RU2805524C1 - Composition for obtaining protective oleophobic coating - Google Patents

Abstract

FIELD: chemical technology.

SUBSTANCE: composition for producing an oleophobic coating, which can be used to treat textile materials. The composition includes, parts by weight: polyvinyl chloride - 100, dioctyl phthalate - 36-44, additional plasticizer ester based on oleic acid and isoamyl alcohol - 12-16, mineral filler - 28-32, stabilizer - Na-salt of 6-chloro polymer, 2-oxo,3-benzoxazolylmethyl(meth)acrylate - 0.1-0.3, oleophobizer - vinylethynyldihydroxychlorosilane - 0.1-0.5 and pigment - 0.09-0.13.

EFFECT: improved physical, mechanical, and chemical protective properties of the surface of textile materials, which makes it possible to produce high-quality workwear with an extended service life and resistance to oils, fats and hydrocarbons.

1 cl, 3 tbl, 3 ex

Description

The invention relates to chemical technology, in particular to the creation of compositions for a protective oleophobic coating of textile material. The composition includes polyvinyl chloride, fatty acid esters, mineral filler, stabilizer, vinylethynyldihydrosichlorosilane and pigment. Textiles, etc. are treated with this composition. material or products made from it.

A known PVC composition containing polyvinyl chloride and a plasticizer [SU 487090, Polyvinyl chloride composition, publ. 07/02/1973].

However, the composition is not sufficiently resistant to hydrocarbons.

Also known is a composition for producing protective coatings by dipping the composition into a solution or applying it to a fabric base containing: PVC, dioctyl phthalate, mineral filler, stabilizer, polyethylsiloxane liquid and pigment [RU 2101314 ST, Composition for obtaining a protective coating, publ. 01/11/1995]

However, this composition has a low viscosity, which indicates insufficient reaction of the original ingredients with each other.

The closest analogue is the composition for obtaining a protective coating [UZ IAP 05443, Composition for obtaining a protective coating, publ. 25.07. 2017].

This technical solution is accepted as a prototype (analogue), it is also a basic object.

This composition is characterized by acid- and alkali-repellent properties and thermal stability.

This composition is technically and economically unprofitable due to its instability: viability is no more than 16 days.

Another disadvantage of this composition is its high degree of viscosity, which does not provide good protective properties of the treated surface when applying the composition to fabric by dipping, as well as the unstable quality of workwear in terms of oil resistance during operation.

Moreover, this composition does not contain the necessary components that impart stability to textile materials against the action of hydrocarbons, oils and fats.

The plasticizer contained in the known composition, sodium naphthenate, is highly soluble in many organic solvents, which is sodium soap of naphthenic acids of petroleum products (hydrocarbons). In this regard, the presence of sodium naphthenate in the composition for obtaining an oleophobic protective coating is not desirable, because Sodium naphthenate contained in a composition applied to textile material can easily be washed out when contaminated with the hydrocarbon from which it was extracted.

The next disadvantage of this composition is that the sodium salt of 2-oxo,3-benzoxazolyl (meth)acrylate has a less stabilizing effect for the oleophobic composition, due to the fact that it does not have active terminal elements in the benzoxal ring.

The next disadvantage of this composition is the presence of polyethylsiloxane liquid. The introduction of polyethylsiloxane liquid (technical product GKZh-94) into the composition leads to uneven distribution of the water repellent due to its high molecular weight, which leads to an increase in viscosity, which makes it difficult for the composition to diffuse into the fabric structure.

The objective of the proposed technical solution is to develop a composition for oleophobic finishing of textile materials, obtaining increased physical, mechanical and chemical properties of the latter, used for the manufacture of high-quality workwear with an extended service life and resistance to oils, fats and hydrocarbons.

