An anti-icing, in particular for the protection of aircraft icing

 

(57) Abstract:

Describes an anti-icing, in particular for the protection of aircraft icing containing allenglish with 2-3 carbon atoms or oxacillinase with 4 to 6 carbon atoms, or a mixture, a polymeric thickener, a non-ionic surfactant based ethoxylate alcohol and water, characterized in that the nonionic surfactant formed from the alcohol with 6-22 carbon atoms, substituted 1-10 molecules of low molecular weight accelerated, the tool further comprises a water-soluble salt of an inorganic acid or a low molecular weight carboxylic acid or their mixture, imidazole and/or triazole compounds as corrosion inhibitor and as a polymeric thickener is a water-soluble cross-linked homopolymer of acrylic and/or methacrylic acid, and the homopolymer and the mixture have an average molecular weight of 750,000 - 1.250.000 and 0.5 wt.%-aqueous solution with pH 7 at 20C viscosity 1000 - 13000 mPas, measured by the Brookfield viscometer at 20 rpm in the following ratio, wt.%: a) 35-70 at least one alkalophilus with 2-3 carbon atoms and/or oxacillinase gene surfactants, g) of 0.03 to 1.0 at least one water-soluble salt of an inorganic acid and/or a low molecular weight carboxylic acids, d) from 0.01 to 1.0 in at least one imidazole and/or triazole compounds as corrosion inhibitor, (e) water to 1000, the weight percent relative to the tool. The technical result is an increase in time protect aircraft against re-icing and improve its sakaemachi. 8 C.p. f-crystals, 5 PL.

The invention relates to anti-icing and means for anti-icing of aircraft on the basis of glycols and water with a water-soluble crosslinked acrylic polymer as a thickener.

An anti-icing and means for anti-icing of aircraft (hereinafter briefly referred to anti-icing or icing fluids are used to remove ice, snow and/or frost from the surface of the aircraft and to prevent such deposits on these surfaces. The period of time during which the liquid icing provides protection against re-education of ice, snow and/or frost on the aircraft, called time protection against re-icing- "Holdovertime". B "Recommandations for de-/AntiIcing of Assali (ISO) specifications 11075, 11076 and 11078 subdivide nezahodnye (type I) and thickened (type II) liquid anti-icing of aircraft. Fluid II, thanks to the thickener, are pseudo-plastic consistency (non-Newtonian rheology). From anti-icing of aircraft of type II, in particular, expect that they may have more long-term protection against re-icing bearing areas before the start under extreme weather conditions, such as snow or hail, and good runoff at the start of the aircraft. According to the standard ISO 11078, which entered into force in 1993, the defense against re-icing should be at least 30 minutes at -5oC in the so-called "test of the resistance of the water jet" [liquid icing previously subjected to shear load from 3500 rpm for 5 minutes]. In accordance with the latest requirements of some aviation companies is time protection against re-icing should be significantly greater than the specified 30 minutes while simultaneously, if possible, improved runoff. Sakaemachi, basically, the better, the lower the viscosity of the liquid against freezing when the outside temperature.

It is not the other. For example, the long time protection against re-icing can be provided by using high molecular weight thickener. The resulting highly viscous film for a long time remains unchanged at rest plane and provides the desired long-term protection against re-icing ("Holdovertime"). This film, however, due to its high viscosity at rest and high yield strength is insufficient flows rapidly at the start of the aircraft. Good statemost provide fluids that form a relatively low viscosity film. Because such films are rather unstable and in a short time break, then they cannot provide the required protection against re-icing.

Thus, both properties Holdovertime" and statemost oppose each other.

There have been many experiments on the production of thickened liquids icing, providing long-lasting protection against re-icing and have a good runoff. For example, according to US-A-5118435, both properties must be retained if the thickener is a mixture of acrylic homopolymers with srednem icing contains the specified mixture of thickeners and optionally nonionic detergent from the group of apes and anionic detergent from the group of alkylarylsulfonates.

