Influence of poly(bisphenol A carbonate) and poly(ethylene terephthalate) on poly(vinyl chloride) dehydrochlorination

Recycling of poly(vinyl chloride) (PVC) waste is a serious problem because of its high chlorine content. Dehydrochlorination of PVC-containing polymer waste produces solid residue char, for which conversion to pyrolysis oil in a petrochemical plant seems to be an attractive way of recycling PVC waste. Unfortunately, some polymer admixtures react with HCl and cause formation of chloroorganic compounds in a char. This article describes the influence of polycarbonates and poly(ethylene terephthalate) on thermal feedstock recycling of PVC wastes using a two-stage method. It was found that the presence of polycarbonate causes the formation of small amounts of benzyl chloride and other chloroaryl or chloroalkylaryl compounds. Poly(ethylene terephthalate) interacts with HCl forming significant amounts of various chlorocompounds – mainly chloroethyl esters of terephthalic and benzoic acids, but derivatives possessing chlorine directly connected to the aromatic ring are also formed.     

Depolymerization of Waste PET with Phosphoric Acid–Modified Silica Gel Under Microwave Irradiation

Chemical recycling of waste poly(ethylene terephthalate) (PET) using phosphoric acid–modified silica gel as a solid catalyst is reported. Advantageously, microwave irradiation was used to progress the depolymerization of PET. In this study, depolymerization of PET with a small amount of water is suggested as a suitable method. The depolymerized product, terephthalic acid was obtained and assigned by ¹H NMR and FT-IR spectroscopy. Finally, over 90 % conversion to terephthalic acid was achieved when waste plastic bottles were treated with the method. This results confirm the importance of the microwave power technique as a promising recycling method for plastic bottles made from PET, resulting in monomer recovery in addition to substantial energy saving.     

PET from Used Beverage Bottles: A Material for Preparation of Biologically Degradable Copolyesters

Poly(ethylene terephthalate) from used colorless beverage bottles was solvolyzed by ethane-1,2-diol. Hydroxyl end-groups present in the mixture of polyols formed were used to initiate the polymerization of ??-caprolactone (CLO) at 190?°C. Polycondensation (190?°C) of the reaction mixture containing an equilibrium amount of lactone corresponding to the reaction temperature yield an aliphatic?Caromatic copolyester. A variety of copolyesters containing 20?C60?mol. % CLO structural units was prepared. The microstructure of their macromolecules was analyzed using ¹H?NMR spectroscopy. Copolyesters were characterized by thermal analysis and tensile tests and their biodegradation potential was checked by the composting test.     

Crosslinking of Polyvinyl Alcohol (PVA) and Effect of Crosslinker Shape (Aliphatic and Aromatic) Thereof

In the presented work, the effect of crosslinker geometry on the properties of PVA is reported. The aliphatic (suberic) and aromatic (terephthalic) dicarboxylic acids are used as crosslinker molecules. On the basis of tensile test and thermal properties, it is observed that crosslinking of PVA by suberic acid is more effective than terephthalic acid. The maximum strength measured in crosslinked samples is 32.5 MPa for suberic acid crosslinked PVA which is higher than that of neat PVA (22.6 MPa). Swelling study shows that 8 h crosslinked terephthalic acid (35% w/w) samples have a minimum of 5.4% of water uptake compared to neat PVA, which dissolves readily in water. DTGA shows that the decomposition temperature of crosslinked PVA is 345?°C while neat PVA has a decomposition temperature of 315?°C. FTIR spectroscopy confirms the formation of crosslink ester bond in crosslinked PVA. The crosslinked samples kept for bio-degradation show maximum degradation in terephthalic acid (15% w/w) crosslinked PVA.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

Synthesis and Characterization of Chitosan-Grafted-Poly(2-Hydroxyaniline) Microstructures for Water Decontamination

Chitosan as a biopolymer, biodegradable, safe, non-toxic and widely abundant in nature was grafted with poly(2-hydroxyaniline) (P2-HA) through aqueous chemical oxidative copolymerization using ammonium persulphate in acetic acid medium. The grafting conditions were studied by varying grafting parameters. The effect of oxidant, 2-hydroxyaniline (2-HA) and acetic acid concentrations on the rate of copolymerization was studied. The synthesized graft characterized using UV–Vis, FTIR, TGA, XRD, and scanning electron microscope and compared with chitosan and P2-HA. The grafting enhances the thermal properties of chitosan. The effect of temperature on the rate of grafting copolymerization reaction was studied. The apparent activation energy (Ea) of the copolymerization reaction found to be 21.1116 kJ/mol. Also, ΔH^* and ΔS^*, were calculated and found to 22.8630 kJ/mol and ?109.4290 J/mol K respectively. The mechanism of the grafting copolymerization reaction discussed. Chitosan, P2-HA and chitosan-graft-P2-HA used for the removal of Cr, Fe, Mn, Cu and Zn divalent ions from a contaminated water samples. The adsorption isotherm parameters are given.     

