BG109625A - Alkyd resins with waste polyethyleneterephtalate - Google Patents

Abstract

Alkyd resins containing waste polyethyleneterephtalate will find application in the production of air dried varnish and paint coatings used in everyday life as well as in industry. They have improved quality characteristics concerning the dry substance content, thus reducing the relative share of solvents in the end product; they do not contain any catalyst of the alcoholys is of the polyethyleneterephtalate, and the method of obtaining them runs without the participation of a catalyst. There is no catalyst in the composition of alkyd resins with waste polyethyleneterephtalate, and the weight ratio of the rest of the components is as follows: waste polyethyleneterephtalate from 4,0 to 15,0; polybasic acid, which is phthalic anhydride, from 10,0 to 20,0; alcohols, which are pentaerithritol, from 4,0 to 13,0; and trimethylolpropane from 3,0 to 15,0, as well as modifiers of the alkyd resin, which are vegetable fatty acids, from 15,0 to 65,0, or a mixture of vegetable fatty acids from 15 to 35 and vegetable oils from 20,0 to 40,0. The vegetable fatty acids are thalic and/or sunflower-seed, and the vegetable oils are sunflower-seed and/or soy-bean. The resins have acid number 7 mg KOH/g, dry residue 80 percent, resin viscosity in 50 percent solution in mineral turpentine under DIN 4 at 20 degrees C is 20-25 s. The method for obtaining the resins runs at two stages with no catalysts in the polyethyleneterephtalate alcoholysis. At the first stage, a reactor with nitrogen medium and supplied with a stirrer is charged with 2,0 to 7,5 parts by weight of pentaerithritol; the temperature is raised up to 200 degrees C, whereon there are dosed 4,0 to 15,0 parts by weight of waste polyethyleneterephtalate, the temperature is raised up to 240 degrees C and is kept at that level for 2 hours up to the end of the alcoholysis, preserving on-glass transparency for 30 min. The mixture is cooled down to 150 degrees C, there are charged 50,0 to 65,0 parts by weight of fatty acids and 12,0 to 19,9 parts by weight of phthalic anhydride, and the temperature is raised up to 160-170 degrees C and kept at that level for 1 hour, and after that it is cooled down to 130 degrees C. The second half of the pentaerithritol is charged in a quantity of 2,0 to 7,5 parts by weight, the temperature is raised up to 160 degrees C and kept at that level for 1,5 hour, whereupon the temperature is raised up to 240 degrees C at a speed of 20 degrees C/h, and when the temperature reaches 200 degrees C there is dosed 5 percent of the total mass of orthoxylene for azeotropic distillation up to reaching acid number 7 mg KOH/g, then it is diluted with mineral turpentine up to 80 percent of dry residue, resin viscosity in 50 percent solution in mineral turpentine under DIN 4 at 20 degrees C is 20-25 s. In a certain case, additional alcoholysis is carried out of vegetable oils in a quantity of 20,0 to 40,0 parts by weight with 4,0 to 13,0 parts by weight pentaerithritol at a temperature of 250 degrees C, and the process keeps running at that temperature up to achieving solubility of one part of reaction mixture with 6 parts of ethanol.

Description

Technoblast

Alkyd resins containing smooth polyethylene terephthalate will find use in the manufacture of air-drying coatings for use in the domestic and industrial sectors.

P. Background of the Invention

It is known from (1) an alkyd resin with a smooth polyethylene terephthalag based on polybasic acids and alcohols and catalysts for the saccharification of polyethylene terephthalate-cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, tetraisopropyl titanate.

It is known from (2) alkyd polyethylene terephthalate-based alkyd resin based on polyvalent alcohols / diglycerin, triglycerin, pentaerythritol, /, polyvalent acids / phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydryltetrahydlethylacetylacrylate

It is known from (3) an alkyd resin with polyethylene terephthalate based on poly-basic acids and alcohols, catalysts for the alcoholysis of polyethylene terephthalate-zinc oxide, lithium hydroxide.

