COMPOSITIONS OF POLYESTERS AND POLYESTER-AMIDE IMIDES USED FOR WIRE ENAMELS

Abstract: A wire enamel blend is disclosed which is made up of four components: a crosslinkable polyester, a linear polyes­ ter, a polyester amide-imide component, and optionnally, a cresol formaldehyde resin. The cross-linkable polyester is the reaction product of a polyol which is mixture of diol and a triol, a polyfunctional carboxylic compound, and a catalyst. The linear polyester is the reaction product of a diol, a polyfunctional carboxylic compound, and a catalyst. The polyester-amide-imide component is the reaction product of a diamine, trimellitic anhydride, and a polyester which in turn is the reaction product of a polyol, a polyfunctional car­ boxylic compound, and a catalyst. The cresol formaldehyde resin is the reaction product of a phenol, formaldehyde, and a amine catalyst. All of the four components are in a solution of a carbitol. The blend also contains a fatty acid component which may be reacted into any of its polyester components.

Description: POLYESTER-AMIDE-IMIDE WIRE ENAMELS Polyester-amide-imide wire enamels which are used commercially are high molecular weight, high viscosity, difficultly soluble polymers requiring strong,.nox- ious solvents in large quantities, not only for application to wire, but also for proper reaction in the kettle. One widely used commercial polyester-amide-imide wire enamel is made by blending four reaction products (see U.S. Patent 3,555,113): (1) a polyester-amide-imide with high amideimide content (which requires a high solvent content, specifically cresylic acid, in the reaction kettle to keep the reaction mixture mobile during critical periods of the reaction); (2) a polyester; (3) a polyurethane blocked isocyanate; and (4) a low molecular weight phenolic resin. The final resin is dissolved to 25% to 30% solids in a cresylic acid-aromatic hydrocarbon solvent mixture. The effluent from the stoving of this wire enamel is ecologically unacceptable and must be burned in an incinerator. U.S. Patent Specification No. 4,117,032 (Kwiecinski), discloses a wire-coating powder prepared by first formulating a solventless aromatic polyester-amide-imide. Excess polyol is used to replace the solvent. Accordingly, the present invention resides in a polyester-amide-imide wire enamel blend characterized in that said blend comprises: (A) a solution in a carbitol. of a cross-linkable polyester comprising the reaction product of: (i) a polyol which is d niiLil-e oi a and a triol; (2) a polyfunctional carboxylic compound at least 80% by weight selected from the group consisting of terephthalic acid, isophthalic acid, alkyl esters of terephthalic acid or isophthalic acid up to C3, and mixtures thereof; (3) a catalyst; (B) a solution in a carbitol of a linear polyester comprising the reaction product of: (1) a diol; (2) a carboxylic compound at least 80% by weight selected from the group consisting of terephthalic acid, isophthalic acid, alkyl esters up to C3 of terephthalic acid or isophthalic acid, and mixtures thereof; (3) a catalyst; and a solution in a carbitol of a polyester-amide-imide component comprising the reaction product of: (1) a polyester which comprises the reaction product of (a) a polyol which is a mixture of a diol and a triol; (b) a polyfunctional carboxylic compound at least 80% by weight selected from terephthalic acid; isophthalic acid, alkyl esters up to C3 of terephthalic acid or isophthalic acid, and mixtures thereof; (c) a catalyst; (2) a diamine; and, (3) trimellitic anhydride; and, said polyester-amide-imide wire enamel blend also containing a fatty acid component which may be reacted into any of its polyester components. We have found that a polyester-amide-imide wire enamel blend having excellent properties can be made at a very high solids concentration using an ecologically acceptable solvent. The solvents used in this invention are carbitols, which are high-boiling and have been designated under Rule 66 as ecologically acceptable solvents. The resin is applied to wire in the conventional manner and its properties on wire match those of good class 150so to class 1800C conventional wire enamels. The following is a description of the ingredients used in practicing this invention. SOLVENT The solvent is a carbitol, that is, a diethyler;e glycol monoalkyl ether or a diethylene glycol monoalkyl ether acetate where the alkyl group is C1 Lo 4 ¯as esters are