurements and optical microscopy. Independently from the feed composition, it is observed that the reaction steps are: (i) partial hydrolysis of isocyanate caused by water traces, (ii) incomplete trimerization of isocyanate to give isocyanurate, and (iii) formation of oxazolidone and complete conversion of isocyanate. At the highest concentration of the soft macrodiepoxyde (PEGDGE), the AISOX resin is in the rubbery state at room temperature and shows an elastomeric behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43404.     

Preparation and properties of 4, 4′‐diphenylmethane diisocyanate blocking modified poly(propylene carbonate)

Poly(propylene carbonate) (PPC) is inferior in thermal stability and liable to incur thermal degradation, especially in the existence of residual bimetal catalyst. In this article, PPC containing residual catalyst was end‐capped with 4, 4′‐diphenylmethane diisocyanate (MDI) through melt compounding. The blends were characterized by infrared spectra, melt flow index (MFI), gel permeation chromatography (GPC), gel content measurement, thermogravimetric analysis, scanning electron microscopy, and tensile test. The effect of MDI on thermal stability, molecular weight, and tensile properties of PPC was studied. Thermal degradation kinetics of neat PPC and PPC+MDI blending samples was discussed with Friedman method. MFI, GPC, and gel content measurements showed that mainly end‐capping reaction was carried out on PPC chains when 0.1% of MDI was added. However, as the amount of MDI exceeded to 0.3%, end‐capping, chain‐extension, and crosslinking reactions were synchronously carried out on PPC. Results showed that the end‐capping, chain‐extension, and crosslinking reaction occurring between PPC and MDI could effectively inhibit the unzipping degradation even when the residual catalyst was not removed thoroughly. When the content of MDI reached 1.0%, the initial degradation temperatures (T_‐5%) increased from 176.26°C for neat PPC to 259.56°C. As a result, the processing temperature range and processing time were largely extended, and the heat resistance of PPC was improved remarkably. Meanwhile, the tensile property of the modified PPC was enhanced obviously. It may be due to the fact that the molecular weight and gel content of PPC were increased with the increasing amount of MDI. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The use of poly (ε‐caprolactone) to enhance the mechanical strength of porous Si‐substituted carbonate apatite

Poly(ε‐caprolactone) (PCL)/silicon‐substituted carbonate apatite (Si‐CO3Ap) composite derived from the interconnected porous Si‐CO3Ap reinforced with molten PCL was prepared. PCL was used to improve the mechanical properties of a porous apatite by a simple polymer infiltration method, in which the molten PCL was deposited through the interconnected channel of porous Si‐CO3Ap. The PCL covered and penetrated into the pores of the Si‐CO3Ap to form an excellent physical interaction with Si‐CO3Ap leading to a significant increase in diametral tensile strength from 0.23 MPa to a maximum of 2.04 MPa. The Si‐CO3Ap/PCL composite has a porosity of about 50–60% and an interconnected porous structure, with pore sizes of 50–150 μm which are necessary for bone tissue formation. These results could pave the way for producing a porous, structured biocomposite which could be used for bone replacement. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of poly(urethane acrylate) films for ultraviolet‐curable coatings

Four different UV‐curable poly(urethane acrylate)s were prepared through the reaction of two diisocyanates [i.e., toluene‐2,4‐diisocyanate (TDI) and isophorone diisocyanate (IPDI)] and two polyols [i.e., polycaprolactone triol (PCLT) and polycaprolactone diol (PCLD)], and they were characterized with Fourier transform infrared spectroscopy. The mechanical properties, thermal properties, and water sorption of the cured poly(urethane acrylate)s were also investigated with respect to the chemical structures of the polyols and diisocyanates. In comparison with linear PCLD–TDI and PCLD–IPDI, crosslinked PCLT–TDI and PCLT–IPDI with trifunctional PCLT showed relatively high thermal decomposition temperatures. The hardness and modulus of the UV‐cured poly(urethane acrylate) films, which were measured by a nanoindentation technique, were in the following increasing order: PCLD–IPDI ～ PCLD–TDI < PCLT–IPDI ～ PCLT–TDI. The pencil hardness was 3H for PCLT–IPDI and PCLT–TDI and HB for PCLD–IPDI and PCLD–TDI. Two urethane acrylates prepared from the trifunctional polyol showed better acid and alkali resistances than those made from the bifunctional polyol. These mechanical properties and chemical resistances may have been strongly dependent on the chain flexibility of the molecules and crosslinking density. Regardless of the functionality in the polyol, the change in the yellowness index showed a lower value in the poly(urethane acrylate) coating containing the aliphatic diisocyanate IPDI in comparison with the corresponding poly(urethane acrylate) with the aromatic diisocyanate TDI. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Application of response surface methodology to evaluate the effect of dry‐spinning parameters on poly (ε‐caprolactone) fiber properties