According to US-A-5334323 (EP-A-360183) the desired properties is obtained in the case of thickened liquid anti-icing of aircraft on the basis of glycols and water, if using one crosslinked polyacrylic acid, and in addition to nonionic detergent from the group alkoxysilane higher alcohols and set the pH value of the liquid with sodium hydroxide or hydroxides of sodium and potassium in them a certain ratio. As a possible homopolymer acrylic acid, you can specify all that in the form of 0.5 wt.%-aqueous solution at pH values of 7.0 have a viscosity of from 5000 to 60000 mPas at 20oC, measured using Brookfield viscometer (Brookfield-Viskosimeter) at 20 Rev/m In the particular case, however, called and recommend only CARBOPOL 934 company B. F., Goodrich Chemical GmbH, Germany. As shown brochure GC-67 1984 (German translation) company B. F., Goodrich Chemical GmbH on its products-carbopol (comparative table 1 on page 3 and pages 20 and 43), CARBOPOL 934 has a molecular weight of about 3000000 and in the form specified a 0.5% aqueous solution has a viscosity from about 30500 to 39400 mPas. Used in US-A-5334323 a homopolymer of acrylic acid is, therefore, (as recommended above US-patents) of high molecular weight which describe anti-icing of aircraft, forming a film with high resistance to shear and consist of propylene glycol, polyacrylamide of phosphate of sodium, or boraxo, of Nonylphenol ethoxylated or ethoxylated olejowego alcohol with a degree of amoxilonline 17 and water in a given volume.

The specified level of technology shows that to ensure the desired properties you can use acrylic homopolymers with high viscosity (approximately 30,000 to 40,000 mPas) and high molecular weight (from about to 3500000 2500000). Found that the thickened liquid anti-icing of aircraft on the basis of glycols and water with long lasting protection against re-icing "Holdovertime and good Sakamoto get when using acrylic homopolymer or a mixture of acrylic homopolymers with a relatively low molecular weight and relatively low viscosity in combination with higher alkoxycarbonyl alcohol and a water-soluble salt compound to maintain in the liquid a certain concentration of salt. This is a completely unexpected result. The triple combination, according to the invention consisting of a specified weight and average level of viscosity thickener specified nonionic detergent and the specified zoo provides both long-time protection against re-icing, and good statemost.

A tool with a polymeric thickener icing and anti-icing according to the invention consists mainly of:

a) 35-70 weight. %, preferably 40-60 wt.%, at least, alkalophiles with 2-3 carbon atoms or oxacillinase with 4-6 carbon atoms or mixtures thereof,

b) 0.05 to 1.5 wt.%, preferably 0.1 to 1.0 wt.% water-soluble cross-linked homopolymer acrylic acid or methacrylic acid or a mixture of such homopolymers, and the homopolymer and the mixture are, respectively, the average molecular weight of from 750000 to 1250000 and 0.5 wt.%-aqueous solution with a pH value of 7.0 and a temperature of 20oC has a viscosity of from 1,000 to 13,000 mPas, measured with the Brookfield viscometer at 20 rpm,

C) 0.02 to 1.5 weight. %, preferably 0.05 to 1.00 wt.%, at least, nonionic detergent, formed from the alcohol with 6 to 22 carbon atoms, preferably 8-18 carbon atoms, which is substituted by 1-10 molecules of low molecular weight accelerated,

g) of 0.03-1.0 wt.%, preferably 0.05 to 0.4 wt.%, at least one water-soluble salts of inorganic acids or carboxylic acids or mixtures thereof,

d) from 0.01 to 1.0 weight. %, preferably 0.03 to 0.7 wt.%, at least one connection is everything, to 100 wt.%,

the weight percent relative to the funds.

Components a) are preferably ethylene glycol, propylene glycol (1,2-propylene glycol or 1,3-propylene glycol), diethylene glycol, dipropyleneglycol or a mixture of two or more of these glycols and propylene glycols are particularly preferred. Glycols are used primarily to reduce the freezing point and, along with water, are the main components of the liquid.