Synthesis and Characterisation of Polyester Based on Isosorbide and Butanedioic Acid

Copolyesters based on isosorbide and butanedioic acid in combination with monomers such as adipic acid and dimethyl terephthalate, poly(isosorbide-co-butanedioic acid) (and -co-adipic acid) and poly(isosorbide-co-butanedioic acid-co-dimethyl terephthalate), were synthesized and characterized. Linear OH-functionalized polyesters were obtained via melt polyesterification of dicarboxylic acids with OH-functional monomers. The type of end-group was controlled by the monomer stoichiometry and hydroxyl functional group is formed in time. Average molecular masses of synthesised polyesters were measured by gel permeation chromatography. The glass transition temperatures and thermal stability of the obtained polyesters were effectively adjusted by varying polymer composition and molar mass. Addition of adipic acid or dimethyl terephthalate increased glass transition temperatures of obtained polyesters. Thermal stability of obtained polyester slightly increases by the increasing of dimethyl terephthalate content. Molecular structures of obtained polyester were assessed by Fourier transform infrared spectra and ¹H NMR spectroscopy.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.     

Recovery of benzene-rich oil from the degradation of metal- and metal oxide-containing poly(ethylene terephthalate) composites

Pure poly(ethylene terephthalate) (PET) resin and metal-/metal oxide-containing PET composites were thermally decomposed in the presence of Ca(OH)₂ using a tube reactor. The effects of batch and continuous processing, the presence of Ca(OH)₂, and PET size on benzene production were investigated. A maximum benzene yield and purity of 82.9 % and 78.8 wt%, respectively, were obtained at 700 °C in the presence of Ca(OH)₂ when using small PET particles; further, a continuous feed reactor was favored over a batch reactor. Effective contact between PET and Ca(OH)₂ was important in the PET degradation, which promoted hydrolysis of PET and decarboxylation of terephthalic acid, whereas pyrolysis was suppressed. Furthermore, the results of thermal decomposition of PET-based waste—PET-based X-ray films, magnetic tape, and prepaid cards—indicated that the metal and metal oxides contained in the waste had no significant catalytic effect on PET degradation or on the recovery of benzene-rich oil in the presence of Ca(OH)₂.     

New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.     

Hydrolyzable poly(ethylene terephthalate)

Due to the enormous annual increase in the volume of municipal solid waste, society's attention is focused on how to manage the solid waste problem. Plastic materials not only contribute a great deal to the litter problem but also create serious danger to the ecology. Every year, countless birds, sea turtles, and other marine mammals die from eating or getting entangled in plastic litter. Synthesizing degradable polymers can have a great impact on solving the problem of plastic litter. We have modified the structure of poly(ethylene terephthalate) to make it degradable in typical environmental conditions in presence of water. The change of physical properties of modified poly(ethylene terephthalate), resulting from hydrolysis, has been monitored and compared with those of pure poly(ethylene terephthalate).     

Dielectric and Material Properties of Poly (Vinyl Alcohol): Based Modified Red Mud Polymer Nanocomposites

Red mud emerges as the major waste material during production of alumina from bauxite by the Bayer??s process. Based on economics as well as environmental related issues, enormous efforts have been directed worldwide towards red mud management issues i.e. of utilization, storage and disposal. The present research work has been undertaken with an objective to explore the use of red mud as a reinforcing material in the polymer matrix as a low cost option. The silicate layered red mud was organophilized by aniline formaldehyde and to know the effect of various filler loading on the material properties of PVA-organophilized red mud composites, prepared by a conventional solvent casting technique and comparison of the same with that of the virgin poly (vinyl alcohol) (PVA), various characterizations was done. The modified red mud was typically characterized by X-ray diffraction. The X-ray diffraction pattern of the composite materials was also studied. The morphological image of the composite materials was studied by scanning electron microscopy (SEM). Transmission electron microscopy (TEM) was used to characterize the dispersion of the red mud within the composite materials. The surface topography of the composite materials was studied by Atomic Force Microscopy (AFM). The dielectric properties of composite materials were investigated in wide frequency ranges from 1?MHz to 1?GHz.     