preferred because they react less into the polymer, and acetate esters are preferred because they are commercially available. Specifically, the preferred carbitols are diethylene glycol monoethyl ether (commonly called "carbitol"), and diethylene glycol monoethyl ether acetate (commonly called "carbitol acetate"), because they are high-boiling solvents and are ecologically acceptable. Other carbitols which can be used include diethylene glycol monobutyl ether, diethylene glycol monopropyl ether acetate, etc. POLYOL Diols which can be used in this invention include cyclohexanedimethanol, triethylene glycol, ethylene glycol, 1,4-butane diol, neopentyl glycol, propylene glycol, 1,5-pentanediol, etc. The preferred diols are triethylene glycol, ethylene glycol, 1,4-butane diol, and neopentyl glycol because they have been found to work well and are inexpensive. Triols which can be used in this invention include tris (2-hydroxyethyl) isocyanurate (THEIC), glycerol, trimethylol ethane, and trimethylol propane. The preferred triol is THEIC because it produces wire enamels having better thermal properties. FATTY ACID The fatty acid is a Cl2 to C18 monocarboxylic unsaturated acid. Fatty acids which can be used in this invention include soya, linseed, tung, etc. The preferred fatty acid is soya because it produces wire enamels having good thermal stability and it is relatively inexpensive. DIAMINE Suitable diamines include meta phenylene diamine, methylene dianiline, 2,6-diamino toluene, 2,4diamino toluene, etc. The preferred diamine is meta phenylene diamine because it produces enamels having greater thermal stability. In the preferred method of making the polyesteramide-imide wire enamel blend of this invention, four Components are first separately prepared. These compo nents are a r'jr-linkable polyester, ci linens pOlyLttI a polyester-amide-imide, and a cresol formaldehyde resin. PREPARATION OF CROSS-LINKABLE POLYESTER The cross-linkable polyester is prepared by first mixing together a polyol, a polyfunctional carboxylic compound, a diethylene glycol monoalkyl ether acetate (hereinafter called a "carbitol acetate"), and a catalyst. A fatty acid is preferably also included in the composi- tion. The polyol is a mixture of a triol and diol in molar ratio of triol to diol of infinity to about 1:1. The preferred molar ratio of triol to diol is about 5:1 to about 15:1. The amount of polyol used in the composition should be the stoichiometric equivalent required to react with the carboxylic acid plus about 30 to about 60 equivalent percent in excess. The carboxylic compound must be at least 80% selected from the group consisting of terephthalic acid, isophthalic acid, or alkyl esters of terephthalic acid or isophthalic acid up to C3. The rest of the carboxylic compound used in the composition may be trimellitic acid, trimellitic anhydride, maleic anhydride, adipic acid, or another aliphatic carboxylic acid. Mixtures of various acids or their esters are also contemplated. The preferred acid is terephthalic acid because it is inexpensive. It is preferable to use the dimethyl esters of the acids as they react more easily. The amount of carbitol acetate in the composition should be about 5 to about 20% by weight, based on the total composition of cross-linkable polyester. The catalyst is a condensation catalyst if the carboxylic compound has acid or anhydride groups and is ar ester-interchange catalyst if the carboxylic compound is an ester. The ester-interchange catalyst is preferably an organic titanate ester such as tetraisopropyl titanate or butyl titanate. Tetraisopropyl titanate is preferred. The condensation catalyst is preferably dibutyl tin oxide. Butyl stannoic acid can also be used, but dibutyl tin oxide is preferred. The amount of catalyst used should be about 0.5 to about 2 g. per mole of dicarboxylic acid. The fatty acid, which is preferably present in the cross-linkable polyester, should be used in an amount equal to about 5 to about 10 mole percent of the amount of carboxylic compound. Once the composition is prepared, it is heated to form the cross-linkable polyester. A suitable and preferred reaction schedule is to heat rapidly to 180 C, then to increase the temperature at a rate of 10 C per hour up to 2050C, then to increase the temperature at a rate of 150C per hour up to 2500C. A carbitol is then added to bring the solids content down to about 55 to about 75% solids. PREPARATION OF LINER