MXPA98004790A - Hidroxifuncional polyesters of low molecular weight for revestimien - Google Patents

Abstract

The present invention relates to a polyester composition having a number average molecular weight (Mn) of between about 500 and about 1000, a weight average molecular weight (Mn) of between about 600 and about 2000, a polydispersity below about 2. , preferably less than about 1.8, hydroxyl functionality of between about 160 and about 260, and an acid number less than about 10, less than about 5% of the OH groups of the polyester are pendent, the remainder is terminal. Between about 10 and about 50% by weight of the monomers that are used to form the polyester composition are anhydrides having the formula: wherein R1 is a non-aromatic, saturated or unsaturated hydrocarbon chain having between 6 and 30 carbon atoms, R2 is hydrogen or a non-aromatic saturated or unsaturated hydrocarbon having between 1 and 8 carbon atoms, and R1 and R2 have in total, between 8 and 30 carbon atoms

Description

HIDROXIFUNCIONAL POLYESTERS OF LOW MOLECULAR WEIGHT FOR COATINGS The present invention is directed to low molecular weight polyesters having hydroxyl functionality, whereby it can be formulated in suitable coating polymers with OH reactive crosslinking agents. More specifically, the invention is directed to these polymers having long hydrocarbon side chains which act to reduce the viscosity of the coating compositions and provide coatings with improved flexibility.

Background of the Invention U.S. Patent Nos. 4,403,093 and No. 4,659,778, the teachings of each of which are incorporated herein by reference, show the growth or step-by-step increase of the polyesters. In step-by-step increment, each step of the chain elongation is carried out substantially until completion before another step of elongation of the polymer chain. The low molecular weight polyesters produced by this step-wise chain elongation are formulated with suitable crosslinking agents to form coating compositions.

Of specific interest in the present are the hydroxy-functional or molecular weight polyester compositions formed by reacting a multifunctional alcohol (polyol) with carboxylic anhydrides in relative equivalents to provide a chain composition terminated in caroxyl, and subsequently the reaction of the carboxyl-terminated chain composition with sufficient levels of oxirane-containing compound (s) to obtain a polyester terminated in idroxilw. Although the polyester has the substantial terminal functional nidroxyl, it does not substantially contain internal or pending idroxyl functionality. Here, these polyester compositions are produced with low viscosities whereby it is possible to formulate coating compositions with high content of solids with low VOC. Surprisingly, the coatings formed from the polyesters of the present invention provide cured coating compositions with improved flexibility. With the coating in liquid form, improved pigment wetting is observed through the use of the polyesters according to the invention. The aforementioned US Patent No. 4,403,093, by Hartman et al., Discloses a polyester formed by reacting an anhydride with a diol to obtain a seruiéstei and subsequently reacting the half ester with a difunctional oxirane compound to form a hydroxyl terminated polyester. The difunctional oxirane is internally incorporated within the polyester chain by providing two hydroxyl groups pendant from the chain, ie, they are non-terminal hydroxyl groups. The polyesters produced in this patent are crosslinked to form coatings. For the purpose of the present invention, where a highly flexible coating is desired, the pendant hydroxyl groups are undesirable because they give rise to high crosslink density which reduces the flexibility of the cured coating which is formed from the polyester and a crosslinker. The aforementioned U.S. Patent No. 4,659,778 also shows the low molecular weight polyesters that can be crosslinked. This patent, however, is specifically shown against the use of high molecular weight anhydrides such as dodecenylsuccinic anhydride. Applicants herein find that these high molecular weight anhydrides when incorporated into short polymers of low dispersity polymers provide coating compositions with low viscosity, excellent pigment wetting and provide coating films with superior flexibility.

SUMMARY OF THE INVENTION In accordance with the invention, a poεter composition having a number average molecular weight (M) is provided., - between about 500 and about 1000, a weight average molecular weight (mw) of between about 600 and about 2000, a poly dispersity of below 2, preferably below about 1.3, hydroxyl functionality of between 2 and 3, Hydroxyl number of between about 160 and about 260, preferably between about 180 and about 260, and an acid number less than 10 and preferably below about 5. Of the hydroxyl groups of the polyester, less than 5% are slopes of the string (that is, not terminals). Between about 10 and about 50% by weight of the monomers used to form the composition polyester are anhydrides having the formula: O O O 11 / \ l C C I I R ^ CH-CH-R wherein R1 is a non-aromatic, saturated or unsaturated hydrocarbon chain having between 6 and 30 carbon atoms, R2 is hydrogen or a saturated or unsaturated non-aromatic hydrocarbon having between I and 8 carbon atoms, and R "and R ~ have , in totai, between 8 and 30 carbon atoms A preferred monomer of the formula (I) is the dodecenylsuccinic anhydride (DD? A) alternatively named dihydride-3- (tetrapropenyl) -2, -furandione), in general available as a mixture of isomers Polyester, alone or in admixture with other polyesters, together with a suitable hydroxyl-reactive crosslinking agent, such as an aminoplast resin or a block isocyanate, is useful as a coating composition.

