Polyelectrolyte complex beads composed of water‐soluble chitosan/alginate: Characterization and their protein release behavior

Polyelectrolyte complex (PEC) beads were prepared from water‐soluble chitosan (WSC) and alginate complex solution with different ratios by dropping method, and all procedures used were performed in aqueous medium at neutral environment. The structure and morphology of the beads were characterized by IR spectroscopy and scanning electron microscopy (SEM). IR spectroscopy confirmed the electrostatic interactions between amino groups of WSC and carboxyl groups of alginate. SEM showed internal section of the PEC bead, which had porous structure compared with compact structure of alginate beads. The swelling behavior, encapsulation efficiency, and release behavior of bovine serum albumin (BSA) from the beads at different pHs were investigated. PEC beads demonstrated different responses to pH from alginate beads. The ratio of WSC to alginate influenced the encapsulation and release of BSA. At pH 1.2, small amount (< 15%) of BSA was released from the PEC beads except AC12. However, at pH 7.4, a large amount (> 80%) of BSA was released from AL in the first 3 h due to the rapid disintegration of the beads, whereas BSA release was retarded from complex beads due to the forming of PEC. The results suggested that the WSC/alginate beads could be a suitable polymeric carrier for site‐specific protein drug delivery in the intestine. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4614–4622, 2006     

Microwave assisted glycolysis of poly(ethylene terephthalate) catalyzed by 1‐butyl‐3‐methylimidazolium bromide ionic liquid

The combination of ionic liquid (IL) associated with microwave energy may have some potential application in the chemical recycling of poly (ethylene terephthalate). In this processes, glycolysis of waste poly (ethylene terephthalate) recovered from bottled water containers were thermally depolymerized with solvent ethylene glycol (EG) in the presence of 1‐butyl‐3‐methyl imidazolium bromide ([bmim]Br) as catalyst (IL) under microwave condition. It was found that the glycolysis products consist of bis (2‐hydroxyethyl) terephthalate (BHET) monomer that separated from the catalyst IL in pure crystalline form. The conversion of PET reach up to 100% and the yield of BHET reached 64% (wt %). The optimum performance was achieved by the use of 1‐butyl‐3‐methyl imidazolium bromide as a catalyst, microwave irradiations temperature (170–175°C) and reaction time 1.75–2 h. The main glycolysis products were analyzed by ¹H NMR, ¹³C NMR, LC‐MS, FTIR, DSC, and TGA. When compared to conventional heating methods, microwave irradiation during glycolysis of PET resulted in short reaction time and more control over the temperature. This has allowed substantial saving in energy and processing cost. In addition, a more efficient, environmental‐friendly, and economically feasible chemical recycling of waste PET was achieved in a significantly reduced reaction time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41666.     

Calcium‐carboxymethyl chitosan hydrogel beads for protein drug delivery system

In this study, carboxymethyl chitosan (CMC) hydrogel beads were prepared by crosslinking with Ca²⁺. The pH‐sensitive characteristics of the beads were investigated by simulating gastrointestinal pH conditions. As a potential protein drug delivery system, the beads were loaded with a model protein (bovine serum albumin, BSA). To improve the entrapment efficiency of BSA, the beads were further coated with a chitosan/CMC polyelectrolyte complex (PEC) membrane by extruding a CMC/BSA solution into a CaCl₂/chitosan gelation medium. Finally, the release studies of BSA‐loaded beads were conducted. We found that, the maximum swelling ratios of the beads at pH 7.4 (17–21) were much higher than those at pH 1.2 (2–2.5). Higher entrapment efficiency (73.2%) was achieved in the chitosan‐coated calcium‐CMC beads, compared with that (44.4%) in the bare calcium‐CMC beads. The PEC membrane limited the BSA release, while the final disintegration of beads at pH 7.4 still leaded to a full BSA release. Therefore, the chitosan‐coated calcium‐CMC hydrogel beads with higher entrapment efficiency and proper protein release properties were a promising protein drug carrier for the site‐specific release in the intestine. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3164–3168, 2007     