Poly(hydroxyalkanoate) Biosynthesis from Crude Alaskan Pollock (Theragra chalcogramma) Oil

Six strains of Pseudomonas were tested for their abilities to synthesize poly(hydroxyalkanoate) (PHA) polymers from crude Pollock oil, a large volume byproduct of the Alaskan fishing industry. All six strains were found to produce PHA polymers from hydrolyzed Pollock oil with productivities (P; the percent of the cell mass that is polymer) ranging from 6 to 53% of the cell dry weight (CDW). Two strains, P. oleovorans NRRL B-778 (P = 27%) and P. oleovorans NRRL B-14682 (P = 6%), synthesized poly(3-hydroxybutyrate) (PHB) with number average molecular weights (M_n) of 206,000 g/mol and 195,000 g/mol, respectively. Four strains, P. oleovorans NRRL B-14683 (P = 52%), P. resinovorans NRRL B-2649 (P = 53%), P. corrugata 388 (P = 43%), and P. putida KT2442 (P = 39%), synthesized medium-chain-length PHA (mcl-PHA) polymers with M_n values ranging from 84,000 g/mol to 153,000 g/mol. All mcl-PHA polymers were primarily composed of 3-hydroxyoctanoic acid (C_8:0) and 3-hydroxydecanoic acid (C_10:0) amounting to at least 75% of the total monomers present. Unsaturated monomers were also present in the mcl-PHA polymers at concentrations between 13% and 16%, providing loci for polymer derivatization and/or crosslinking. Mention of trade names or commercial products in this article is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

Interfaces in Cross-Linked and Grafted Bacterial Cellulose/Poly(Lactic Acid) Resin Composites

This article presents approaches to maximize the mechanical performance of bacterial cellulose/poly(lactic acid) composites through chemical modification of the interface. This is achieved by both cross-linking the layered bacterial cellulose structure and by grafting maleic anhydride to the matrix material. Unmodified and glyoxalized bacterial cellulose (BC) networks have been embedded in poly(lactic acid) (PLA) resin and then in maleated resin using a compression molding method. The effect of these chemical modifications on the physical properties of these composites is reported. The tensile properties of the composites showed that Young??s moduli can be increased significantly when both BC networks and PLA were chemically modified. Interface consolidation between layers in BC networks has been achieved by glyoxalization. The effect of these modifications on both stress-transfer between the fibers and between the matrix and the fibers was quantified using Raman spectroscopy. Two competitive deformation mechanisms are identified; namely the mobility between BC layers, and between BC and PLA. The coupling strength of these interfaces could play a key role for optimization of these composites?? mechanical properties.     

Study on Properties of Poly(urethane-ester) Synthesized from Prepolymers of ε-Caprolactone and 2,2-Dimethyl-1,3-Propanediol Monomers and Their Biodegradability

Poly(urethane-ester) was prepared by polymerization of 4,4′-methylenebis(phenyl isocyanate) (MDI) and prepolymers of ε-caprolactone and 2,2-dimethyl-1,3-propanediol monomers P(CL-DP) with various chain lengths as polyol sources. Characterizations of poly(urethane-ester) were carried out by analysis of functional groups (FTIR), thermal properties (DTA/TGA), mechanical properties (Tensile tester), crystallinity (XRD), and biodegradability. The chain length of prepolymers used in polymerization has a significant effect in properties of poly(urethane-ester) as well as their biodegradability. The formation of poly(urethane-ester) was indicated by the presence of new absorption peaks at wave number of 3,348.2 and 1,596.9 cm^?1 for urethane (–NH–) and aromatic groups in chain of polymers, respectively. The increase chain length of prepolymer used in polymerization with 4,4′-methylenebis(phenyl isocyanate) was observed the increase thermal property and crystallinity of poly(urethane-ester). However, the maximum mechanical property and also biodegradability in activated sludge were observed in poly(urethane-ester) prepared by polymerization of 4,4′-methylenebis(phenyl isocyanate) (MDI) and P(CL-DP) prepolymers with DP/CL ratio of 1/20. Apparently, the amorphous parts of polymers are rapidly decomposed by enzymes of microorganisms, so the crystallinity on the whole of poly(urethane-ester) increases after incubation time of 30 days.     