1P.Technical Summary of the Invention

The composition of the alkyd resins with waste polyethylene terephthalate according to the invention does not contain a catalyst, and the other components are in the following amounts / parts by weight: waste polyethylene terephthalate from 4.0 to 15.0, polybasic acid which is phthalic anhydride from 10.0 to 20 , 0, alcohols being pentaerythritol 4.0 to 13.0 and trimethylolpropane 3.0 to 15.0 and alkyd resin modifiers being vegetable fatty acids 15.0 to 65.0 or a mixture of vegetable fatty acids from 15 to 35 parts by weight and vegetable oils from 20.0 to 40.0 parts by weight. Vegetable fatty acids are tall and / or sunflower and vegetable oils are sunflower and / or soy.

The resins of the invention have the following characteristics: acid number 7 mg KOH / g, dry residue 80%, resin viscosity in 50% solution in mineral turpentine according to DIN 4 at 20 ° C is 20-25 s.

• ·

The process for the preparation of alkyd resins with waste polyethylene terephthalate according to the invention is carried out in the absence of catalysts for the alcoholysis of the polyethylene terephthalate, the process proceeding in two stages, the first step being charged from 2.0 to 7 in a nitrogen medium reactor equipped with a stirrer. , 5 parts by weight of pentaerythritol, the temperature rises to 200 ° C, then doses from 4,0 to 15,0 parts by weight of waste polyethylene terephthalate, the temperature rises to 240 ° C and is kept for 2 hours until the end of alcoholism while maintaining transparency OCT on glass for 30 min. The mixture is then cooled to 150 ° C and charged from 50.0 to 65.0 parts by weight of fatty acids and from 12.0 to 19.0 parts by weight of phthalic anhydride. The temperature is raised to 160-170 ° C, followed by holding for 1b, then cooling to 130 ° C. Charge the second half of pentaerythritol in an amount of 2.0 to 7.5 parts by weight, raise the temperature to 160 ° C and hold for 1.5 hours, after which the temperature rises to 240 ° C at a rate of 20 ° C / h, at a temperature of 200 ° C, 5% of the total mass of ortho xylene for azeotropic distillation is dosed to an acid number of 7 mg KOH / g. This is followed by dilution with mineral turpentine to a dry residue of 80%, the viscosity of the resin in a 50% solution in mineral turpentine according to DIN 4 at 20 ° C is 20-25 s. In this case, the alcoholysis of vegetable oils in an amount of 20.0 to 40.0 parts by weight with 4.0 to 13.0 parts by weight of pentaerythritol is carried out at a temperature of 250 ° C and the process is continued at that temperature until solubility is achieved after mixing. one part reaction mass with 6 parts ethanol.

Alkyd resins with waste polyethylene terephthalate according to the invention will be used for the production of air-drying paints.

The chemical characteristics of the raw materials used according to the invention are:

Pentaerythritol has a melting point of 256-260 ° C. Trimethylolpropane has a melting point of 57 ° C and an acid number of 0.2 mg KOH / g.

Phthalic anhydride is 99.8% and a melting range of 130.8-133.0 ° C. Sunflower oil has acidity as oleic acid 0.2%, iodine number 110-143 gJ2 / 100g oil • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Soybean oil has an acidity as oleic acid of 0.6%, iodine number 120-143 gJ2 / 100 g oil

Tall fatty acids have an acid number of 193 mg KOH / g, iodine number 110-143 gJ2 / 100 g of fatty acids

Sunflower fatty acids have an acid number of 194-204 mg KOH / g, iodine number 125-136 gJ2 / 100 g of fatty acids

The waste polyethylene terephthalate has a melting point of 250-255 ° C. The mineral turpentine has a flame temperature of 33 ° C, density at 20 ° C of 0.795g / cm, boiling range of 165-200 ° C.

The alkyd resins according to the invention have exceptionally good qualitative characteristics relating to the dry matter content, which allows reducing the relative proportion of solvents in the final product. These characteristics are due to the fact that the alkyd resins of the invention do not contain a catalyst for the alcoholysis of polyethylene terephthalates and the process for their preparation is carried out without the participation of a catalyst.

Examples for carrying out the invention

Example 1.