Poly (ε‐caprolactone) fibers were prepared by dry‐spinning method. The effect of processing parameters on linear density, mechanical, and morphological properties of fibers was investigated using the response surface methodology (RSM). This method allowed evaluating a quantitative relationship between polymer concentrations, spinning speed, and draw ratio on the properties of the fibers. Polynomial regression model was fitted to the experimental data to generate predicted response. The results were subjected to analysis of variance to determine significant parameters. It was found that all three parameters had significant effect on linear density of fibers. Combined effect of concentration and spinning speed was observed in which the linear density of fiber was more sensitive to changes in the solution concentration at lower spinning speed. Polymer concentration had the largest influence on the mechanical properties of fibers. An average cross‐sectional radius of fibers was affected by concentration and draw ratio in opposite manner. Among all three parameters, only polymer concentration had significant effect on circularity of fiber cross sections. By applying the RSM, it was possible to obtain a mathematical model that can be used to better define processing parameters to fabricate dry‐spun PCL fiber in a more rational manner. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42113.     

Oligonucleotides‐decorated‐poly(N‐vinyl pyrrolidone) nanogels for gene delivery

Pulsed electron‐beam irradiation of a semi‐dilute poly(N‐vinyl pyrrolidone) (PVP) aqueous solution in the presence of acrylic acid has led to a carboxyl functionalized nanogel system. Nanoparticles hydrodynamic size and surface charge density, in water and as a function of pH, were investigated by dynamic light scattering and laser doppler velocimetry, respectively. Nanogels (NGs) were proved not to be cytotoxic at the cellular level. Indeed, they rapidly bypass the cellular membrane to accumulate in specific cell portions of the cytoplasm, in the perinuclear area. The availability of pendant carboxyl groups on the crosslinked PVP NGs core prompted us to attempt their decoration with a single strand oligonucleotide, which holds a terminal amino group. The recognition ability of the attached single helix of its complementary strand was investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39774.     

Monitoring of the discoloration on γ‐irradiated PE and EVA films to evaluate antioxidant stability

γ‐Irradiated films could provoke unexpected interaction with proteins for instance just after irradiation and not necessarily after 12 months indicating there is no more reactive species. The optical properties of two multilayer films [polyethylene (PE)/ethylene vinyl alcohol (EVOH)/PE and ethylene vinyl acetate (EVA)/EVOH/EVA] after different γ‐irradiation doses is then studied in this work. The investigation on these films, either non‐irradiated or γ‐irradiated (up to 270 kGy), is performed by colorimetry measurement over time (up to 12 months) to assess the generation of new species inside the materials. The color change is directly correlated with absorbed γ‐doses. Over time, the color decreases and goes back to its initial time level. This discoloration evolution could be therefore used as an indication of the completion of the generated species reactions induced by γ‐irradiation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46114.     

Design and in vivo assessment of polyester copolymers based on trimethylene carbonate and ε‐caprolactone

Poly(trimethylene carbonate‐co‐caprolactone) (PTCL) copolymers with various trimethylene carbonate ratios were synthesized by ring‐opening polymerization and were used to prepare implants for an in vivo experiment. Medical silicone rubber was used as the control. Implants were prepared by compression molding with a laboratory instrument. The properties of these copolymer implants were investigated. PTCL implants and silicone rubbers were implanted subcutaneously in the dorsal region of New Zealand white rabbits. The assessment was performed 1, 2, 3, 4, 5, 6, 7, and 8 months postoperatively by the determination of the weight loss, water uptake, thermal behavior, molecular weight of the explanted implants, and histological examination. During the 8‐month implantation, the value of maximum weight loss was found to be 25%. A continuous decrease in the molecular weight occurred. No remarkable tissue reactions were observed during degradation, and foreign‐body reactions were similar to those of silicone rubbers, which are commercially available materials. In this study, we aimed to indicate the likely clinical behavior but good biodegradable properties of PTCL copolymers compared to those of silicone rubber. This may open a new avenue of application for them in the drug industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41815.     