Detailed description of certain preferred embodiments The polyester compositions according to the invention are formed in a polycondensation reaction between the polyols, mainly diols, and the anhydrides of the dicarboxylic acids with dicarboxylic acids in amounts sufficient to provide the polyesters at least partially terminated with carboxylic acid functionality followed by reaction with mono oxirane compounds to produce the low molecular weight hydroxyl polyesters and low polydispersity. The polyesters that are formed are substantially linear, the products being mainly diols and anhydrides of dicarboxylic acids and crowned by monofunctional epoxy molecules. However, a small amount of triols, for example, trimethylol propane (TMP) can be used to provide some branching in some of the polyester chains. Preferably not more than about 10 or mole, more preferably not more than about 5c mole of the total polyol content consists of triols. The polystyres according to the present invention with the lower chain lengths and lower polydispersity can conveniently be formed in a stepwise reaction, ie, by the reaction, in a first step, of a polyol or mixture of polyols with an anhydride or mixture of anhydrides to approximately one mole of anhydride for the hydroxyl equivalent of the polyol (ES) to form a carboxyl-terminated chain composition, and in a second step, the reaction of the carboxyl-terminated chain composition to a compound which have oxirane mono functionality or compound mixture having mono oxirane functionality in at least one equivalent of the carboxylic acid functionality of the intermediate polyester chain. However, the polyesters according to the invention can be produced in a simple polycondensation reaction between anhydride (s) and polyol (s) in a COOH / OH ratio of between about 2.00 and about 0.625 to form a polyester having at least minus some functionality of terminal carboxylic acid and subsequently the terminal coronation of the chain with a compound having mono oxirane (mono epoxy) functionality. Among the polyols that can be used are those containing from about 2 to 20 carbon atoms. Preferred are aliphatic polyols, particularly aliphatic diols or triols, more preferably those containing from 2 to 10 carbon atoms. Examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1-butanediol, 1,5-pentanediol, glycerol, 1, 2, 3-butanetriol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 2- methyl-l, 3-propanediol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolethane, trimethylolpropane, triethylene glycol, 2,2,4-trimethylpentane-1,3-diol, 2,2-dimethyl-3-hydroxypropionate. 2,2-dimethyl-3-hydroxypropyl and 1,4-cyclohexanedimethanol. Preferred are aliphatic diols or triols which are selected from the classes consisting of neopentyl glycol, 2,2,4-trimethylpentan-1,3-diol, 2,2-dimethyl-3-hydroxypropionate 2,2-dimethyl-3. -hydroxypropyl, diethylene glycol, 2-methyl-l, 3-propanediol, dipropylene glycol, 1,6-hexanediol and trimethylol propane. As noted, triols, such as trimethylol propane, can be used at low levels to provide branching. Higher functionality polyols such as tetroles can be used but are not preferred, and very low levels are used if they are used. An example of tetro! it would be l 7t, 3, 4-butane tetrol. The anhydrides of the formula (I) such as DDSA and octadecenylsuccinic anhydride in the low molecular weight polyesters of the present invention provide low viscosity to the liquid polyester compositions and improved flexibility of the cured coatings. The anhydrides of the formula (I) can be used as the sole anhydride (s), but they are commonly used together with other anhydrides such as succinic anhydride, methylsuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, clorendric anhydride, itaconic anhydride, citraconic anhydride and maleic anhydride. The anhydrides of the formula (I) comprise between about 10 and about 50% by weight of the monomers that are used to form the polyester composition, preferably between about 20 and about 40: by weight. The total content of the anhydride monomer varies in a range of 0.3: 1.00 to 1.00: 1.00, on a molar basis for the hydroxyl equivalent of the polyol content, whereby the anhydride content reacts with the polyol content in an ester forming reaction to provide a chain composition terminated in carboxyl. The molar ratio of the anhydride content to the hydroxyl equivalent of the polyol content can vary in a range of 0.3: 1.00 to 1.00: 1.00, preferably in a range of 0.90: 1.00 to 1.00: 1.00, and