Alkyd resins synthesized from postconsumer PET bottles

Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding postconsumer bottles was carried out in the presence of xylene and an emulsifier at 180 °C. The product was separated from EG, water and xylene by filtration and was extracted by water at boiling point three times. The remaining solid was named water insoluble fraction (WIF). The filtrate was cooled to 4 °C and the crystallized solid obtained by filtration was named water-soluble crystallizable fraction (WSCF). These fractions were characterized by acid value (AV), hydroxyl value (HV) determinations. WSCF and WIF were used for preparation of the alkyd resins. Three long oil alkyd resins were prepared from phthalic anhydride (PA) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin), glycerin (G), sunflower oil fatty acids (SOFA) and glycol (EG) (reference alkyd resin) or depolymerization product of the waste PET (PET-based alkyd resin). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Physical properties (drying times, hardness and abrasion resistance) and thermal degradation stabilities of the PET-based alkyd resins are better than these properties of the reference alkyd resin.     

Investigation of the effect of hydrolysis products of postconsumer polyethylene terephthalate bottles on the properties of alkyd resins

Hydrolysis of waste polyethylene terephthalate (PET) flakes obtained from grinding postconsumer bottles was carried out at 200–230°C and molar ratios of PET/H₂O were taken as 1/5; 1/10; 1/20. The reaction products, when extracted with boiling water, yielded a water soluble crystallizable fraction (WSCF) and a water insoluble fraction (WIF). These fractions were characterized by acid and hydroxyl value determinations and DSC analysis. WSCF and WIF were used for preparation of alkyd resins. Five long oil alkyd resins were prepared from phthalic anhydride (PA) (reference alkyd resin) or hydrolysis products of the waste PET (PET‐based alkyd resin), pentaerithrithol (PE), soybean oil fatty acid (SOFA), and ethylene glycol (EG). Film properties and thermal degradation stabilities of these alkyd resins were investigated. Drying time, hardness, alkaline resistance, and thermal oxidative degradation resistance of the PET‐based alkyd resins are better than these properties of reference resin. The results show that hydrolysis products of waste PET obtained from postconsumer bottles are suitable for manufacturing of alkyd resins. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

Glycolysis of poly(ethylene terephthalate) wastes in xylene

To reclaim the monomers or prepare intermediates suitable for other polymers zinc acetate catalayzed glycolysis of waste poly(ethylene terephthalate) (PET) was carried out with ethylene or propylene glycol, with PET/glycol molar ratios of1 : 0.5–1 : 3, in xylene at 170–245°C. During the multiphase reaction, depolymerization products transferred to the xylene medium from the dispersed PET/glycol droplets, shifting the equilibrium to glycolysis. Best results were obtained from the ethylene glycol (EG) reaction at 220°C, which yielded 80 mol % bis-2-hydroxyethyl terephthalate monomer and 20 mol % dimer fractions in quite pure crystalline form. Other advantages of employment of xylene in glycolysis of PET were improvement of mixing at high PET/EG ratios and recycling possibility of excess glycol, which separates from the xylene phase at low temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2311–2319, 1998     

Unsaturated Polyester Resins Obtained from Glycolysis Products of Waste PET

Abstract

Waste polyethylene terephthalate (PET) flakes were depolymerized by using ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), and triethylene glycol (TEG) in the presence of zinc acetate as catalyst. All glycolysis products were reacted with maleic anhydride and mixed with styrene monomer to get unsaturated polyester (UP) resins. Molecular weights of all synthesized UP resins were determined by end-group analysis. The curing characteristics such as gel time and maximum curing temperatures, and mechanical properties such as hardness, tensile strength, and elastic module of these resins were investigated. The waste PET resins were compared with the reference resins prepared with the same glycols and the properties of the resins were found to be compatible with the properties of the reference resins.     

Synthesis and applications of unsaturated polyester resins based on PET waste

Three types of unsaturated polyester resins were synthesized from the glycolysis of polyethylene terephthalate (PET) plastic waste, considering environment, cost and properties for their applications. These synthesized unsaturated polyester resins could be used for various construction processes and materials such as no dig pipelining (NDR-1), pultrusion (PLR-1) and polymer concrete (PCR-1). PET was taken from common soft-drink bottles, and ethylene glycol (EG), diethylene glycol (DEG) and MPdiol glycol mixtures were used for the depolymerization at molar ratios. The glycolyzed PET 1 ^st products (oligomers) were reacted with maleic anhydride, phthalic anhydride and dicyclopentadiene (DCPD) (especially for polymer concrete) to form unsaturated polyester resins with mixed styrene. The lab scale (1–5 kg) and pilot plant scale-up tests (200 kg) were experimented to evaluate the processing characteristics, viscosity, acid number and curing behaviors. The main properties such as hardness, flexural strength, tensile strength, heat distortion temperature, elongation, and chemical resistance were determined based on the various uses of the three resins. Furthermore, the applicability and the properties of these developed resins were verified through many real application tests.     