Development of shape memory polyurethane based on polyethylene glycol and liquefied 4,4′‐diphenylmethane diisocyanate using a bulk method for biomedical applications

In this study, a series of shape memory polyurethanes (SMPUs) were synthesized successfully by the bulk polymerization method from liquefied 4,4′‐diphenylmethane diisocyanate (L‐MDI), 1,4‐butanediol (BDO) and polyethylene glycol (PEG). The influence of the hard segment content (HSC) on the structure, morphology, properties and biocompatibility of PEG based SMPUs (PEGSMPUs) was carefully investigated. The results show that a microphase separation structure composed of a semicrystalline soft phase and an amorphous hard phase is formed in the PEG6000/L‐MDI/BDO system. Crystallization of the PEG soft segment is influenced by the hard segments. The PEG semicrystalline soft phase serves as a reversible phase while the L‐MDI?BDO hard segment acts as physical netpoints. Finally, a cyclic tensile test shows that all PEGSMPUs have good shape recovery (e.g. above 80%), whereas good shape fixity can only be achieved when the HSC is less than 35 wt%. The Cell Counting Kit 8 assay also demonstrates that only PEGSMPUs containing less than 40 wt% HSC have low cytotoxicity. It is thus concluded that PEGSMPUs bearing both good shape memory effects and good biocompatibility can be used as shape memory materials for biomedical applications when the HSC is less than 35 wt%. © 2014 Society of Chemical Industry     

Mechanistic and catalytic studies of β‐nitroalcohol crosslinking with polyamine

β‐Nitroalcohols (βNAs) are promising corneoscleral crosslinking agents for the treatment of diseases such as keratoconus and myopia. Although it is believed that formaldehyde is released from the crosslinking reactions of βNAs, the mechanism by which βNAs react with amine‐functionalized polymers has yet to be known. In this study, we present the reaction mechanism of the βNA crosslinking. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) data provide strong evidence that formaldehyde is released during the reaction. Catalytic studies show that sodium bicarbonate (NaHCO₃) and salmon testes DNA accelerate the reaction while hydroxynitrile lyase from Arabidopsis thaliana decelerates the crosslinking reaction. These results suggest that βNAs are potential self‐administered crosslinking agents for future clinical use. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of copolymer microstructure on the properties of electrospun poly(l‐lactide‐co‐ε‐caprolactone) absorbable nerve guide tubes

The main objective of this work has been to study the effects of copolymer microstructure, both chemical and physical, on the microporosity, in vitro hydrolytic degradability and biocompatibility of electrospun poly(l ‐lactide‐co‐ε‐caprolactone), PLC, copolymer tubes for potential use as absorbable nerve guides. PLC copolymers with L : C compositions of 50 : 50 and 67 : 33 mol % were synthesized via the ring‐opening copolymerization of l ‐lactide (L) and ε‐caprolactone (C) at 120°C for 72 h using stannous octoate (tin(II) 2‐ethylhexanoate) and n‐hexanol as the initiating system. Electrospinning was carried out from solution in a dichloromethane/dimethylformamide (7 : 3 v/v) mixed solvent at room temperature. The in vitro hydrolytic degradation of the electrospun PLC tubes was studied in phosphate buffer saline over a period of 36 weeks. The microporous tubes were found to be gradually degradable by a simple hydrolysis mechanism leading to random chain scission. At the end of the degradation period, the % weight retentions of the PLC 50 : 50 and 67 : 33 tubes were 15.6% and 70.2%, respectively. Pore stability during storage as well as cell attachment and proliferation of mouse fibroblast cells (L929) showed the greater potential of the PLC 67 : 33 tubes for use as temporary scaffolds in reconstructive nerve surgery. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4357–4366, 2013     

Effects of γ‐aminopropyltriethoxylsilane on morphological characteristics of hybrid nylon‐66‐based membranes before electron beam irradiation

Nylon‐66 is a typical semicrystalline polymer that can be crosslinked using crosslinking agents and electron beam irradiation. Hybrid nylon‐66‐based membranes are more porous but denser compared to the pure nylon‐66 membrane. Besides that, hybrid nylon‐66 membranes exhibit higher water uptake and severe swelling in water. Si/nylon‐66 membranes were prepared by adding γ‐aminopropyltriethoxylsilane (APTEOS). Crosslinked silica in nylon‐66 membranes is confirmed with high gel content and Fourier transform infrared peaks, but XRD results showed that there is a low crystalline degree in these membranes. The thermal stability of hybrid nylon‐66 membranes is also less affected by APTEOS. The crosslinking agent only improves storage modulus in hybrid nylon‐66 membranes. After irradiation, it is learned that APTEOS improves separation performance of nylon‐66 membranes. However, excessive APTEOS causes the ratio of effective thickness over porosity (Δx/A_k) reduces significantly resulting a lower permeability membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compressive properties and creep resistance of a novel,porous, semidegradable poly(vinyl alcohol)/poly(lactic‐co‐glycolic acid) scaffold for articular cartilage repair