Preparation and release behavior of carboxymethylated chitosan/alginate microspheres encapsulating bovine serum albumin

Microspheres were prepared from carboxymethylated chitosan (CM‐chitosan) and alginate by emulsion phase separation. Their structure and morphology were characterized with IR spectroscopy and scanning electron microscopy. Bovine serum albumin (BSA) was encapsulated in the microspheres to test the release behavior. The swelling behavior, encapsulation efficiency, and release behavior of BSA from the microspheres at different pHs and with a pH‐gradient condition were investigated. The BSA encapsulation efficiency was calculated to be 80%. The degree of swelling of the microspheres without BSA loaded at pH 7.2 was much higher than that at pH 1.0. The encapsulated BSA was quickly released in a Tris–HCl buffer (pH 7.2), whereas a small amount of BSA was released under acid conditions (pH 1.0) because of the strong electrostatic interaction between ? NH₂ groups of CM‐chitosan and ? COOH groups of alginic acid and a dense structure caused by a Ca²⁺ crosslinked bridge. For the simulation of the processing of the drug under the conditions of the intestine, the microspheres were tested in a pH‐gradient medium, in which an acceleration of the release occurred at pH 7.4 after a lag time at a low pH (5.8–6.8). At pH 7.4, a large amount of BSA was released from the microspheres in a short time because of the rapid swelling of the microspheres. However, the release only depended on the diffusion of BSA at relatively low pHs, this resulted in a relatively low release. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 878–882, 2004     

Chitosan/polyethylene glycol–alginate microcapsules for oral delivery of hirudin

A mild chitosan/calcium alginate microencapsulation process, as applied to encapsulation of biological macromolecules such as albumin and hirudin, was investigated. The polysaccharide chitosan was reacted with sodium alginate in the presence of calcium chloride to form microcapsules with a polyelectrolyte complex membrane. Hirudin-entrapped alginate beads were further surface coated with polyethylene glycol (PEG) via glutaraldehyde functionalities. It was observed that approximately 70% of the content is being released into Tris-HCl buffer, pH 7.4 within the initial 6 h and about 35% release of hirudin was also observed during treatment with 0.1 M HCl, pH 1.2 for 4 h. But acid-treated capsules had released almost all the entrapped hirudin into Tris-HCl, pH 7.4 media within 6 h. From scanning electron microscopic and swelling studies, it appears that the chitosan and PEG have modified the alginate microcapsules and subsequently the protein release. The microcapsules were also prepared by adding dropwise albumin-containing sodium alginate mixture into a PEG– CaCl₂ system. Increasing the PEG concentration resulted in a decrease rate of albumin release. The results indicate the possibility of modifying the formulation to obtain the desired controlled release of bioactive peptides (hirudin), for a convenient gastrointestinal tract delivery system. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2143–2153, 1998     

Chitosan/calcium–alginate beads for oral delivery of insulin

A mild chitosan/calcium alginate microencapsulation process, as applied to encapsulation of biological macromolecules such as albumin and insulin, was investigated. The microcapsules were derived by adding dropwise a protein-containing sodium alginate mixture into a chitosan–CaCl₂ system. The beads containing a high concentration of entrapped bovine serum albumin (BSA) as more than 70% of the initial concentration were achieved via varying chitosan coat. It was observed that approximately 70% of the content is being released into Tris-HCl buffer, pH 7.4 within 24 h and no significant release of BSA was observed during treatment with 0.1M HCl pH 1.2 for 4 h. But the acid-treated beads had released almost all the entrapped protein into Tris-HCl pH 7.4 media within 24 h. Instead of BSA, the insulin preload was found to be very low in the chitosan/calcium alginate system; the release characteristics were similar to that of BSA. From scanning electron microscopic studies, it appears that the chitosan modifies the alginate microspheres and subsequently the protein loading. The results indicate the possibility of modifying the formulation in order to obtain the desired controlled release of bioactive peptides (insulin), for a convenient gastrointestinal tract delivery system. © 1996 John Wiley & Sons, Inc.     