Component b) is a water-soluble cross-linked homopolymer of methacrylic acid with a specific molecular weight, namely from 750000 to 1250000, and a specific viscosity, namely from 1000 to 13,000 mPas, preferably 2000-7000 mPas, measured using the Brookfield viscometer at 20 rpm 0.5 weight. % aqueous solution (polymer) with a value of pH 7.0 (installed using NaOH) and a temperature of 20oC. Component b) may also be a mixture of water-soluble crosslinked homopolymers of acrylic acid and/or water-soluble cross-linked homopolymers, because of the mix in the form of these solutions have specified viscosity 1000-13000 mPas, preferably 2000 to 7000 mPas, and an average molecular weight from 50,000 to 1250000. Component b) is preferably a homopolymer of acrylic, m is krylovii or methacrylic acid to form the corresponding acrylates, preferably acrylate alkali metal (alkali metal is preferably potassium or sodium) can be used.

The above-mentioned solubility of acrylic homopolymers takes place if, by dissolving 10 g of acrylic homopolymer in 1000 g of water at a temperature of about 20oC after establishing a pH of 7.0 hydroxide of an alkali metal get a clear solution. Suitable according to the invention cross-linked homopolymers of acrylic or methacrylic acids and their alkali metal salts known in the trade under the name CARBOPOL company B. F., Goodrich Chemicl GmbH, Germany. The term homopolymer of acrylic or methacrylic acids see also acrylic polymers, which along with acrylic or methacrylic acid containing up to 5 mol.%, preferably up to 3 mol.% the co monomer selected from the group of the complex C6-C22-alilovic esters of acrylic acid and complex C6-C22-alilovic esters of methacrylic acid. Alkyl group (saturated), which preferably has from 8 to 18 carbon atoms, may be linear or branched, preferably linear. Examples of such comonomers are n-octylacrylate, n-dellaquila, laurelcrest nonionic detergent, preferably from the group comprising alkoxylated fatty alcohol range from 1 to 10 molecules, preferably 1-5 molecules of low molecular weight accelerated. As the oxide alkylene preferred are ethylene oxide or propylene oxide, and particularly preferred ethylene oxide. The alkyl residue in alcohol fatty series contains in General from 6 to 22 carbon atoms, preferably from 8 to 18, and may be linear or branched, with the preferred linear, saturated or unsaturated, preferably, 1 to 3 double bonds. As an example we can mention: oktilovom, decroly, dodecyloxy, isotridecanol and stearyl alcohol, then alerby, cocoalkylamine alcohol and alkilany alcohol, animal fat, and a mixture of fatty alcohols with C12-alkylbis residue and C14-alkyl residue (C12/C14-fatty alcohol) ethoxylated 1 to 10 moles, preferably 1-5 moles of ethylene oxide. Other surfactants, such as anionic compounds from the group of alkylarylsulfonates excluded.

Component d) is a water-soluble salt of an inorganic acid, salt of aliphatic or aromatic carboxylic acid, i.e., mono-, di - or polycarb halogenation acid, silicic acid, phosphoric acid, sulfuric acid and nitric acid. Aliphatic and aromatic acid preferably represent C1-C3- monocarboxylic acids, such as formic and acetic acid, dicarboxylic acids, such as oxalic acid, hydroxycarbonate acid, such as lactic acid and citric acid, and benzoic acid. Water-soluble salts are in General alkali metal salts or salts of alkaline earth metals, and sodium and potassium salts are preferred. Needless to say, to obtain the necessary salt compounds in the liquid icing, you can enter only the appropriate acid, if it already has the sodium ions or potassium. Recommended compounds are low molecular weight and netessine, i.e. they are not surface-active (surfactant), because it does not affect the surface tension of a mixture of glycol/water. As suitable salts of inorganic and organic acids should be in the form of example to call, in particular, sodium and potassium salts of boric, phosphoric or phosphorous, sulfuric, nitric, formic, acetic, oxalic, lactic or citric acid.

AK, for example, benzotriazol or tolyltriazole, or a mixture of these imidazoles and/or triazoles. These triazoles are particularly preferred corrosion inhibitors.