Tissue engineering for articular cartilage repair has shown success in ensuring the integration of neocartilage with surrounding natural tissue, but the rapid restoration of biomechanical functions remains a significant challenge. The poly(vinyl alcohol) (PVA) hydrogel is regarded as a potential articular cartilage replacement for its fair mechanical strength, whereas its lack of bioactivity limits its utility. To obtain a scaffold possessing expected bioactivity and initial mechanical properties, we herein report a novel salt‐leaching technique to fabricate a porous PVA hydrogel simultaneously embedded with poly(lactic‐co‐glycolic acid) (PLGA) microspheres. Through the investigation of environmental scanning electron microscopy, we found that the porous PVA/PLGA scaffold was successfully manufactured. The compression and creep properties were also comprehensively studied before and after cell culturing. The relationship between the compressive modulus and strain ratio of the porous PVA/PLGA scaffold showed significant nonlinear behavior. The elastic compressive modulus was influenced a little by the porogen content, whereas it went higher with a higher PLGA microsphere content. The cell‐cultured scaffolds presented higher compressive moduli than the initial ones. The creep resistance of the cell‐cultured scaffolds was much better than that of the initial ones. In all, this new scaffold is a promising material for articular cartilage repair. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40311.     

New thermoplastic segmented polyurethanes with hard segments derived from 4,4′‐diphenylmethane diisocyanate and methylenebis(1,4‐phenylenemethylenethio)dialcanols

New thermoplastic poly(ether–urethane)s and poly(carbonate–urethane)s were synthesized by a one‐step melt polymerization from poly(oxytetramethylene) diol (PTMO) and poly(hexane‐1,6‐diyl carbonate) diol (PHCD) as soft segments, 4,4′‐diphenylmethane diisocyanate, and 2,2′‐[methylenebis(1,4‐phenylenemethylenethio)]diethanol, 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol or 6,6′‐[methylenebis(1,4‐phenylenemethylenethio)]dihexan‐1‐ol as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), TGA coupled with FTIR spectroscopy, and Shore hardness and tensile testing. The obtained high‐molecular‐weight polymers showed elastomeric or plastic properties. Generally, the PTMO‐based polymers exhibited significantly lower glass‐transition temperatures (up to ?48.1 vs ?1.4°C), a higher degree of microphase separation, and ordering in hard‐segment domains in comparison with the corresponding PHCD‐based ones. Moreover, it was observed that the polymers with the PTMO soft segments showed poorer tensile strengths (up to 36.5 vs 59.6 MPa) but higher elongations at break. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 1% mass loss were in the range 270–320°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Stability of poly(N‐propargylamide)s under ultraviolet irradiation

This article investigates the photostability of poly(N‐propargylamide)s under different conditions, on the basis of which application research for this class of highly functional polymers can be performed. With helical polymer 1 [monomer: C?CCH₂NHCOCH(C₂H₅)₂] taken as a representative, some affecting factors, including the ultraviolet (UV)‐light intensity, presence of oxygen, far‐UV and near‐UV light, and temperature, were investigated. It was found that increasing the UV‐light intensity accelerated the degradation of polymer 1 . When oxygen was present, it also facilitated the degradation. Far‐UV light rather than near‐UV light played a predominant role in initiating the degradation of polymer main chains. Elevating the temperature of the polymer solution during UV irradiation made the degradation accelerate. Storing the polymer under weak UV light, in the absence of oxygen, and at a low temperature was favorable for keeping the polymer stable. These findings are important not only from a scientific point of view but especially for developing practical applications of this type of polymer on the basis of its photodegradability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Photolysis of poly(benzyl methacrylate)s and poly(benzyl acrylate)s in solution and films

Methacrylate and acrylate copolymers containing benzyl or 1‐phenylethyl groups and their monomeric model compounds were irradiated with a 254‐nm light in CH₂Cl₂ and solid films. Low molecular weight and polymeric products were analyzed by gas chromatography (GC) and NMR spectroscopy, respectively, and main‐chain scission efficiencies were determined by gel permeation chromatography (GPC). The results indicate that the ester bond cleavage in the side chain produces alkyl radicals in the main chain, leading to main‐chain scission and crosslinking. The higher stability of tertiary alkyl radicals formed in methacrylate polymers lead to the predominant main‐chain scission in solution. On the other hand, acrylate polymers were less susceptible to photodegradation. The degradabilities of the polymer films reflected those of the polymer solutions, although crosslinking preferentially occurred. The distinct effect of oxygen on the degradation was also observed in solution and films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2227–2236, 2001