The problem is solved by the fact that the composition for the protective coating includes polyvinyl chloride, dioctyl phthalate, an additional plasticizer, vinylethynyldihydroxychlorosilane, a stabilizer, a pigment, a mineral filler, and as an additional plasticizer it contains an ester based on oleic acid and isoamyl alcohol, and a sodium salt as a stabilizer 6-chloro, 2-oxo-3-benzoxazolylmethyl (meth)acrylate, bentonite mat as a mineral filler, with the following component ratio, parts by weight:

Polyvinyl chloride 100 Dioctyl phthalate 36-44 Ester based on oleic acid and isoamyl alcohol 12-16 Bentonite mat 28-32 Na-salt of the polymer 6-chloro,2-oxo,3-benzoxazolylmethyl (meth)acrylate 0.1-0.3 Vinylethynyldihydroxychlorosilane 0.1-0.5 Pigment 0.09-0.13

The proposed composition, in contrast to the known one, provides improved protective properties of the fabric surface and contains polyvinyl chloride as the main film former, vinylethynyldihydroxychlorosilane as an auxiliary film former instead of polyethylsiloxane liquid, and a plasticizer dioctyl phthalate and an additional plasticizer - an ester based on oleic acid and isoamyl alcohol instead of sodium naphthenate, mineral filler - bentonite mat, as a stabilizer for the sodium salt of the polymer 6-chloro, 2-oxo, 3-benzoxazolylmethyl (meth)acrylate instead of the sodium salt of the polymer 2-oxo,3-benzoxazolylmethyl (meth)acrylate.

The cause-and-effect relationship is that the proposed composition containing an ester based on oleic acid and isoamyl alcohol significantly reduces the consumption of expensive dioctyl phthalate, good mixing with dioctyl phthalate, which contributes to better plasticization of polyvinyl chloride and diffusion of the mineral filler and other ingredients, and also increases the effect mixing, which thereby better ensures plasticization, which has a positive effect on the quality of special clothing.

Fusel oil obtained from the Biokime hydrolysis-alcohol plant (Yangiyul, Tashkent region) is used as alcohol. Fusel oil is a by-product of alcohol production, its average composition is 10% ethanol, 13% p-propanol, 15% isobutanol, 51%) isoamyl alcohol, 11% mixed alcohols and water. Its main component is isoamyl alcohol, which forms ester compounds

The reaction for producing ester is carried out in this way: - distilled fatty acids of cotton soap stock and fusel oil are loaded into the reactor, for example, in a ratio of 1:3, and with stirring, concentrated sulfuric acid is slowly added in an amount of 0.5% by weight of the reaction mixture.

An estimated amount of 55.2-108.2 kg of distilled fatty acids of cotton soap stock (containing oleic acid), 35.3-88.2 kg of fusel oil (containing isoamyl alcohol) is loaded into the reactor. Mix carefully. Then, with stirring, 0.45-7.0 kg of sulfuric acid is slowly added and heated. The end of the reaction is determined by the amount of water released from the reaction zone.

At the end of the synthesis, the water in the trap is measured, and the contents of the trap and reactor are transferred to the separating unit.

The amount of water released is 15.0-17.5 liters.

The resulting product is then washed three times by shaking with distilled water until pH 4.5 to remove acid ions. Allow to separate, and the lower layer containing unreacted acids is removed.

After this, wash with 25-30 liters of a solution of 20% calcium carbonate (Na ₂ CO ₃ ) and 30-50 liters of water. After neutralization, wash again with clean water. This procedure is repeated 2-3 times until a neutral environment is achieved.

Reaction modes: temperature 140-150°C, molar ratio of distilled fatty acids and fusel oil 1:3, amount of catalyst 0.5% by weight of the reaction mixture, reaction duration 1.0-2.0 hours. The ether is transferred to a conical flask and dried with anhydrous crystalline sodium sulfate (Na ₂ SO ₄ ). The yield of the ester based on distilled fatty acids of cotton soap stock and fusel oil necessary to obtain the protective olephobic coating composition is 46-73%, depending on the content of basic substances in the original product.