In a quadrangular flask equipped with a stirrer, refrigerator, thermometer and nitrogen supply tube, 114.06 g of trimethylolpropane and 21.88 g of pentaerythritol (half of the total) are cold (cold). The nitrogen is bubbled and the mixture is heated to 200 ° C. . Upon reaching this temperature, 120.94 g of waste polystyrenes terephthalate is dosed. Heating is continued to 240 ° C with continuous stirring. At this temperature, a delay of 2 hours is made. The end of the alcoholysis process is monitored as drops of the mixture are applied to transparent glass and transparency The mixture is cooled to a temperature of 150 ° C, after which 444.54 g of distilled vegetable fatty acids and 117.82 g of phthalic anhydride are dosed. The temperature is raised to 160-170 ° C. The mixture is cooled to 130 ° C. The second half of pentaerythritol of 21.88 g is charged. TeMnepaTypaTa is raised to 160 ° C and maintained for 1 hour.

1.5 h-The temperature is raised to 240 ° C on a regular basis by 20 ° C / b. When the temperature reaches 200 ° C, 5% orthoxylene is dosed for azeotropic distillation. The process is continued at 240 ° C until reaching acid number 7 mg KOH / g, after which the azeotropic agent is vacuumed. The resin is diluted with mineral turpentine to 80% dry ostgms. The resin viscosity in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

Example 2.

In a quadrangular flask equipped with a stirrer, refrigerator, thermometer and nitrogen supply tube, 34.90 g of trimethylolpropane and 55.43g of pentaerythritol (half of the total) are cold (cold). The nitrogen is bubbled and the mixture is heated to 200 ° C. . Upon reaching this temperature, 47.7 g of waste polyethylene terephthalate is dosed. The heating is continued to 240 ° C with continuous stirring. At this temperature, a delay of 2 hours is made. The end of the process is monitored as drops of the mixture are applied to the mixture. transparent glass and transparency was maintained for 30 min.Smesta cooled to a temperature of 150 ° C, then dozrat 529,62g destlirani vegetable fatty acids and phthalic 123,74g

anhydride. The temperature rises to 160-170 ° C, after which a lh is maintained. The mixture is cooled to 130 ° C. The second half of the pentaerythritol 55.43g is charged.TeMnepaTypaTa is raised to 160 ° C and maintained for

The temperature is raised to 240 ° C regularly by 20 ° C / b. When the temperature reaches 200 ° C, 5% orthoxylene is dosed for azeotropic distillation. The process is continued at 240 ° C until an acid number of число mg KOH / is reached. g, after which the azeotropic agent is vacuumed. The resin is diluted with mineral turpentine to 80% dry residue. The resin viscosity in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

Example 3.

In a quadrangular flask equipped with a stirrer, refrigerator, thermometer, and nitrogen supply tube, 83.64 g of trimethylolpropane and 36.34 g of pentaerythritol (half of the total) were charged cold. Nitrogen was bubbled and the mixture was heated to 200 ° C. Upon reaching this temperature 83.64g of polyethylene terephthalate was dispensed. The heating was continued to 240 ° C with continuous stirring. At this temperature, a delay of 2 hours was made. The end of the alcohol process was monitored as drops of the mixture were applied to a clear glass. and transparency and The mixture is cooled to a temperature of 150 ° C and then stirred

· · ···

475.2g of distilled vegetable fatty acids and 128.86 g of phthalic anhydride are matured. The temperature is raised to 160-170 ° C, then a lh is maintained. The mixture is cooled to 130 ° C. The second half of pentaerythritol is charged from 36, 34g. The temperature was raised to 160 ° C and maintained for

The temperature is raised to 240 ° C regularly at 20 ° C / h. When the temperature reaches 200 ° C, 5% orthoxylene is dosed for azeotropic distillation. The process is continued at 240 ° C until an acid number of 7 mg KOH / is reached. g, after which the azeotropic agent is vacuumed. The resin is diluted with mineral turpentine to 80% dry residue. The resin viscosity in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

Example 4.