POLYESTER The linear polyester is prepared from a diol, a dicarboxylic acid, and a catalyst. A fatty acid is also preferably present. The amount of diol used should be the stoichiometric equivalent needed to react with the carboxylic compound, plus about 30 to about 60 equivalent percent in excess. A mixture of diols is preferred to prevent crystallization. The catalysts were described in the discussion of the cross-linkable polyester. The fatty acid which is preferably present should be used in an amount equal to about 3 to about 10 mole percent of the carboxylic compound. The composition is then heated to form the linear polyester. A preferred redaction schedule is to heat rapidly to 160 C and then increase the temperature at a rate of 15 C per hour up LO 260 C, and to hold it at that temperature for eight hours. The composition is then vut with carbitol to about 55 to about 75% solids. PREPARATION OF POLYESTER-AMIDE-IMIDE In making the polyester-amide-imide, it is preferable ro first prepare a polyester. This p@@@@@er is made by reacting ct pyol , a tarbt,xylic compound nc- i catalyst. A fatty acid is preferably also present. The polyol is a mixture of a diol and a triol in a molar ratio of about 1:3 to about 1:10. The preferred molar ratio is about 1:4 to about 1:5. The amount of polyol used should be equal to the stoichiometric equivalent needed to react with the dicarboxylic acid, plus about 80 to 100 equivalent percent in excess. The carboxylic compound was described in the discussion of the cross-linkable polyester. A fatty acid is also preferably present. The amount of fatty acid should be about 5 to about 10 mole percent based on the carboxylic compound. The polyester is prepared by heating this composition, preferably- by heating rapidly to 1800C then at a rate of 150C pr hour to 2200C to an acid number of less than 5. After the polyester is prepared, and while it is still hot, a diamine and trimellitic anhydride are added. The molar ratio of diamine to trimellitic anhydride should be about 1:1 to about 0.8:1. Sufficient diamine and trimellitic anhydride should be used so that the amide plus the imide groups in the polyester-amide-imide component are from 1 to about 2.5 times the number of ester groups. After the diamine and trimellitic anhydride have been added, the composition is heated to produce a clear fluid resin. This may advantageously be accomplished at about 190"C to about 2100C. At this point, it is preferable to add additional trimellitic anhydride to increase the total carboxyls in the reaction by about 3 to about 7 mole percent of the total carboxylic compound. It is also preferable to add THEIC in an amount equal to about 5 to about 10 equivalent percent based on the total polyol. If additional trimellitic anhydride and THEIC are added, the reaction is continued until these ingredients are reacted in. This may be accomplished at about 2000C to about 2100C for about one-half hour for each ingredient. The composition is then cut with carbitol to about 55 to about 75% solids. PREPARATION OF CRESOL FORMALDEHYDE RESIN The cresol formaldehyde resin is prepared by reacting a phenol with formaldehyde in the presence of a amine catalyst. Suitable phenols which can be used include meta para cresol, phenol, t-butyl phenol, etc. The preferred phenol is meta para cresol. Formaldehyde is used as a mixture with water of 40% formaldehyde and 60% water. The molar ratio of phenol to actual formaldehyde present should be about 1.2:1 to about 1.6:1. Amine catalysts which can be used include various amines, such as triethanolamine, dimethylethanol amine, or benzyldimethylamine. The preferred amine catalyst is triethanolamine. The amount of catalyst should be about 5 to about 12% by weight based on the total weight of. the composition. The composition is then heated to form the cresol formaldehyde resin. The reaction is preferably carried on by refluxing for about an hour and one-half at 1000C, decanting off the water, neutralizing the catalyst with salicylic acid, then heating to 40 to 800C under 26 mm of mercury pressure to about 36 poises viscosity. The composition is then cut with carbitol to about 40 to about 60% solids. PREPARATION OF POLYESTER-AMIDE-IMIDE BLEND The polyester-amide-imide wire enamel blend is prepared by mixing together about 30 to about 50% (by weight based on total solids) of the polyester-amide-imide portion, about 20 to about 30% of the linear polyester