most preferably in a range of 0.95: 1.00 to 1.00: 1.00. Oxirane compounds suitable for the reaction with the carboxyl terminated chain composition are monofunctional epoxies, including, but not limited to: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, lignin oxide, styrene oxide , butylglycidyl ether, glycidyl ether and mixtures thereof. The ratio of the oxirane compounds to the anhydride compounds used to form the polyester composition varies over a molar ratio range of 0.020: 1,000, preferably over a range of 0.080: 1,000, preferably a molar ratio of between about 0.9: 1 and approximately 1.1: 1. The lower molecular polyester compositions [sic] of the present invention are formed in two steps. The first step is the reaction of the anhydride with the polyol to form the carboxyl-terminated chain composition and the second step is the reaction of the carboxyl-terminated chain composition with oxirane. This results in a short chain polyester with terminal hydroxyl functionality. The step-by-step formation of the polyester compositions in this manner, including the use of catalysts to improve the respective reactions, is well known in the art, for example, in the above reference to US Patent No. 4, 403, 093. result of the polyester composition that is going to be formed in this way in steps, the chains are short, that is, the low molecular weight and the polydispersity is low. In theory, for example, the use of a single diol species, a single anhydride species in a 1: 1 mol / OH equivalent ratio, and a single oxirane species in a 1: 1 mol / COOH equivalent ratio, would form long unit lengths. 5 monomers of polymer chains, including a central diol monomer, anhydride-side monomers and terminal oxirane monomers. However, in practice, mixtures of diols, anhydride mixtures and optionally mixtures of oxiranes are used, including monomers, particularly polyols or anhydrides such as trimellitic anhydride, with functionality greater than two. Accordingly, the composition of the individual polyester chains will generally vary somewhat in the monomer composition and molecular weight. Although some monomers with functionality greater than 2 can be used, it is highly desired that the functionality of the polyester chain does not exceed 3, lest the crosslink density be too high, resulting in brittleness. To form a curacomposition, such as a coating composition, the polyester compositions, as already described, are combined with a crosslinking agent. The crosslinking agent is one which is capaof reacting the active hydrogens (mainly OH hydrogens) in the polyester to give a thermo-stacomposition after curing. Examples of suitacrosslinking agents are aminoplasts and polyisocyanates including block polyisocyanates. The aminoplasts are obtained by the condensation reaction of formaldehyde with an amine or an amide. The most common amines or amides are melamine, urea or benzoguanamine. However, condensation with other amines or amides may be employed. Although the most commonly used aldheido is formaldehyde, it is possito use other aldehydes such as acetaldehyde, crotonaldehyde, benzaldehyde and furfural. The amino plasto contains similar methylol or alkylol groups, and preferably, at least a portion of these alkylol groups are etherified by reaction with alcohol to provide resins soluin organic solvents. Any monohydric alcohol can be used for this purpose including alcohols such as methanol, ethanol, butanol and hexanol. Preferably, the ammoplastics used are condensed melamine-, urea- or benzoguanamine-formaldehyde etherified with an alcohol containing 1 to 4 carbon atoms, such as methanol, ethanol, butanol or mixtures thereof. The amount of the aminoplast that is used is from about 10 to 70. by weight, preferably from 15 to 50% by weight, based on the total weight of the amincplast and the polyester. Amounts less than 10% by weight will usually result in insufficient curing, while amounts greater than 70% by weight will offer no particular benefit. The block polyisocyanates and polyisocyanates can also be used as curing agents. Examples of suitapolyisocyanates include monomeric polyisocyanates such as toluene diisocyanate and 4,4 '-methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate and NCO prepolymers as the reaction products of the monomeric polyisocyanate as those mentioned above with the polyesters or polyether polyols. A particularly useful isocyanate is the biuret of the 1,6-hexamethylene diisocyanate availacommercially from Bayer® AG as Desmodur® N.

