Alkyd comprising polyethylene terephthalate and novel method for making the same

Abstract

The present disclosure is directed to methods for making an alkyd from polyethylene terephthalate comprising an alcoholysis / glycolysis reaction and a polyesterification reaction. The alcoholysis / glycolysis reaction includes use of a non-reactive solvent and the polyesterification reaction can be completed at a temperature of 240ºC or below. The present disclosure is further directed to alkyds made from these methods, coating compositions comprising these alkyds, and substrates coated with the compositions.

Description

ALKYD COMPRISING POLYETHYLENE TEREPHTHALATE AND NOVEL METHOD FOR MAKING THE SAMECROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application No. 63 / 559,497 filed on February 29, 2024, entitled “Alkyd Comprising Polyethylene Terephthalate and Novel Method for Making the Same”, which is incorporated herein in its entirety.FIELD

[0002] The present disclosure is directed to a method of making an alkyd with polyethylene terephthalate, alkyds made by the method, coating compositions comprising the alkyd, and substrates coated with the coating composition.BACKGROUND

[0003] Alkyds are widely used in coatings, particularly those in which cure or coalescence occurs at or near ambient temperature. Sustainable and other green approaches are gaining interest in the coatings industry. Coatings incorporating recycled material and / or manufactured using reduced energy are desired.SUMMARY

[0004] The present disclosure is directed to a method for making an alkyd with polyethylene terephthalate comprising: (a) an alcoholysis / glycolysis reaction; and (b) a polyesterification reaction, wherein the alcoholysis / glycolysis reaction occurs by heating a first reaction mixture comprising a glyceride, a polyol, polyethylene terephthalate, and a non-reactive solvent to form an alkyd precursor material; and wherein the polyesterification reaction occurs by heating a second reaction mixture comprising the alkyd precursor material, an anhydride and optionally additional non-reactive solvent, to a temperature of 240°C or less, whereby the second reaction mixture undergoes polymerization to form an alkyd. Alkyds made according to these methods, coating compositions comprising the alkyd(s), and substrates coated with such coating compositions are also within the scope of the present disclosure.BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 is a13C NMR in Tetrahydrofuran-Deuterated spectrum of alkyd precursor material made without xylene.

[0006] FIG. 2 is a13C NMR in Tetrahydrofuran-Deuterated spectrum of alkyd precursor material made with xylene.

[0007] FIG. 3 is a13C NMR in Tetrahydrofuran-Deuterated spectrum of alkyd precursor materials made with xylene and without xylene.

[0008] FIG. 4 is a1H NMR in Chloroform-Deuterated spectrum of alkyd product made with (dashed arrow) and without (solid arrow) xylene.

[0009] FIG. 5 shows the results of the corrosion testing as reported in the Examples.DETAILED DESCRIPTION

[0010] The present disclosure is directed to a method for making an alkyd with polyethylene terephthalate (“PET”) comprising: (a) an alcoholysis / glycolysis reaction; and (b) a polyesterification reaction. The alcoholysis / glycolysis reaction occurs by heating a glyceride, a polyol, PET, and a non-reactive solvent to form an “alkyd precursor material”. The glyceride, polyol, PET, and non-reactive solvent mixture are referred to herein as the “first reaction mixture”. The polyesterification reaction occurs by heating alkyd precursor material, an anhydride, and optionally additional non-reactive solvent, to a temperature of 240°C or less, such as 225°C or less, 215°C or less, 210°C or less, 205°C or less or from 205°C to 215°C, whereby the second reaction mixture undergoes polymerization to form an alkyd. “Second reaction mixture” as used herein refers to the mixture of the alkyd precursor material, the anhydride, and, if used, additional non-reactive solvent. Additional components can be in either or both of the first reaction mixture and second reaction mixture, as further discussed herein.

[0011] The first step in the method is an alcoholysis / glycolysis reaction using a first reaction mixture, which comprises a glyceride, a polyol, polyethylene terephthalate and a non- reactive solvent. According to the present disclosure, some or all of the PET can be recycled polyethylene terephthalate (“rPET”). rPET and like terms, as used herein, refer to post-consumer polyester plastic made of terephthalic acid and ethylene glycol. Recycled polyethylene terephthalate is often generated by recycling rPET used as a packaging material for foods, beverages, cosmetics, and household cleaners, but any suitable source may be used. The rPET may be in any form such as flakes, pellets, pieces, chunks, powder, or a combination thereof. rPET is commercially available from Indorama Ventures, Superplasticos LTDA, Grupo Alen, and Greenmind. PET that is not recycled may be referred to herein as virgin. PET and rPET can be used in combination, or the present methods can use only rPET. While the present methods may be described in terms of rPET or PET, either or both may be used.

[0012] The PET in the first reaction mixture may be present in an amount of 1 wt.% or greater, such as 10 wt.% or greater, such as 13 wt.% or greater, and may be present in an amount of 25 wt.% or less, such as 20 wt.% or less, such as 17 wt.% or less, such as 15 wt.% or less. The rPET may be present in an amount of 1 wt.% to 25 wt.%, such as 1 wt.% to 20 wt.%, such as 1 wt.% to 15 wt.%, such as 10 wt.% to 25 wt.%, such as 10 wt.% to 20 wt.%, such as 10% wt. to 17 wt.%, such as 10 wt.% to 15 wt.%, such as 13 wt.% to 25 wt.%, such as 13 wt.% to 20 wt.%, such as 13 wt.% to 17 wt.%, such as 13 wt.% to 15 wt.%. The wt.% is based on the total solids weight of the glyceride, polyol, and PET.

[0013] The term “glyceride” as used herein refers to an oil, fat, and / or fatty acid, such as one having 4-28 C atoms. The glyceride is not limited and may be a monoglyceride, diglyceride, triglyceride or combinations thereof. Examples include triglycerides of fatty acids such as soybean oil, safflower oil, tall oil, coconut oil, palm kernel oil, castor oil, fish oil, linseed oil, tung oil, poppyseed oil, perilla oil, walnut oil, and dehydrated castor oil.

[0014] The glyceride in the first reaction mixture may be present in an amount of 30 wt.% or greater, such as 40 wt.% or greater, such as 45 wt.% or greater, such as 50 wt.% or greater. The glyceride may be present in an amount of 70 wt.% or less, such as 65 wt.% or less, such as 60 wt.% or less. The glyceride may be present in an amount of 30 wt.% to 70 wt.%, such as 40 wt.% to 65 wt.%, such as 45 wt.% to 65 wt.%, such as 50 wt.% to 60 wt.%. The wt.% is based on the total solids weight of the glyceride, polyol, and PET. The amount of glyceride may be such that the carbon chains from the glyceride comprise 30 wt.% to 70 wt.%, such as 40 wt.% to 60 wt.%, based on the total weight of the final alkyd product.

[0015] The term “polyol” as used herein refers to an alcohol comprising two or more hydroxyl functional groups. Polyols having four or more hydroxyl functional groups may be particularly suitable. Suitable polyols include ethylene glycol, glycerin, pentaerythritol or combinations thereof.