portion, about 10 to about 20% of the cross-linkable polyester portion, and up to about 15% of the cresol formaldehyde resin portion. The blend also preferably contains about 2 to about 5% hexamethoxymethyl melamine to improve cut-through, and about 2 to about 5% adhesion promoters such as organic titanates, for example, tetraisopropyl titanate or tetrabutyl titanate. The cresol formaldehyde resin portion is preferably present and a preferred amount is up to about 10%. The blend also preferably contains up to about 2% copper ethyl aceto acetate, cobalt napht:ha nate, or manganese naphthanate (at 6% cobalt or manganese) to improve adhesion. The polyester-amide-imide wire enamel blend also preferably includes up to 20% by weight of an end-blocked isocyanate to improve adhesion as tested for in the Emerson scrape test. A cyclic trimer of toluene diisocyanate end-blocked with phenol or some other end-blocked isocyanate may be used, but the preferred end-blocked isocyanate is a THEIC-terephthalate ester urethane isocyanate blocked with meta para cresol (see Example VI) because it does not detract from flexibility as other isocyanates do. The polyester-amide-imide wire enamel blend con tains no water, no cresylic acid, and no other solvent except for the carbitol. Although water is present with the formaldehyde, it is boiled off before the blend is completed. Mixtures of various components and ingredients are also contemplated. The blend is preferably prepared by mixing at about 80 to about 900C. It is then filtered to remove any solid matter. The polyester-amide-imide wire enamel blend can also be prepared by preparing the cross-linkable polyester, the linear polyester and the polyester-amide-imide component together in sequence in the same reaction vessel. (See Examples 1 and 8). Another alternative is to include all the fatty acids in one of the polyester components instead of dividing it between the three different polyesters. The blend can then be coated onto wire and cured. A suitable cure procedure is to run the wire at a rate of 22 to about 28 feet per minute through a 12-ft. high tower at 4500C. The invention will now be illustrated with reference to the following Examples: EXAMPLE 1 The following reactants are charged into a 3liter, 4-neck reaction flask equipped with a heater, motor stirrer, nitrogen sparge tube, thermometer, and steam condenser: 380.0 g ethylene glycol (6.12 M) 61.2 g triethylene glycol (0.402 M) 116.4 g soya fatty acid (0.414 M) 232.0 g trimellitic anhydride (1.206 M) The mixture is stirred and heated at lO0C per hour from 1800C to 2000C to a clear solution to make a polyester having excess hydroxyl groups. Then the following ingredients are added: 392.0 g methylene dianiline (1.972 M) 448.0 g trimellitic anhydride (2.330 M) The reaction is continued at 185 to 1950C. A hard semi-solid turbid polyester-amide-imide forms which, upon continued heating becomes clear and fairly fluid with a ball and ring softening temperature of 60"C. At this point, the following ingredients are added to the reaction flask: 207.0 g terephthalic acid (1.248 M) 5.6 g dibutyl tin oxide 13.2 g distilled water The reaction is continued at a 150C/hour temperature increase to 190-2250C to esterify more of the excess hydroxyl groups. After 4 hours reaction the resinous solution is clear and a ball and ring softening temperature of 106"C is obtained. The reaction is cooled to 190"C and 261.0 g tris (2-hydroxyethyl) isocyanurate (1.0 M) is added and the reaction is continued for 1/2 hour at 190 to 200"C to a ball and ring softening temperature of 820C. The resinous product is cooled and dissolved into 542 g carbitol and 271 g tetraethylene glycol diacrylate. (The TEGDA is a reactive diluent which was added for smoothness.) The yield of polyester-amide-imide is 2710 g solution at 70% non-volatiles. The solution is coated on 18 AWG copper wire in a 15-ft. vertical wire tower at 4000C maximum temperature, using four passes with standard doghouse dies with 43 co 45 mii diameter openings and a solution temperature of 500C. The wire is smooth at coating speeds of 16 to 22 ft. per minute and 3.5 milts build and has good properties. The wire passes quick snap test, 30% elongation + 1X mandrel, 1X mandrel heat shock at 1750C, 11 to 12 kV electric strength, 230 to 2900C cut through with 2 kg wt. on crossed wires, and 12-lb. Emerson scrape. The thermal life test (1000 V on twisted pairs) shows 84 hours at 2500C, 