The polyethylene can optionally be block. Examples of suitable blocking agents are those materials that would be separated into blocks at elevated temperatures such as caprolactam. The block isocyanates that can be used to form stable systems of a package. Polyfunctional isocyanates with free isocyanate groups can be used to form two-pack systems at room temperature. In these systems, the polyester and curing agent i = ocyanate are mixed before application. The amount of the isocyanate or block polyisocyanate curing agent that is used can vary from about 0.2 to 1.5, preferably from 0.3 to 1.3, equivalents of NCO per equivalent of active hydrogen in the polyester. Depending on the weight, the ratio of isocyanate or isocyanate in curative blocks to polyester is generally within the ranges of weight ratios of the curative aminoplast to the polyester stated above. Because polyester compositions incorporating sufficient amounts of anhydride monomer of the formula (I) have low viscosities, solutions with high solids content of the polyesters in organic solvent can be formed and used in coating compositions. This produces coating compositions with low VOCs.

The coating compositions with high solids content preferably contain more than 50? of non-volatile solids by volume and more preferably containing more than 60% volatile solids by volume. In addition to the polyester oligomer and optionally the crosslinking agent, the high solids coating composition may optionally contain other hydroxyl functional polymers, pigment, liquid diluent, plasticizer, antioxidants. - UV light absorbers, surfactants, flow control agents. , as is well known in the art. Examples of fluidity controlling agents are cross-linked polymeric micro particles as described in U.S. Patent No. 4,147,688. The coating compositions employing the polyesters of the present invention are especially suitable for coil and spray coating application, although it is possible to use, if desired, other conventional coating methods including brushing, dipping and fluid coating. Normal spray techniques and equipment are used. The high solids coatings used by the polyesters of the present invention can be applied on almost any substrate including wood, metal, glass, cloth, plastic, foams and the like, as well as various primers. The coating compositions employing the polyesters of the present invention are useful for a wide range of applications. These can be used to coat automotive parts such as car bodies and truck cabins. They can also be used for other coating applications as coatings for appliance parts such as refrigerators and washing machines. In general, the thicknesses of the coating will vary depending on the desired application. In general, coatings from about 0.1 to 5 mils (0.0254 mm to 0.127 mm) have been found useful in most applications, and coatings from about 0.8 to 1.2 mils (0.2032 to 2.59 mm) have been found most useful.

After application to the substrate, the coatings are cured. The curing is usually carried out at temperature from about 100 ° to 260 ° C, and in most cases, the curing period is from about 15 seconds to about 30 minutes. Higher or lower temperatures with correspondingly longer or shorter times may be used, although the exact best curing period will depend on the nature of the substrate, as well as the specific components used in the process. formulation of the coating compositions. If a coating is applied on a coil line, the composition is usually cured in a coil oven with a temperature and sealing time determined in accordance with the specific coating composition. With aminoplast curing agents, acidic catalysts can be used, if desired, as these allow the use of lower temperature and shorter times for curing. The polyester compositions of the present invention can be used as the polyester component alone of a coating composition, and the coatings formed from this composition exhibit surprisingly good flexibility. The polyester compositions of the present invention are also advantageously used as additives for polyester coating compositions, such as those used in coil coating operations. In polyester coating compositions, the polyesters will usually have number average molecular weights of between about 2000 and about 3000 and HO rates between about 30 and about 50. With the use of some polyesters such as the main polyester, between about 70 and about 90% by weight of the total content of the polyester, together with a coating composition according to the invention as a minor polyester, ie, between about 10 and about 20% by weight, certain advantages are achieved. The solids levels of the coating can be raised, better wetting of the pigment is observed and surface defects of the applied and cured coating are eliminated or suppressed. The invention will also be described in relation to the following examples. Unless otherwise indicated, all parts are by weight.

Example 1 Polyester 1 is formulated as follows (percentages by weight based on 100% solids, 99.98% of which are monomeric components of polyester): 1. MP Diol * (Arc) monomer 0.50 2. TMP monomer 5.19 3. Italic monomeric anhydride 31.45 4. HHPA ^ monomer 0.50 . 1, 6-Hexanediol monomer 12.00 6. DDSA "'' monomer 30.60 7. Trifenil phosphite 0.02 oxidation inhibitor 8. Solvent Butyl Acetate 15.12 9. catalyst dimethyl benzylamine 0.24 . Propylene oxide monomer 19.50 11 butyl acetate solvent 2.53 -2-methyl-l, 3-propanediol-hexahydrophthalic anhydride ^ dodecenyl anhydride = uccinic (Milliken) Load of solids 100o in weight Theoretical losses - Solids yield 100.00 Solution yield 117.65 The cooling water was applied to a reactor. Components 1-7 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65-80 ° C to melt the components. The start of an exotherm was observed. The cooling was so necessary to keep the temperature below 140-145 ° C. The reaction mixture was maintained for 15 minutes at the peak of the exotherm. The reaction mixture was cooled to 105-115 ° C and components 8 and 9 were added. The mixing was for 15 minutes and the temperature was adjusted to 100 ° C. The acid number and viscosity were measured for this first stage. With the reaction mixture at 100 ° C, component 10 was added as fast as possible. The temperature li > rose to 115-120 ° C was maintained until the acid number was reduced to 1.7-4.3. (If necessary, add additional propylene oxide (in excess) to achieve the desired acidity index).

