RU2183216C2 - Aircraft treatment composition - Google Patents

Abstract

FIELD: special-purpose fluids. SUBSTANCE: invention provides multi-purpose aircraft fluid based on aqueous solution of glycols and/or glycerol (ca. 40%) thickened with polymer thickener (at least 0.05%) and/or its neutralization salt, neutralization agent, in particular sodium hydroxide, to provide pH value close to 7.1, a surfactant forming associate with thickener, corrosion inhibitor, colorant, and water - the balance. Thickener contains, wt.%: one or more α-,β--unsaturated carboxylic acids bearing one monoethylenic bond, 1-99.9; one or more unsaturated monomers with preferably macromonomers containing at least one side hydrophobic fragment, 0.1-99; and one or more unsaturated monomer with polyethylenic bonds. EFFECT: increased resistance to drops of viscosity and other critical parameters provoked by action of heat and/or shear forces. 21 cl, 31 tbl

Description

 Related patents and applications that have a general purpose and are incorporated into this description by reference include US patent applications that have the following numbers: 887645, 887646, 887642, 887673, 887672, 887641, 887648, 887647, 887644 and 887671.

 The present invention relates to compositions based on glycol or glycerol, intended to eliminate or prevent icing of airplanes, hereinafter sometimes referred to together under the common name "aircraft liquids" (SJ). Thickeners are added to these liquids in the form of some polymers containing macromonomers bearing hydrophobic fragments that thicken the above liquids, while the thickening process proceeds by an associative mechanism. In particular, the present invention relates to liquids that eliminate or prevent icing of airplanes (sometimes hereinafter referred to as VLW and RLW, respectively), which have improved thermal stability and therefore find wider use as deicers (which are stored and used at elevated temperatures). Since the aircraft fluids claimed in the present invention have found application both in the form of products for eliminating and for preventing icing, hereinafter in the text they are sometimes referred to under the general name "general purpose aircraft fluids" (SSS).

 Aircraft that are parked on the ground, or temporarily parked there in between flights, are able to accumulate snow, ice, snow pellets or hoarfrost on their surface in cold winter weather. The presence of such deposits, especially on the aerodynamic surfaces of an aircraft, is generally unsafe and creates conditions that impede launch, or, at least, is highly undesirable during take-off and in the initial period of flight, since even small deposits can lead to serious deterioration of the aerodynamic characteristics of the wing , sometimes causing an airplane crash when leaving the ground or during launch and resulting in loss of life.

 Glycols have long been used in aqueous solutions of various concentrations as deicers, which are sprayed onto the surface of an aircraft to remove deposits from snow, ice, cereals and hoarfrost. Such glycol liquids, to eliminate icing of aircraft, are usually used in a heated state in order to more effectively break the adhesion of the surface to ice or to melt snow. A typical liquid deicer for aircraft consists of mixtures of alkaline glycol (usually ethylene glycol, propylene glycol and / or diethylene glycol) and water (as solvent), taken in approximately equal weight proportions and having a pH of 7.3-9.0. These fluids contain ionic corrosion inhibitors, flame retardants, and surfactants, which help to wet the surface of the aircraft during a spray operation. Instead of glycol in such liquids, glycerin is optionally used to remove icing, and their preparation is carried out in the same way. It is further intended that any reference to glycol liquids to remove icing on aircraft (VLA) or to prevent icing (AL) or to so-called general purpose aircraft liquids (LSS) will also include liquids prepared using glycerin used in place of or in addition to one or more glycols.

 Provided that the hot liquid is used at a sufficiently close distance from the surface, the use of heated liquid minimizes its amount necessary to remove snow and ice. VLW can also be used in high pressure flow to remove snow and ice deposits from the surface of a plane with a strong stream of liquid.

 After such a treatment, the VLF remains on the surface of the aircraft in the form of a film in order to later serve already as an anti-icer, which provides long-term antifreeze protection and delays the subsequent formation or growth of deposits of snow, ice, snow pellets or frost on the surface of the aircraft. The same aircraft fluids in various concentrations can be successfully used both for removal and for the prevention of icing. However, without a thickener, VLF are able to drain from the inclined surface of the wings or tail and from the almost vertical surface of the fuselage and the tail stabilizer. Therefore, in the absence of a thickener, they provide only limited protection against icing.

