Development of Thixotropic Coatings Using Dimerized Soybean Oil Fatty Acids: The Case of Polyamide of 1,2-Phenylene Diamine

Soybean oil (SBO) was dimerized and the crude dimer acid product reacted with 1,2-phenylene diamine at 210 ± 5 °C under inert atmosphere to obtain fatty polyamide (FPA). The FPA was used to modify a commercial alkyd resin by reacting a mixture of the alkyd resin with 5 wt% of FPA at 120 °C for 80 min under inert atmosphere. The FTIR spectrum of the FPA modified resin showed evidence of higher degree of H-bonding than was found for the unmodified alkyd. White gloss coatings of 15, 20, 25, and 30% solids were formulated from the modified and unmodified resins and examined for performance with respect to: leveling, sag resistance, drying time, pigment settling, skinning tendency and film hardness. Results showed that the unmodified alkyd coatings exhibited good leveling but poor sag resistance at all solid contents. In contrast, FPA modified alkyd coatings combined good leveling with high sag resistance indicating their thixotropic nature. A strong tendency to pigment settling was observed for unmodified alkyd coatings but was not observed in the FPA modified alkyd coatings. The modified alkyd coatings showed skinning while the unmodified alkyd coatings did not skin. A 30% solids coating formulation of the FPA modified resin showed shorter surface dry time but longer hard dry time than the unmodified alkyd resin coating.     

Oxygen and Water Barrier Properties of Coated Whey Protein and Chitosan Films

Films of whey protein and chitosan acetic acid salt have lower oxygen permeability than, for example, ethylene-co-vinylalcohol under dry conditions, but water and water vapor seriously impair the gas barrier properties. To reduce the oxygen permeability at 90% relative humidity and the water-vapor transmission rate at 100% relative humidity, the films were coated with an alkyd, a beeswax compound, or a nitrocellulose lacquer. Permeability and transmission rate measurements were performed in accordance with standard methods and showed that the beeswax compound and the nitrocellulose were appropriate as water-vapor barriers. Overall migration to water was measured after 10 days exposure time, with the coated surface exposed to the water, showing that the alkyd-coated and the nitrocellulose-coated films were both below the safety limit for food contact. Water absorbency tests, performed by the Cobb method, showed that the films coated with the beeswax compound or with nitrocellulose lacquer exhibit lower absorbency than the alkyd-coated films.     

Alkyd-amino resins based on waste PET for coating applications

Waste polyethylene terephthalate (PET) flakes were depolymerized by using propylene glycol (PG) in the presence of zinc acetate as catalyst. Glycolysis reaction products of waste PET obtained by using PET/glycol molar ratio 1/2. Two short oil alkyd resins of high acid values (30-40mgKOH/g) were prepared from phthalic anhydride (PA), glycerin (G), coconut oil fatty acids (COFA) and glycolyzed products of waste PET (PET-based alkyd resins) or glycols (PG) (reference alkyd resins). These alkyd resins were blended with 30%, 40%, and 50% of a commercial urea-formaldehyde, melamine-formaldehyde and urea-formaldehyde/melamine-formaldehyde mixture (1/1 weight ratio) and heated at 140 degrees C. The physical and chemical properties such as drying time, hardness, abrasion resistance, adhesion strength, water resistance, alkaline resistance, acid resistance, gelation time, and thermal oxidative degradation resistance (with thermogravimetric analysis, TGA) of these alkyd-amino resins were investigated. The properties of the waste PET-based resins were found to be compatible with the properties of the reference resins.     

Novel Biodegradable Cast Film from Carbon Dioxide Based Copolymer and Poly(Lactic Acid)

Poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) blends with different levels of chain extender were prepared and cast into films. The effect of chain extender on the mechanical, thermal and barrier properties of the films were investigated. With the inclusion of the chain extender, the compatibility and interfacial adhesion between the two polymer phases were significantly improved by a mean of forming a PLA–chain extender–PPC copolymer. Reactions between the chain extender, PLA and PPC were observed through FTIR study. SEM study also confirmed the improved compatibility and interfacial adhesion. The elongation at break of the compatibilized film with optimal amount of chain extender showed dramatic increase by up to 1940 %. DSC studies revealed that chain extender hindered the crystallization of the film which explained the decrease in both water and oxygen barrier when adding chain extender. PLA was found to be able to enhance both oxygen and water barrier of the blend as compared to neat PPC, while in the case of the blend with chain extender, oxygen and water barrier properties exhibited reduction at the beginning. However, when increasing chain extender concentration, these two barrier performance exhibited an upward trend. It was found that PLA/PPC blend showed much better oxygen barrier property than both parent polymers, which can be ascribed to the acceleration effect of PPC on the crystallization of PLA.     