1308 hours at 2250C and 11,300 hours at 2000C indicating a 20,000 hours-life at 1950C. EXAMPLE 2 - PART I The following reactants are heated in a 1L reaction flask equipped as in Example 1 to prepare a polyester: 212.0 g ethylene glycol 135.2 g triethylene glycol 101.0 g tris (2-hydroxyethyl) isocyanurate 56.0 g soya fatty acid 4.7 g dibutyl tin oxide 263.0 g terephthalic acid The reaction mixture is heated with stirring and nitrogen sparging to 1800C to 2200C at 150C/hour until a 3.8 acid number is obtained. At this point, additional ingredients are charged to prepare a polyester-amide-imide component: 335.6 g meta phenylene diamine 596.0 g trimellitic anhydride The reaction is continued at 190 to 2100C resulting in a turbid semi-solid material progressing to a clear fluid resin with a 1000C ball and ring softening temperature. At this point, 48.0 g trimellitic anhydride is added and the reaction continued for 1/2 hour at 190 to 2000C. The reaction is cooled to 1900C and 130.4 g of tris (2-hydroxyethyl) isocyanurate is added. The reaction is continued at 205 to 2100 to a ball and ring softening temperature of rll50C. It is then cooled and diluted with 728.0 g of carbitol. The yield is 2356.0 g of solution at 70% non-volatiles. PART II The following ingredients are charged into a 2L reaction flask to prepare a cross-linked polyester: 522.2 g tris (2-hydroxyethyl) isocyanurate 30.0 g triethylene glycol 388.2 g dimethyl terephthalate 40.3 g soya fatty acids 3.0 g tetra isopropyl titanate in 100 g carbitol acetate With nitrogen sparging and a steam condenser, the mixture is heated at 180 to 2050C at 100C per hour, then with a short air condenser to 2500C. The reaction is held at 2500C for 2 hours and cooled to 200"C where 300 g of carbitol is added. The yield is 1233 g of solution at 68% non-volatiles. PART III The following ingredients are added to a 5-liter re-action flask to prepare a linear polyester: 1941.0 g dimethyl terephthalate 310.5 g ethylene glycol 300.5 g 1,4-butanediol 348.0 g neopentyl glycol 500.5 g triethylene glycol 121.0 g soya fatty acids 15.0 g tetra isopropyl titanate in 125 g xylene With nitrogen sparging and a steam condenser, the ingredients are heated 1600C to 2600C at 150C per hour and the reaction continued for 8 hours at 2600C. The resinous mixture is cooled and 1090 g of carbitol is added. The yield is 3706 g of a turbid solution at 69% non-volatiles PART IV A 3-liter reaction flask is charged with the following ingredients t.) prepare a phenol formaldehyde resin: 1376.0 g meta para cresol 605.0 g formaldehyde (40%) 23.4 g triethanolamine The mixture is stirred and heated with g water cooled reflux condenser attached with condensate ret:-rncd to the flask for 1-1/2 hours at reflux. The reaction is cooled to 550C, allowed to settle in a separatory funnel and removed from the water layer. It is recharged to the reaction flask and 21.7 g of salicylic acid is added and the product is heated 40 to 800C at 26 mm Hg pressure until a viscosity of 36 poises is obtained. At this point, 1695 g cresylic acid is added and a solution.is obtained containing 29% non-volatiles. (The use of cresylic acid is not part of this invention, but illustrates the prior procedure. See Example 4, Part 11 where a carbitol is substituted for the cresylic acid.) The following blend is prepared from the previously prepared solutions: 164.9 g of Part I 110.0 g of Part III 55.0 g of Part II 36.8 g of Part IV 13.6 g of hexamethoxymethyl melamine (Cymel 301 - American Cyanamide) 13.6 g of tetraisopropyl titanate dissolved in 13.6 g cresylic acid 1.35 g of copper ethyl aceto acetate 10.4 g of cobalt naphthanate at 6% cobalt The blend is stirred and heated for 1 hour at 80 to 90 C. The blend has a viscosity of 13,000 cp at 400C and a non-volatile content of 60%. When die-coated on #18 AWG copper wire with six passes at 22 ft/min to 28 ft/min, it gives a very smooth coating with good flexibility (20 to 30% elongation plus 1S mandrel) which passes 1X heat shock at 170C to 2000C, 3020C cut-through, 11 to 12 kV electric strength, and 20-lb. Emerson scrape. Preliminary thermal life test on twisted pairs (12 hours at 2750C; 228 hours at 2500C; and > 1.700 hours at 2250C) indicate a thermal life of 20,000 hours above 1900C. EXAMPLE 3 This example shows a much-improved Emerson scrape and cut-through temperature with slightly lower flesibility and coating smoothness. PAK'T I The following ingredients are charged