Effects of urea formaldehyde resin to film properties of alkyd–melamine formaldehyde resins containing organo clay

Organo clay modified alkyd resins were prepared and these modified alkyd resins were cured with different ratios of melamine formaldehyde and urea formaldehyde resins in this work. Alkyds formulated to have oil content 40% were prepared with phthalic anhydride (PA), glycerine (G), coconut oil fatty acid (COFA), dipropylene glycol (DPG) and organo clay. “K alkyd constant system” was used for the formulation calculations of the alkyd resins. Alkyd resins were blended with 40% of a commercial melamine formaldehyde. The films of the alkyd–amino resins were prepared from 60% solid content xylene solutions using 50 μm applicators. After the films were cured at 140 °C for 2 h in an oven, properties of the films were determined. The film properties of the alkyd–amino resins such as drying degree, hardness, adhesion strength, abrasion resistance, water, acid, alkaline, solvent resistance, and resistance to environmental conditions were investigated. The addition of the urea formaldehyde resin and organo clay has positive effect on the physical and chemical resistance of the alkyd–amino resins.     

超/亚临界水中聚对苯二甲酸乙二醇酯的解聚

采用间歇式高压反应装置研究了聚对苯二甲酸乙二醇酯(PET)在超/亚临界水中的解聚,考察了投料比、反应温度及反应时间对PET解聚率及主产物对苯二甲酸(TPA)和乙二醇(EG)产率的影响.固相产物采用傅里叶红外光谱(FT-IR)、液相色谱(HPLC)进行分析,液相产物采用气相色谱(GC)和气-质联谱(GC-MS)进行分析....     

Synthesis and film properties of epoxy esters modified with amino resins from glycolysis products of postconsumer PET bottles

Glycolysis of waste polyethylene terephthalate (PET) flakes obtained from grinding postconsumer bottles was carried out at 225–250°C and molar ratios of PET/ethylene glycol were taken as 1/1, 1/1.5, 1/5, and 1/10. Reaction product was extracted by hot water for three times and water‐soluble crystallizable fraction and water‐insoluble fraction were obtained. These fractions were characterized by acid and hydroxyl value determinations, differential scanning calorimeter analysis, and ¹H‐NMR analysis. Glycolysis product was used for synthesis of PET‐based epoxy resin. This epoxy resin was used to prepare epoxy ester resins having 40% and 50% oil content. Epoxy ester resin having 40% oil content was modified with urea‐formaldehyde and melamine‐formaldehyde resins for synthesis of epoxy ester–amino resin. Physical and chemical film properties of epoxy ester and modified epoxy ester resins were investigated. All the epoxy ester and modified epoxy ester films were having excellent adhesion, water, and salt water resistance properties. Modification of PET‐based epoxy ester resins with amino resin has significantly improved hardness, impact resistance, and alkaline and acid resistance of resin films. As a result, PET oligomers obtained from glycolysis of postconsumer PET bottles are suitable for manufacturing of amino‐resin‐modified epoxy ester resins that have improved physical and chemical surface coating properties. POLYM. ENG. SCI., 55:2519–2525, 2015. © 2015 Society of Plastics Engineers     

Synthesis of unsaturated polyester resin from postconsumer PET bottles: Effect of type of glycol on characteristics of unsaturated polyester resin

Postconsumer PET bottles including water and soft‐drink bottles were depolymerized by glycolysis in excess glycols, such as ethylene glycol, propylene glycol, and diethylene glycol, in the presence of a zinc acetate catalyst. The obtained glycolyzed products were reacted with maleic anhydride and mixed with a styrene monomer to prepare unsaturated polyester (UPE) resins. These resins were cured using methyl ethyl ketone peroxide (MEKPO) as an initiator and cobalt octoate as an accelerator. The physical and mechanical properties of the cured samples were investigated. It was found that the type of glycol used in glycolysis had a significant effect on the characteristics of the uncured and cured UPE resins. Uncured EG‐based UPE resin was a soft solid at room temperature, whereas uncured PG‐ and DEG‐based resins were viscous liquids. In the case of the cured resins, the EG‐based product exhibited characteristics of a hard and brittle plastic, while the PG‐based product did not. The DEG‐based product exhibited characteristics of hard and brittle plastic after strain‐induced crystallization had occurred. In addition, it was also found that no separation of the type of bottles was needed before glycolysis, since UPE resins prepared from water bottles, soft‐drink bottles, and a mixture of both bottles showed the same characteristics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 788–792, 2003     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