An efficient recycling process of glycolysis of PET in the presence of a sustainable nanocatalyst

We demonstrate that the catalyst Perkalite F100 efficiently works as a nanocatalyst in the depolymerization of poly(ethylene terephthalate) (PET). After depolymerization of PET in the presence of ethylene glycol and the Perkalite nanocatalyst, the main product obtained was bis(2‐hydroxylethyl) terephthalate (BHET) with high purity, as confirmed by Fourier transform infrared spectroscopy and NMR. The BHET monomers could serve directly as starting materials in a further polymerization into PET with a virgin quality and contribute to a solution for the disposal of PET polymers. Compared with the direct glycolysis of PET, the addition of a predegradation step was shown to reduce the reaction time needed to reach the depolymerization equilibrium. The addition of the predegradation step also allowed lower reaction temperatures. Therefore, the strategy to include a predegradation step before depolymerization is suitable for increasing the efficiency of the glycolysis reaction of PET into BHET monomers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46285.     

Recycling of waste poly(ethylene terephthalate) into flame‐retardant rigid polyurethane foams

Waste poly(ethylene terephthalate) (PET) textiles were effectively chemical recycling into flame‐retardant rigid polyurethane foams (PUFs). The PET textile wastes were glycolytically depolymerized to bis(2‐hydroxyethyl) terephthalate (BHET) by excess ethylene glycol as depolymerizing agent and zinc acetate dihydrate as catalyst. The PUFs were produced from BHET and polymeric methane diphenyl diisocyanate. The structures of BHET and PUFs were identified by FTIR spectra. The limiting oxygen index (LOI) of the PUFs (≥23.27%) was higher than that of common PUFs (16–18%), because the aromatic substituent in the depolymerized products improved the flame retardance. To improve the LOI of the PUFs, dimethyl methylphosphonate doped PUFs (DMMP‐PUFs) were produced. The LOI of DMMP‐PUFs was approached to 27.69% with the increasing of the doped DMMP. The influences of the flame retardant on the foams density, porosity, and compression properties were studied. Furthermore, the influences of foaming agent, catalyst, and flame retardant on the flame retardation were also investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40857.     

Attapulgite‐supported aluminum oxide hydroxide catalyst for synthesis of poly(ethylene terephthalate)

A novel nanocomposite catalyst was prepared from immobilization of aluminum oxide hydroxide onto the attapulgite. Characterizations with scanning electron microscopy (SEM) and wide angle X‐ray diffraction (XRD) of the as‐prepared catalyst revealed that AlO(OH) nanoparticles were distributed on the attapulgite. Thermogravimetric analysis‐infrared spectrometry (TGA‐IR) of the mixture prepared by mixing of bishydroxy ethylene terephthalate (BHET) and the catalyst indicated that attapulgite‐supported aluminum oxide hydroxide catalyst can catalyze BHET polycondensation under the applied conditions. A kinetic model for determining the activation energy has been applied to evaluate the catalyst activity. The catalyst activity was examined through comparative experiments, and the results showed that the new catalyst exhibited higher activity for BHET polycondensation under identical reaction conditions, and the viscosity‐average molecular weight of poly(ethylene terephthalate) (PET) product obtained was increased about 2000 g/mol. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Glycolyzed PET waste and castor oil‐based polyols for two‐pack coating systems

Useful coating products may be obtained by chemical valorization (glycolysis) of post‐consumed poly(ethylene terephthalate) (PET) wastes. Glycolysis of PET waste was carried out using poly(ethylene glycol) (PEG) of various molecular weights (200, 400, 600). The depolymerized oligoesters obtained were transesterified with castor oil which results in the formation of saturated hydroxyl‐functional polyester polyols. Two‐pack coating systems were formulated using these resins as base component and melamine formaldehyde resins as hardener component. Cured films were tested for their mechanical and chemical performances. The glycolysis of PET using PEG and polyester polyol formation was characterized using Fourier transform infrared spectroscopy and the molecular weights were determined using gel permeation chromatography. Copyright © 2006 Society of Chemical Industry     