into a 3liter reaction flask to prepare a cross-linked polyester: 57.0 g triethylene glycol 210.0 g ethylene glycol 755.0 g dimethyl terephthalate 203.0 g tris (2-hydroxyethyl) isocyanurate 3.0 g tetraisopropyl titanate in 15.0 g cresylic acid 37.5 g xylene With nitrogen sparging and a steam-cooled reflux condenser, the ingredients are heated 1600C-2600C at 15"C/h then cooled to 2000C and the following added: 462.0 g dimethyl terephthalate 618.0 g tris (2-hydroxyethyl) isocyanurate 3.0 g tetraisopropyl titanate in 15.0 g cresylic acid The reaction is continued at 190-2250C at 150C/ hours and then diluted with 600 g carbitol acetate and 600 g carbitol. A yield of 3070 g of solution at 60% nonvolatiles is obtained. The following blend is prepared: 620.0 g of Part I of Example 2 443.0 g of Part I of Example 3 102.3 g of Part IV of Example 2 18.8 g of tetraisopropyl titanate dissolved in 37.6 g of cresylic acid 160.0 g of tetraethylene glycol diacrylate The blend is stirred and heated at 80 to 900C for 1 hour. The solution is coated on #18 AWG copper wire in a 15-ft. vertical tower with the following results: Baking range 22 to 28 ft/min, flexibility 10 to 25% elongation plus 1X mandrel, fairly smooth with slight waviness, heat shock 1X at 1750C, cut-through 3800C, Emerson scrape 26 to 30 lb. Thermal life data indicate a 20,000 hours life above 1800C. EXAMPLE 4 This blend contains only Rule 66 solvent and is completely free of the non-desirable cresylic acid solvent. The solution blend coated on #18 AWG copper wire yields a film with very good smoothness, flexibility, and heat shock, but lower Emerson scrape and thermal life than that of Example 3. PART I The polyester-amide-imide composition is as follows (5-liter flask): 227.1 g ethylene glycol 183.3 g triethylene glycol 110.1 g 1,4-butanediol 127.5 g neopentyl glycol 84.0 g soya fatty acid 31.8 g distilled water 7.05 g dibutyl tin oxide 394.5 g terephthalic acid With nitrogen sparging and steam-OsCled reflux condenser, the ingredients are heated 180 to 2200C at 150C/hour to an acid-number--of 3.0. At this point, the following ingredients are added: 377.4 g meta phenylene diamine 230.1 g 4,4'-methylene dianiline 894.0 g trimellitic anhydride The reaction is continued at 190 to 2100C to a 920C ball and ring softening temperature. The reaction is cooled to 1750C and 72.0 g of trimellitic anhydride is added and the reaction is continued at 190 to 2000C for 1/2 hour where 195.6 g of tris (2-hydroxyethyl) isocyanurate is added. The reaction is continued at 205 to 2100C until a ball and ring softening temperature of 115"C is obtained. The resin is dissolved in 1116.0 g of carbitol. A yield of 3602 g of solution at 70% non-volatiles is obtained. PART II This resin preparation is the same as that of Part IV of Example 2 except that the 1695 g of cresylic acid solvent at the end of the reaction is replaced by 524 g of carbitol acetate. A yield of 1935 g of solution at 8.6 solids is obtained. The following ingredients are blended: 186.5 g Part I, Example 4 57.2 g Part II, Example.2 129.2 g Part III, Example 2 56.0 g tetraethylene glycol diacrylate 40.5 g Part II, Example 4 11.2 g tetraisopropyl titanate dissolved in 11.2 g carbitol The solution blend is stirred and heated at 80 to 900C for 1 hour. The blend is diecoated on #18 AWG copper wire at six passes and is very smooth at 3.0 to 3.5 mils build at 22 ft/min. All samples are very flexible, passing 30% elongation plus 1X mandrel, and also pass 2500C 1X heat shock. The cut-through temperature at 22 ft/min is 3100C and the Emerson scrape is 12 to 14 lb. The thermal life data (12 hours- at 2750C, 156 hours at 2500C, 528 hours at 2250C and 1350 hours at 2000C) extrapolates to -1650C for a 20,000 hour life. EXAMPLE 5 The reactions and blend are exactly the same as those of Example 2 except that in Part I of Example 2 the 335.6 g of meta phenylenediamine is replaced by 304.0 g of 2,4-diamino toluene and 76.0 g of 2,6-diamino toluene. The resulting blend is coated on #18 AWG copper wire at 22 to 28 ft/min and is smooth with good flexibility (20 to 30% elongation + 1X mandrel), 175 to 2250C 1X heat shock, 3100C cut-through, and 14 to 16 lb. Emerson scrape. EXAMPLE 6 This blend is the same as that of Example 3 except that it includes an end-blocked ester-urethaneisocyanate prepared in the following manner with the following ingredients added to a 3-liter flask: 522.0 g tris (2-hydroxyethyl) isocyanurate 