The use of aminolysis,aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder

This work is concerned with the use of aminolysis, aminoglycolysis, and simultaneous aminolysis–hydrolysis products of waste PET for production of paint binder based on alkyd resin. For this purpose, first, aminolysis, aminoglycolysis, and simultaneous hydrolysis–aminolysis reactions of waste PET were carried out in the presence of different chemical agents in xylene medium at high pressures. Reactions of waste PET flakes obtained from grinding postconsumer water bottles were carried out in an autoclave at higher temperatures. Then, four alkyd resins, formulated to have oil content 40–50%, were prepared using these depolymerization products. One of resins is “reference alkyd resin” which was prepared by using soybean oil fatty acid, phthalic anhydride, glycerine, and ethylene glycol for comparison. Other three alkyds are “depolymerization product‐based alkyd resins” in which depolymerization products is used instead of ethylene glycol. Then, the physical and chemical surface coating properties and thermal behaviors of alkyd resins films were investigated comparatively. As a result, we concluded that aminolysis, aminoglycolysis, and simultaneous aminolysis‐hydrolysis products of waste PET are suitable for manufacturing both air drying and oven curing paint binder based on alkyd resins. The film prepared from alkyd resin based on simultaneous aminolysis‐hydrolysis product showed extremely good surface coating properties and thermal stability. POLYM. ENG. SCI., 54:2272–2281, 2014. © 2013 Society of Plastics Engineers     

An investigation on synthesis of alkyd resin with sorbitol

Sorbitol, as an abundant, cheap and renewable resource, is considered as a potential raw material for the manufacture of alkyd resin. In this study, the kinetics on preparation of alkyd resin using phthalic anhydride, sorbitol and soya bean fatty acid as raw materials is investigated. Three kinds of sorbitol based alkyd resins (SAR) samples having fatty acid content (OL_f) of 42% (SAR1), 52% (SAR2) and 62% (SAR3) were prepared with phthalic anhydride, sorbitol aqueous solution and soya bean fatty acid using fatty acid method. Kinetic studies showed that the initial and latter stages of the reaction follow a second-order rate law. The second-order rate constants were found to be of the order of 10⁻⁵ g/mg KOH/min. Molecular weight and polydispersity index were determined by GPC and end-group analysis. The number average molecular weight of the alkyd resins ranged from 1435 to 1626 and the weight average molecular weight ranged from 3041 to 3648. A large polydispersity index was found in a range from 2.12 to 2.24. The varnish of alkyd resin SAR1 containing 50% 200# solvent gasoline and 1.25% cobalt naphthenate (drying agent) by weight dried faster than the others. The physical and chemical film properties of the sorbitol based alkyd resins were determined and compared with standard alkyd resins. The results showed that the performance of alkyd resin having fatty acid contents (OL_f) of 42% (SAR1) was almost the same as the standard alkyd resins. It could be a choice binder for alkyd resin paint and helpful to reduce production cost.     

Characterization of unsaturated polyester and alkyd resins using one‐ and two‐dimensional NMR spectroscopy

One‐ (1D) and two‐dimensional (2D) ¹H‐ and ¹³C‐NMR spectroscopy was used to characterize polyester and alkyd resins used in the coatings industry. The wealth of chemical composition information of the ¹H‐ and ¹³C‐NMR 1D spectra of the resins is revealed through 2D NMR experiments that spread chemical shifts in two dimensions, thus facilitating the peak assignment of the various components of the resins. It is shown that the types of polyols, acids, and vegetable oils used to modify the resins can be efficiently traced by NMR spectroscopic techniques. Information on the quantitative composition of the resins and especially the abundance of unsaturated fatty acid double bonds, which influences resin dryability and hardness, can be easily extracted from the ¹H‐NMR spectra upon successful assignment. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1881–1888, 2003     

Styrene–hydroxyethyl acrylate copolymer based alkyd resins with a comb‐type structural morphology obtained with a high solid content