Component e) is preferably fully desalted water. The pH of the liquid according to the invention is in the field of 7-11, preferably 7-9. Since this pH is not reached in and of itself, it set using, preferably, hydroxide of alkali metals, such as sodium hydroxide and/or potassium hydroxide. To adjust the value of pH is possible to use also other basic compounds such as alkylamines followed, as butylamine, hexylamine, octylamine or sonnyaman and/or alkanolamine as mono-, di - or triethanolamine.

Manufacture of liquid anti-icing according to the invention is carried out by mixing the individual components in any order, for example, in the mixer with stirrer at room temperature (15-30oC).

Liquid anti-icing type II to a high degree meets the previously mentioned requirements. Using the entered target salt compound in combination with a special thickener and nonionic powerbasic long time "Holdovertime and good statemost. According to the invention eliminates the opposition both properties: "Holdovertime" and sakaemachi. This unexpected result is achieved thanks to an unexpected synergism between the thickener from low to medium molecular weight, nonionic surface-active agent and salt. Their interaction leads to a long-time protection against re-icing, and a marked reduction in viscosity with increasing shear and, respectively, to the desired sakaemachi.

The invention is illustrated in more detail by the following examples and examples for comparison.

For comparison, the values of the homopolymers of acrylic acid of various molecular weights on time "Holdovertime" and sakaemachi, in the examples according to the invention and corresponding examples for comparison in each case is used so much thickener to both liquid icing had the same viscosity at 20oC and 0.3 R/m If we compare example 1 according to the invention and example 1 for comparison, obviously get more time "Holdovertime in example 1 according to the invention, since the viscosity value at 0oC and -10oC is significantly lower than in example 1 for comparison. This is totally unexpected resulto example for comparison, despite the lower the viscosity, the longer the time Holdovertime" and, due to lower viscosity, good statemost.

Example 1. Get liquid anti-icing of aircraft of type II with the following composition and in the following order:

50,00% wt. 1,2-propylene glycol,

0,17 weight. % stitched homopolymer acrylic acid with an average molecular weight of about 1250000 and viscosity 6050 mPas 0.5 wt.%-aqueous solution with a pH value of 7.0 (installed with NaOH), measured with the Brookfield viscometer at 20 rpm and 20oC,

0.10 wt.% the alcohol ethoxylate fatty row of C12-alcohol and 2 moles of ethylene oxide,

0.10 wt.% potassium nitrate,

0.05 wt.% benzotriazole,

the rest is water to 100 %.

The homopolymer and benzotriazol, surfactants and sodium nitrate dissolved in water at 20oC under stirring. Then add 1,2-propylene glycol and with the help of sodium hydroxide establish a pH value of 7.2.

The resulting liquid icing is checked against viscosity and Holdovertime".

The results are presented below:

- "Holdovertime" (according to the test of the resistance of the water jet when -5oC) - 52 minutes

Values of viscosity at +20oC, 0oC, -10of.

The example for comparison

Get liquid anti-icing of aircraft of type II with the following composition and in the following order:

50,00% wt. 1,2-propylene glycol,

0.30 weight. % stitched homopolymer acrylic acid with an average molecular weight of about 3000000 and viscosity 23750 mPas 0.5 wt.%-aqueous solution with a pH value of 7.0 (installed with NaOH), measured with the Brookfield viscometer at 20 rpm and 20oC,

0.10 wt.% the alcohol ethoxylate fatty row of C12- alcohol and 2 moles of ethylene oxide,

0.10 wt.% sodium nitrate,

0.05 wt.% benzotriazole,

the rest is water to 100 %.

The homopolymer and benzotriazol, surfactants and sodium nitrate dissolved in water at 20oC under stirring. Then add 1,2-propylene glycol and with the help of sodium hydroxide establish a pH value of 7.2.

The resulting liquid anti-icing check on the viscosity and Holdovertime".

The results are presented below:

- "Holdovertime" (according to the test of the resistance of the water jet when -5oC)- 43 minutes

Values of viscosity at +20oC, 0oC, -10oC and in each case at 0.3 rpm (0,084 with-1shear rate) and 30 rpm (8,4 c-1) see table. 2.