Physical Characterization of Biodegradable Films Based on Chitosan,Polyvinyl Alcohol and <Emphasis Type="Italic">Opuntia</Emphasis> Mucilage

This study aimed to develop and characterize biodegradable films containing mucilage, chitosan and polyvinyl alcohol (PVA) in different concentrations. The films were prepared by casting on glass plates using glycerol as plasticizer. Mechanical properties, water vapor and oxygen barrier, as well as the interaction with water, were measured. The compatibility of the film-forming components and the uniformity of the films were determined by zeta potential and SEM, respectively. The glycerol and mucilage allowed obtaining more hydrophilic films. The barrier properties of the films made from 100 % chitosan were similar to composed films containing PVA up to 40 %. The results of this study suggest that the interaction between chitosan and mucilage could increase water vapor permeability. The films prepared from either 100 % chitosan or PVA showed a more hydrophobic behavior as compared to the composed films. The films were homogenous since no boundary or separation of components was observed, indicating a good compatibility of the components in the films.     

Investigation of Synthesis of Copolymers from the Waste Products of Industrial Oil Refinement having Adhesion Properties and Strength to the Thermal Destruction

In this study, the waste products of industrial vegetable oil refinement were transformed into the glycidyl ester for preventing the effects of them to the environment, the ways for evaluating them in polymer chemistry were investigated, copolymers having high adhesion property and strength to the thermal destruction were synthesized and the area of their usage was determined. For this reason, the waste product of sunflower oil refination as a vegetable oil in the industry; soap stock (SS) was converted to the unsaturated glycidyl esters by the interaction with epichlorohidrine in the alkaline medium. After that the copolymerization of synthesized unsaturated glycidyl esters and the other waste product of oil refinement fatty acid (FA) with styrene in the radicalic initiator medium were investigated and copolymers that have high strength to the thermal destruction and adhesion property were synthesized. From the results of TGA and DTA analysis, it was determined that synthesized copolymers have low loss of weight at high temperature. The structures of copolymers were fixed by spectral and chemical analysis methods.     

Analysis of the Structure-Properties Relationships of Different Multiphase Systems Based on Plasticized Poly(Lactic Acid)

Poly(lactic acid) is one of the most promising biobased and biodegradable polymers for food packaging, an application which requires good mechanical and barrier properties. In order to improve the mechanical properties, in particular the flexibility, PLA plasticization is required. However, plasticization induces generally a decrease in the barrier properties. Acetyl tributyl citrate (ATBC) and poly(ethylene glycol) 300 (PEG), highly recommended as plasticizers for PLA, were added up to 17 wt% in P(D,L)LA. In the case of PEG, a phase separation was observed for plasticizer contents higher than 5 wt%. Contrary to PEG, the T_g decrease due to ATBC addition, modelled with Fox’s law, and the absence of phase separation, up to 17 wt% of plasticizer, confirm the miscibility of PLA and ATBC. Contents equal or higher than 13 wt% of ATBC yielded a substantial improvement of the elongation at break, becoming higher than 300%. The effect of PLA plasticization on the barrier properties was assessed by different molecules, with increasing interaction with the formulated material, such as helium, an inert gas, and oxygen and water vapour. In comparison to the neat sample, barrier properties against helium were maintained when PLA was plasticized with up to 17 wt% of ATBC. The oxygen permeability coefficient and the water vapour transmission rate doubled for mixtures with 17 wt% ATBC in PLA, but increased five-fold in the PEG plasticized samples. This result is most likely caused by increased solubility of oxygen and water in the PEG phase due to their mutual miscibility. To conclude, ATBC increases efficiently the elongation at break of PLA while maintaining the permeability coefficient of helium and keeping the barrier properties against oxygen and water vapour in the same order of magnitude.     

Synthesis of Alkyd Resin from Non-Edible Jatropha Seed Oil

The kinetics of polyesterification of glycerol, phthalic anhydride and jatropha oil leading to the formation of alkyd resins were studied. A series of alkyd resins having different amount of jatropha oil viz., 40–80% have been prepared by employing two stage alcoholysis-polyesterification process. The extent of reaction and average degree of polymerisation were calculated from the end group analysis of the reaction mixture withdrawn at regular intervals of time. The initial reaction rates followed the second order kinetics and thereafter deviations were observed. An appreciable degree of conversion was noticed from the extent of the reaction which lies in the range of 49.5–62.5%. The average degree of polymerisation calculated in the region of deviation from second order suggested the occurrence of chain branching at relatively shorter intervals along the polymer chain. The second order rate constants were found to be of the order of 10⁻⁵ g (mg KOH)⁻¹ min⁻¹.     