166.0 g terephthalic acid 11.0 g distilled water 2.5 g dibutyl tin oxide With nitrogen sparging and a downward water con denser to condense out the water of reaction, the mixture is heated at 2100C to 2600C at 150C/hour until 44.5 g wit er- is cursdtnsed out whence 552 g (arbitol acetate is added and the solution is cooled. In a separate container, 690 g of a mixture containing 80%, 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate is added slowly to 531 g carbitol and reacted 1/2 hour at 1000C whence 360 g of carbitol acetate is added. This product is cooled and added to the 3-liter reaction flask and reacted 1 hour at 100 to 1050C. The yield is 2775 g of solution at 50% non-volatiles. A blend is prepared the same as that of Example 3 except that 168 g of the above-prepared solution is added. When coated on #18 AWG copper wire, the same properties as those of Example 3 are obtained except that the wire is smoother and slightly higher Emerson scape (32 lb) is obtained. EXAMPLE 7 In this example, the ester-amide-imide portion does not contain a fatty acid. Fairly smooth coatings with good properties are obtained. The ester-amide-imide composition is as follows: 106.0 g ethylene glycol 67.6 g triethylene glycol 10.6 g distilled water 2.35 g dibutyl tin oxide 131.5 g terephthalic acid The ester portion is reacted 1800C to 2200C to a clear solution and the amide-imide portion is charged: 57.0 g carbitol acetate (solvent) 167.8 g meta phenylenediamine 298.0 g trimellitic anhydride The reaction is continued at 190 to 2100C through the semi-solid to a clear state where 43.2 g trimellitic anhydride is added and the reaction continued 1/2 hour at 190 to 2000C. Then 115.7 g tris (2-hydroxyethyi) isocyanurate is added and the reaction is continued tln additional 3, hours at 205 to 2100C, whence 285 g carbi lol is added ind the solution is cooled. A yield of 1148 g of slut ion al. 70"l. non-volatile is obtained. The hollowing blend is prepared completely free of the.non-desirable cresylic acid solvent: 186.5 g polyester-alnide- imide of this example 75.2 g Part II of Example 2 111.2 g Part III of Example 2 56.0 g tetraethylene glycol diacrylate 40.7 g Part II of Example 4 11.2 g tetraisopropyl titanate in 11.2 g carbitol This blend coats fairly smoothly on #18 AWG copper wire at 22 ft/min to 32 ft/min coating speed. The flexibility is 25% to 30tXÓ elongation plus 1X mandrel, the 1X heat shock passes at 2000C to 2250C, the cut-through temperature is 3320C at 22 ft/min bake, and the Emerson scrap-e is 13 to 16 lb. EXAMPLE 8 This example has fair heat shock and good cutthrough with fair flexibility and coating smoothness. This resin contains about 1% by weight of cresylic acid. The following ingredients are charged into a reaction flask to prepare a polyester-amide-imide: 187.2 g trimellitic anhydride 87.2 g meta phenylene diamine 33.6 g triethylene glycol 112.3 g ethylene glycol 59.1 g tris (2-hydroxyethyl) isocyanurate 1.2 g tetraisopropyl titanate 2.0 g carbitol With nitrogen sparge and air-cooled condenser, the ingredients are heated forming a turbid semi-solid state which breaks up at about 18500. The reaction is continued at 19000 until clarity is achieved and then cooled to 1700C. At this point, 83.6 g meta phenylene diamine and 172.8 g trimellitic anhydride are added. Again while being heated a semi-solid state forms. The reaction is continued to 19800 where a clear solution is obtained. The reaction is then cooled to 1700C where :3nol:her 108 g trimellitic anhydride addition is made. The reaction is taken 170 C to 190 C at the rale of IO" per hour. At this point 44.6 g maleic anhydride is added and reacted to clarity in ¯15 min. at which point 84 g of tris (2-hydroxyethyl) isocyanurate is added. The reaction is continued for 1/2 hour at 1850 to 190 C. The reaction is stopped at this point by adding 200 g of carbitol acetate and 300 g of carbitol. The yield is 1308 g at 62% non-volatile material. A blend is then prepared of the following previously prepared solution: 170.0 g of polyester-amide-imide of this example 112.8 g of Part I, Example 3 30.3 g of Part IV, Example 2 The blend is then coated on #18 AWG copper wire in a 15-ft. vertical tower at speeds of-. 22 to 28 ft/min utilizing only four passes. The build is 2.4 to 2.7 mil with good flexibility of 20% + 1X mandrel, a 1X heat shock of 200 C and cut-through of 3770C. The film is fairly smooth and has an Emerson scrape of 10 to 12 lb.