The properties of the polyester composition are as follows: Viscosity (at 85 solids) U-W Non-volatile materials ~ 85 ± 1 Solvent butyl acetate Color 6 max. IA / NV (acidity index, in 2-5 solids) Weight per gallon (WPG) 9.05 ± 00.10 IOH / NV (hydroxyl index based on 200 ± 15 solids) NV transparent appearance (non-volatile volume) 81.5% Flammability temperature 27.8 ° C Example 2 A white coating composition utilizing polymer 1 is formulated as follows: Component Function Lbs Gals Polymer 1 19,478. 152 Drsperbyk® 110 Dispersing agent 0.335 0. . 40 n-Pentyl Propionate Solvent 0.726 0. . 99 SC-100 Aromatic solvent 1.351 0. . 186 Bentone®SD-2 Pixotropic agent 0.201 0. . 014 tami zar with agi tation. UNCLE. Pigment 42,348 1.312 Sandgrind at 7 + NS Degradation Polymer 1 9,142 1,010 R-1239 Polyester 3,996 0.451 Flexibilizer Epon®828 Epoxy 0.614 0.065 Cymel®303 Retilaculator 14.812 1.481 Melamine Methylamyl ketone Solvent 1.830 0.882 Propionate n- Solvent 0.269 0.120 Pentyl Add the following two components with agitation Nacure®XP-383 Acid catalyst 0.558 0.68 Nacure®2258 Acid catalyst 0.558 0.68 Pre-clarify the following components and add Silicone DC 200 (vise agent for control 0.022 0.003 10 cts)? C-100 Fluency 0.201 0.028 Solvent aromatice Mix the following two solvents and adjust the viscosity and VOC Solvent n-pentyl propionate 1.473 0.203 Solvent n-butyl acetate 1.473 0.201 100.00 7.76 or of non-volatile 86.29 weight / gal 12.88 VOC approximately 1.77 The coating composition was applied by electrostatic disc in phosphatized steel at a wet film thickness of 1.35 mil (0.03429) and, it was dried and baked for 10 minutes at 350 ° F (177 ° C). A dry film of 1 mil (0.0254 mm) thickness was obtained with pencil hardness 2H brightness at 60 ° C of 94 and direct and inverse shock values of 80. t > Example 3 Polyester 2 is formulated as follows (weight percentages based on 100% solid, 99.93% of which are monomeric components of polyester): 1. MP diol "(Arc) monomer 5.73 2. TMP monomer 0.49 3. Italic anhydride monomer 0.49 4. HHPA "monomer 32.66 . 1, 6-Hexanediol monomer 11.67 6. DDSA "monomer 30.08 7. Trifenil phosphite 0.02 oxidation inhibitor 8. Solvent Butyl Acetate 14.85 9. Di ethyl benzylamine catalyst 0.25 . Monomer Propylene Oxide 18.86 11 Solvent Butyl Acetate 2.55 12-methyl-l, 3-propanediol "hexahydrophthalic anhydride Dodecenylsuccinic hexahydride (Milliken) Solids loading 100% by weight Theoretical losses - Solids yields 100.00 Solution yield 117.65 Water was applied to a reactor for cooling. The reactor was sealed and slowly heated to 65-80 ° C to melt the components.The start of an exotherm was observed.Cooling was necessary to keep the temperature below 140-145. C. The reaction mixture was maintained for 15 minutes at the peak of the exotherm, the reaction mixture was cooled to 105-115 ° C and components 8 and 9 were added. Mixing was for 15 minutes and the temperature was adjusted to 100 ° C. The acid number and viscosity were measured for this first stage.With the reaction mixture at 100 ° C, the component 10 was added as fast as possible.The temperature rose to 115-120 ° C and was maintained until the acid number was reduced to 1.7-4.3. (If necessary, add additional propylene oxide (in excess) to achieve the desired acid value).

The properties of the polyester composition are as follows: Viscosity (at 85% solids) U-W Non-volatile materials 85 ± 1 Solvent butyl acetate Color 6 max.

IA / NV (acid value, in solids) Weighs per gallon (WPG) 9.00 ± 00.10 IOH / NV (hydroxyl index based on 246 ± 15 solids) Appearance Transparent NV (volume of non-volatile) 81.6o Temperature of flammability: i '"- • H / * Cño ^, The polymer 2 can be replaced by the polymer 1 in the coating formulation of example 2.

