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     

水分散型醇酸树脂的合成及性能研究

以脂肪油、邻苯二甲酸酐、偏苯三酸酐和三羟甲基丙烷为主要原料合成了水分散性醇酸树脂。以原料中酸酐的比例为基础设计了合成配方,讨论了合成工艺、脂肪油的种类和比例以及醇解催化剂对水分散性醇酸树脂性能的影响。     

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.     

Alkyd resins based on waste PET for water-reducible coating applications

Simultaneous glycolysis and neutral hydrolysis of waste PET flakes obtained from grinding post-consumer bottles was carried out in the presence of xylene and an emulsifier at 170 °C. The product was separated from ethylene glycol (EG), water, and xylene by filtration, and was extracted by water at boiling point thrice. 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) and hydroxyl value (HV) determinations. WSCF and WIF were used for preparation of the water-reducible 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), fatty acids (FA), 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 and hardness) and thermal degradation stabilities of the PET-based alkyd resin is better than these properties of the reference alkyd resin.     

紫胶改性水性醇酸树脂的合成工艺研究

从改进树脂综合性能着手,研究了水性醇酸树脂的合成工艺。确定了以熔融法和分步加料来制备醇酸树脂。以紫胶部分替代三羟甲基丙烷,顺丁烯二酸酐/偏苯三酸酐部分替代苯酐,所得水性醇酸树脂的干燥性能、硬度和柔韧性等性能得以提高。紫胶用量以5%为宜。     

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.     

一种高档PU亚光漆用醇酸树脂的开发

以豆油酸、苯酐、新戊二醇、二甘醇和季戊四醇等原料合成了用于PU亚光漆的醇酸树脂。讨论了原料的种类及合成工艺对漆膜消光性能的影响。以经过优化选择的醇酸树脂配制的高档PU亚光漆具有良好的消光性。     

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。     

Effects of oil type on the properties of short oil alkyd coating materials

Short-oil alkyd resins were prepared by using five different oil types: corn oil, rice bran oil, sunflower oil, soya bean oil and dehydrated castor oil (DCO). Among these, soya bean oil gave alkyd resin with the darkest color because oxidation occurred. Auto air-dried coating films were developed and it was shown that film prepared from rice bran oil-based alkyd exhibited the longest drying time due to the low number of double bonds compared to other and the extra natural antioxidant in rice bran oil. DCO alkyd-based film revealed the shortest drying time, the greatest hardness but the poorest alkali and sea-water resistance. This is caused by the differences in the type of fatty acid and double bonds, the high amount of double bonds being in DCO. In addition, an increase in the reaction temperature only had an influence on darkening the alkyd color and decreasing the drying time of coating films. In terms of technical properties and cost competitiveness, soya bean oil-based film is the best. Coating films derived from all oil-based alkyds, except DCO, look promising for use in surfboard manufacturing.     

水溶性醇酸氨基烘漆的研制

采用饱和脂肪酸、苯酐、三羟甲基丙烷、新戊二醇和偏苯三酸酐合成水溶性醇酸树脂,与甲醚化三聚氰胺甲醛树脂制备水溶性醇酸氨基烘漆。该水溶性醇酸氨基烘漆的漆膜性能均达到并超过溶剂型醇酸氨基烘漆的漆膜性能。讨论了酸值、羟值、油度、氨基树脂、中和剂、助溶剂和树脂结构等因素对树脂合成及应用性能的影响。水溶性醇酸氨基烘漆与水性醇酸防锈底漆配套使用具有优异的防腐性能。     

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     

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     

利用工业级对苯二甲酸合成醇酸树脂漆

使用工业级对苯二甲酸(CTA)代替现在大量使用的苯酐等二元酸,成功地合成了CTA醇酸树脂。所得树脂漆料各项性能均达到使用苯酐合成的同类产品的国家标准。有些性能如光泽、干率、硬度等甚至优于用苯酐生产的同类产品。在漆厂现有反应设备和工艺条件无需做大的改变条件下,使用CTA合成CTA醇酸树脂,可降低原料成本15%～20%。     

氧化蜡改性醇酸树脂蜡性能的影响研究

以蓖麻油、甘油、邻苯二甲酸酐、费托合成蜡A28及氧化石蜡为原料合成油溶性醇酸树脂蜡。分别考察了聚酯化反应时间,A28蜡及氧化石蜡加入量对中、长油度醇酸树脂蜡酸值、针入度、滴熔点的影响。实验结果表明制备醇酸树脂蜡的较佳配方为:蓖麻油72.1g、甘油21.7g、邻苯二甲酸酐40.5g、A2817.1g、聚酯化反应时间4h,合成的醇酸树脂蜡酸值:18.96mgKOH/g、滴熔点102℃、针入度13.40mm。     

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.     

Effect of karawila (Momordica charantia) seed oil on synthesizing the alkyd resins based on soya bean (Glycine max) oil

Air drying long oil alkyd resins of 65% oil length were synthesized from a blend of soya bean (Glycine max) oil and karawila (Momordica charantia) seed oil. Different proportions of karawila seed oil (w/w% 10, 20, 30, 40 and 50) were blended with soya bean oil to examine the effect of karawila seed oil on the drying behavior of alkyds synthesized from soya bean oil. A sharp variation of viscosity is only observed for alkyd resins having more than 40% (w/w) of karawila seed oil. The polyesterification time was reduced and correspondingly the extent of polymerization was also reduced up to 30% (w/w). Significant variation in transesterification time was also observed for 30% (w/w). However, further increase in karawila seed oil above 40% (w/w) had only a marginal effect on the polyesterification reaction. The drying properties of the alkyd resins had been significantly improved with the increase of karawila seed oil up to 30% (w/w) but further increase in karawila seed oil resulted in poor drying characteristics. The film properties (drying time, hardness, adhesion, chemical resistance and gloss) of the alkyd resins were determined. The optimum film properties were recorded for the oil blend with 30% (w/w) karawila seed oil and 70% (w/w) soya bean oil.     

Factors influencing the stability and film properties of acrylic/alkyd water-reducible hybrid systems using a response surface technique

Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.     

Wasserlösliche Harze auf Basis verzweigtkettiger Carbonsäuren

Water Soluble Resins Based on Branched Chain Carboxylic Acids Water soluble alkyd resins were prepared from pentaerythritol, phthalic anhydride, adipic acid and glycidyl esters of branched chain fatty acids having 9 to 11 C-atoms (?CARDURA”? E). The relationship of the water solubility and stability of aqueous solution of these resins with the parameters of formulation is shown. These alkyd resins were combined with melamine-formaldehyde resins, applied in conventional manner, baked, and the properties of the films were determined. Furthermore, the above baking paint combinations were electrophoretically applied.     

高固体分PTA醇酸树脂的合成及应用

采用树脂级对苯二甲酸(PTA)代替苯酐作为二元酸,并筛选出一种高效酯化催化剂,利用醇酸树脂溶剂法合成工艺,制备了固体分大于73%的高固体分醇酸树脂。用该树脂制备的涂料性能良好,且成本优势明显。     

The effects of anhydride type and amount on viscosity and film properties of alkyd resin

In this study, a modified method for preparing low viscosity alkyd resin was suggested. For this purpose the preparation of sunflower oil-based alkyd resins were achieved into two steps. First sunflower oil and glycerol were reacted to form partial glycerides, and then, after removing free glycerol, esterification reaction was achieved between partial glycerides and anhydride. Glutaric, maleic, phthalic and succinic anhydride were used. Sunflower oil alkyd resins were also prepared by classical method. The results obtained were compared with each other. By the modified method low viscosity and good film properties resins could be prepared.