RU2699645C1 - Method of preparing amber lacquers - Google Patents

Abstract

FIELD: paint industry.SUBSTANCE: invention relates to a method of preparing amber lacquer widely used in painting, as well as for protection of various surfaces from microorganisms and biocorrosion. Method involves cleaning amber from oxide crust and grinding amber to 0.5–5 mcm. Suspended in solvent, amber is subjected to ultrasound treatment with frequency of 22–44 kHz, after which it is dissolved at boiling temperature of used solvent in capacity with reflux condenser. Solvent used is ethanol, acetone, white spirit, turpentine.EFFECT: invention provides amber lacquer with high concentration of amber in it, making 59–73 %, while reducing time of obtaining the target product to 4–6 hours.5 cl, 1 dwg, 1 tbl, 4 ex

Description

The invention relates to the field of chemical technology and biotechnology and is intended for the preparation, in particular, of amber varnishes, widely used in painting, as well as for protecting various surfaces (wood, metals, glass, plastics, nails) from microorganisms and biocorrosion.

The aim of the invention is to simplify and accelerate the process of preparing amber varnishes.

The goal is achieved by pre-treatment of waste mechanical processing of amber and / or amber small, unsuitable for further jewelry processing in an aqueous solution containing NaCl and citric acid (C ₆ H ₈ O ₇ ) in the field of ultrasound (patent for invention RU 2626468, IPC С04В 41 / 53, 07.28.2017), rinsing, drying, grinding to a size of 0.5-5 μm, suspending the crushed amber in a solvent (ethanol, methanol, acetone, nefras-C4-155 / 200 (white spirit), turpentine, etc. ), in the ratio 1: 1-1: 10, processing the suspension at room temperature ultrasound m with a frequency of 22-44 kHz for 5-50 minutes, and a power density of 0.1-10 W / cm ³ , followed by dissolution for 1-10 hours, depending on the physicochemical properties and, in particular, boiling point solvent used, in a tank with attached reflux condenser.

Amber varnishes obtained by the aforementioned method are both an independent value for protecting surfaces, for example, from biocorrosion, and as a semi-product introduced, for example, in artistic oil paints, in cosmetic compositions, or as a means of protecting toenails from fungal infections in public baths, pools beaches.

Despite all the advances in the technique of obtaining coatings with desired properties, amber varnish is still considered one of the best. Its use is very promising for covering musical instruments, furniture, underwater parts of ships. Furniture covered with amber lacquer, for a long time maintains an even radiant shine, the bottom of the ship does not grow with mollusks (Violetta Boguchar. Resin amber centuries. Http://malahov-plus.com/main/in-addition2/316-smola-vekov-jantar.html) . Known technologies for preparing varnish take a long time (hours and even days), and are associated with the loss of a significant part of amber (NN Moshkov. Unknown about the known. Amber is beauty, health and longevity by nature. Kaliningrad, 2008. 82 pp.) .

A known method of preparing amber varnish, including coarse grinding of amber, subsequent heating to 160 ° C, melting amber, mixing with linseed oil (1: 1) and thinner with white spirit or turpentine (1: 2), boiling the mixture for 3- 4 hours and prolonged sedimentation of coarse, not completely dissolved completely particles (Zemetis M.M. Essays on the problem of violin varnish. Riga, 1963 http://www.balalaika-master.ru/paper/010/).

A known method for producing amber varnish, including grinding amber to particles ≤7 mm in size, subsequent heating with drying oil, in a ratio of approximately (1: ≤20), to a temperature at which amber softens, swells and floats to the surface of drying oil. The mixture is subjected to further heat treatment with a limited oxygen supply, and a temperature of ≥350 ° C, for several hours until a uniform consistency is formed (patent for invention US 6011097, C09D 191/00, 04.01.2000). The above methods associated with the dry distillation of amber, accompanied by heating to high temperatures and the destruction of the primary structure of amber, make it possible to obtain, as a rule, a dark varnish, require a long time to obtain it and special measures to limit the access of oxygen, and only 15- 20% of the initial product - amber goes into solution (Srebrodolsky B.I. Amber. M., Nauka, 1984, p. 110; Srebrodolsky B.I. The world of amber. - Kiev, Naukova Dumka, 1988, p. 143).

A known method of producing amber varnish by dissolving pre-fused and transformed into amber rosin raw materials. The method is difficult to implement and, ultimately, allows you to get not amber varnish, but varnish from amber rosin (Volkov P. Production of varnishes. St. Petersburg, Printing house bro Panteleev, 1882.330 s .; http: // www. backtomusic.ru/do/acoustic/varnish).

There is a method that provides accelerated preparation of amber varnish and a more complete dissolution of amber due to the use of ultrasound after dissolving the main part of amber in hot linseed oil at 120-160 ° C for 40-80 min (patent for the invention No. RU 2543169, C09D 004/00, 02.27.2015), however, aimed only at the preparation of oil varnish.