To obtain an ester, to increase the amount of product formed and shift the equilibrium of the esterification reaction, the available product, alcohol, is taken in excess. With an excess of alcohol, almost all of the acid can react, but with a large excess of alcohol, the yield of the ester decreases (Table 2). The high yield of the ester based on distilled fatty acids of cotton soap stock and fusel oil to obtain the composition of the protective oleophobic coating in the second embodiment is 73%.

The main indicators of an ester based on distilled fatty acids of cotton soap stock and fusel oil necessary for obtaining a composition of a protective olephobic coating are presented in table. 1.

The bulk of these compounds are in a saturated state of 66.25%, as well as an unsaturated state of 33.75%.

The use of an ester based on distilled fatty acids of cotton soap stock and fusel oil to obtain a protective olephobic coating composition provides improved plasticizing ability compared to sodium naphthenate or other plasticizers.

Na - salt of the polymer 6-chloro,2-oxo,3-benzoxazolylmethyl (meth)acrylate is prepared in this way: - 7.2 kg of acrylic acid (or 8.5 kg of methacrylic acid) and a cooled concentrated solution of caustic soda was slowly added to it through another measuring cup (a concentrated solution of caustic soda is prepared in advance in a ratio of 8:1 methanol and water) until a neutral reaction. After reaching a neutral environment, a small excess (≈10%) of (meth)acrylic acid is again introduced and stirring is continued for 2.0 hours. Then a sample is taken. After redissolution in methanol and reprecipitation with ether, the salt is washed with ether or acetone. Determine the bromine number per double bond with bromide-bromate for unsaturation of 94-96%. Next, the initiator dinitrile azobiisobutyric acid is added to the same reactor with constant stirring in an amount of 1.0% by weight of the reacting monomers at a temperature of 65°C of the reaction medium. The reaction is continued for 2.0 hours. Based on the formation of a viscous solution, a sample is taken and the viscosity of the solution is determined using an Ubbelohde viscometer. When the viscosity [η]=0.5 dl/g is reached, the reaction is stopped. In the case of [η]>0.5 dl/g, the reaction is continued, a sample is again taken for analysis and the procedure is repeated.

The synthesized sodium salt of poly(meth)acrylic acid with a viscosity [g)]=0.5 dl/g is pumped into the reactor using a plunger pump. Then, 10.4 kg of N-chloromethyl, 6-chloro, benzoxazolone are gradually poured into the reactor containing the sodium salt of poly(meth)acrylic acid in portions with stirring. The reaction is continued with constant stirring for 3.0 hours at a temperature of 40-45°C of the reaction medium. When a homogeneous viscous solution is formed, a sample is taken and checked for the degree of substitution of the heterocyclic group up to 10%. If necessary, the polymer is precipitated with a mixture of solvents: acetone: water in a ratio of 10:1, the polymer is filtered and dried to constant weight under atmospheric conditions [Kadirow T.J., Ruziew R.R., Yariew O.M. Synthese, Strukturuntersung und Eigenschaften eines neuen Fungisids zur Schimmel-Schutz-AusrUstung von Ledern//Journal “Leder und Hautemarkt”, Germany, 2002, N 10. - S. 40-42.].

Thus, the production of a functional Na - salt of the polymer 6-chloro, 2-oxo, 3-benzoxazolylmethyl (meth)acrylate with a predetermined and controlled content of reactive groups in the composition of a protective olephobic coating for cotton fabric ensures stability of prolonged action, which makes them very promising in technological finishing processes of the textile and clothing industry.

Instead of polyethylsiloxane liquid, vinylethynyldihydroxychlorosilane is used as siloxanes [Akhmedov V.N., Kodirov T.Zh., Toshev A.Yu. Technological possibilities for obtaining new silicon-organic mono(poly)mers based on vinylethynyltrichlorosilane. Chemical industry. St. Petersburg.2009. No. 7, t.86. pp. 379-382]. The synthesis process can be carried out in ethyl ether, benzene, chloroform or tetrohydrofuran.