Nowadays, so many studies are being carried out with the goal of obtaining environmentally friendly materials. In this study, styrene–hydroxyethyl acrylate copolymer (St‐co‐HEA) based alkyd resins with high solid contents and comb‐type structural morphologies were synthesized from St‐co‐HEA and macromonomers [MMs; dimethylol propionic acid modified with different proportions of tall oil fatty acids (TOFAs)]. The molar mass and gloss values of St‐co‐HEA were lower than those of the alkyd resins, but the thermal stability, viscosity, and glass‐transition temperature exhibited the opposite behavior. In all cases, the conversion percentage was higher than 80 %. The hydroxyl value and viscosity of the alkyd resins decreased with the TOFA content present in the MMrs, but the molar mass and the thermal stability increased. The rheological behavior of these resins was mainly pseudoplastic. Furthermore, the viscosity values were lower than 10 Pa s. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43996.     

Performance of expanded graphite and expanded milled‐graphite fillers in thermosetting resins

Epoxy/expanded graphite (EG) and polyester/EG composites were prepared with the aid of sonication, while epoxy/expanded‐milled graphite (epoxy/milled‐EG) and polyester/expanded‐milled graphite (polyester/milled‐EG) composites were prepared on a three‐roll paint mill. The epoxy/EG and polyester/EG composites exhibit a sharp insulator/semiconductor transition at markedly low percolation thresholds, due to the vermicular shape of EG having high aspect ratio and surface area. The morphologies of epoxy and polyester resins incorporated with EG and milled‐EG fillers were observed by scanning electron microscopy (SEM). The results of dynamic mechanical analysis of the composites reveal that both EG and milled‐EG fillers increase the T_g of the epoxy matrix. Milled‐EG increases the G′ of the epoxy matrix, while EG decreases the G′ of the epoxy matrix, due to the existence of abundant pores in EG. The milled‐EG filler has the same effect on the polyester matrix as on the epoxy matrix, but the EG filler has no significant effect on the mechanical properties of polyester matrix. POLYM. COMPOS., 26:526–533, 2005. © 2005 Society of Plastics Engineers     

Interaction between wood and polyurethane‐alkyd lacquer resulting in a decrease in the glass transition temperature

The long‐term properties of paint and glue are of great interest to both manufacturers and users of these materials. If a good bond is achieved, the surface between the wood and the paint or glue will be less susceptible to degradation. Thus, the wood and polymer must be compatible and develop some kind of bonding force between them. A high degree of interaction between wood and commercial polyurethane‐alkyd lacquer was shown as a decrease by 10°C of the glass transition temperature (T_g) for the lacquer on wood compared to the pure lacquer. The lacquer also demonstrated good adhesion to wood at a microscale. The interaction was investigated with dynamic mechanical thermal analysis and scanning electron microscopy fractography. The reason for the decrease in Tg is probably because of the lacquer having a higher free volume when applied to the wood, most likely due to it being subjected to tensile forces developed during the drying of the lacquer. Results from investigations of wood impregnated with two different acrylates, a polymethylmethacrylate and a more hydrophilic acrylate, support the suggestion that a decrease in T_g will occur if the polymer adheres to wood, but that poor interaction with little or no adhesion will result in no decrease in T_g. This article also presents results of the dynamic mechanical behavior of Scots Pine in the tangential direction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 595–605, 2002     

Effect of branching in hyperbranched alkyd on the performance of alkyd polyurethane coating

Hyperbranched alkyd was synthesized by single‐step approach using trimethylolpropane, mono pentaerythritol as core material, and 2,2‐bis(methylol)propionic acid (DMPA), a combination of dehydrated castor oil fatty acid and coconut oil fatty acid as chain extender. A series of hyperbranched alkyds were prepared at different degree of branching in the alkyd structures by changing the amount of DMPA in the alkyd resin formulation. The resins were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance (NMR) spectroscopic technique. These hyperbranched alkyds were converted into polyurethane coating after reaction with hexamethylene diisocyanate trimer at a definite ratio in the presence of dibutyltin dilaurate as a catalyst. The effect of branching and polymeric chain entanglement on the glass transition temperature, T_g of the alkyd polyurethane coating (APUC) was studied by differential scanning calorimetry technique. The performance of such APUC in terms of gloss, gloss retention under accelerated QUV radiation, natural outdoor exposed condition, mechanical, and corrosion resistance properties were enhanced with the increase of polymeric chain entanglement, i.e., compactness or higher order of branching in the alkyd resin structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45835.     