Effect of γ‐irradiation on glycolysis of PET waste and preparation of ecofriendly coatings using bio‐based and recycled materials

Recycling of postconsumer poly (ethylene terephthalate) (PET) is a worldwide concern due to large increasing volume of these materials produced by society. In the present study, we report the effect of gamma irradiation on degradation of PET and its subsequent effect on glycolysis by using excess ethylene glycol (EG). The results as analyzed by molecular weight determination showed that extent of depolymerization of PET were dose dependent. The doses of 30, 50, 70, and 100 kGy resulted in decrease in the molecular weight by about 15%, 25%, 30%, and 40% respectively. The irradiated waste PET samples were further subjected to glycolysis using EG by conventional and microwave method which resulted in increased yield of monomeric product, bis (2‐hydroxyethylterephthalate) (BHET). The recycled material, BHET, was then used in combination with bio‐based monomers to prepare a new eco‐friendly polyester polyol which was analyzed for hydroxyl, saponification, acid value and further characterized by FTIR, ¹HNMR, and GPC techniques for molecular weight determination. Polyurethane coatings were prepared from the polyester polyol and various commercial polyisocyanate curing agents. The coated films were evaluated for their performance properties. Thermal properties of coatings were investigated by differential scanning calorimetry and thermogravimetric analysis. POLYM. ENG. SCI., 55:2653–2660, 2015. © 2015 Society of Plastics Engineers     

Optimization of phthalic/maleic anhydride‐endcapped PET oligomers using response surface method

Poly(ethylene terephthalate) (PET) from off‐grades of industrial manufacturers was partially and thoroughly depolymerized in order to synthesize PET oligomers and bis(hydroxyethyl) terephthalate (BHET), respectively. Design of experiments and analysis of variance (ANOVA) were applied for optimization of samples. Effects of reaction time, volume of glycol, catalyst concentrations, and particle size of off‐grade PET were investigated. The optimal conditions to synthesize PET oligomers (3–8 repeating units) were glycol/PET molar ratio of 1, a weight ratio (catalyst to PET) of 0.5 wt%, using granule‐shape. On the other hand, a reaction time of 180 min, a weight ratio (catalyst to PET) of 0.25 wt%, and glycol/PET molar ratio of 5 were obtained as the suitable conditions of BHET production. Then, endcapped PET oligomers, as a compatibilizer for preparing PET nanocomposites, were produced via reaction between maleic anhydride/phthalic anhydride (MA/PhA) composition. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 produced the best results based on d‐spacing and peak shift of nanocomposite samples. Moreover, the reaction of MA and BHET from glycolyzation of PET was successfully performed at 160°C and 190°C for 8 h. The optimum conditions were compared with a synthesized PET. POLYM. ENG. SCI., 54:417–429, 2014. © 2013 Society of Plastics Engineers     

Cu(II)‐incorporated,histidine‐containing,magnetic‐metal‐complexing beads as specific sorbents for the metal chelate affinity of albumin

N‐Methacryloyl‐(L )‐histidine methyl ester (MAH) was synthesized from metharyloyl chloride and histidine. Spherical beads with an average size of 150–250 μm were obtained by the suspension polymerization of ethylene glycol dimethacrylate and MAH in an aqueous dispersion medium. Magnetic poly(ethylene glycol dimethacrylate‐co‐N‐Methacryloyl‐(L )‐histidine methyl ester) [m‐p(EGDMA‐co‐MAH)] microbeads were characterized with swelling tests, electron spin resonance, elemental analysis, and scanning electron microscopy. The specific surface area of the beads was 80.1 m²/g. m‐p(EGDMA‐co‐MAH) microbeads with a swelling ratio of 40.2% and 43.9 μmol of MAH/g were used for the adsorption of bovine serum albumin (BSA) in a batch system. The Cu(II) concentration was 4.1 μmol/g. The adsorption capacity of BSA on the Cu(II)‐incorporated beads was 19.2 mg of BSA/g. The BSA adsorption first increased with the BSA concentration and then reached a plateau, which was about 19.2 mg of BSA/g. The maximum adsorption was observed at pH 5.0, which was the isoelectric point of BSA. The BSA adsorption increased with decreasing temperature, and the maximum adsorption was achieved at 4°C. High desorption ratios (>90% of the adsorbed BSA) were achieved with 1.0M NaSCN (pH 8.0) in 30 min. The nonspecific adsorption of BSA onto the m‐p(EGDMA‐co‐MAH) beads was negligible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2669–2677, 2004     