The technology for producing vinylethynyldihydroxychlorosilane includes the following stages:

drying the corresponding solvents and preparing solutions of reacting substances;

- carrying out the Grignard reaction with intense stirring at a temperature of 60-70°C for 6.0-8.0 hours and then cooling and at an equimolecular ratio of the reactants;

- washing the reaction mixture four to five times with water (to remove the released

magnesium chlorobrome;

- solvent distillation;

- isolation of the target product by vacuum distillation;

- hydrolysis of the product with water;

- purification of the target product by rectification.

To dry and purify the starting reagents and solvents, the required amount of ethyl ether (or benzene) is loaded into the reactor and heated to a boiling point of 74±2.0°C (or benzene to 78±2.0°C). The condensate is sent to a heat exchanger, from where the distilled and purified ethyl ether (or benzene) enters the dispenser collection for distillates.

103.78 liters of ethyl ether (or 88.73 liters of benzene) are dosed into the reactor and 53.29 liters of silicon tetrachloride are introduced with stirring and then the temperature is raised to 60°C and 68.42 liters of vinylethynylmagnesium bromide are added there in portions over 45 -50 min. Next, with continuous stirring, the temperature is raised to 70°C and the reaction continues for another 4.0-5.0 hours. After the time has elapsed, stop stirring and cool to 10.0±2.0°C for about 2.0 hours.

The resulting mixture is fed into a storage tank using a pump, where the reaction product is washed with a flow rate of about 600% water. The washing process is controlled until chlorine ions appear in the wash water, with a test with silver nitrate to remove magnesium chlorobrome.

The reaction mixture of vinylethynyltrichlorosilane, freed from magnesium chlorobrome, is fed into the separator. The distillation of the ethyl ether solvent is carried out at a temperature of 35.6 ° C (or benzene at 80.1 ° C) by vacuum distillation using a vacuum pump with a pressure for ethyl ether 1.8-2.0 or benzene 5.0-5.2 mmHg Art. Vapors from the solvent ethyl ether (or benzene) are fed into the refrigerator, where they are condensed and sent for reuse to the reactor. The yield of the intermediate product is at least 72% by weight of the initial mixtures.

The resulting vinylethynyltrichlorosilane is fed into the settling tank and then, from there, the intermediate product in the amount of 81.63 liters is sent to the mixer. When mixing vinylethynyltrichlorosilane, 182.57 liters are introduced into the mixer. water for 2.0 hours in a temperature range of 146±5°C for hydrolysis of the intermediate product.

The hydrolyzed intermediate product is fed into a heating cube for transfer to a distillation column connected to a reflux condenser. Next, the rectified product is cooled in a refrigerator, and then the target product vinylethynyldihyrochlorosilane is collected in a collector.

Yield of vinylethynyldihydroxychlorosilane product from

vinylethynyltrichlorosilane with ethyl ether - 75.46 l (58%), with benzene - 70.60 l (58%) with a boiling point of 96 ° C / 6 mm Hg. Art.; n ²⁰ o 1.4560; d ²⁰ 4 1.0183.

The use of this vinylethynyldihydroxychlorosilane instead of polyethylsiloxane liquid makes it possible to obtain a protective polymer composition based on polyvinyl chloride with an unexpected effect for hydrocarbon-resistant fabric.

The proposed composition is obtained as follows.

Example 1. 48 parts by mass are poured into a mixer equipped with a mechanical stirrer. dioctyl phthalate and 12 parts by mass. ester based on distilled fatty acids of cotton soap stock and fusel oil, mix for 30 minutes, then pour in 0.1 parts by mass. vinylethynyldihydroxychlorosilane and mixing is continued for another 45-50 minutes. 0.1 parts by mass is then added to the mixture with stirring. polymer stabilizer sodium salt 6-chloro,2-oxo,-3-benzoxazolylmethyl(meth)acrylate, and after 30-35 minutes 100 parts by mass are introduced. Emulsion PVC grade PVХЕ-6250Zh, stirring is continued for another 60-70 minutes with continuous rotation of the mixer. After the time has elapsed, 0.09 parts by mass are added. finely ground pigment (according to color) and 28 parts by mass. mineral filler - bentonite mat and then mixing is carried out for another 35-40 minutes. When ready, the composition, which has a homogeneous substance, is unloaded and loaded into a paint grinder (or ball mill), ground for 6-8 hours, followed by filtration through a mesh with a hole size of 100 microns.