In a quadrangular flask equipped with a stirrer, a refrigerator, a thermometer and a nitrogen supply tube, charge 176.41 g of sunflower oil in cold nitrogen and the mixture is heated to 160 ° C. At this temperature, it is dosed 44.98 g of pentarerititol and 0.05 g of lead oxide. The mixture is heated to 250 °. The process is then continued at this temperature until solubility is achieved after mixing one part of the reaction mass with 6 parts of ethanol. The mixture is cooled to 180 ° C and charged 89, 16 g of trimethylolpropane. The temperature was raised to 200 ° C and then charged 119, 98 g of polyethylene terephthalate was removed. The temperature was raised to 240 ° C while the process was continued at this temperature until the alcoholysis of the polyethylene terephthalate was complete. The process of polyethylene terephthalic alcohol is monitored by droplets of the mixture applied to clear glass and transparency and maintained for 30 pip. After cooling to 160 ° C, 280.86 g of distilled vegetable fat and 119.5 g are dosed. phthalic anhydride. The mixture is heated to 180 ° C and maintained at this temperature for 1 b. After heating to 200 ° C for 2 b. Upon reaching a temperature of 200 ° C, 5% of the total mass of ortho xylene for azeotropic distillation is dosed .The mixture is heated to 240 ° C at a rate of 20 ° C / h. the process is continued at this temperature until an acid number of 7 mg KOH / g is reached, after which the azeotropic agent is evacuated. The resin is diluted with mineral turpentine to 80% dry residue - Viscosity of the resin in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

· · ·

Example 5.

In a quadrangular flask equipped with a stirrer, a refrigerator, a thermometer and a nitrogen supply tube, charge 246.20 g of sunflower oil in cold nitrogen and the mixture is heated to 160 ° C. At this temperature, it is dosed 93.41 g of pentarerititol and 0.058 g of lead oxide. The mixture was heated to 250 °. The process was then continued at this temperature until solubility was achieved after mixing one part of the reaction mass with 6 parts of ethanol. The mixture was cooled to 180 ° C and charged 31.78 g of trimethylolpropane. The temperature rises to 200 ° C and then charges 39.9 4 g of waste polyethylene terephthalate. The temperature was raised to 240 ° C

the process being continued at this temperature until the alcoholysis of the polyethylene terephthalate is complete. The process of polyethylene terephthalic alcohol is monitored by droplets of the mixture applied to clear glass and transparency and maintained for 30 minutes. Cooling to 160 ° C is followed by dosing of 278.14 g of distilled vegetable fatty acids and 144.3lg. phthalic anhydride. The mixture is heated to 180 ° C and maintained at this temperature for 1 b.Then heated to 200 ° C for 2 h-When reaching a temperature of 200 ° C 5% of the total mass of ortho xylene is dosed. azeotropic distillation. The mixture was heated to 240 ° C at a rate of 20 ° C / h..P. the process is continued at this temperature until an acid number of 7 mg KOH / g is reached, after which the azeotropic agent is evacuated. The resin is diluted with mineral turpentine to 80% dry residue. The viscosity of the resin in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

Example 6

In a quadrangular flask equipped with a stirrer, a refrigerator, a thermometer and a nitrogen supply tube, cold 340.89 g of sunflower oil is charged with nitrogen and the mixture is heated to 160 ° C. At this temperature, it is dosed 43.22 g of pentarerititol and 0.054 g of lead oxide. The mixture was heated to 250 °. The process was then continued at this temperature until solubility was achieved after mixing one part of the reaction mass with 6 parts of ethanol. The mixture was cooled to 180 ° C and charged to 67.3 lg trimethylolpropane. The temperature was raised to 200 ° C and then charged to 100 ° C , 77 g of polyethylene terephthalate wastes. The temperature was raised to 240 ° C.

the process being continued at this temperature until the alcoholysis of the polyethylene terephthalate is complete. The polyethylene terephthalalcohol alcohol process is monitored by droplets of the mixture applied to clear glass and transparency and maintained for 30 minutes. Cooling to 160 ° C is followed by 152.24 g of distilled vegetable fatty acids and 118.06 g. phthalic anhydride. The mixture is heated to 180 ° C and maintained at this temperature for 1 b.Then heated to 200 ° C for 2 b.When reaching a temperature of 200 ° C, 5% of the total mass of ortho xylene is dosed. azeotropic distillation. The mixture is heated to 240 ° C at a rate of 20 ° C / h. The process is continued at this temperature until an acid number of 7 mg KOH / g is reached, after which the azeotropic agent is evacuated. The resin is diluted with mineral turpentine to 80% dry residue. The resin viscosity in 50% solution in mineral turpentine according to DIN 4 at 20 ° C-20-25 s.