溶胶-凝胶法制备PET/SiO2纳米复合材料及其TG、DSC分析

采用溶胶-凝胶（sol-gel）法，将正硅酸乙酯和水加入到制备聚对苯二甲酸乙二酯（PET）的中间产物对苯二甲酸双羟乙酯(BHET)中,在液态下均匀混合，高温下快速发生溶胶-凝胶反应，再按PET缩聚反应制得PET/SiO₂纳米复合材料。通过TEM、TG、DSC对材料进行了表征和研究。结果表明，SiO₂在PET中均匀分散，其尺寸在10～100 nm之间，PET/SiO₂纳米复合材料的热降解活化能较普通PET有明显提高，但初始降解温度和结晶性能均有所降低。     

Dual‐responsive semi‐interpenetrating network beads based on calcium alginate/poly(N‐isopropylacrylamide)/poly(sodium acrylate) for sustained drug release

To improve the mechanical strength of natural hydrogels and to obtain a sustained drug‐delivery device, temperature‐/pH‐sensitive hydrogel beads composed of calcium alginate (Ca‐alginate) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared in the presence of poly(sodium acrylate) (PAANa) with ultrahigh molecular weight (M_η ≥ 1.0 × 10⁷) as a strengthening agent. The influence of PAANa content on the properties, including the beads stability, swelling, and drug‐release behaviors, of the hydrogels was evaluated. Scanning electron microscopy and oscillation experiments were used to analyze the structure and mechanical stability of the hydrogel beads, respectively. The results show that stability of the obtained Ca‐alginate/PNIPAAm hydrogel beads strengthened by PAANa the alginate/poly(N‐isopropyl acrylamide) hydrogel bead (SANBs) was significantly improved compared to that of the beads without PAANa (NANBs) at pH 7.4. The swelling behavior and drug‐release capability of the SANBs were markedly dependent on the PAANa content and on the environmental temperature and pH. The bead sample with a higher percentage of PAANa exhibited a lower swelling rate and slower drug release. The drug release profiles from SANBs were further studied in simulated intestinal fluid, and the results demonstrated here suggest that SANBs could serve as a potential candidate for controlled drug delivery in vivo. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pretreatment of low-grade poly(ethylene terephthalate) waste for effective depolymerization to monomers

Pretreatment process of silica-coated PET fabrics, a major low-grade PET waste, was developed using the reaction with NaOH solution. By destroying the structure of silica coating layer, impurities such as silica and pigment dyes could be removed. The removal of impurity was confirmed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). The pretreated PET fabric samples were used for depolymerization into its monomer, bis(2-hydroxylethyl) terephthalate (BHET), by glycolysis with ethylene glycol (EG), and zinc acetate (ZnAc) catalyst. The quality of BHET was confirmed by DSC, TGA, HPLC and NMR analyses. The highest BHET yield of 89.23% was obtained from pretreated PET fabrics, while glycolysis with raw PET fabric yielded 85.43%. The BHET yield from untreated silica-coated PET fabrics was 60.39%. The pretreatment process enhances the monomer yield by the removal of impurity and also improves the quality of the monomer.     