Unsaturated polyesters from PET waste: Kinetics of polycondensation

PET waste was glycolyzed by propylene glycol at different weight ratios. The glycolyzed products were analyzed for hydroxyl value, number average molecular weight, and the amount of free glycol. The glycolyzed products were reacted with maleic anhydride at a hydroxyl to carboxyl ratio of 1.1. The control resin was a general purpose unsaturated polyester prepared by reacting phthalic anhydride, maleic anhydride, and propylene glycol. The heating schedule of the polyesterification was comparable to that normally employed in the industrial process, with two isothermal plateau of 3–4 h at 180 and 200°C. The rate of reactions and rate constants were determined separately at 180 and 200°C. The kinetics of the PET-based unsaturated polyesters was compared with that of the general purpose resin. It was found that the PET waste could be depolymerized by propylene glycol to a molecular weight range of 276–480. The polyesterification reactions followed a third-order kinetics. The rates of polyesterification of PET based systems were higher than that of the general purpose resin. PET-based systems were higher than that of the general purpose resin. PET-based systems took about 10 h to reach an acid value of 32 mg KOH/g whereas the general purpose resin took about 25 h to reach the same acid value.     

Depolymerization of poly(ethylene terephthalate) resin under pressure

The process of depolymerization of PET resin by EG glycolysis under pressure is investigated. The kinetics of this pressurized depolymerization of PET resin is discussed. It was found that the rate of depolymerization is dependent of temperature, pressure, and concentration ratio of EG to PET. The rate of depolymerization is proportional to the square of EG concentration and faster than that under atmospheric pressure. Glycolyzed products under pressure consist of the PET monomer, BHET, and oligomers, mostly dimer and trimer. An equilibrium between BHET and oligomers is attained quickly soon after the depolymerization step is completed in the case of a higher ratio of EG/PET used. In the case of lower ratio of EG/PET, the final product now consists of higher molecular weight of oligomers rather than monomer, dimer, and trimer.     

Hydrolytic depolymerization of poly(ethylene terephthalate) under microwave irradiation

This article covers the depolymerization of poly(ethylene terephthalate) (PET) under microwave irradiation in neutral water. The reaction was carried out in a sealed reaction vessel in which the pressure (or temperature) was controlled. The hydrolytic product contained terephthalic acid, ethylene glycol, and diethylene glycol characterized by IR spectrometry and gas chromatography. The undepolymerized PET was identified by gel permeation chromatography. Both the yield of terephthalic acid and the degree of PET depolymerization were seriously influenced by pressure (or temperature), the weight ratio of water to PET, and the reaction time. The applied irradiation power had little influence on the degree of PET depolymerization. With a pressure of 20 bar (temperature = 220°C), a reaction time of 90–120 min, and a weight ratio of water to PET of 10:1, the PET resin was depolymerized completely. The molecular weight and the molecular weight distribution indicated that the hydrolytic depolymerization of PET obeyed the regular chain‐scission mechanism to some extent. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 719–723, 2005     

New epoxy resins based on recycled poly(ethylene terephthalate) as organic coatings

Glycolysis of poly(ethylene terephthalate), PET, waste using trimethylol propane (TMP), triethanolamine (TEA), diethylene glycol (DEG) and diethanolamine (DEA) was used to produce suitable hydroxy-oligomers for epoxy. The glycolyzed products were reacted with epichlorohydrine to prepare a series of di- and tetraglycidyl epoxy resins with different molecular weights. The glycolysis was carried out in presence of manganese acetate as a catalyst at normal and high pressure in presence and absence of xylene at 210 °C. The produced resins were cured with different mole ratios of 1-(2-amino ethyl) piprazine as curing agent at room temperature. The mechanical properties of the cured epoxy resins were evaluated. The chemical resistances of the cured resins were evaluated through salt spray resistance, hot water, solvents, acid and alkali resistance measurements. The data indicate that the cured epoxy resins based on glycolyzed oligomer of PET and DEA have excellent chemical resistances as organic coatings among other cured resins.     