[0016] The polyol in the first reaction mixture may be present in an amount of 5 wt.% or greater, such as 10 wt.% or greater, such as 15 wt.% or greater. The polyol may be present in an amount of 25 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less. The polyol may be present in an amount of 5 wt.% to 25 wt.%, such as 5 wt.% to 20 wt.%, such as 10 wt.% to 15 wt.%. The wt.% is based on the total solids weight of the glyceride, polyol, and PET.

[0017] The term “non-reactive solvent” as used herein refers to any aromatic or linear solvent that will not undergo a reaction with any of the components in either the first reaction mixture or the second reaction mixture; suitable solvents will form an azeotrope with the water generated as a by-product of the alcoholysis / glycolysis reaction. Examples include solvents having one or more aromatic rings, such as xylene, toluene, cumene, pseudocumene, anisole, linear alkyl benzenes (LAB), phenylxylylethane (PXE), diisopropylnaphthalenes (DIN), benzyl toluene, and / or diphenyl ethane, and linear solvents, such as acetonitrile. Combinations of any of these can be used.

[0018] The non-reactive solvent in the first reaction mixture may be present in an amount of 5 wt.% or less, such as 2.5 wt.% or less, such as 1 wt.% or less based on the total solids weight percent of the first reaction mixture. The non-reactive solvent may be present in an amount of at least 0.5 wt.% to 5 wt.%, such as 1 wt.% to 2 wt.%, based on the total solids weight of the first reaction mixture. One skilled in the art will appreciate that the use of a non-reactive solvent during the alcoholysis / glycolysis reaction, particularly in the amounts described, such as 5 wt.% or less, is distinct from methods in which solvent is added upon completion of the alcoholysis / glycolysis reaction and / or to promote the polyesterification reaction to form the final alkyd. That is, the non-reactive solvent as used in the present disclosure is not a co-solvent but rather is used to form an azeotrope that allows for the removal of water during the alcoholysis / glycolysis step, such as through the use of a Dean-Stark Trap. Removal of the water helps drive the degradation of PET.

[0019] The first reaction mixture may comprise a catalyst. Suitable catalysts include tin catalysts, such as monobutyltin hydroxide, monobutyltin oxide, dibutyltin oxide, monobutyltin- 2-ethyl hexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc catalysts, such as zinc acetate, manganese catalysts, such as manganese acetate, cobalt catalysts, such as cobalt acetate, calcium catalysts, such as calcium acetate, lead catalysts, such as lead acetate, litharge, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, and the like. The catalyst may be present in an amount of 0.1 wt.% to 1 wt.%, such as 0.2 wt.% to 0.75 wt.%, such as 0.25 wt.% to 0.5 wt.%, based on the total solids weight percent of the first reaction mixture. The catalyst may be added in one or more charges.

[0020] During the alcoholysis / glycolysis reaction, the glyceride, polyol and PET is combined and heated, typically to a temperature of 270°C or less, such as 260°C or less, or250°C or less, or 240°C or less, or from 240°C to 250°C. The glyceride, polyol and PET can be combined at substantially the same time, or the glyceride and polyol can be combined first and then PET added. The PET may be added in one or more charges, such as two or more charges, or three or more charges, such as at intervals of 10-15 minutes. The non-reactive solvent may be added when the glyceride, polyol, and PET achieve a temperature of 240°C to 250°C.

[0021] Heating of the first reaction mixture after addition of non-reactive solvent should continue until the PET degrades and undergoes condensation with the glyceride, such as the monoglycerides formed during alcoholysis. As the reaction proceeds, the mixture becomes transparent; heating can be stopped when the desired level of transparency or semi-transparency is achieved. Transparency and like terms mean that there is little or no cloudiness or turbidity in the reaction mixture and an observer can see an object clearly when looking through the mixture; semi-transparent and like terms means an observer can see an object through the mixture, although the object may be blurred. Transparency in the first reaction mixture is assessed visually; when the observer can see through the solution, it is considered transparent or semitransparent, depending on the sharpness of the object being observed. Because rPET is often opaque and / or colored (such as blue or green) the level of transparency may also indicate the amount of degradation of the rPET, with clearer / colorless mixtures representing greater degradation of rPET. It is typically desired to degrade as much PET as possible, such as all or substantially all the PET. Transparency is typically achieved according to the present methods after 30 minutes but may take longer, such as 1 hour or 1.5 hours.

[0022] The product resulting from the alcoholysis / glycolysis reaction is referred to herein as the “alkyd precursor material” or sometimes as the “intermediate product”. The degradation of the PET and its reaction with the glyceride and polyol result in the formation of monomeric units containing specifics groups: aromatic esters with PET (“GARE”) and alcohol esters with PET (“GALE”). It is desirable that the molar ratio of GARE to GALE in the intermediate product be close to 50:50, such as 40:60, or 60:40, or any numbers within these ranges. An alkyd precursor material (and the resulting alkyd) with a GARE to GALE molar ratio of 40:60 to 60:40 is said to be “homogenous”, to have achieved “homogeneity”, or like expressions. Having GARE and GALE in molar ratio ranges of 40:60 to 60:40 will lead to a more homogenous structure of the final alkyd, where the oligomers of degraded PET, also referred to herein as “PET moieties”, and the fatty acids of triglycerides will be more homogenously distributed in thefinal alkyd. Use of a non-reactive solvent in the manner disclosed herein drives the formation of GARE and GALE, with GARE being preferentially formed. It is especially desirable to have a greater amount of GARE than GALE. Use of an alkyd precursor material with GARE to GALE molar ratios as described helps ensure that the resulting alkyd will also comprise a homogeneous ratio. Failure to remove the water produced as a byproduct during the heating of the first reaction mixture results in formation of species other than GARE and GALE, which species are generally undesirable.

[0023] It was surprisingly discovered that the addition of non-reactive solvent, such as xylene, during the alcoholysis / glycolysis reaction shortens the amount of time it takes to achieve homogeneity in the intermediate product and also surprisingly drove the preferential formation of GARE. FIGS. 1 and 2 demonstrate this by comparing the Nuclear Magnetic Resonance Spectra for the alkyd precursor material resulting from the same alcoholysis / glycolysis reaction run without xylene (FIG. 1) and with xylene (FIG. 2). As shown in FIG. 2, with xylene, homogeneity was achieved when measured at 30 minutes, with GARE being the predominant species in the 30-, 60-, and 90-minute measurement. In contrast, in FIG. 1, without xylene, homogeneity was not reached at 60 minutes and when measured at 90 minutes GALE was predominant. FIG. 3 provides more detail of the reaction products and amounts achieved with and without xylene. The reaction mixture used to generate the intermediate products represented in FIGS. 1-3 included soybean oil, pentaerythritol and rPET prepared as generally described in the examples.