Preparation and in vitro evaluation of new pH‐sensitive hydrogel beads for oral delivery of protein drugs

New biodegradable pH‐responsive hydrogel beads based on chemically modified chitosan and sodium alginate were prepared and characterized for the controlled release study of protein drugs in the small intestine. The ionotropic gelation reaction was carried out under mild aqueous conditions, which should be appropriate for the retention of the biological activity of an uploaded protein drug. The equilibrium swelling studies were carried out for the hydrogel beads at 37°C in simulated gastric (SGF) and simulated intestinal (SIF) fluids. Bovine serum albumin (BSA), a model for protein drugs was entrapped in the hydrogels and the in vitro drug release profiles were established at 37°C in SGF and SIF. The preliminary investigation of the hydrogel beads prepared in this study showed high entrapment efficiency (up to 97%) and promising release profiles of BSA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Glycolysis of postconsumer polyethylene terephthalate waste

Glycolytic depolymerization of polyethylene terephthalate (PET) bottle waste was attempted using ethylene glycol (EG) in the presence of chlorides of zinc, lithium, didymium, magnesium, and iron as catalysts. Virtual monomer bis (2‐hydroxyethyl terephthalate) (BHET) was obtained in all cases with nearly 74% yield, the highest yield being achieved with zinc chloride catalyst 0.5% w/w, PET : EG ratio 1 : 14 and 8 h under reflux conditions. The results were comparable to other catalysts like common alkalis, acids, and salts of some earth metals and zeolites used earlier although parameters of glycolysis were observed to vary depending on the catalyst. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyester polyols for polyurethanes from pet waste: Kinetics of polycondensation

The kinetics of polyesterification of the glycolyzed PET waste with adipic acid is reported. Glycolysis of PET waste was carried out with ethylene glycol at three different ratios of PET waste to glycol. The glycolyzed products could be readily polyesterified by reacting with adipic acid, to give polyester polyols with low acid number. Kinetics of polyesterification of the glycolyzed product made from 62.5% ethylene glycol (EG) and 37.5% waste were investigated further at different hydroxyl to carboxyl ratios. Reaction conditions were nonisothermal, comparable to the industrial process scheme consisting of two isothermal regions at 170° and 200°C. The kinetic results of the polyesterification of glycolyzed PET waste are compared to the polyesterification of pure diols, namely ethylene glycol and bis(hydroxyethyl) terephthalate (BHET) with adipic acid. The reactions follow second-order kinetics at 170°C and the rate of polyesterification of the mixed diol system from PET waste lies intermediate between those of the pure diols, namely, EG and BHET. Ethylene glycol exhibited the highest reactivity. At 200°C the kinetic plots of the mixed diols from PET waste were nonlinear, and thus the reaction may not follow second-order kinetics. The nonlinearity is explained in terms of the different reactivities of the different diol species in the reaction mixture. The polyester polyols, when cured with polymeric 4,4′ diphenyl methane diisocyanates, gave polyurethane rigid foams and elastomers.     

Enhanced dynamic mechanical and shape‐memory properties of a poly(ethylene terephthalate)–poly(ethylene glycol) copolymer crosslinked by maleic anhydride

Dimethyl terephthalate (DMT) and ethylene glycol (EG) were used for the preparation of poly(ethylene terephthalate) (PET), and poly(ethylene glycol) (PEG) was added as a soft segment to prepare a PET–PEG copolymer with a shape‐memory function. MWs of the PEG used were 200, 400, 600, and 1000 g/mol, and various molar ratios of EG and PEG were tried. Their tensile and shape‐memory properties were compared at various points. The glass‐transition and melting temperatures of PET–PEG copolymers decreased with increasing PEG molecular weight and content. A tensile test showed that the most ideal mechanical properties were obtained when the molar ratio of EG and PEG was set to 80:20 with 200 g/mol of PEG. The shape memory of the copolymer with maleic anhydride (MAH) as a crosslinking agent was also tested in terms of shape retention and shape recovery rate. The amount of MAH added was between 0.5 and 2.5 mol % with respect to DMT, and tensile properties and shape retention and recovery rate generally improved with increasing MAH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 27–37, 2002