The composition of the resulting composition and the test results of the main indicators are given in table. 2.

In the proposed composition, a decrease in the amount of initial components leads to a decrease in viscosity, and an increase leads to rigidity and a reduction in the viability of the composition.

The results obtained, shown in Table 2, prove that the proposed composition has higher performance compared to the known prototype composition. In the proposed composition, high viscosity indicates the best reaction of the original components with PVC compared to the prototype.

The proposed composition is used to process products made from cotton fabric art. 365 and flannel art. 1638G using the dipping method. After the excess composition has drained off, the product is sent for gelation.

Gelation is carried out in a heating cabinet at a temperature of 160-180°C for 5-7 minutes.

At the same time, the proposed composition is applied to fabric with a thickness of 0.2 mm and subjected to heat treatment at a temperature of 160-180°C for 2 minutes. The composition consumption per 1 m of surface is 0.4 kg.

This technology for preparing and applying an olephobic composition for fabric can be carried out at any enterprise in the textile or clothing industry, since the application technology does not require additional costs or special equipment. The application process can be carried out under normal conditions, using the dipping method, applying either with a spray bottle or with a roller through a squeegee.

Before and after applying a protective coating, all processes and operations for manufacturing a textile fabric or garment remain unchanged.

The results of testing the resulting olephobic coating for physical and chemical parameters in comparison with GOST 2.4.310-2016 - Special clothing to protect workers from exposure to oil and petroleum products are given in table. 3.

The protective properties of the proposed composition allow it to be used to cover mittens, aprons, special clothing that are resistant to oil, oil and other hydrocarbons.

ANALOGUES

1. SU 487090, Polyvinyl chloride composition, publ. 07/02/1973

2. RU 2101314 C1, Composition for obtaining a protective coating, publ. 01/11/1995

3. UZ IAP 05443, Composition for obtaining a protective coating, publ. 25.07. 2017

4. Kadirow T.J., Ruziew R.R., Yariew O.M. Synthese.; Strukturuntersung und Eigenschaften eines neuen Fungisids zur Schimmel-Schutz-Ausriistung von Ledern//Journal “Leder und Hautemarkt”, Germany, 2002, N 10. - S. 40-42.

5. Akhmedov B.N., Kodirov T.Zh., Toshev A.Yu. Technological possibilities for obtaining new silicon-organic mono(poly)mers based on vinylethynyltrichlorosilane. Chemical industry. St. Petersburg. 2009, no. 7, t. 86, pp. 379-382.

Claims (2)

A composition for producing an oleophobic coating, including polyvinyl chloride, dioctyl phthalate, an additional plasticizer, a mineral filler, a stabilizer, an oleophobizer and a pigment, characterized in that it contains an ester based on oleic acid and isoamyl alcohol as an additional plasticizer, and Na-salt as a stabilizer polymer 6-chloro,2-oxo,3-benzoxazolylmethyl(meth)acrylate, and vinylethynyldihydroxychlorosilane as an oleophobizer, with the following component ratio, parts by weight: Polyvinyl chloride 100 Dioctyl phthalate 36-44 Oleic ester based acid and isoamyl alcohol 12-16 Bentonite mat 28-32 Na-salt of polymer 6-chloro,2-oxo,3- benzoxazolylmethyl(meth)acrylate 0.1-0.3 Vinylethynyldihydroxychlorosilane 0.1-0.5 Pigment 0.09-0.13