For more effective protection, aircraft fluids typically contain a thickener and it is desirable that they have the following characteristics (none of which impede their use for removing ice):
(a) the formation of a continuous film after application by means of a standard spray device, even on non-horizontal surfaces of the aircraft, which are decisive in relation to its aerodynamic characteristics during launch or take-off, for example, a vertical tail stabilizer, but at the same time do not interrupt the smooth contour line fuselage surfaces;
(6) long-lasting anti-icing protective effect; and
(c) viscous and rheological characteristics that accelerate the formation of a strong effective protective film, but nevertheless allow the liquid coating to drain off the surface of the wings as a result of the action of the shear force of the wind when it is off the ground before the aircraft turns.

 Prior art icing fluids (AI) are thickened, as a rule, with compounds having very large molecules (for example, xanthan gum or various organic polymers, such as some acrylics), the thickening effect of which is determined by molecular weaving and intermolecular friction (adhesion) ) Such thickeners have disadvantages due to the fact that they do not provide optimal non-Newtonian behavior (i.e., their viscosity does not decrease fast enough and / or wide extensively under the action of shear wind) for use in all weather conditions and on relatively slow turbojet aircraft devices such as scheduled airplanes. In addition, these thickeners are subject to excessive viscosity reduction as a result of high shear forces from the operation of the spray heads used to apply the working fluid to the surface of the aircraft.

 An important step forward in the technology of aircraft icing prevention liquids was provided by the compositions proposed in U.S. Patent 5,461,100 and in U.S. Patent Application 08/065237, with its filing date May 20, 1993, both pending and general purpose. Both of these documents are hereby incorporated by reference. These inventions are based on the unexpected discovery of the authors that some polymer thickeners containing macromonomers, the thickening effect of which is due to the association among hydrophobic groups, have specific effectiveness as thickeners for glycol-based fatty acids. These liquids provided the creation of such liquid products that prevent the formation of ice, which have a significantly longer protection time compared to previous compositions for this purpose, but like the last of these newly created products have found limited use as liquids to eliminate icing, as achieved with their help the protective time tended to decrease due to prolonged heating at temperatures that are dealt with in ice removal operations.

 The present invention is based on the unexpected discovery that such icing-preventing liquid compositions can be improved in such a way as to significantly improve their thermal stability, making them more useful for use as liquid materials for eliminating (and also preventing) icing.

 The present invention provides a composition that retains its purpose for protection against icing and at the same time is much more useful for use as an ice removal liquid. It is a solution based on glycol or glycerol, thickened with a polymer, preferably containing a macromonomer and carrying a hydrophobic group. The polymer content is not more than 5 wt.% Of the total weight of the composition. The polymer is present in the aircraft fluid in an amount sufficient to thicken it in order to enhance the adhesion of the fluid to the surface of the stationary aircraft, but at the same time providing the possibility of its removal caused by the shear force of the wind during its run up to a full revolution. Improved thermal stability is achieved by using a certain amount of a suitable stabilizing base, preferably by adding a stabilizing salt and controlling the glycol and / or glycerol content and the pH of the liquid.

 Accordingly, the present invention provides a composition for combating icing of aircraft with improved thermal stability, including a mixture of glycol and / or glycerol, water, preferably an alkali-swellable polymer thickener carrying hydrophobic groups, the thickening effect of which proceeds mainly by the intermolecular associative mechanism among these hydrophobic groups moreover, this fluid has sufficient viscosity to adhere to the aerodynamic surface of an aircraft in a state of and quiet, but at the same time remains sufficiently fluid under the influence of wind shear forces to flow off the airfoil surfaces of the aircraft when it reaches the value of the take-off speed, or close to it. Preferably, the thickener comprises a macromolecule backbone to which hydrophobic groups are attached via flexible end chains, and where, in particular, these flexible end chains include one or more hydrophilic polymers. In addition, it is desirable that these flexible end chains are long enough so that the hydrophobic groups are located outside any "carboxyl" environment of the main polymer chain, that is, without any electronic influence from the carboxyl groups attached to the main chain. Although the thickeners of the present invention exhibit a significant deviation in molecular weight, depending on their molecular composition (which is actually one of their advantages), it is preferred that each repeating unit has a molecular weight of not more than 6000, more preferably not more than 3000.