Aminolysis and aminoglycolysis of waste poly(ethylene terephthalate)

This paper describes the chemical degradation of waste poly(ethylene terephthalate) (PET) with polyamines or triethanolamine, the characteristics of the products, and a search for ways to use these products. Solvolysis of the polymer ester bonds was caused by diethylenetriamine, triethylenetetramine, and their mixtures, as well as mixtures of triethylenetetramine and p-phenylenediamine or triethanolamine. Products of aminolysis or aminoglycolysis of PET obtained in reactions performed at 200–210°C (with a molar ratio of the recurrent polymer unit to amine of 1 : 2) have been characterized using nuclear magnetic resonance (NMR). Viscosity and hydroxyl number measurements have been done for PET/triethanolamine products. Substances from aminolytical reactions with polyamines were tested as hardeners for liquid epoxy resins, and the product of polymer aminoglycolysis with triethanolamine was tested as an epoxy resin hardener, e.g., for water-borne paints, and a polyol component for rigid polyurethane foams. The compositions of epoxy resin hardeners have been characterized using DSC and rheometry. Comparative analyses of the hardened epoxy materials have been done on the basis of glass temperature and mechanical properties data, as well as some specific properties of the coating materials and rigid polyurethane foams. Received: September 15, 2000 / Accepted: September 21, 2000     

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Application of recombinant gene technology for production of polyhydroxyalkanoic acids: Biosynthesis of poly(4-hydroxybutyric acid) homopolyester

Screening of a large number of bacteria revealed several strains, which utilize 1,4-butanediol and/or 4-hydroxybutyric acid (4HB) as a carbon source for growth and for synthesis of polyhydroxyalkanoic acids (PHA) containing 4HB as one constituent among others (mostly 3-hydroxybutyric acid). However, none of the wild-type strains investigated in this study was able to produce a homopolyester consisting solely of 4HB. Only several poly(3-hydroxybutyric acid)-leaky mutants ofAlcaligenes eutrophus strain JMP222 synthesized poly(4HB) homopolyester, which amounted to approximately 10% (w/w) of the cellular dry matter. If the PHA synthase structural gene ofA. eutrophus strain H16 was expressed in these mutants, the amount of poly(4HB) was increased to approximately 30% (w/w). The occurrence of poly(4HB) was demonstrated by gas chromatographic as well as¹H and¹³C nuclear magnetic resonance spectroscopic analysis.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Modification of Thermo-Mechanical Properties of Recycled PET by Vinyl Acetate (VAc) Monomer Grafting Using Gamma Irradiation

Vinyl acetate (VAc) monomer of different percentage was grafted onto the recycled polyethylene terephthalate (r-PET) films using gamma irradiation. The properties of these modified films were characterized by Fourier transform infrared spectroscopy (FTIR), mechanical properties testing (Tensile strength, Elongation at break), dynamic mechanical analysis (DMA) and thermo-gravimetric analysis (TGA). The Tensile Strength (TS) of the modified PET film increased by 132.25?% to the highest value of 50.12 MPa at 15% VAc monomer concentration at 3 kGy gamma dose, while the elongation at break (EB) decreased by 31.83?%. FTIR was used to investigate the molecular interaction of the modified films. TGA revealed that curve of the modified PET film shifted toward higher temperature region by 95?°C, which is very close to that of PET film made from virgin flakes. The results indicate that modified PET films of better mechanical and thermal properties were successfully prepared using VAc monomer grafting by gamma irradiation technique.     

Synthesis of copolyesters containing poly(ethylene terephthalate) and poly(ε-caprolactone) units and their susceptibility toPseudomonas sp. lipase

Copolyesters containing poly(ethylene terephthalate) (PET) and poly(-caprolactone) (PCL) were synthesized from PET and PCL homopolymers by transesterification reaction at 270°C in the presence of catalyst. The copolyesters were characterized by¹³C-NMR and differential scanning calorimetry (DSC). The degradation behavior of PCL byPseudomonas sp. lipase in buffer solution (pH 7) and tetrahydrofuran (THF) was investigated by gel permeation chromatography (GPC) and¹H-NMR. From these experiments, it was found thatPseudomonas sp. lipase acted endoenzymatically on PCL. Using this lipase, degradation tests for PET/PCL copolyesters whose PCL content was below 50% by weight were also performed in buffer solution (pH 7). However, evenPseudomonas sp. lipase with high degradation activity on PCL did not easily degrade the PCL unit in PET/PCL copolyesters.