The effect of alkyd resins on the properties of AA‐NC semi‐IPNs as binders in wood finish

Wood coatings of AA‐NC semi‐interpenetrating polymer networks (semi‐IPNs), made from acid curing amino‐alkyd resins (AA) and nitrocellulose (NC), were prepared by sequential polymerization method. To investigate the effects of oil length on the properties of AA‐NC semi‐IPNs, three grades of alkyd resins (Alkyd) containing 38, 48, and 58% oil were synthesized with phthalic anhydride, glycerol, and soybean oil, employing alcoholysis method. The butylated urea formaldehyde resin (UF) and melamine formaldehyde resin (MF) were also prepared in this study. The AA‐NC semi‐IPNs were maintained at a weight ratio of AA : NC of 25 : 75, where the AA was the composition of MF : UF : Alkyd of 7.5 : 22.5 : 70 (by weight), and 10% of p‐toluene sulfonic acid solution (concentration, 25% in isopropyl alcohol) based on the weight of amino resins was added as acid catalyst. The properties of coatings such as viscosity, drying time, and gel time, and the properties of films including adhesion, hardness, abrasion resistance, impact resistance, tensile strength, released formaldehyde, lightfastness, solvent resistance, and durability were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1923–1927, 2004     

Fabrication of nano calcium fluoride impregnated organic polyester alkyd coating for anticorrosive and antibacterial applications

The advent of organic polyester alkyd resin has revolutionized the coating industry due to its good adherence to any substrate, high gloss, and greater drying speed. This work deals with the characterization of nano calcium fluoride (CaF₂ Nps) incorporated polyester alkyd coating for efficient multifunctional coating applications. The CaF₂ Nps are prepared by employing a facile co-precipitation process. The prepared particles are characterized using X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) to analyze their size and morphology. By employing the ball milling technique, the CaF₂ Nps along with other additives are mixed with alkyd resin to form a coating. The spreading ability, volatile and non-volatile content, surface roughness, and coating thickness are evaluated. The minimal inhibitory concentration (MIC) is estimated by the turbidimetric assay method against gram-negative and gram-positive bacteria strains. Since these pigments hold very good antibacterial properties, the CaF₂ are impregnated in alkyd resin coating, in which CaF₂ nanoparticles are used as pigments. To reduce the nosocomial infection spreading in the hospital environment the formulated paint is analyzed for its antibacterial and anticorrosive studies. The current study confirmed CaF₂ impregnated organic alkyd resin coating possesses promising comparable properties which would be a good choice for coatings, addressing multifunctional properties.     

Infrared laser‐ignited horizontal frontal polymerization of versatile unsaturated polyester resins

Infrared laser‐ignited horizontal frontal polymerization is applied for the synthesis of unsaturated polyester resin (UPER) by copolymerizing unsaturated polyester with styrene (St), methyl methacrylate (MMA), and 2‐dimethylamino ethyl methacrylate (DMAEMA) monomers. Dependence of frontal velocity and temperature on the initiator and monomer concentration is discussed for St‐based UPER. These resins have also been characterized by Fourier transform infrared, thermogravimetric analysis, and scanning electron microscopy. The results reveal St‐based resins have superior crosslinked networks. Besides, the thermo‐pH responsiveness behaviors of DMAEMA‐based resins are demonstrated by swelling measurements under the conditions of different temperatures and pH values. Moreover, by introducing CdSe@ZnS quantum dots and CsPbBr₃ perovskites into St‐ and MMA‐based resins, respectively, we realize the in situ generation of CdSe@ZnS‐UPER and CsPbBr₃‐UPER composites with good fluorescence properties and fluorescent stability, which have potential application in optoelectronic devices such as light‐emitting diode and perovskite solar cells. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45935.     