[0024] The rapid homogeneity achieved according to the present disclosure may be because of the condensation reactions between acid groups of oligomers of degraded PET and hydroxy groups of the polyol promoted by removal of water by the azeotrope between the water and the non-reactive solvent, driving the production of GARE bond types. As more GARE bond types are produced, more acidic groups (from degraded PET) are consumed, thereby causing the acid number to drop. Accordingly, it was yet another surprising result to achieve an intermediate product that can have an acid number of 2 or below, such as 1.5 or below, such as 1 or below or from 0 to 5; the low acid value of the intermediate can contribute to a low acid number in the final alkyd.

[0025] The intermediate product may have a weight average molecular weight (“Mw”) of 1,500 g / mol or greater, such as 1,600 g / mol or greater, such as 1,700 g / mol or greater, such as1,800 g / mol or greater, such as l,900g / mol or greater, such as 2,000 g / mol or greater, or from 1,000 g / mol to 3,000 g / mol. Molecular weight of the intermediate product and the final alkyd as reported herein is measured by using gel permeation chromatography using Waters 2695 separation module with a Waters 2140 differential refractometer (RI detector) and alkyd standards (“Gel Permeation Chromatography”).

[0026] The alkyd precursor material of the present disclosure may be defined as having a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm, and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is 0.25 or greater, such as 0.50 or greater, such 0.75 or greater, such as 1 or greater, such as 1.25 or greater. This is also illustrated in FIG. 2.

[0027] The alkyd precursor material from the alcoholysis / glycolysis reaction may optionally be allowed to cool to a temperature less than 200°C, such as 190°C or less, or 180°C or less, or 170°C to 180°C prior to beginning the polyesterification step. The second step in the present method is a polyesterification reaction using a second reaction mixture. The second reaction mixture comprises the alkyd precursor material from the alcoholysis / glycolysis reaction, (which comprises GARE, GALE, any other species that may have formed, and any remaining non-reactive solvent), and an anhydride. Additional non-reactive solvent can also be added as needed to drive removal of water during the polyesterification step.

[0028] The term “anhydride” as used herein refers to an acid anhydride of a carboxylic acid. Examples include maleic anhydride, phthalic anhydride, or combinations thereof. The anhydride in the second reaction mixture may be present in an amount of 5 wt.% or greater, such as 10 wt.% or greater, such as 15 wt.% or greater, based on the total solids weight of the second reaction mixture. The anhydride may be present in an amount of 25 wt.% or less, such as 20 wt.% or less, such as 15 wt.% or less, based on the total solids weight of the second reaction mixture. The anhydride may be present in an amount of 5 wt.% to 25 wt.%, such as 5 wt.% to 20 wt.%, such as 10 wt.% to 15 wt.%, based on the total solids weight of the second reaction mixture.

[0029] During the polyesterification reaction, the second reaction mixture is heated to a temperature of 240°C or less, such as 225°C or less, 220°C or less, 215°C or less, 210°C or less,205 °C or less or from 200°C to 240°C. The ability to conduct polyesterification at temperatures of 240°C or lower was another surprising result of the present methods and contributes to sustainability through energy reduction. As noted, additional non-reactive solvent may be added to the second reaction mixture. The second reaction mixture may be heated until the acid value of the mixture is 15 or less, such as 10 or less, such as 5 or less, such as 1 or less as measured according to ASTM D 1639-90 (1996). This may take 6 hours or less, such as 5 hours or less, such as 4 hours or less, such as 3 hours or less, or from 2 to 6 hours.

[0030] The present disclosure is further directed to an alkyd formed from the methods disclosed herein. The alkyd may comprise residues of various materials in the reaction mixtures such as 30 wt.% to 70 wt.% of the glyceride, such as 40 wt.% to 65 wt.%, such as 45 wt.% to 65 wt.%, such as 50 wt.% to 60 wt.%; 5 wt.% to 25 wt.% of the polyol, such as 5 wt.% to 20 wt.%, such as 10 wt.% to 15 wt.% ; 1 wt.% to 25 wt.% of the PET and / or rPET, such as 1 wt.% to 20 wt.%, such as 1 wt.% to 15 wt.%, such as 1 wt.% to 25 wt.%, such as 10 wt.% to 20 wt.%, such as 10 wt.% to 17 wt.%, such as 10 wt.% to 15 wt.%, such as 13 wt.% to 25 wt.%, such as 13 wt.% to 20 wt.%, such as 13 wt.% to 17 wt.%, such as 13 wt.% to 15 wt.%; and / or 5 wt.% to 25 wt.% of the anhydride, such as 5 wt.% to 20 wt.%, such as 10% wt. to 15 wt.%, where weight percent is based on the total weight of the alkyd.

[0031] The final alkyd may exhibit a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm, and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from H1Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration of 3.0 to 4.2 ppm is 0.01 or greater, such as 0.04 or greater, such as 0.10 or greater, such as 0.14 or greater, such as 0.16 or greater. FIG. 4 illustrates the peaks associated with GARE and GALE in an alkyd made with xylene (dashed arrow) and without xylene (solid arrow). As can be seen throughout the spectra, and particularly in the area where the two arrows are pointing, the presence of additional peaks, which represent the presence of undesirable reaction products. The present methods result in a “cleaner” alkyd with fewer of those peaks.

[0032] The alkyd may have an acid number of 15 mg KOH / g or lower, such as 10 mg KOH / g or lower, such as 5 mg KOH / g or lower, such as 1 mg KOH / g or lower, or from 0 KOH / g to 10 KOH / g, and may have a weight average molecular weight (Mw) of 5,000 g / mol or greater, such as 20,000 g / mol or greater, such as 50,000 g / mol or greater, such as 80,000 g / mol or greater, such as 90,000 g / mol or greater, such as 100,000 g / mol or greater, such as 110,000g / mol or greater, such as 120,000 g / mol or greater or from 50,000g / mol to 150,000 g / mol. An alkyd having a Mw of 80,000 g / mol or greater may contribute to fast drying properties as compared to one with a lower Mw.

[0033] An alkyd product suitable for use commercially will generally possess one or more of transparency, color compatibility and / or, a viscosity of 400 mPa- s or greater, such as 600 mPa-s or greater, such as 800 mPa-s. Viscosity as reported herein was measured at a shear rate of 0.01 s1(on an Anton Paar MCR 92 rheometer at 110°C using a 15 mm diameter parallel plate and a 0.5 mm gap). The present methods provide for more control on structure homogeneity of the intermediate product as compared to methods known in the art, which in turn contributes to a better control of the final properties of the alkyd. For example, greater homogeneity of the alkyd precursor material leads to a more soluble alkyd in non-polar solvents such as mineral spirits, naphtha gas, hexane, and other alkanes. An alkyd having lower homogeneity may make necessary the use of more polar solvents, such aromine or pine oil, or dowanols, to dissolve.