Example 4 The polyester is formulated as follows (percentages by weight based on 100% solid, 99.98% of which are monomeric components of the polyester): 1. MP Diol1 (Arc) monomer 40.61 2. TMP monomer 0.42 3. Monomeric italic anhydride 27.66 4. HHPA monomer 0.42 . 1, 6-Hexanediol monomer 9.93 6. DDSA monomer 25.60 7. Fascat 4100 catalyst 0.09 8 Triphenyl phosphite oxidation inhibitor 0.02 9 Solvent butyl acetate 18.53 N, N-dimethyl benzylamine catalyst 0.02 11 Monomer propylene oxide 0.38 12 Solvent Butyl Acetate 1.05 Cooling water was applied to the reactor. Components 1-8 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65 -10 ° C to melt the components. The start of the exotherm was observed. And the reaction temperature was maintained at 80 ° C for 1 hour. The reactor was heated to 230 ° C and the viscosity and index were monitored until a maximum value of 10 was obtained. The reactor was cooled to 130 ° C and then ingredients 9 and 10 were added. Ingredient 11 was charged to the reactor for a 30 minute interval and the reactor was maintained at 130 ° C for 1 hour. The acid number and viscosity were measured until an acid number of 3.0 to 5.0 was obtained (the additional ingredient 11 is added if necessary to obtain the desired acid number).

The properties of the polyester composition are as follows: Viscosity (at 85% solids) W- Non-volatile materials 81.8 Butyl acetate solvents Color 2-3. IA / NV (acid number, in the 3 .6 solids) Weight per gallon (WFG) 8.80 IOH / NV (hydroxyl index based on 132.8 solids) Appearance Transparent NV (volume of non-volatile) - 78.2 Temperature of flammability 27.8 ° C The polymer 3 can be replaced by polymer 1 in the coating formulation of example 2.

Example 5 Polyester 4 is formulated as follows (percentages by weight based on 100% solid, 99.98% of which are monomeric components of the polyester): 1. MP diol- (Arc) monomer 33. 78 2. TMP monomer 0. 47 3. Chloride monomeric anhydride 30 .21 4. HHPA monomer 0. 47 . 1, 6-hexanediol monomer 11 .24 6. DDSA monomer 28. 97 7. Fascat 4100 catalyst 0.11 8 Trienyl phenyl oxidation inhibitor 0.02 9 Solvent Butyl Acetate 8.37 N, N-dimethyl benzylamine catalyst 0.02 11 Monomer propylene oxide 0.40 12 Solvent Butyl Acetate 1.00 Cooling water was applied to the reactor. Components 1-8 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65-80 ° C to diffuse the components. The start of the exotherm was observed. And the reaction temperature was maintained at 80 ° C for 1 hour. The reactor was heated to 230 ° C and the viscosity and index were monitored until a maximum value of 10 was obtained. The reactor was cooled to 130 ° C and then ingredients 9 and 10 were added. Ingredient 11 was charged to the reactor for a 30 minute interval and the reactor was maintained at 130 ° C for 1 hour. The acid number and viscosity were measured until an acid number of 3.0 to 5.0 was obtained (the additional ingredient 11 is added if necessary to obtain the desired acid number).

The properties of the polyester composition are as follows: Viscosity (at 85o solid) Y-Z Non-volatile materials 84.5 Butyl acetate solvent Color 2-3. IA / NV (acid value, at 1.72 solids) Weight per gallon (WPG) 8.87 IOH / NV hydroxyl index based on 185.4 solids) Appearance Transparent NV (non-volatile volume) 81.3 Flammability temperature 27.8 ° C Polymer 4 can be replaced by polymer 1 in the coating formulation of Example 2.

Example 6 The polyester 5 is formulated as follows (percentages by weight based on 100% solid, 99.98% of which are monomeric components of the polyester): 1. MP diol1 (Arc) monomer 28.94 2. TMP monomer 4.38 3. monomeric phthalic anhydride 29.46 4. HHPA monomer 0.46 . 1, 6-hexanediol monomer 11.92 6. DDSA monomer 28.67 7. Fascat 4100 catalyst 0.10 8 Triphenyl phosphite 0.01 oxidation inhibitor 9 Solvent Butyl Acetate 11.73 N, N-dimethyl benzylamine catalyst 0.02 11 Monomer propylene oxide 1.59 Cooling water was applied to the reactor. Components 1-8 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65-80 ° C to melt the components. The start of the exotherm was observed. And the reaction temperature was maintained at 80 ° C for 1 hour. The reactor was heated to 230 ° C and the viscosity and index were monitored until a maximum value of 10 was obtained. The reactor was cooled to 130 ° C and then ingredients 9 and 10 were added. Ingredient 11 was charged to the reactor for a 30 minute interval and the reactor was maintained at 130 ° C for 1 hour. The acid number and viscosity were measured until an acid number of 3.0 to 5.0 was obtained (the additional ingredient 11 is added if necessary to obtain the desired acid number).