用废旧电路板热解油制备酚醛树脂

在碳酸钙存在下，采用热解技术将废旧电路板中的树脂转化为富含酚的热解油，然后直接加入甲醛溶液反应制备热解油型酚醛树脂，实现了废旧电路板中树脂的再生，酚醛树脂的性能结构类似于氨催化的酚醛树脂。实验结果表明：在n（甲醛）：n（热解油）为1．8～2．1的条件下，无需外加催化剂，在60，80，90℃下分别反应30min制备的热解油型酚醛树脂的性能最佳，且可满足GB／T14732—93《木材工业胶黏剂用脲醛、酚醛、三氧氰胺甲醛树脂》中层压材料用酚醛树脂产品的相关标准。     

Organic–Inorganic Hybrid Coatings for the Modification of Barrier Properties of Poly(lactic acid) Films for Food Packaging Applications

Organic–inorganic hybrid coatings based on poly(ε-caprolactone), poly(ethylene oxide) or poly(lactic acid) as organic phase and silica from tetraethoxysilane as inorganic phase were prepared by the sol–gel approach. Coatings were applied onto poly(lactic acid) films for food packaging in order to improve its barrier properties towards oxygen and water vapour. All the prepared coatings were dense, homogeneous layers characterized by a good adhesion to the substrate. The permeance of the coating layers resulted one order of magnitude lower than that of the uncoated poly(lactic acid) (PLA) film. The hydrophilic character of the coating did not permit to gain a significant decrease in the water vapour permeance. The perfect visual transparency of the coatings allows their application without worsening of the esthetical properties of the substrate PLA film.     

Effect of Manufacturing Process and Xanthan Gum Addition on the Properties of Cassava Starch Films

The objective of this work was to manufacture biodegradable films by two different processes (casting and extrusion), from different combinations of cassava starch and xanthan gum. These films were produced by casting and by extrusion from six different starch-xanthan gum combinations (0, 2, 4, 6, 8 and 10% w/w), containing glycerol as plasticizer (20% w/w) and were also characterized according to their microstructure, optical, mechanical, and barrier properties. Scanning electron microscopy of the starch-xanthan gum extruded films showed reticulated surface and smooth interior, suggesting that xanthan was driven to the surface and gelatinized starch to the interior of the films during extrusion. Films manufactured by casting were entirely homogeneous. In general, casted films presented lower opacity and water vapor permeability and higher stress at break than films manufactured by extrusion. Xanthan gum addition affected mechanical properties of starch films, improving their stress and strain at break, especially for extruded samples, but these properties did not show stability at different RH conditions.     

Influence of Glutaraldehyde Crosslinking and Alkaline Post-treatment on the Properties of Chitosan-Based Films

Depending on the modifications proposed, chitosan films present different characteristics, for instance correlated to hydrophilicity, chemical and mechanical properties. The aim of this study was to evaluate the influence of glutaraldehyde crosslinking and an alkaline post-treatment with NaOH on the characteristics of chitosan based films. Films were obtained by casting and characterized by thickness, swelling degree, mechanical and thermal properties and chemical structure. The water vapor permeability (WVP) was also evaluated for food packaging application. It was observed that crosslinking and NaOH post-treatment have great influence on the chitosan films characteristics. Crosslinking reduced the swelling degree of films and increased its fragility, whereas NaOH treatment also reduces the swelling degree and changes mechanical properties, acting in the same way as a crosslinker. The WVP analyses showed that the basic treatment could substitute the glutaraldehyde crosslinking for film water stability, without greatly compromising the barrier properties of chitosan based films.     

Properties and biodegradability of chain-extended copoly(succinic anhydride/ethylene oxide)

Chain-extension reactions were carried out using titanium-iso-propoxide (TIP) as a catalyst for a series of polyesters or copolyesterethers with low molecular weights (M _n =1500–10,000) synthesized by the ring-opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO). The copolymers having aM _n from 25,000 to 50,000 of different properties were obtained. Both the melting point (T _m ) and the fusion heat (H), which indicate the crystallinity of the copolymers, rose with an increase in SA content in the copolymers. Semitransparent films were prepared by compression molding of the copolymers. The biodegradation of the copolymer films was evaluated by enzymatic hydrolysis by lipases and by an aerobic gas evolution test in standard activated sludge. The hydrolyzability of these copolymers by three kinds of lipases was affected by their copolymer composition SA/EO, form, andM _n . The copolyesterether (SA/EO=43/57,M _n =48,900) was more easily biodegraded by standard activated sludge compared to the polyester (SA/EO=47/53,M _n =36,300).Presented at the Pacifichem-95, December 17–22, 1995, Honolulu, Hawaii.     