[0034] The present disclosure is further directed to a coating composition comprising any of the alkyds described herein. Coating compositions according to the present disclosure can be formulated using any means known in the art using the alkyds of the present disclosure and one or more standard additives such as water, solvents such as organic solvents, pigments, dyes, fillers such as calcium carbonate, clay, silica, talc and the like, abrasion-resistant particles, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, reactive diluents, driers, catalysts, reaction inhibitors, adhesion promoting components, such as acids and acid derivatives, phosphatized epoxy, silanes, such as epoxy silanes or amine silanes, and other customary additives known to those skilled in the art. The coating compositions of the present disclosure comprising the alkyd described herein may be formulated, for example, with one or more drying agents and optionally a dye or stain to form a varnish for wood, may be formulated with pigments to form an enamel for metallic substrates, may be formulated for application to concrete and other roadway substrates and / or for other architectural substrates.

[0035] The alkyd in the coating composition may be present in a solids weight percent of 40 wt.% or greater, such as 45 wt.% or greater, such as 50 wt.% or greater, such as 55 wt.% or greater, or from 30 wt.% to 60 wt.% based on the total solids weight of the coating composition.The PET, such as rPET, in the coating composition, introduced through the alkyd, may be 5 wt.% or greater, such as 10% or greater, such as 15% or greater, such as 20% or greater, or from 1% to 25%, with wt.% based on the total solids weight of the coating composition. Accordingly, the present disclosure provides alkyds and coating compositions having recycled content when rPET is used.

[0036] Coating compositions as described herein may be applied to a substrate and dried or coalesced. As used herein, the term “cure”, “coalesce”, or like terms refers to the process by which a coating composition hardens to form a coating. Coalescing may include the coating composition being cured (e.g. hardening by being crosslinked, either by itself or via a crosslinking agent) or the coating composition being dried. The alkyds of the present disclosure and coating layers formed from coating compositions comprising these alkyds may be Set to touch in 90 minutes + / - 20 minutes; and / or have Tack free time of 90-120 minutes; and / or Dry hard time of 6 hours + / - 30 minutes.

[0037] As reported herein, Set to touch dry time, Tack free dry time and Dry hard time were measured using the BYK Drying Time Recorder at 3 mils wet film thickness (“WET”) coated on glass panels, 50% relative humidity and 25°C. The test measures five states as illustrated below: (1) Leveling; (2) Set to touch time; (3) Tack free time; (4) Dry hard time; and (5) Dry through time.

[0038] The BYK Drying Time Recorder was used according to the SM 315-05 test method. For test method SM 315-05, a cube applicator BA 30 (150 um) in accordance with SM 220-01 test method was used. The glass panels used were 30.5 x 2.5 cm and sample in accordance with SM 201-01 test method was used. The standard climate was 23 + / - 2°C and 50 + / - 5% RH.

[0039] To conduct the BYK Drying Time Recorder, drawdowns were made with the cube applicator in accordance with the SM 220-01 test method. Glass panels were placed on the drying recorder with wet paint distributed along the glass panels according to the wet film thickness as indicated above (3 mils). Needles with a 5-gram weight were placed on the glass panels in the wet paint. The recorder speed was set and the weighted needles passed through thepaint on the glass panels. The total time for the following drying stages starting from time zero were recorded as they were observed.

[0040] (1) In the “leveling” stage the paint is still wet and levelling. (2) In the “setting” stage the paint is set to touch and dust-free (“SET TO TOUCH”). (3) In the “tearing” stage the surface is drying (“TACK FREE”). (4) In the “tracking” phase the surface is dry and drying through (“DRY HARD”). (5) In the “dry through” phase the surface is completely dried.

[0041] The compositions of the present disclosure can be applied to the surface of a substrate in any number of different ways, such as brushes, rollers, films, trowels, spatulas, dips, spray guns, sprays or applicator guns. Upon application, the coating layer can be dried or cured by any suitable means known to those skilled in the art. Examples include ambient curing, baking in a thermal oven, induction heating, infrared heating, exposure to actinic radiation, and / or combinations thereof. For example, the coating may be cured or coalesced at ambient conditions, or at moderately elevated conditions such as at a temperature up to 60°C. “Ambient” conditions generally refer to room temperature and humidity conditions and may be 10°C to 32°C and 20% relative humidity to 80% relative humidity, while slightly thermal conditions are just above 32°C.

[0042] The coating compositions of the present disclosure can be applied to any substrate including architectural component(s), roadway substrate(s), automotive substrate(s), marine substrate(s), industrial substrate(s), packaging substrate(s), wood substrate(s), such as flooring and furniture, apparel, electronics including housings and circuit boards and including consumer electronics such as housings for computers, notebooks, smartphones, tablets, televisions, gaming equipment, computer equipment, computer accessories, MP3 players, glass and transparencies, sports equipment including golf balls, and the like. The term “architectural component(s)” refers to any component used in building a structure, such as roofs, bricks, vinyl siding, concrete, cement, cement board, MDF (medium density fiberboard) and particle board, gypsum board, wood, wood composite, veneer, stone, metal, plastics, wall paper and textile, etc., which may be pre-primed by waterborne or solvent borne primers, and may be an interior or exterior wall of a building or residence. The term “roadway substrate(s)” includes asphalt, macadam, concrete and cement.

[0043] Suitable substrates can be, for example, metallic or non-metallic. Metallic substrates include tin, steel, tin-plated steel, chromium passivated steel, galvanized steel,aluminum, aluminum foil. Metal sheet as used herein refers to flat metal sheet and coiled metal sheet, which is coiled, uncoiled for coating and then re-coiled for shipment to a manufacturer. Non-metallic substrates include those listed above as well as polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly (ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, PET, polycarbonate, polycarbonate acrylobutadiene styrene (“PC / ABS”), polyamide, glass, paper, cardboard, textiles, leather both synthetic and natural, and the like.

[0044] The substrate may optionally be subjected to other treatments prior to coating with the present compositions. For example, the substrate may be cleaned, sanded, abraded, and / or pretreated. These optional treatments may be used on their own or in combination.

[0045] As used herein, “including,” “containing”, “such as”, and like terms means “including / containing / such as but not limited to” and are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, ingredients or method steps. Nevertheless, they also include the more restrictive terms “consisting of’ and “consisting essentially of.” As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, ingredient or method step. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, ingredients or method steps “and those that do not materially affect the basic and novel characteristic(s)” of what is being described.

[0046] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. For example, although reference is made herein to “a” glyceride, “a” polyol, “a” non-reactive solvent, and “an” anhydride, a combination (i.e., a plurality) of these materials may be used.

[0047] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more other intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0048] The solids content as reported herein was determined by ASTM D 4713-12 (2020). The Gardner viscosity as reported herein was determined by ASTM D 1545-13 (2017) measured at 25°C. The Gardner Color as reported herein was determined by ASTM D 1544-04 (2018). The Brookfield viscosity as reported herein was determined by ASTM D 2196-20 (2020) measured at room temperature at Spindle #1, 20 RPM. The acid number as reported herein was determined by ASTM D 1639-90 (1996). The solubility of resins as reported herein was determined by ASTM D 1889-00 (2007).