The problem posed in the present method is solved by pre-treatment of waste of mechanical processing of amber and / or amber, small, unsuitable for further jewelry processing in an aqueous solution containing NaCl and citric acid (C ₆ H ₈ O ₇ ) in the ultrasound field (patent for invention RU 2626468, IPC С04В 41/53, 07/28/2017), rinsing, drying, grinding to a size of 0.5-5 microns, suspending crushed amber in a solvent (ethanol, methanol, acetone, nefras-C4-155 / 200 (white spirit), turpentine, etc.), in a ratio of 1: 1-1: 10, processing the suspension at room temperature by ultrasound with a frequency of 22-44 kHz for 5-50 minutes, and a power density of 0.1-10 W / cm ³ , followed by dissolution for 1-10 hours depending on the physicochemical properties and, in particular, temperature boiling the solvent used, in a container with an attached reflux condenser.

At lower power densities of ultrasound, its effectiveness decreases, at higher - the likelihood of unwanted sound-chemical reactions increases (Akopyan V.B., Ershov A.Yu., Fundamentals of the interaction of ultrasound with biological objects, Moscow, Bauman Russian State Technical University , 2006, 223 p.).

The technical result is achieved by using a simple design (Fig. 1), containing a container 1, with crushed amber suspended in a solvent, heated on, for example, an electric stove 2 with a sand bath 3, and equipped with a reflux condenser 4, cooled by running water and providing vapor recovery and return them into a container with a boiling suspension, as well as limiting the contact of the boiling liquid with oxygen. The proposed method for obtaining amber varnish includes:

- preliminary cleaning of raw materials - wastes of mechanical processing of amber and / or amber of small fractions unsuitable for further jewelry processing in an aqueous solution, NaCl and citric acid (C ₆ H ₈ O ₇ ) in an ultrasound field with a power density of 1-10 W / cm within 5-10 minutes;

- rinse in clean water;

- drying;

- mechanical grinding of pieces of amber to particles with a size of 0.5-5 microns;

- suspension of crushed amber in a solvent (ethanol, methanol, acetone, nefras-C4-155 / 200 (white spirit), turpentine, etc.) in a ratio of 1: 1-1: 10, depending on the properties of the solvent;

- sonication with a frequency of 22-44 kHz for 5-50 minutes, and a power density of 0.1-10 W / cm ³ ,

- dissolution of crushed and suspended amber within 1-10 hours, depending on the properties of the selected solvent at its boiling point,

- removal of extraneous and insoluble particles of amber by filtration;

- packaging of finished amber varnish.

To compare the properties of varnishes obtained by dissolving amber powder in various solvents, we used the method, which is a chain of sequentially implemented standard laboratory methods:

- taking into account the mass ratio of amber powder and added solvent →

→ applying a standard amount, for example, 1 ml of the finished product on a smooth, horizontal surface of a plate of the same material (for example, aluminum) at a fixed temperature, for example, at 30 ° C, under conditions of free spreading of varnish →

→ drying the plate to a constant weight →

→ measuring the spreading area of a standard amount of varnish →

→ measuring the thickness of the obtained film using, for example, a coating thickness gauge RICHMETERS GY-910 and at the same time performing additional control of drying the film to a constant thickness →

→ measuring the area of a spot formed during spreading and drying a standard amount of varnish, using any of the many methods of measuring areas, for example, using a palette →

→ calculation of the amount of dry matter in the film by multiplying the film area by its thickness →

→ calculation of the concentration of dissolved amber in the varnish, taking into account the amount of dry matter in 1 ml of spreading varnish →

→ assessment of the solubility of amber in the form of a powder with micron particles in a particular solvent based on the data obtained (concentration of amber in the varnish and the initial ratio of amber to solvent).

The invention is illustrated by examples, which are not, however, limiting.

Example 1

Amber mechanical waste and a small fraction of amber unsuitable for jewelry are cleaned of the oxide film by washing in an aqueous solution, NaCl and citric acid in an ultrasound field with a power density of 5 W / cm ³ for 5-10 minutes; rinse with clean water, dry, crush amber in a planetary mill to a particle size of 2.5 ± 3 μm, suspend crushed amber in ethanol in a ratio of 1: 5, and expose it at room temperature to ultrasound at a frequency of 22 kHz for 20 minutes and power density 5 W / cm ³ , dissolve amber, crushed and suspended, in ethanol for 4 hours at a boiling point of 78.4 ° C, then cool, remove foreign and insoluble particles of amber by filtration.

The prepared varnish is evaluated by the concentration of amber dissolved in ethanol, for which, 1 ml of varnish is poured onto a clean, flat, horizontal surface of an aluminum plate heated to 30 ° C, 1 mm thick, dried, the thickness of the formed film is measured using a Richmeters GY-910 thickness gauge , its area by applying a palette and, based on the data obtained, the concentration of amber in the solution was calculated.