Claims: What we claim is: 1. A polyester-amide-imide wire enamel blend characterized in that said blend comprises: (A) a solution in a carbitol of a cross-linkable polyester comprising the reaction product of: (1) a polyol which is a mixture of a diol and a triol; (2) a polyfunctional carboxylic compound at least 80% by weight selected from terephthalic acid, isophthalic acid, alkyl esters of tere phthalic acid or isophthalic acid up to C3, and mixtures thereof; (3) a catalyst; (B) a solution in a carbitol of a linear polyester comprising the reaction product of: (1) a diol; (2) a carboxylic compound at least 80% by weight selected from terephthalic acid, iso phthalic acid, alkyl esters up to C3 of tere phthalic acid or isophthalic acid, and mixtures thereof; (3) a catalyst; and (C) a solution in a carbitol of a polyester-amideimide component comprising the reaction product of: (1) a polyester which comprises the reaction product of (a) a polyol which is a mixture of a diol and a triol; (b) a polyfunctional carboxylic compound t .east 80% by weight selected from tere phthalic acid, isophthalic acid, alkyl esters up to C3 of terephthalic acid or isophthalic acid, and mixtures thereof; (c) a catalyst; (2) a diamine; and, (3) trimellitic anhydride; and, said polyester-amide-imide wire enamel blend also cofftain- ing a fatty acid component which may be reacted into any of its polyester components. 2. A wire enamel blend according to claim 1, characterized in that the molar ratio of triol to diol in the cross-linkable polyester is from infinity to 1:1 and the molar ratio of triol to diol in the polyester-amideimide is from 1:3 to 1:10. 3. A wire enamel blend according to claim 1 or 2 characterized in that the cross-linkable polyester includes from 5 to 10 mole percent based on the carboxylic acid of a C12 to C18 monocarboxylic unsaturated acid, linear polyester includes from 3 to 10 mole percent based on the carboxylic acid of a C14 to C18 monocarboxylic unsaturated acid, and the polyester portion of the polyester-amide-imide includes from 5 to 10 mole percent based on the carboxylic acid of a monocarboxylic unsaturated acid. 4. A wire enamel blend according to claim 1, 2 or 3, characterized in that carboxylic acid in the crosslinkable polyester, in the linear polyester, and in the polyester-amide-imide, is a dimethyl ester of terephthalic acid. 5. A wire enamel blend according to any o claims 1 to 4, characterized in that the blend includes a solution in a carbitol of a cresol formaldehyde resin Comprising the reaction product of a phenol. formaldehyde, and an amine catalyst. 6. A wire enamel blend according to claim 5, characterized in that that amount of said cresol formaldehyde resin is about 7 to about 14% by weight based on total @@@@@@ 7. A wire enamel bler,d according to any of claims 1 to 6 characterized in that the amount of polyester-amide-imide by weight based on total solids is from 30 to 50%, the amount of linear polyester by weight based on total solids is from 20 to 30%, and the amount of cross-linkable polyester by weight based on total solids is from 10 to 20%. 8. A wire enamel blend according to any of claims 1 to 7, chal-acterized in that the blend includes frolll 2 5% by weight based on total solids of an adhesion promoter and up to 2% by weight based on total solids of copper ethyl aceto acetate, cobalt naphthanate or manganese naphthanate at 6% cobalt or manganese. 9. A wire enamel blend according to claim 8, characterized in that the adhesion promoter is tetraispropyl titanate. 10. A wire enamel blend according to any of claims 1 to 9, characterized in that the cross-linkable polyester, the linear polyester, and the polyester-amideimide are prepared in seQuence in the same reaction vessel. 11. A wire enamel blend according to any of aims 1 to 1O, characterized in that the diol in the linear polyester is a mixture of diols. 12. A wire enamel blend according to any of claims 1 to 11, characterized in that the carbitol at least one of diethylene glycol monoethyl ether and diethylene glycol monoethyl ether acetate. 13. A wire enamel blend according to any of claims 1 to 12, characterized in that the diol used in components of the blend is at least one of triethxrlene glycol, ethylene glycol, 1.4-butane diol and neopentyl glycol and the triol ustd in the components of The end I S Lris (2-hydroxyethyl) isocyanurate. 14. A zaire enamel blend according to any of films 1 to .;, h:ract--re4 in that the fatty acid is s a 15. A wire enamel blend according to any of claims 1 to 14, characterized in that the diamine used in making said polyester-amide-imide component is meta phenylene diamine. 16. A method of making a polyester-amide-imide wire enamel composition characterized by heating and mixing the blend of any of the preceding claims at from 80 to 90 C.

Inventors: KWIECINSKI, JAMES ROBERT, SATTLER, FRANK ANTON
Applicants: WESTINGHOUSE ELECTRIC CORPORATION
Application year: 1979
Main classification: H01B3
IPC codes: C09D167, H01B3