[0049] Aspects of the disclosure include:

[0050] Aspect 1. A method for making an alkyd with polyethylene terephthalate (“PET”) comprising: an alcoholysis / glycolysis reaction; and a poly esterification reaction; wherein the alcoholysis / glycolysis reaction occurs by heating a first reaction mixture comprising a glyceride, PET, and a non-reactive solvent to form an alkyd precursor material; and wherein the polyesterification reaction occurs by heating a second reaction mixture comprising the alkyd precursor material, an anhydride, and, optionally, additional non- reactive solvent, to a temperature of 240°C or less whereby the second reaction mixture undergoes polymerization to form an alkyd.

[0051] Aspect 2. The method of aspect 1, wherein the glyceride comprises triglyceride of fatty acids.

[0052] Aspect 3. The method of aspect 1 or 2, wherein the polyol has 2 or more hydroxyl groups.

[0053] Aspect 4. The method of any preceding aspect, wherein the polyol has 3 or more hydroxyl groups.

[0054] Aspect 5. The method of any preceding aspect, wherein the polyol has 4 or more hydroxyl groups.

[0055] Aspect 6. The method of any preceding aspect, wherein the polyol has 5 or more hydroxyl groups.

[0056] Aspect 7. The method of any preceding aspect, wherein the PET comprises virgin PET, or recycled PET or a mixture thereof.

[0057] Aspect 8. The method of any preceding aspect, wherein the non-reactive solvent has one or more aromatic rings.

[0058] Aspect 9. The method of any preceding aspect, wherein the non-reactive solvent comprises xylene.

[0059] Aspect 10. The method of any preceding aspect, wherein the non-reactive solvent comprises toluene.

[0060] Aspect 11. The method of any preceding aspect, wherein the anhydride comprises an acid anhydride of a carboxylic acid.

[0061] Aspect 12. The method of any preceding aspect, wherein the acid anhydride of the carboxylic acid comprises maleic anhydride, phthalic anhydride, or mixtures thereof.

[0062] Aspect 13. The method of any preceding aspect, wherein the second reaction mixture further comprises additional non-reactive solvent.

[0063] Aspect 14. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 30 wt.% or greater, based on total solids weight of the glyceride, polyol, and PET.

[0064] Aspect 15. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 40 wt.% or greater, based on total solids weight of the glyceride, polyol, and PET.

[0065] Aspect 16. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 45 wt.% or greater, based on total solids weight of the glyceride, polyol, and PET.

[0066] Aspect 17. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 50 wt.% or greater, based on total solids weight of the glyceride, polyol, and PET.

[0067] Aspect 18. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 70 wt.% or less, based on total solids weight of the glyceride, polyol, and PET.

[0068] Aspect 19. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 65 wt.% or less, based on total solids weight of the glyceride, polyol, and PET.

[0069] Aspect 20. The method of any preceding aspect, wherein the first reaction mixture comprises the glyceride in an amount of 60 wt.% or less, based on total solids weight of the glyceride, polyol, and PET.

[0070] Aspect 21. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 5 wt.% or greater, based on the total solids weight of the glyceride, polyol, and PET.

[0071] Aspect 22. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 10 wt.% or greater, based on the total solids weight of the glyceride, polyol, and PET.

[0072] Aspect 23. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 15 wt.% or greater, based on the total solids weight of the glyceride, polyol, and PET.

[0073] Aspect 24. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 25 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0074] Aspect 25. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 20 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0075] Aspect 26. The method of any preceding aspect, wherein the first reaction mixture comprises the polyol in an amount of 15 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0076] Aspect 27. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 1 wt.% or greater, based on the total solids weight the glyceride, polyol, and PET.

[0077] Aspect 28. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 10 wt.% or greater, based on the total solids weight of the glyceride, polyol, and PET.

[0078] Aspect 29. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 13 wt.% or greater, based on the total solids weight of the glyceride, polyol, and PET.

[0079] Aspect 30. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 25 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0080] Aspect 31. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 20 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0081] Aspect 32. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 17 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0082] Aspect 33. The method of any preceding aspect, wherein the first reaction mixture comprises the PET in an amount of 15 wt.% or less, based on the total solids weight of the glyceride, polyol, and PET.

[0083] Aspect 34. The method of any preceding aspect, wherein the first reaction mixture comprises the non-reactive solvent in an amount of 0.5 wt.% or greater, based on total solids weight of the first reaction mixture.

[0084] Aspect 35. The method of any preceding aspect, wherein the first reaction mixture comprises the non-reactive solvent in an amount of 1 wt.% or greater, based on total solids weight of the first reaction mixture.

[0085] Aspect 36. The method of any preceding aspect, wherein the first reaction mixture comprises the non-reactive solvent in an amount of 5 wt.% or less, based on total solids weight of the first reaction mixture.

[0086] Aspect 37. The method of any preceding aspect, wherein the first reaction mixture comprises the non-reactive solvent in an amount of 2.5 wt.% or less, based on total solids weight of the first reaction mixture.

[0087] Aspect 38. The method of any preceding aspect, wherein the first reaction mixture comprises the non-reactive solvent in an amount of 1 wt.% or less, based on total solids weight of the first reaction mixture.

[0088] Aspect 39. The method of any preceding aspect, wherein the PET is added to the glyceride and the polyol in one or more charges and in intervals of 10-15 minutes.

[0089] Aspect 40. The method of any preceding aspect, wherein the PET is added to the glyceride and the polyol in two or more charges and in intervals of 10-15 minutes.

[0090] Aspect 41. The method of any preceding aspect, wherein the PET is added to the glyceride and the polyol in three or more charges and in intervals of 10-15 minutes.

[0091] Aspect 42. The method of any preceding aspect, wherein the non-reactive solvent is added to the glyceride, polyol, and PET when the reaction mixture achieves a temperature of 250°C or less.

[0092] Aspect 43. The method of any preceding aspect, wherein the non -reactive solvent is added to the glyceride, polyol, and PET when the reaction mixture achieves a temperature of 240°C or less.

[0093] Aspect 44. The method of any preceding aspect, wherein the non-reactive solvent is added to the glyceride, polyol, and PET when the reaction mixture achieves a temperature of 240°C to 250°C.

[0094] Aspect 45. The method of any preceding aspect, wherein the first reaction mixture is heated until the desired transparency is achieved.

[0095] Aspect 46. The method of any preceding aspect, wherein the desired transparency is transparent or semi-transparent.

[0096] Aspect 47. The method of any preceding aspect, wherein the first reaction mixture is heated for 30 minutes until the desired transparency is achieved.

[0097] Aspect 48. The method of any preceding aspect, wherein the first reaction mixture is heated for 1 hour until the desired transparency is achieved.

[0098] Aspect 49. The method of any preceding aspect, wherein the first reaction mixture is heated for 1.5 hours until the desired transparency is achieved.

[0099] Aspect 50. The method of any preceding aspect, wherein the first reaction mixture is heated until the alkyd precursor material has achieved homogeneity.