The properties of the polyester composition are as follows: Viscosity (at 85 solids) Y- Non-volatile materials 83.9 Butyl acetate solvent Color 2 IA / NV (acid value, in 1.8 solids) Weight per gallon (WPG) 9.01 IOH / NV (hydroxyl number based on 245.2 solids) Appearance Transparent NV (volume of non-volatile) 80.2 Temperature of ignitability 27.8 ° C The polymer 5 can be replaced by polymer 1 in the coating formulation of example 2.

Example 7 Polyester 6 is formulated as follows (percentages by weight based on 100% solids, 99.98% of which are monomeric components of polyester): 1. MP diol "(Arc) monomer 30.72 2. TMP monomer 4.35 3. Monomeric italic anhydride 29.23 4. HHPA monomer 0.46 . 1, 6-hexanediol monomer 11.83 6. DD? A monomer 28.45 7. Fascat 4100 catalyst 0.10 8 Triphenyl phosphide 0.01 oxidation inhibitor 9 Solvent Butyl Acetate 11.73 N, N-dimethyl benzilai catalyst 0.02 11 Monomer propylene oxide 0.37 Cooling water was applied to the reactor. Components 1-8 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65-80 ° C to melt the components. The start of the exotherm was observed. And the reaction temperature was maintained at 80 ° C for 1 hour. The reactor was heated to 230 ° C and the viscosity and index were monitored until a maximum value of 10 was obtained. The reactor was cooled to 130 ° C and then ingredients 9 and 10 were added. Ingredient 11 was charged to the reactor during a 30 minute interval and the reactor was maintained at 130 ° C for 1 hour. The acid number and the viscosity were measured until an acid value of 3.0 to 5.0 was obtained (the additional ingredient 11 is added if necessary to obtain the desired acid value).

The properties of the polyester composition are as follows: Viscosity (at 8. solid) Y-Z Non-volatile materials 84.2 Butyl acetate solvent Color 2-3 IA / NV (acid value, in 3.0 solids) Weight per gallon (WPG) 8.91 IOH / NV (hydroxyl index based on 210.4 solids) Appearance Transparent NV (volume of non-volatile) 80.8 Temperature of flammability 27.8 ° C The polymer 6 can be replaced by polymer 1 in the coating formulation of example 2.

Example 8 Polyester 7 is formulated as follows (percentages by weight based on 100% solids, 99.98% of which are monomeric components of polyester): 1. MP diol "(Arc) monomero 32. 73 2. TMP monomer 0. 47 3. Phthalic anhydride monomer 0. 47 4. HHPA monomero 32. 73 . 1, 6-hexanediol monomer 11. 19 6. DDSA monomer 28. 83 7. Fascat 4100 catalyst 0. 10 8 Triphenyl phosphite 0.02 oxidation inhibitor 9 Solvent Butyl Acetate 12.35 N, N-dimethyl benzylamine catalyst 0.04 11 Monomer propylene oxide 0.52 12 Solvent butyl acetate 3.90 Cooling water was applied to the reactor. Components 1-8 were charged while purging the reactor with inert gas. The reactor was sealed and slowly heated to 65-80 ° C to melt the components. The start of the exotherm was observed. And the reaction temperature was maintained at 80 ° C for 1 hour. The reactor was heated to 230 ° C and the viscosity and index were monitored until a maximum value of 10 was obtained. The reactor was cooled to 130 ° C and then ingredients 9 and 10 were added. Ingredient 11 was charged to the reactor for a 30 minute interval and the reactor was maintained at 130 ° C for 1 hour. The acid number and viscosity were measured until an acid number of 3.0 to 5.0 was obtained (the additional ingredient 11 is added if necessary to obtain the desired acid number).

The properties of the polyester composition are as follows: Viscosity (at 85μ of solid) X- Non-volatile materials 84.9 Butyl acetate solvent Color 2-3 IA / NV (acid value, in the 3.6 solids) Weight per gallon (WPG) 8.80 IOH / NV (hydroxyl number 179.3 based on solids) Appearance Transparent NV (volume of non-volatile) 81.9 Temperature of flammability 27.8 ° C The polymer 7 can be replaced by polymer 1 in the coating formulation of example 2.