Palm Oleic Acid Based Alkyds: Effect of the Fatty Acid Content on the Polyesterification Kinetics

The kinetic behavior of polyesterification of the alkyd resins synthesized using glycerol and phthalic anhydride modified with oleic acid from the palm oil at temperatures between 120 and 240 °C was studied. Three alkyds having oleic acid contents of 28, 40, and 65% were prepared by employing fatty acid method. The extent of the polyesterification reaction and average degree of polymerization were monitored by determining the acid number of the aliquot of the reaction mixture at various intervals of time and by measuring the volume of water evolved. Kinetic studies revealed that initial reaction rates followed a second-order kinetics up to certain limit and thereafter deviations were observed. The extent of reaction varied from 77.4 to 86.3% before deviation for all the three samples and exhibited a considerable degree of conversion. The second-order rate constants calculated from the linear part were found to be of the order of 10⁻⁵ g (mg KOH)⁻¹ min⁻¹. Molecular weight of the alkyd samples was determined by GPC; number average molecular weight of the alkyds ranged from 980 to 2,070.     

Production of carbon-based precursor from non-recyclable waste poly(ethylene) terephthalate: effect of multilayer structure on carbonized product

Journal of Material Cycles and Waste Management - In this paper, the carbonization of multilayer PET containing an oxygen barrier layer was investigated. The oxygen barrier layer was identified as...     

Development of Ambient Cured Polyesteramide Coatings from Linseed Oil: a Sustainable Resource

The resourceful employment of vegetable oil based polymers in coating applications that yield novel properties, faces challenges usually in their processing. We have developed polyesteramide coatings from linseed (Linnum ussitatissium seeds) oil with improved coating properties. Linseed oil was first converted into N, N-bis 2-hydroxy ethyl linseed oil fatty amide diol (HELA). The resin was synthesized by the reaction of HELA with ethylenediaminetetraacetic acid (EDTA) to develop ethylenediamine polyesteramide (Ed-PEA). The latter was further treated with poly (styrene co-maleic anhydride) (SMA) in different (35–50) phr (part per hundred part of resin) to obtain ambient cured polyesteramide (AC-PEA). The structural elucidation of polymeric resin (AC-PEA) was carried out by FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopic techniques. Thermal behavior of AC-PEA was studied by thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC). The coatings of AC-PEA were prepared on mild steel strips to investigate their physico-mechanical and anticorrosive behavior (in acid, alkali, water and xylene). It was found that among all the samples, the one having 45 phr of SMA showed the best physico-mechanical and corrosion resistance performance. The thermal stability performance suggests that AC-PEA45 system could be safely used up to 150 °C.     

Properties of Wheat-Gluten/Montmorillonite Nanocomposite Films Obtained by a Solvent-Free Extrusion Process

This is, to our knowledge, the first study of wheat-gluten-based nanocomposite films prepared by a solvent-free extrusion process. Wheat gluten/montmorillonite nanocomposite films were obtained in a single screw-extruder using urea as a combined denaturant and plasticizer. The oxygen permeability and water vapor transmission rate of the films decreased by respectively factors of 1.9 and 1.3 when 5 wt.% clay was added. At the same time, the stiffness increased by a factor of 1.5, without any critical loss of extensibility. Field emission scanning electron microscopy (FE-SEM) and Energy-dispersive X-ray analysis indicated that the clay particles were layered mainly in the plane of the extruded film. It was possible to identify individual platelets/tactoids with FE-SEM and, together with findings from transmission electron microscopy, atomic force microscopy and X-ray diffraction, it was concluded that the clay existed as individual clay platelets, intercalated tactoids and agglomerates. Thermogravimetric analysis showed that the thermal stability of the extrudates was improved by the addition of clay.     

Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

Nanocomposite Film Based on Gluten Modified with Heracleum persicum Essence/MgO/Polypyrrole: Investigation of Physicochemical and Electrical Properties

In this study, the wheat gluten film was prepared. Heracleum persicum essence, magnesium oxide nanoparticles and polypyrrole were used to modify the structure of the wheat gluten film. Physicochemical properties of the prepared films such as thickness, solubility, moisture absorption ability, antioxidant properties, and electrical conductivity of the films were investigated. Also, the mechanical, structural and thermal properties of the films were investigated by techniques such as SEM, FTIR, XRD, TGA, DTA and tissue analysis. SEM images showed that the essence and polypyrrole strengthened the gluten film structure and made it more resistant to the passage of gases. FTIR spectra confirmed the electrostatic interactions between gluten and essence and polypyrrole. XRD spectra showed the amorphous structure of gluten film and its composites. The results of thermal analysis showed that polypyrrole greatly increased the thermal resistance of the film and the nanoparticles had little effect on the thermal resistance. Thickness, solubility, moisture content and ability to absorb moisture were further affected by the essential oil. The antioxidant and electrical conductivity of the film was greatly increased in the presence of all three additives of essence, magnesium oxide nanoparticles and polypyrrole. The gluten–essence–MgO–PPy (Glu–E–MgO–PPy) composite film had the most antioxidant properties. Glu–E–MgO–PPy film with important electrical conductivity and antioxidant properties has the potential to be used as an active and intelligent film in the packaging of perishable food products.