The properties of modern universal icing fluids for aircraft anti-icing (aforementioned USZh) can also be characterized by the results of standard airline tests for the following parameters: durability (protection time) when spraying with water (Water Spray Endurance Time) (WSET), length of movement of the boundary layer (Boundary Layer Displacement Thickness) (BLDT) and viscosity. Thus, the present invention provides USJ in which the WSET parameter is at least about 30 minutes, preferably about 80 minutes, and the BLDT parameter is less than 11 mm, preferably less than 10 mm, and more preferably less than 8 mm at -20 ^{° C.} .

 The present invention also provides a method for thickening a water-glycol or water-glycerin aircraft liquid, which comprises mixing it with a thickener. In addition, the invention provides a method for controlling icing of aircraft, comprising both a method of preventing and eliminating icing, and comprising applying a fluid containing a thickener to the aerodynamic surface of the aircraft.

The thickeners proposed in the present invention, preferably obtained from polymerizable carboxylic acids, copolymerized with macromonomers bearing hydrophobic groups. Thus, preferred macromonomer-containing polymers used in the present invention include:
(A) 1-99.9, preferably 10-70% by weight of one or more α-, β- unsaturated carboxylic acids with a monoethylene bond, usually methacrylic acid;
(B) 0-98.9, preferably 30-85 weight. % of one or more unsaturated monomers with mono-ethylene bond, usually ethyl acrylate;
(C) 0.1-99, preferably 5-60 weight. % of one or more unsaturated mono-ethylene-linked macromonomers; and
(D) 0-20, preferably 0-10 weight. % or more of one or more unsaturated monomers with a monoethylene bond, usually trimethylol propane triacrylate.

 The macromonomer portion preferably includes at least about 5 weight. % polymer.

The fluid used is preferably a standard Type II anti-icing aircraft fluid, known as a joint product of the Society of Automotive Engineers (SAE) / International Standards Organization (USA) and the International Organization for Standardization (ISO) ISO) This liquid is thickened with a macromonomer-containing polymer in an amount of not more than 5 wt.%. It is desirable that this polymer thickener is present in an amount of from 0.05 to 4 wt.%, Preferably from 0.1 to 2 wt.%
The glycol or glycerol component of this composition is preferably ethylene glycol, alone or in combination with other glycols, such as diethylene or propylene glycol, and / or glycerol. The glycol or glycerin component is preferably present in an amount of at least about 40 weight. %, preferably 50-95 weight. %, more preferably 60-70 weight. % Since the freezing point curves are different for other glycols and glycerol, their preferred concentrations differ from ethylene glycol concentrations, but can be taken from the prior art.

 The desired alkalinity (pH) is obtained by mixing with a neutralizing base, which is an amine, such as an alkylamine or alkanolamine, or preferably an alkali metal hydroxide, or a combination of these compounds. The use of alkali metal hydroxides only, that is, in the absence of an amine, is preferred, with the use of sodium hydroxide being particularly preferred. The amount of neutralizing base should be sufficient to bring the pH of the solution to at least 7.1, preferably 8.5 to 9.5. Higher pH will improve the thermal stability of the liquid, however, they are not preferred, since such environments are more aggressive with respect to aluminum.

Anti-icing fluids for general purpose aircraft (USG) may also contain an alkali metal hydroxide salt and a weak acid, which serves as an auxiliary base or stabilizing salt. Salts with a lower molecular weight are more effective. Preferably, but not necessarily, the alkali metal residue in the salt molecule is the same as in the neutralizing base; for example, sodium acetate works well with sodium hydroxide. Low salt concentrations are preferred since higher concentrations (even if they further improve thermal stability) tend to decrease the protection time for the liquid used in the anti-icing mode. Preferred concentrations of stabilizing salt are 0-0.10 weight. %, more preferably 0.0005-0.02 weight. %
Accordingly, the present invention provides a composition for anti-icing aircraft, comprising both preventing and eliminating icing, and comprising an aqueous glycol or glycerin solution thickened with a polymer thickener and / or its salt after neutralization, taken in an amount sufficient to thicken this composition and its adhesion to the surface of the aircraft, which is at rest, but at the same time ensuring its removal under the action of shear forces of the wind during take-off of the aircraft. The polymer includes the following components in weight. % of the total polymer:
(A) 1-99.9% of one or more α-, β-unsaturated carboxylic acids with a monoethylene bond;
(B) 0-98.9% of one or more unsaturated monomers with monoethylene bond;
(C) 0.1-99% of one or more monoethylenically unsaturated monomers, preferably macromonomers containing at least one side hydrophobic group, preferably a complex; and
(D) 0-20% or more of one or more unsaturated monomers with a polyethylene bond;
and the composition includes the following components in weight. % of the total weight of the composition:
(1) at least about 40% of one or more glycols or glycerol, or mixtures thereof;
(2) at least about 0.05% of a thickener;
(3) a hydroxide, preferably a monovalent metal hydroxide, more preferably an alkali metal hydroxide, and preferably in the absence of amines, in an amount sufficient to provide a pH of at least about 7;
(4) a surfactant that forms an associate with a thickener in an amount sufficient to enhance the thickening effect;
(5) an optional corrosion inhibitor in an effective amount;
(6) optionally one or more dyes; and
(7) water - the rest.