Fatty acid‐based comonomers as styrene replacements in soybean and castor oil‐based thermosetting polymers

In this study, a fatty acid‐based comonomer is employed as a styrene replacement for the production of triglyceride‐based thermosetting resins. Styrene is a hazardous pollutant and a volatile organic compound. Given their low volatility, fatty acid monomers, such as methacrylated lauric acid (MLA), are attractive alternatives in reducing or eliminating styrene usage. Different triglyceride‐derived cross‐linkers resins were produced for this purpose: acrylated epoxidized soybean oil (AESO), maleinated AESO (MAESO), maleinated soybean oil monoglyceride (SOMG/MA) and maleinated castor oil monoglyceride (COMG/MA). The mechanical properties of the bio‐based polymers and the viscosities of bio‐based resins were analyzed. The viscosities of the resins using MLA were higher than that of resins with styrene. Decreasing the content of MLA increased the glass transition temperature (T_g). In fact, the T_g of bio‐based resin/MLA polymers were on the order of 60°C, which was significantly lower than the bio‐based resin/styrene polymers. Ternary blends of SOMG/MA and COMG/MA with MLA and styrene improved the mechanical properties and reduced the resin viscosity to acceptable values. Lastly, butyrated kraft lignin was incorporated into the bio‐based resins, ultimately leading to improved mechanical properties of this thermoset but with unacceptable increases in viscosity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Alkyd–epoxy blends as multipurpose coatings

The alkyd resins of three different compositions based on nahar seed oil (Mesua ferrea), phthalic anhydride, and maleic anhydride were synthesized by an alcoholysis method. These alkyd resins were blended with a commercially available epoxy resin (Araldite 250, Ciba Geigy, Mumbai, India) separately to study the performance of the blends as coatings. The morphology of the blends was studied with scanning electron microscopy. The drying time, gloss, flexibility, pencil hardness, adhesion, pressure test, and chemical resistance under different conditions were measured for this purpose. The thermal characteristics of the blends were also investigated by thermogravimetric analysis. The studies showed better performance of the blends with respect to the drying time, hardness, flexibility, gloss, pressure test, thermal stability, and chemical resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 516–521, 2006     

Resins and additives for powder coatings and alkyd paints, based on renewable resources

Due to limited fossil resources and an increased need for environmentally friendly, sustainable technologies, the importance of using renewable feedstocks in the paint and coatings area will increase in the decades to come. This paper highlights some of the perspectives in this area. Alkyd resins for high-solid paints and reactive diluents, completely based on commercially available renewable resources, were prepared and characterized. Alkyd resins based on sucrose and unsaturated fatty acids or oils showed a low intrinsic viscosity, making them suitable to be used in high-solid alkyd paints. Reactive diluents based on similar starting materials showed excellent properties with regard to thinning behavior and effect on drying characteristics. Powder coating polyester resins were synthesized, starting from isosorbide and diacids. Polyester resins with glass transition temperatures up to 70°C were obtained. Incorporation of small amounts of other diols and trifunctional components was found to improve color and coating properties. In order to create completely renewable resin systems, the development of renewable drying agents for alkyds and crosslinkers for powder coatings is in progress. Presented at the XXVIII FATIPEC Congress, in Hungary, June 2006.     