[0100] Aspect 51. The method of any preceding aspect, wherein the first reaction mixture is heated until the alkyd precursor material comprises a molar ratio of 40 to 60% GARE to GALE.

[0101] Aspect 52. The method of any preceding aspect, wherein the first reaction mixture is heated until the alkyd precursor material comprises a molar ratio of 50 to 50% GARE to GALE.

[0102] Aspect 53. The method of any preceding aspect, wherein the first reaction mixture is heated until the alkyd precursor material comprises a molar ratio 60 to 40% GARE to GALE.

[0103] Aspect 54. The method of any preceding aspect, wherein the alkyd precursor material contains a molar ratio of GARE to GALE of 60% to 40% after heating for 90 minutes or less.

[0104] Aspect 55. The method of any preceding aspect, wherein the alkyd precursor material contains a molar ratio of GARE to GALE of 60% to 40% after heating for 60 minutes or less.

[0105] Aspect 56. The method of any preceding aspect, wherein the alkyd precursor material contains a molar ratio of GARE to GALE of 40% to 60% after heating for 90 minutes or less.

[0106] Aspect 57. The method of any preceding aspect, wherein the alkyd precursor material contains a molar ratio of GARE to GALE of 40% to 60% after heating for 60 minutes or less.

[0107] Aspect 58. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 1,500 g / mol or greater as determined according to Gel Permeation Chromatography .

[0108] Aspect 59. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of l,600g / mol or greater as determined according to Gel Permeation Chromatography .

[0109] Aspect 60. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of l,700g / mol or greater as determined according to Gel Permeation Chromatography .

[0110] Aspect 61. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of l,800g / mol or greater as determined according to Gel Permeation Chromatography .

[0111] Aspect 62. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 1 ,900g / mol or greater as determined according to Gel Permeation Chromatography .

[0112] Aspect 63. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 2,000 g / mol or greater as determined according to Gel Permeation Chromatography .

[0113] Aspect 64. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 3,000 g / mol or less as determined according to Gel Permeation Chromatography .

[0114] Aspect 65. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 2,700 g / mol or less as determined according to Gel Permeation Chromatography .

[0115] Aspect 66. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 2,500 g / mol or less as determined according to Gel Permeation Chromatography .

[0116] Aspect 67. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 2,100 g / mol or less as determined according to Gel Permeation Chromatography .

[0117] Aspect 68. The method of any preceding aspect, wherein the alkyd precursor material has a Mw of 1,000 g / mol to 3,000 g / mol as determined according to Gel Permeation Chromatography .

[0118] Aspect 69. The method of any preceding aspect, wherein the alkyd precursor material has an acid number below 2.

[0119] Aspect 70. The method of any preceding aspect, wherein the alkyd precursor material has an acid number below 1.5.

[0120] Aspect 71. The method of any preceding aspect, wherein the alkyd precursor material has an acid number below 1.

[0121] Aspect 72. The method of any preceding aspect, wherein the alkyd precursor material has an acid number of 0 to 5.

[0122] Aspect 73. The method of any preceding aspect, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 0.25.

[0123] Aspect 74. The method of any preceding aspect, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 0.50.

[0124] Aspect 75. The method of any preceding aspect, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 0.75.

[0125] Aspect 76. The method of any preceding aspect, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 1.

[0126] Aspect 77. The method of any preceding aspect, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 1.25.

[0127] Aspect 78. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 5 wt.% or greater, based on the total solids weight of the second reaction mixture.

[0128] Aspect 79. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 10 wt.% or greater, based on the total solids weight of the second reaction mixture.

[0129] Aspect 80. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 15 wt.% or greater, based on the total solids weight of the second reaction mixture.

[0130] Aspect 81. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 25 wt.% or less, based on the total solids weight of the second reaction mixture.

[0131] Aspect 82. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 20 wt.% or less, based on the total solids weight of the second reaction mixture.

[0132] Aspect 83. The method of any preceding aspect, wherein the second reaction mixture comprises the anhydride in an amount of 15 wt.% or less, based on the total solids weight of the second reaction mixture.

[0133] Aspect 84. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 200°C or greater.

[0134] Aspect 85. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 210°C or greater.

[0135] Aspect 86. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 220°C or greater.

[0136] Aspect 87. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 240°C or less.

[0137] Aspect 88. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 225 °C or less.

[0138] Aspect 89. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 220°C or less.

[0139] Aspect 90. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 215°C or less.

[0140] Aspect 91. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 210°C or less.

[0141] Aspect 92. The method of any preceding aspect, wherein the second reaction mixture is heated to a temperature of 205 °C or less.

[0142] Aspect 93. The method of any preceding aspect, wherein the second reaction mixture may be heated until the acid value of the mixture is 15 or less as measured according to ASTM D 1639-90 (1996).

[0143] Aspect 94. The method of any preceding aspect, wherein the second reaction mixture may be heated until the acid value of the mixture is 10 or less as measured according to ASTM D 1639-90 (1996).

[0144] Aspect 95. The method of any preceding aspect, wherein the second reaction mixture may be heated until the acid value of the mixture is 5 or less as measured according to ASTM D 1639-90 (1996).

[0145] Aspect 96. The method of any preceding aspect, wherein the second reaction mixture may be heated until the acid value of the mixture is 1 or less as measured according to ASTM D 1639-90 (1996).

[0146] Aspect 97. The method of any preceding aspect, wherein the second reaction mixture achieves the desired acid value in 2 hours or greater.

[0147] Aspect 98. The method of any preceding aspect, wherein the second reaction mixture achieves the desired acid value in 6 hours or less.

[0148] Aspect 99. The method of any preceding aspect, wherein the second reaction mixture achieves the desired acid value in 5 hours or less.

[0149] Aspect 100. The method of any preceding aspect, wherein the second reaction mixture achieves the desired acid value in 4 hours or less.

[0150] Aspect 101. The method of any preceding aspect, wherein the second reaction mixture achieves the desired acid value in 3 hours or less.

[0151] Aspect 102. An alkyd produced by the method of any preceding aspect.

[0152] Aspect 103. The alkyd of aspect 102, wherein the alkyd has an acid value of 15 mg KOH / g or lower.

[0153] Aspect 104. The alkyd of aspects 102-103, wherein the alkyd has an acid value of 10 mg KOH / g or lower.

[0154] Aspect 105. The alkyd of aspects 102-104, wherein the alkyd has an acid value of 5 mg KOH / g or lower.

[0155] Aspect 106. The alkyd of aspects 102-105, wherein the alkyd has an acid value of 1 mg KOH / g or lower.

[0156] Aspect 107. The alkyd of aspects 102-106, wherein the alkyd has an acid value of 0 mg KOH / g.

[0157] Aspect 108. The alkyd of aspects 102-107, wherein the alkyd has an acid value of 0 mg KOH / g to 10 mg KOH / g.

[0158] Aspect 109. The alkyd of aspects 102-108, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.01.

[0159] Aspect 110. The alkyd of aspects 102-109, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.04.