 In its preferred embodiment, the composition described above also contains an effective amount, preferably at least about 0.0005 weight. % auxiliary base, preferably weak, such as acetate, phosphate and the like.

 In addition, the present invention includes the aircraft icing composition described above, obtained by mixing the ingredients according to the recipe above.

 Additionally, the present invention provides a method for producing the above-described anti-icing composition of aircraft, comprising mixing the ingredients according to the recipe above.

 The composition claimed in the present invention, optionally obtained in the form of a concentrate suitable for dilution, if desired, to satisfy any requirements regarding its action in the mode of preventing and eliminating icing of aircraft, individually or together.

 As previously mentioned, VLW is used to remove ice, hoarfrost, accumulated snow or slush from the surfaces of the aircraft, while the RLF prevents the buildup of ice, snow, snow pellets and other forms of ice deposits on clean planes of the aircraft after ice removal. A typical icing liquid (ILC) consists of a mixture of alkaline ethylene, propylene or diethylene glycol or glycerol and water (as a solvent), taken in approximately equal weight proportions, ready to use, or may be mixed with more than 80 weight . % glycol or glycerol to obtain a concentrate that is diluted in the field. The pH of the mixture is 7.1-9.5, preferably 8.5-9.5. The liquid also contains ionic corrosion inhibitors, flame retardants, dyes and surfactants that help wetting the surface of the aircraft during the spraying operation, as well as other optional substances known from the prior art, provided that they do not interfere directly with the applied liquid destination.

 A typical anti-icing fluid (RLI) includes the same components listed above as a typical VLI, but additionally contains rheological modifiers. Common rheological modifiers used for icing control fluids include crosslinked polyacrylates, carboxypolymethylene and polysaccharides (xanthan gum and carrageenan). Worldwide airlines that operate at congested airports requiring longer-term protection against snow, ice, freezing rain or hoarfrost use such liquid chemical de-icers.

 An ideal thickener acts on the coolant while the aircraft is stationary in order to prevent the accumulation of freezing rain, snow, slush or ice on a clean surface after removing the ice and accelerating the adhesion of the composition to the vertical surfaces of the aircraft body. To minimize the loss in lift, the applied LIF is very diluted under the action of shear, as a result of which it easily drains from the wing of the aircraft during the take-off run to a full turn at a time when the lift (which acts vertically on the aerodynamic surface of the aircraft) is sufficient so that the pilot can take off, which corresponds to a shear force of about 10 Pa. The viscosity of the coolant should not change much with temperature or with dilution with water: a viscosity that does not change or even slightly increases with dilution correlates with “overtime” - the period of time during which the aircraft can survive in bad weather without the need for additional processing to eliminate icing. One of the important decisions, due to which the claimed aircraft liquids surpass the prior art, is to obtain compositions that, although they undergo significant dilution, still retain satisfactory performance. These universal aircraft liquids (USG) can either be diluted slightly and used to prevent icing of large fixed-wing aircraft or scheduled (charter) airplanes, or diluted stronger for use (when heated) as a means to remove ice for all types of aircraft. The present compositions differ from previously known deicers in that the proposed formulation was chosen in order to improve their thermal stability while maintaining all other necessary properties, as well as to ensure that diluted products still have low freezing temperatures, which makes them possible to use in hard weather conditions.