Example 2

0.20 weight. % stitched homopolymer acrylic acid with an average molecular weight of about 750, 000 and a viscosity of 3,000 mPas to 0.5 wt.%-aqueous solution with a pH value of 7.0 (installed with NaOH), measured with the Brookfield viscometer at 20 rpm and 20oC,

0.10 wt.% the alcohol ethoxylate fatty row of C12-alcohol and 2 moles of ethylene oxide,

0.05 wt.% sodium sulfate,

0.05 wt.% benzotriazole,

the rest is water to 100 %.

The manufacturer carried out as described in example 1.

The resulting liquid anti-icing check on the viscosity and Holdovertime".

The results are presented below:

- "Holdovertime" (according to the test of the resistance of the water jet when -5oC) - 55 minutes

Values of viscosity at +20oC, 0oC, -10oC and in each case at 0.3 rpm (0,084 with-1shear rate) and 30 rpm (8,4-1) see table. 3.

Example 3

Get liquid anti-icing of aircraft of type II with the following composition and in the following order:

50,00% wt. 1,2 - propylene glycol,

0,13 weight. % stitched homopolymer acrylic acid with an average molecular weight of about 1250000 and a viscosity of 4400 mPas 0.5 wt.%-aqueous solution with a pH value of 7.0 (to ascertain the alcohol fatty row of C14-alcohol and 4 moles of ethylene oxide,

0.08 wt.% dihydrogenphosphate potassium,

0.05 wt.% benzotriazole,

the rest is water to 100 %.

The resulting liquid anti-icing check on the viscosity and Holdovertime".

The results are presented below:

- "Holdovertime" (according to the test of the resistance of the water jet when -5oC) - 49 minutes

Values of viscosity at +20oC, 0oC, -10oC and in each case at 0.3 rpm (0,084 with-1shear rate) and 30 rpm (8,4 c-1) see table. 4.

Example 4

Get liquid anti-icing of aircraft of type II with the following composition and in the following order:

50,00% wt. 1,2 - propylene glycol,

0,25 weight. % stitched comprimere acrylic acid with an average molecular weight of about 1000000, containing as co monomer 2 mol.% complex dodecylamide of methacrylic acid, the molar percent relative to the entire polymer. The polymer has a viscosity of 8000 mPas 5 wt.%-aqueous solution with a pH value of 7.0 (installed with NaOH), measured with the Brookfield viscometer at 20 rpm and 20oC,

0.10 wt.% the alcohol ethoxylate fatty row of C16- alcohol and 7 moles of ethylene oxide,

0.08 wt.% dihydrogenphosphate sodium,

The resulting liquid anti-icing check on the viscosity and Holdovertime".

The results are presented below:

- "Holdovertime" (according to the test of the resistance of the water jet when -5o(C) - 58 minutes

Values of viscosity at +20oC, 0oC, -10oC and in each case at 0.3 rpm (0,084 with-1shear rate) and 30 rpm (8,4-1) see table. 5.

1. An anti-icing, in particular for the protection of aircraft icing, and containing at least one allenglish with 2 to 3 carbon atoms, or oxacillinase with 4 to 6 carbon atoms, or a mixture, a polymeric thickener, neinogennye surfactant-based ethoxylate alcohol and water, characterized in that at least one neinogennye surfactant formed from the alcohol with 6 to 22 carbon atoms, substituted 1 - 10 molecules of low molecular weight accelerated, the tool further comprises at least one water-soluble salt of an inorganic acid or a low molecular weight carboxylic acid or a mixture of at least one imidazole and/or triazole compound as a corrosion inhibitor and as a polymeric thickener is a water-soluble cross-linked homopolymer acne 0.5 weight. % aqueous solution with pH value of 7 at 20oC have a viscosity of 1000 to 13000 MPa s, measured by the Brookfield viscometer at 20 rpm./min, in the following ratio, wt.%: a) 35 - 70 of at least one alkalophilus with 2 to 3 carbon atoms and/or oxacillinases 4 to 6 carbon atoms, b) 0,05 - 1,5 water-soluble polymeric thickener, in) of 0.02 to 1.5 at least one nonionic surfactant, d) of 0.03 to 1.0 at least one water-soluble salt of an inorganic acid and/or a low molecular weight carboxylic acids, d) from 0.01 to 1.0 in at least one imidazole and/or triazole compounds as corrosion inhibitor, (e) water to 100 the weight percent relative to the tool.