Example 7.

In a homogenizer of 2 l, equipped with silica quartzite, 400g 80% alkyd resin with polyethylene terephthalate, 120 g titanium dioxide, 3 g Bentone 34, 420 g mineral carbonate, 12 g, mineral terpene 15 g are disperse. about 4500 rpm for 30 minutes. Then, with stirring, 12 g of lead octoate 11%, 1.4 g of cobalt naphthenate 4%, 5.0 g of calcium octoate 10%, methylethylketoxime 5 g - the resulting paint has a viscosity 100s according to DIN 4 at 20 ° C.

Claims (2)

Patent Claims 9 9 f »9 ·· 9999 • · 9 9 99 • 99 • 99 · · 9 · 9 · 9 999 9 9 1. Composition of alkyd resins containing polyethylene terephthalate containing poly-basic acids, alcohols, a modifier and catalyst for the alcoholysis of polyethylene terephthalate, characterized in that it contains in the following quantities / parts by weight /: waste polyethylene terephthalate from 4.0 to 15.0 , polybasic acid - phthalic anhydride from 10.0 to 20.0, alcoholiclopentaerythritol from 4.0 to 13.0 and trimethylolpropane from 3.0 to 15.0 and alkyd resin modifiers which are vegetable fatty acids from 15.0 to 65,0 or a mixture of vegetable fatty acids of 15 to 35 parts by weight. and vegetable oils from 20.0 to 40.0 wt.h., the resin having the following characteristics - acid number 7 mg KOH / g, dry residue 80%, viscosity of the resin in 50% solution in mineral turpentine according to DIN 4 at 20 ° C is 2025 s. Composition of alkyd resins with polyethylene terephthalate waste according to claim 1, characterized in that the vegetable fatty acids are tall and / or sunflower oil and the vegetable oils are sunflower and / or soybean. v 3-Method for the preparation of alkyd resins with waste polyethylene terephthalate, characterized in that the process is carried out by catalytic alcoholysis of the polyethylene terephthalate, the process proceeding in two stages, in a first step in a nitrogen reactor equipped with a stirrer, charged with 2, 0 to 7.5 parts by weight of pentaerythritol, the temperature rises to 200 ° C, doses from 4.0 to 15.0 parts by weight of waste polyethylene terephthalate, the temperature rises to 240 ° C and is maintained for 2 hours up to end of alcoholysis while maintaining transparency on glass in for 30 minutes, after which the mixture was cooled to 150 ° C and charged from 50.0 to 65.0 parts by weight of fatty acids and from 12.0 to 19.0 parts by weight of phthalic anhydride, the temperature increased to 160 -170 ° C, followed by retention for 1b, then cooled to 130 ° C, loading the second half of pentaerythritol in an amount of 2.0 to 7.5 parts by weight, raising the temperature to 160 ° C and holding for 1 , 5 j, after which the temperature is increased to 240 ° C at a rate of 20 ° C / h, at a temperature of 200 ° C, 5% of the total mass of ortho xylene is used for azeotropic distillation, to an acid number of 7 mg KOH / g, , Ice that "·" ·· diluted with white spirit to a dry residue of 80%, a viscosity of the resin in 50% solution in mineral turpentine under DIN 4 at 20 ° C is 20-25 s. and, optionally, the alcoholization of vegetable oils in an amount of 20.0 to 40.0 parts by weight with 4.0 to 13.0 parts by weight of pentaerythritol at 250 ° C while continuing the process at that temperature until solubility after mixing one part reaction mass with 6 parts ethanol. Use of alkyd resins with waste polyethylene terephthalate according to claim 1 for the production of airborne paint and varnish materials.