 The anti-icing fluids (eliminating or preventing the formation of ice) claimed in the present invention and having the necessary performance characteristics can be obtained from standard glycol and / or glycerol-based compositions by using a macromonomer-containing polymer as a thickening agent. Macromonomer-containing polymer is intended to be used as the main thickener for standard glycol and / or glycerin-based liquids used to eliminate or prevent icing of aircraft. These anti-icing compositions, referred to as Type II fluids from the Society of Automotive Engineers and Transportation Engineers (USA) and the International Organization for Standardization (ISO), contain a thickener, and the macromonomer-containing polymers disclosed herein are particularly suitable for use as thickeners for these fluids.

 Compositions for removing and preventing the formation of ice on a glycol base are well known and have been used for decades to combat icing aircraft. The main component of this composition, which provides the properties necessary to achieve this goal, is a water-soluble glycol compound. Glycol-based fluids typically contain one or more glycols selected from ethylene, propylene, and diethylene glycols and mixtures thereof. Along with or instead of the listed products, other glycols, glycerin or polyols with depressant properties that lower the freezing point can be used.

 A preferred formulation contains ethylene glycol as the main glycol component, preferably in an amount of at least about 80 weight. % Propylene and / or diethylene glycol may also be present in the glycol-based fluid. Diethylene glycol in combination with propylene glycol is another glycol formulation that is also suitable for use in the present invention. In addition, the glycol component can be replaced with glycerol and used in a mixture with glycol or other glycols. The choice and relative amounts of specific glycol compounds present in glycol-based products will depend on the specific anti-icing and antifreeze properties that this liquid would have desirable, for example, freezing point, pour point, etc.

 The composition for eliminating or preventing icing (hereinafter sometimes referred to simply as anti-icing liquid) is an aqueous solution, i.e. a product obtained by diluting ethylene glycol or other suitable glycol or glycerol with water. Glycol or glycerin must be present in the aqueous solution in an amount of at least about 40 weight. %, preferably about 50 weight. %, up to 95 weight. % The most preferred range of glycol or glycerol is 60-75 weight. % The combined glycol (or glycerin) and aqueous component of the liquid is preferably at least about 90 weight. %, more preferably, about 97 weight. % of the total weight of the composition.

It is desirable that the glycol or glycerol content is sufficient to provide a freezing point of the liquid below -10 ^{° C.} , more preferably below -30 ^° C. For liquids to be used undiluted and diluted, it is especially important that the glycol levels or glycerol was kept high enough in undiluted liquid so that the dilution also provided low freezing temperatures.

 As the neutralizing agent, amine, alkanolamine, alkali metal hydroxide or some combination thereof can be used. It is preferable to use only alkali metal hydroxides, but sodium hydroxide is particularly preferred in this case. Although amines, for example triethanolamine, monoethanolamine, triethylamine and the like, are approved for use, the use of certain amines (e.g. triethanolamine) is not preferred, since such amines appear to reduce thermal stability. The amount of neutralizing base used should be sufficient to bring the pH of the solution to at least 7.1, preferably 8.5 to 9.5. Although the upper limit of pH is not a critical parameter, it is assumed that it must be maintained below that value at which corrosion of the surface of the aircraft body can occur. In the absence of the authors ’intentions to relate this to any particular theory, it can be assumed that a high pH is desirable in order to minimize the hydrolysis of the hydrophobic groups of associative thickeners of the present invention.

 Such hydrolysis can lead to losses in hydrophobic association and, consequently, to a reduced viscosity at low shear.

 An optional but highly preferred aspect of the present invention is the use of an auxiliary base, which can also be considered as a stabilizing salt or buffer. Such a salt may be any alkali metal hydroxide or weak acid salt, however, salts with lower molecular weight are more effective. Preferred weak bases include acetates, phosphates and the like. Preferably, the alkali metal residue in the salt molecule is the same as the strong neutralizing base cation, for example, sodium acetate works well with sodium hydroxide; however, in many cases, salts of other or mixed cations can be effectively used. As a general recommendation, it is assumed that the auxiliary base has a pKa of an acid conjugate of less than 10, preferably less than 5.