2. Means under item 1, characterized in that component b) is a water-soluble crosslinked homopolymer acrylic or methacrylic acid or a mixture of such homopolymers, and the homopolymer and the mixture are, respectively, the average molecular weight of the 750,000 - 1250000 and a 0.5 wt.%-aqueous solution with pH value of 7 at 20oC have a viscosity of 2000 to 7000 MPa s, measured by the Brookfield viscometer at 20 rpm./m

3. Means under item 1 or 2, characterized in that component b) is a and CLASS="ptx2">

4. The tool p. 1 or 2, characterized in that component b) is an ethoxylate of a fatty alcohol range from 8 to 18 carbon atoms and with 1 to 5 molecules of ethylene oxide.

5. Tool according to one or more paragraphs.1 to 4, characterized in that component d) is a water-soluble salt of boric acid, halogenations acid, silicic acid, phosphoric acid, sulfuric acid or nitric acid as an inorganic acid or WITH1-C3-monocarboxylic acid, dicarboxylic acid, hydroxycarbonic acid or benzoic acid as the aliphatic or aromatic carboxylic acids.

6. Tool according to one or more paragraphs.1 to 4, characterized in that component d) is a water-soluble salt of an alkali metal boric acid, phosphoric acid, phosphorous acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, lactic acid or citric acid.

7. Tool according to one or more paragraphs.1 - 6, characterized in that it contains, wt%: 40 - 60 component (a); 0.1 to 1.0 component b); 0,05 - 1,0 component); 0,05 - 0,4 component g) of 0.03 to 0.7 component d); component (e) rest.

8. The product p. the measure of acrylic and/or methacrylic acid, moreover, a homopolymer or a mixture have an average molecular weight of 750,000 - 1.250.000 and a 0.5 wt.%-aqueous solution with pH value of 7 at 20oC have a viscosity of 2000 to 7000 MPa s, measured by the viscometer of Buckfield at 20 rpm./min, a) is 0.02 - 1.5 ethoxylate fatty alcohol range from 8 to 18 carbon atoms and with 1 to 5 molecules of hydroxy ethylene, g) of 0.03 to 1.0 water-soluble alkali metal salt of boric acid, phosphoric acid, phosphorous acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, lactic acid or citric acid, d) from 0.01 to 1.0 benzotriazole or tolyltriazole, e) rest water to 100.

9. Means under item 8, characterized in that it contains, wt%: 40 - 60 component (a); 0.1 to 1.0 component b); 0,05 - 1,0 component); 0,05 - 0,4 component g); 0,03 - 0,7 component d component e) the rest is up to 100.

 

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29 cl, 11 dwg, 7 tbl, 2 ex

FIELD: motor-car industry; other industries; methods of production of the anti-icing reactant.

SUBSTANCE: the invention is pertaining to the method of production of the anti-icing reactants for maintenance of roads in winter. The method of production of the anti-icing reactant based on sodium chloride and calcium chloride provides for mixing of the sodium chloride with calcium chloride and their heating and drying. Sodium chloride crystals are coated with the atomized solution of calcium chloride and dried in the "boiling bed" kiln with production of the double-layer granules, the outer layer of which is composed out of calcium chloride. Sodium chloride crystals are coated with calcium chloride in two phases. The forming small particles of calcium chloride are fed into the cyclone, whence the cyclone dust of the calcium chloride is fed into the mixer for intermixing with the wet crystals of sodium chloride. The produced anti-acing reactant has the improved physicochemical thermodynamic properties.

EFFECT: the invention ensures, that the produced anti-acing reactant has the improved physicochemical thermodynamic properties.

3 cl, 1 ex, 2 tbl

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