- Example 9 A white coating composition using the polymer 5 is formulated as follows: COMPONENT FUNCTION LBS GAL? R-2643 Polyester resin 185.2 21.4 Methyl isoamyl ketone Solvent 61.7 9.1 Screening with agitation TiO¿ Pigment 370.7 11.5 Sandgrind a 7. 5 Hegman Degradation R-2643 Polyester resin 326.7 37.7 Resi ine 751 Melamine crosslinker 85.06 9.7 Polymer 5 Polyester resin 68.16 7.7 R-3571 Polyester resin 13.23 1.6 Epon 828 Epoxy resin 9.03 0.9 the following components are added with agitation Nacurel557 Acid catalyst 9.88 1.3 premezaclar the following two components and add Silwet L-7500 Silicone agent for the control of the fluidity 2.47 0.3 Coroc-A-620-A2 Acrylic resin 0.74 0.1 Mix the following three solvents and adjust the viscosity and the VOC n-Butanol solvent 22.2 3.3 acetone solvent 22.2 3.4 butylcarbitol acetate solvent 22.2 2.7 i non-volatile 70.3 weight / gal '10.84 VOC 3.0 The coating composition was applied by coil coating to aluminum metal (pretreatment 1500.) at a wet film thickness of 1.45 mil (0.03683 mm), dried and baked during 22 seconds to achieve a PMT of 450 ° F (232 ° c). A dry film of 0.8 mil (0.02032 mm) thickness was obtained with pencil hardness H, OT, gloss at 60 ° C of 95.2.

Example 10 A coating composition using polymer 5 is formulated as follows: COMPONENT FUNCTION LB? GALS R-4350 polyester resin 33.19 3.77 PM Acetate solvent 2.73 0.34 sift with TiO pigment agitation 37.99 1.1S Sandgpnd a 7 Hegman Degradation R-4350 Polyester resin 3.00 0.34 Polymer 5 Polyester resin 7.96 0.90 Resimine 751 Melamine crosslinker 9.09 1.03 R-35712 Acrylic resin 1.06 0.12 Coroc A-620-A2 Acrylic resin 0.21 0.03 Premezaclar the following two components and add Versaflow Base Polyethylene resin 0.21 0.03 Silewt L-7500 Silicone agent for 0.21 0.03 fluidity control Add the following components with agitation Nacure 1051 catac acid 0.42 0.05 Epon 1001 epoxy resin 1.82 0.20 Add ei next sun to adjust viscosity and VOC n-Butanol solvent 2.11 0.31 or non-volatile 80.0 weight / gal 12.0 VOC 2.40 The coating composition was applied by coil coating to aluminum metal (1500 pretreatment) at a wet film thickness of 1.19 mil (0.030226 mm) and, dry and oven for 30 seconds to achieve a PMT of 450 ° F (232 ° C). The dry film of 0.8 mil (0.02032 mm) thickness was achieved with pencil hardness H, IT, gloss to 60 ° C of 93.5.

Claims (9)

1. A polyester composition having a number average molecular weight (Mn) of between about 500 and about 1000, a weight average molecular weight (M ") of between about 600 and about 2000, a polydispersity below about 2, a hydroxyl functionality of between 2 and 3, a hydroxyl number of between about 160 and about 260, and an acid number less than about 10, no more than about 5% of the hydroxyl group groups are pendent, between about 10 and about 50% by weight of The monomers that are used to form the polyester composition are anhydrides having the formula: OOO 1 / \ lcc (I) Rl -CH-CH- R2 Where R is a non-aromatic, saturated or unsaturated hydrocarbon chain having between 6 and 30 carbon atoms, R is hydrogen or a saturated or unsaturated non-aromatic hydrocarbon having between 1 and 8 carbon atoms, and R1 and R; they have in total, between 8 and 30 carbon atoms.

2. The paliester according to claim 1, wherein the anhydrides of the formula (I) comprises anhydride - - dodecenylsuccinic.

3. The polyester according to claim 1, having a polydispersity of about 1.8 or less.

4. A composition comprising the polyester of claim 1, in combination with a reactive hydroxy reactive curative.

5. The polyester composition according to claim 1, formed from the polycondensation of carboxylic anhydride and polyol in a molar ratio of the anhydride to the hydroxyl equivalent of the polyol in the range of 0.3: 1.00 to 1.00: 1.00 followed by the reaction with a monofunctional oxidic compound in a ratio of oxidant to anhydride in the range of 0.020: 1,000 to 1,100: 1,000.

6. The polyester composition of claim 5, wherein the molar ratio of the anhydride to the hydroxyl equivalent of the polyol is 0.3: 1.00 and a ratio of oxidane to anhydride is 0.020: 1,000.

The polyester composition of claim 5, wherein the molar ratio of the anhydride to the hydroxyl equivalent of the polyol is 0.3: 1.00 and a ratio of oxidane to anhydride is 0.080: 1,000.

8. The polyester composition of claim 5, wherein the molar ratio of the anhydride to the hydroxyl equivalent of the polyol is 1.00: 1.00 and a ratio of oxidane to anhydride is 1,000: 1,000.

9. In a coating composition containing a polyether binder wherein the improvement consists of the polyester binder comprising at least about 10 or by weight of the polyester composition of claim 1.