[0160] Aspect 111. The alkyd of aspects 102-110, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.10.

[0161] Aspect 112 The alkyd of aspects 102-111, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.14.

[0162] Aspect 113. The alkyd of aspects 102-112, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.16.

[0163] Aspect 114. The alkyd of aspects 102-113, wherein the Mw of the alkyd is 120,000 g / mol or greater.

[0164] Aspect 115. The alkyd of aspects 102-114, wherein the Mw of the alkyd is 110,000 g / mol or greater.

[0165] Aspect 116. The alkyd of aspects 102-115, wherein the Mw of the alkyd is 100,000 g / mol or greater.

[0166] Aspect 117. The alkyd of aspects 102-116, wherein the Mw of the alkyd is90,000 g / mol or greater.

[0167] Aspect 118. The alkyd of aspects 102-117, wherein the Mw of the alkyd is80,000 g / mol or greater.

[0168] Aspect 119. The alkyd of aspects 102-118, wherein the Mw of the alkyd is50,000 g / mol or greater.

[0169] Aspect 120. The alkyd of aspects 102-119, wherein the Mw of the alkyd is50,000g / mol to 150,000 g / mol.

[0170] Aspect 121. The alkyd of aspects 102-120, wherein the Mw of the alkyd is 80,000 g / mol to 150,000 g / mol.

[0171] Aspect 122. The alkyd of aspects 102-121, wherein the alkyd comprises over 50 wt.% of GARE where wt.% is based on the total weight of the alkyd.

[0172] Aspect 123. The alkyd of aspects 102-122, wherein the alkyd comprises no more than 60 wt.% of GARE where wt.% is based on the total weight of the alkyd.

[0173] Aspect 124. The alkyd of aspects 102-123, wherein the alkyd comprises 1 wt.% to 25 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0174] Aspect 125. The alkyd of aspects 102-124, wherein the alkyd comprises 1 wt.% to 20 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0175] Aspect 126. The alkyd of aspects 102-125, wherein the alkyd comprises 1 wt.% to 15 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0176] Aspect 127. The alkyd of aspects 102-126, wherein the alkyd comprises 10 wt.% to 20 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd

[0177] Aspect 128. The alkyd of aspects 102-127, wherein the alkyd comprises 10 wt.% to 17 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0178] Aspect 129. The alkyd of aspects 102-128, wherein the alkyd comprises 10 wt.% to 15 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0179] Aspect 130. The alkyd of aspects 102-129, wherein the alkyd comprises 13 wt.% to 25 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0180] Aspect 131. The alkyd of aspects 102-130, wherein the alkyd comprises 13 wt.% to 20 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0181] Aspect 132. The alkyd of aspects 102-131, wherein the alkyd comprises 13 wt.% to 17 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0182] Aspect 133. The alkyd of aspects 102-132, wherein the alkyd comprises 13 wt.% to 15 wt.% of the PET moieties, where wt.% is based on the total weight of the alkyd.

[0183] Aspect 134. A coating composition comprising the alkyd of aspects 102-133, wherein the coating composition is Set to touch in 90 minutes + / - 20 minutes.

[0184] Aspect 135. The coating composition of aspect 134, wherein the coating composition has a Tack free time of 90 to 120 minutes.

[0185] Aspect 136. The coating composition of aspects 134-135 wherein the coating composition has Dry hard time of 6 hours + / - 30 minutes.

[0186] Aspect 137. The coating composition of aspects 134-136, wherein the coating composition contains rPET in an amount of 20 wt.% or greater with wt.% based on the total solid weight of the composition.

[0187] Aspect 138. The coating composition of aspects 134-137, wherein the coating composition contains rPET in an amount of 15 wt.% or greater with wt.% based on the total solid weight of the composition.

[0188] Aspect 139. The coating composition of aspects 134-138, wherein the coating composition contains rPET in an amount of 10 wt.% or greater with wt.% based on the total solid weight of the composition.

[0189] Aspect 140. The coating composition of aspects 134-139, wherein the coating composition contains rPET in an amount of 5 wt.% or greater with wt.% based on the total solid weight of the composition.

[0190] Aspect 141. The coating composition of aspects 134-140, wherein the coating composition contains rPET in an amount of 1 wt.% to 25 wt.% with wt.% based on the total solid weight of the composition.

[0191] Aspect 142. The coating composition of aspects 134-141, further comprising one or more additives and / or solvent.

[0192] Aspect 143. The coating composition of aspects 134-142, wherein the additive comprises a drier, a filler, a pigment, and / or a dye.

[0193] Aspect 144. A coated substrate comprising a coating layer deposited from the coating composition of any of aspects 134-143.

[0194] Aspect 145. The coated substrate of aspect 144, wherein the substrate is an architectural component.

[0195] Aspect 146. The coated substrate of aspects 144-145, wherein the substrate comprises a roadway substrate.

[0196] Aspect 147. The coated substrate of aspects 144-146, wherein the roadway substrate comprises concrete or asphalt.

[0197] Aspect 148. The coated substrate of aspects 144-147, wherein the substrate comprises wood.

[0198] Aspect 149. The coated substrate of aspects 144-148, wherein the substrate comprises metal.

[0199] Aspect 150. The coated substrate of aspects 144-149, wherein the substrate comprises wood and / or metal.EXAMPLES

[0200] The following examples are intended to illustrate the present disclosure and should not be construed as limiting the present disclosure in any way. Unless otherwise specified, “parts” means parts by weight and “percent” means percent by weight.Example 1 and Comparative Examples 1 and 2Step 1: Alcoholysis / Glycolysis

[0201] Examples 1 and 2 and Comparative Examples 1 and 2 were prepared using the amounts shown in Table 1 (Step 1) and 2 (Step 2). A reactor equipped with a thermometer, stirrer, heater, condenser and Dean Stark trap was charged with soybean oil, pentaerythritol, glycerin and 0.02-0.05 parts of dibutyltin oxide and heated to 180°C. Once at 180°C, rPET was added in 10-minute intervals three times, and the vessel gradually heated to 250°C; the reaction proceeded for one hour. Then 0.75% w / w of xylene was added with respect to the total amount of solid reactants in the reactor with high stirring being maintained. After one hour at 250°C, a clear homogeneous solution of rPET-monoglyceride was obtained. About 1% of water, based on the total amount of solids, was stripped out from the reactor. A solubility test was conducted to confirm the reaction was completed. A homogeneous solution was obtained without any rPET or glyceride / oil precipitating out. The reactor was allowed to cool to 180°C. Hydroxy values, acid values and Mw for each of the reaction products are also reported in Table 1.Step 2: Polyesterification