Solvent blends based on dipropylene glycol dimethyl ether for the production of alkyd and polyester resins by the azeotropic process

Solvent blends based on dipropylene glycol dimethyl ether (DPGDME) and non-HAP hydrocarbons were evaluated as xylene replacements for the preparation of alkyd and polyester resins by the solvent reflux process. Screening criteria included water partitioning properties, autoignition temperature, distillation profile, and water removal efficiency. A series of resins was also prepared by an identical procedure in order to compare the performance of the DPGDME solvent blends with that of the xylene control. Several of the DPGDME/hydrocarbon blends exhibited desirable partitioning properties and autoignition temperatures >350°C. These blends were close-boiling and when distilled in the presence of water, formed minimum boiling pseudo-heterogeneous azeotropes containing about 50% water. Size exclusion chromatography data showed that resins made with the DPGDME blends had essentially the same molecular weight distribution profile as those made with xylene. Oxygenated Solvents Group, 1691 N. Swede Rd., Midland, MI 48674     

Heat Transfer Studies in an Agitated Vessel During Aqueous Alkaline Depolymerization of Poly(Ethylene Terephthalate) (PET) Waste

Depolymerization reactions of poly(ethylene terephthalate) (PET) waste in aqueous sodium hydroxide solution were carried out in a batch reactor at 150°C at atmospheric pressure. Disodium terephthalate (terephthalic acid salt) and ethylene glycol (EG) remain in the liquid phase. Terephthalic acid (TPA) salt was converted into TPA. The produced monomeric products (TPA and EG) were recovered. Various design parameters were estimated. Design of a batch reactor was undertaken for depolymerization of PET waste in aqueous sodium hydroxide solution. As expected, the Reynolds numbers, Prandtl numbers, Nusselt numbers, coil-side heat transfer coefficients, and overall heat transfer coefficients were consistent with the fluid velocities. It shows excellent potential for commercialization of the depolymerization of PET waste.     

Chemical recycling of post-consumer PET: Alkyd resins synthesis

The recycling of post-consumer poly(ethylene terephtalate) (PET) is a worldwide concern due to its environmental impact and the large and increasing volume of these materials produced by society. We use post-consumer PET in alkyd resin synthesis for coatings, replacing a fraction of phthalic anhydride (PA) and ethylene glycol (EG) of conventional synthesis for post-consumer PET.     

水性苯丙共聚物改性醇酸树脂的制备及性能

以油酸、季戊四醇、邻苯二甲酸酐、苯甲酸为原料,采用丙二醇甲醚醋酸酯（PMA）为溶剂合成了基体醇酸树脂;用过氧化苯甲酰、过氧化苯甲酸叔丁酯双引发剂、分步引发烯类单体共聚,制备了一种苯丙烯树脂,并对醇酸树脂改性制得了水性醇酸树脂。考察了不同油度对水性醇酸树脂结构与性能的影响。通过FTIR、TGA、DLS分别对树脂的结构、稳定性和乳液性能进行了表征。测定了树脂的漆膜性能,包括耐水性、表干时间、硬度、电化学性能。结果表明,n（油酸）∶n（季戊四醇）∶n(邻苯二甲酸酐)∶n（苯甲酸）=1∶1∶1∶0.3,油度为47%时,聚合物乳液粒径为74.4 nm,PDI为0.262,胶膜的吸水率为14.5%,接触角为70.87?,有较好的耐水性。改性醇酸树脂的表干时间缩短为0.5 h,实干时间缩短为24 h,硬度达HB。     

Mechanical characterization and chemical resistances of cured unsaturated polyester resins modified with vinyl ester resins based on recycled poly(ethylene terephthalate)

Unsaturated polyester resin (UP) was prepared from glycolyzed oligomer of poly(ethylene terephthalate) (PET) waste based on diethylene glycol (DEG). New diacrylate and dimethacrylate vinyl ester resins prepared from glycolysis of PET with tetraethylene glycol were blended with UP to study the mechanical characteristics of the cured UP. The vinyl ester resins were used as crosslinking agents for unsaturated polyester resin diluted with styrene, using free‐radical initiator and accelerator. The mechanical properties of the cured UP resins were evaluated. The compressive properties of the cured UP/styrene resins in the presence of different vinyl ester concentrations were evaluated. Increasing the vinyl ester content led to a pronounced improvement in the compression strength. The chemical resistances of the cured resins were evaluated through hot water, solvents, acid, and alkali resistance measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3175–3182, 2007