Quantitative determination of the distribution of free hydroxylic and carboxylic groups in unsaturated polyester and alkyd resins by 31P‐NMR spectroscopy

Quantitative ³¹P‐NMR spectroscopy is used to measure the hydroxyl and carboxyl content of some polyester resins (short‐ and long‐oil alkyds, polyols, polyesters) through derivatization of the —OH protons with 2‐chloro‐4,4,5,5‐tetramethyldioxaphospholane I. This methodology is shown to be superior to titration methods, since it can (a) discriminate between primary and secondary hydroxyl groups, (b) identify individual alcohols and acids present, (c) measure the amount of free fatty acids in oil‐modified alkyds, and (d) provide lower limits for the number‐averaged molecular weight of the resins and exact values for linear polyesters. A major advantage of the technique is that the NMR measurements are made on unmodified resins in their final product form supplied by the manufacturer. The information obtained is important for the characterization of the alkyd resins and affects drastically their physical properties and performance as products. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1635–1642, 2002     

Nanostructuration of Unsaturated Polyester by All‐Acrylic Block Copolymers, 1 ‐ Use of High‐Molecular‐Weight Block Copolymers

Nanostructuration of maleate and orthophthalic unsaturated polyester (UP) resins was achieved by the use of high molecular weight amphiphilic PBA‐b‐P(MMA‐co‐DMA)₂ triblock copolymers. PBA is fully immiscible in cured UP resins, and the miscibility of P(MMA‐co‐DMA) random copolymers can be ensured with a minimum DMA content of 12 mol‐%. When using the triblock copolymers, fully transparent and nanostructured thermosets are obtained with a minimum DMA content in the outer blocks; the value of which is higher than 12 mol‐% and depends on the UP chemical structure. Finally, the fracture toughness of nanostructured thermoset was evaluated: for a triblock copolymer content as low as 5 wt.‐%, a 50% increase of K_Ic was obtained, as compared to the neat thermoset.

     

Soybean‐ and castor‐oil‐based thermosetting polymers: Mechanical properties

Maleic anhydride modified soybean‐ and castor‐oil‐based monomers, prepared via the malination of the alcoholysis products of the oils with various polyols, such as pentaerythritol, glycerol, and bisphenol A propoxylate, were copolymerized with styrene to give hard rigid plastics. These triglyceride‐based polymers exhibited a wide range of properties depending on their chemical structure. They exhibited flexural moduli in the 0.8–2.5 GPa range, flexural strength in the 32–112 MPa range, glass transition temperatures (T_g) ranging from 72 to 152°C, and surface hardness values in the 77–90 D range. The polymers prepared from castor oil exhibited significantly improved modulus, strength, and T_g values when compared with soybean‐oil‐based polymers. These novel castor and soybean‐oil‐based polymers show comparable properties to those of the high‐performance unsaturated polyester (UP) resins and show promise as an alternative to replace these petroleum‐based materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1497–1504, 2006     

Comparison of Oleo‐ vs Petro‐Sourcing of Fatty Alcohols via Cradle‐to‐Gate Life Cycle Assessment

Alcohol ethoxylates surfactants are produced via ethoxylation of fatty alcohol (FA) with ethylene oxide. The source of FA could be either palm kernel oil (PKO) or petrochemicals. The study aimed to compare the potential environmental impacts for PKO‐derived FA (PKO‐FA) and petrochemicals‐derived FA (petro‐FA). Cradle‐to‐gate life cycle assessment has been performed for this purpose because it enables understanding of the impacts across the life cycle and impact categories. The results show that petro‐FA has overall lower average greenhouse gas (GHG) emissions (～2.97 kg CO₂e) compared to PKO‐FA (～5.27 kg CO₂e). (1) The practices in land use change for palm plantations, (2) end‐of‐life treatment for palm oil mill wastewater effluent and (3) end‐of‐life treatment for empty fruit bunches are the three determining factors for the environmental impacts of PKO‐FA. For petro‐FA, n‐olefin production, ethylene production and thermal energy production are the main factors. We found the judicious decisions on land use change, effluent treatment and solid waste treatment are key to making PKO‐FA environmentally sustainable. The sensitivity results show the broad distribution for PKO‐FA due to varying practices in palm cultivation. PKO‐FA has higher impacts on average for 12 out of 18 impact categories evaluated. For the base case, when accounted for uncertainty and sensitivity analyses results, the study finds that marine eutrophication, agricultural land occupation, natural land occupation, fossil depletion, particulate matter formation, and water depletion are affected by the sourcing decision. The sourcing of FA involves trade‐offs and depends on the specific practices through the PKO life cycle from an environmental impact perspective.     