[0202] Upon cooling, phthalic anhydride and maleic anhydride were added to the reactor and heated to 210 -215°C. Xylene was added. The reaction was allowed to proceed for3-3.5 hours. The amount of water removed during the polyesterification reaction by the azeotrope formation with xylene was 1-2% of the total mass of the reaction mixture. To confirm the reaction was completed, the acid number and Gardner viscosity were measured for samples taken from the reactor and diluted to 55% solid content using mineral spirits as a solvent. An acid value below 10 mg KOH / g and a Gardner viscosity of U-V in a Gardner scale were specified as the standard target values. The final 100% solid alkyd was diluted to 55% using mineral spirits. The properties of the final alkyd are described in Table 2.TABLE 1TABLE 2COATING EXAMPLESDrying Time

[0203] The alkyd of Example 1 (made from 15.8% rPET with xylene in Step 1), Example 2 (made from 20% rPET with xylene in Step 1), Comparative Example 1 (conventional alkyd), and Comparative Example 2 (made from 15.8% rPET without xylene in Step 1) were diluted to 55 wt.% of total solids in 45% of mineral spirits. A dryer system was added. The coating compositions were applied to glass panels and tested using the BYK Drying Time Recorder according to ASTM D 1640 (2022). The dryness test results of the coatings as measured using the BYK Drying Time Recorder, obtained as described above, are reported in Table 3.TABLE 3H:M (Hour:Minutes)

[0204] Although Example 1 was moderately slower in reaching the Set to touch time, it had a faster Tack free test time and Dry hard time as compared to the comparative examples. Although Example 2 was moderately slower in reaching Set to touch time and Tack free time, it had a faster Dry hard time as compared to Comparative Example 1 , which did not contain rPET or use xylene during the alcoholysis / glycolysis reaction. The addition of xylene during the alcoholysis / glycolysis reaction produced an alkyd with faster drying properties than without.Corrosion Resistance

[0205] Steel panels coated with the coating compositions of Example 1, Comparative Example 1 and Comparative Example 2 were evaluated for corrosion resistance according to ASTM B 117-18 (2018).

[0206] FIG. 5 shows the results of the salt spray test after 48 hours, 96 hours, 144 hours, 192 hours and 240 hours. These results show that incorporation of recycled material into an alkyd results in corrosion resistance comparable, if not better than an alkyd without (Example 1 versus Comparative Example 1 ) and also that the alkyd produced according to the present disclosure (i.e. with xylene in the first step) resulted in better corrosion resistance than an alkyd made without xylene in the first step (Example 1 versus Comparative Example 2).

Claims

What is claimed is:

1. A method for making an alkyd with polyethylene terephthalate (“PET”) comprising: an alcoholysis / glycolysis reaction; and a poly esterification reaction; wherein the alcoholysis / glycolysis reaction occurs by heating a first reaction mixture comprising a glyceride; a polyol having 2 or more, 3 or more, 4 or more or 5 hydroxyl groups; PET, virgin PET, recycled PET or a mixture thereof; and a non-reactive solvent having one or more aromatic rings, to form an alkyd precursor material; and wherein the polyesterification reaction occurs by heating a second reaction mixture comprising the alkyd precursor material, an anhydride and, optionally, additional non-reactive solvent to a temperature of 240°C or less whereby the second reaction mixture undergoes polymerization to form an alkyd.

2. The method of claim 1, wherein the glyceride comprises triglyceride of fatty acids.

3. The method of any preceding claim, wherein the non -reactive solvent comprises xylene and / or toluene.

4. The method of any preceding claim, wherein the anhydride comprises maleic anhydride, phthalic anhydride, or a mixture thereof.

5. The method of any preceding claim, wherein the first reaction mixture comprises a glyceride in an amount of 30 wt.% or greater; a polyol in the amount of 5 wt.% or greater; virgin PET or recycled PET, or a mixture thereof, in the amount of 1 wt.% or greater; and a non-reactive solvent in the amount of 5 wt.% or less; and wherein the second reaction mixture comprises anhydride in an amount of 5 wt.% or greater.

6. The method of any preceding claim, wherein the PET is added to the glyceride and the polyol in one or more charges, or two or more charges, or three or more charges and in intervals of 10-15 minutes.

7. The method of any preceding claim, wherein the non-reactive solvent is added to the glyceride, polyol and PET when the reaction mixture achieves the temperature from 240°C to 250°C.

8. The method of any preceding claim, wherein the first reaction mixture is heated until the desired transparency is achieved, and / or when the alkyd precursor material has achieved homogeneity.

9. The method of any preceding claim, wherein the alkyd precursor material contains a molar ratio of GARE to GALE of 60% to 40 % or 40% to 60% or any number within those ranges after heating for 90 minutes or less.

10. The method of any preceding claim, wherein the alkyd precursor material has a Mw from 1,000 g / mol to 3,000 g / mol wherein Mw is determined according to Gel Permeation Chromatography.

11. The method of any preceding claim, wherein the alkyd precursor material has an acid number from 0 to 5.

12. The method of any preceding claim, wherein the alkyd precursor material exhibits a plurality of peaks associated with GARE in the range of 43.1 to 44.0 ppm and a plurality of peaks associated with GALE in the range of 44.2 to 45.4 ppm, on a spectra obtained from C13 Nuclear Magnetic Resonance (NMR) spectroscopy and the ratio of signal integration of 43.1 to 44.0 ppm to signal integration of 44.2 to 45.4 ppm is at least 0.25.

13. An alkyd produced by the method of any preceding claim.

14. The alkyd of claim 13, wherein the alkyd has an acid value from 0 mg KOH / g to 10 mg KOH / g.

15. The alkyd of any preceding claim, wherein the alkyd exhibits a plurality of peaks associated with GARE in the range of 3.6 to 3.7 ppm and GALE in the range of 3.8 to 3.9 ppm, on a spectra obtained from Hl Nuclear Magnetic Resonance (NMR) spectroscopy when the ratio of signal integration between 3.0 to 4.2 ppm is at least 0.01.

16. The alkyd of any preceding claim, wherein the Mw of the alkyd is from 50,000g / mol to 150,000 g / mol.

17. The alkyd of any preceding claim, wherein the alkyd comprises no more than 60 wt.% of GARE, where weight percent is based on the total weight of the alkyd.

18. The alkyd of any preceding claim, wherein the alkyd comprises 1 wt.% to 25 wt.% of PET moieties, where wt.% is based on the total weight of the alkyd.

19. A coating composition comprising the alkyd of any of claims 13 to 18, wherein the coating composition is Set to touch in 90 minutes + / - 20 minutes; and / or is Tack free time in 90 to 120 minutes; and / or is Dry hard time in 6 hours + / - 30 minutes.

20. The coating composition of claim 19, wherein the coating composition contains rPET in an amount of 5 wt.% or greater with wt.% based on the total solid weight of the coating composition.

21. A coated substrate comprising a coating layer deposited from the coating composition of any of claims 19 to 20.

22. The coated substrate of claim 21 , wherein the substrate is an architectural component.

23. The coated substrate of claim 21, wherein the substrate comprises a roadway substrate.

24. The coated substrate of claim 21 , wherein the roadway substrate comprises concrete and / or asphalt.

25. The coated substrate of claim 21, wherein the substrate comprises wood and / or metal.

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