Example 2

Amber mechanical waste and a small fraction of amber unsuitable for jewelry are cleaned of the oxide film by washing in an aqueous solution, NaCl and citric acid in an ultrasound field with a power density of 5 W / cm ³ for 5-10 minutes; rinse with clean water, dry, crush amber in a planetary mill to a particle size of 2.5 ± 3 μm, suspend crushed amber in acetone in a ratio of 1: 5, subject to ultrasound at room temperature with a frequency of 22 kHz for 20 minutes, and power density 5 W / cm ³ , dissolve amber, crushed and suspended, in acetone for 4 hours at a boiling point of 56.2 ° C, then cool, remove extraneous and insoluble particles of amber by filtration.

The prepared varnish is evaluated by the concentration of amber dissolved in acetone, for which, 1 ml of varnish is poured onto a clean, flat, horizontal surface of an aluminum plate heated to 30 ° C, 1 mm thick, dried, the thickness of the formed film is measured using a Richmeters GY-910 thickness gauge and its area by applying a palette, after which, based on the data obtained, the concentration of amber in the solution is calculated.

Example 3: Waste from machining amber and / or a fine, unsuitable for processing amber fraction is cleaned of the oxide film by washing in an aqueous solution, NaCl and citric acid in an ultrasound field with a power density of 5 W / cm ³ for 5-10 minutes; rinse with clean water, dry, crush amber in a planetary mill to a particle size of 2.5 ± 3 μm, suspend crushed amber in turpentine in a ratio of 1: 5, subject to the action of ultrasound at room temperature with a frequency of 22 kHz for 30 minutes, and power density 8 W / cm ³ , amber is dissolved, crushed and suspended in turpentine for 6 hours at a boiling point of 161 ° C, then it is cooled, extraneous and insoluble particles of amber are removed by filtration.

The prepared varnish is evaluated by the concentration of amber dissolved in turpentine, for which 1 ml of varnish is poured onto a clean, flat, horizontal surface of an aluminum plate heated to 30 ° C, 1 mm thick, dried, the thickness of the formed film is measured using a Richmeters GY-910 thickness gauge and its area by applying a palette, after which, based on the data obtained, the concentration of amber in the solution is calculated.

Example 4: Waste from machining amber and a fine, unsuitable for processing amber fraction are cleaned of the oxide film by washing in an aqueous solution, NaCl and citric acid in an ultrasound field with a power density of 5 W / cm ³ for 5-10 minutes; rinse with clean water, dry, crush amber in a planetary mill to a particle size of 2.5 ± 3 microns, suspend crushed amber in white spirit at a ratio of 1: 5, and expose it at 40 ° C to ultrasound at a frequency of 22 kHz for 30 minutes and with a power density of 5 W / cm ³ , amber is dissolved, crushed and suspended in white spirit for 6 hours at a boiling point of 165 ° C, after which extraneous and insoluble particles of amber are cooled and removed by filtration.

The prepared varnish is evaluated by the concentration of amber dissolved in white spirit, for which, 1 ml of varnish is poured onto a clean, flat, horizontal surface of an aluminum plate heated to 30 ° C, 1 mm thick, dried, the thickness of the formed film is measured using a Richmeters GY- thickness gauge 910 and its area by applying a palette, after which, based on the data obtained, the concentration of amber in the solution is calculated.

Thus, the set of distinctive features of the described invention ensures the achievement of the specified result.

Using the proposed invention allows to reduce the time to obtain the finished product - amber varnish with a high content of amber.

An additional search for known solutions showed that the claimed invention does not follow explicitly from the prior art for a specialist, since the use of ultrasound allows pre-treatment of amber, accelerating its swelling, reducing its losses, and using a reflux condenser makes it possible to avoid solvent loss, reduce contact of the treated solution with oxygen, and, consequently, prevent its oxidation and color change, to ensure the highest possible increase in temperature creating amber in a particular solvent, while maintaining a constant dissolution temperature equal to the boiling point of the solvent, to prevent overheating of the amber suspension in the solvent.

Claims (5)

1. The method of preparation of amber varnishes, including cleaning amber from oxide peel, grinding amber to a size of 0.5-5 microns, characterized in that the amber suspended in a solvent is subjected to sonication at a frequency of 22-44 kHz, after which it is dissolved at a temperature boiling the solvent used in a reflux tank. 2. A method of preparing amber varnishes according to claim 1, characterized in that ethanol is used as a solvent. 3. A method of preparing amber varnishes according to claim 1, characterized in that acetone is used as a solvent. 4. The method of preparation of amber varnishes according to claim 1, characterized in that white spirit is used as a solvent. 5. A method of preparing amber varnishes according to claim 1, characterized in that turpentine is used as a solvent.

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