Miscibility of polymer blends of poly(styrene‐co‐4‐hydroxystyrene) with bisphenol‐A polycarbonate

The miscibility of blends of bisphenol‐A polycarbonate (BAPC) and tetramethyl bisphenol‐A polycarbonate (TMPC) with copolymers of poly(styrene‐co‐4‐hydroxystyrene) (PSHS) was studied in this work. It has been demonstrated that BAPC is miscible with PSHS over a region of approximately 45–75 mol % hydroxyl groups in the copolymer. TMPC has a wider miscible window than BAPC when blended with PSHS. The blend miscibility was considered to be driven by the intermolecular attractive interactions between the hydroxyl groups of the PSHS and the π electrons of the aromatic rings of both polycarbonates (PCs). As the FTIR measurements showed, after blending of BAPC with PSHS, there is no visible shift of the carbonyl band of BAPC at 1774 cm⁻¹, whereas the stretching frequency of the free hydroxyl groups of the copoly‐ mers at 3523 cm⁻¹ disappeared. The large positive values of the segment interaction energy density parameter B_st‐HS calculated from the group contribution approach indicated that the intramolecular repulsive interaction may also have played a role in the promotion of the blend miscibility. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 639–646, 1999     

Fullerene‐functionalized polycarbonate: Synthesis under microwave irradiation and nonlinear optical property

Fullerenation of polycarbonate (PC), a commercially important optical polymer, was achieved by direct reaction of C₆₀ and PC in the presence of azo‐bis‐isobutyronitrile (AIBN), using 1,1,2,2‐tetrachloroethane as the solvent under microwave irradiation (MI). Compared with conventional heating process, MI could significantly enhance the rate of the fullerenation under identical reaction conditions. The C₆₀ content of the fullerene‐functionalized polycarbonate (C₆₀‐PC) could be controlled via varying the C₆₀/PC feed ratio and the reaction time. The C₆₀‐PCs are soluble in common organic solvents such as THF and chloroform. The products were characterized by gel permeation chromatography, UV–vis, FTIR, TGA, DSC, ¹H NMR, and ¹³C NMR. The reaction of C₆₀ with PC under MI was monitored by electron spin resonance spectra, the fullerene radicals were detected in reaction solutions and also in the solid product polymers, indicating the radical mechanism of the reaction. The nonlinear optical property of C₆₀‐PCs in THF was investigated by the open‐aperture z‐scan technique at 527 nm, and its nonlinear absorption coefficient was found to be in the same order as that of C₆₀. POLYM. ENG. SCI., 46:399–405, 2006. © 2006 Society of Plastics Engineers     

Fire‐retardant hybrid thermosetting resins from unsaturated polyesters and polysilazanes

This introduces an organic–inorganic thermosetting hybrid resin system based on unsaturated polyester and polysilazanes. It shows the chemical modification of unsaturated polyester structures by end capping to enable the combination of both components. In general, halogen‐free unsaturated polyesters are not fire‐retardant and have to be equipped with additives. Fillers and intumescent additives are preponderantly used in today's fire‐retardant formulations. In contrast to these fire‐retardants, polysilazanes act as ceramizing agents. Polysilazanes are suitable fire‐retardants for resin transfer molding due to their low viscosity. Both burning behavior and glass transition temperature (T_g) are investigated as important application properties. In contrast to state‐of‐the‐art fire‐retardant formulations polysilazane‐based thermosetting hybrid resins burn with high intensity and fast extinction. Therefore, total heat and smoke emission is decreased. The formation of ceramic structures during burning results in high residual mechanical properties and a low mass loss. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40375.