 The method for preparing the claimed compositions is non-determining and includes simple mixing of various ingredients with stirring for a sufficient time (usually about 15-20 minutes) to obtain the proper mixture and associative thickening. A preferred method for preparing the composition includes the following steps: (a) preparing a concentrate by adding, with stirring, to an aqueous-glycol or water-glycerin mixture used as a solvent, surfactant and thickener in an amount of 1-20 weight. % of the total amount of solvent; (b) adding with stirring the concentrate (a) to the remainder of the solvent, followed by stirring sufficient to obtain a homogeneous suspension; (c) adding with stirring a neutralizing agent to suspension (b), followed by stirring sufficient to obtain a homogeneous solution. This preferred method provides more efficient mixing and thickening as compared to simple mixing.

  Illustrative macromonomer-containing polymers used in the present invention and methods for their preparation are disclosed in co-pending U.S. Application No. 887,647, which is hereby incorporated by reference. In the polymers used in the present invention, there is a large proportion of one or more monomeric α-, β-unsaturated carboxylic acids with monoethylene bonds. Various acids can be used, such as acrylic, methacrylic, ethacrylic, α-chloroacrylic, crotonic, fumaric, citraconic, mesaconic, itaconic, maleic and the like, including mixtures thereof. Methacrylic acid is preferred, in particular at a concentration of at least about 49 weight. % of polymer. A large proportion of the carboxylic acid as a monomer is desirable in order to obtain a polymer structure capable of swelling or dissolving and providing the necessary thickening agent when reacted with an alkali, for example sodium hydroxide.

 The polymers used in the present invention may also contain a significant proportion of one or more unsaturated monoethylene-linked monomers. Preferred monomers give water-insoluble polymers during homopolymerization and are esters of acrylic and methacrylic acids such as ethyl acrylate, butyl acrylate or the corresponding methacrylate. Other monomers used include styrene, alkyl styrenes, vinyl toluene, vinyl acetate, vinyl alcohol, acrylonitrile, vinylidene chloride, vinyl ketones and the like. Non-reactive monomers are preferred, these include monomers in which a single ethylene group is the only chemically active group under polymerization conditions. However, in some cases, monomers can be used, including groups that are capable of reacting under heat treatment conditions or being reactive with divalent metal ions (in zinc oxide), for example, hydroxyethyl acrylate.

 Other exemplary unsaturated monomers with monoethylenically bonds include, for example propyl, izopropilmetakripat, butyl methacrylate, n-amilmetakrilat, sec-amilmetakrilat, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethylhexyl methacrylate, krotilmetakrilat, cinnamyl methacrylate, oleilmetakrilat, ritsinoleilmetakrilat, hydroxyethyl methacrylate, hydroxypropyl methacrylate , vinyl propionate, vinyl butyrate, vinyl tert-butyrate, vinyl caprate, vinyl stearate, vinyl plaurate, vinyl oleate, vinyl methyl ether, vinyl ethyl ester vinyl, n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl isooctyl ether, vinyl phenyl ether, α-chlorovinyl phenyl ether, vinyl β-naphthyl ether, methacryonitrile, acrylamide, methacrylamide alkyl acrylamides, N-vinylpyrrolidone, N-vinyl-3-morpholinones, N-vinyloxazolidone, N-vinylimidazole and the like, including mixtures thereof.

где R¹ представляет собой одновалентный остаток замещенного или незамещенного гидрофобного соединения;
каждый R² - одинаковый или различный и представляет собой замещенный или незамещенный двухвалентный углеводородный остаток;
R³ представляет собой замещенный или незамещенный двухвалентный углеводородный остаток;
R⁴, R⁵ и R⁶ - одинаковые или различные и представляют собой водород или замещенный или незамещенный одновалентный углеводородный остаток;
z - величина, большая или равная нулю.Macromonomers used in the present invention are represented by the formula:

where R ¹ represents a monovalent residue of a substituted or unsubstituted hydrophobic compound;
each R ² is the same or different and represents a substituted or unsubstituted divalent hydrocarbon residue;
R ³ represents a substituted or unsubstituted divalent hydrocarbon residue;
R ⁴ , R ⁵ and R ⁶ are the same or different and represent hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue;
z is a value greater than or equal to zero.

 The macromonomers used in the present invention are prepared by standard methods that do not include complex hydrophobic compounds as provided herein. Illustrative methods are described, for example, in US Pat. , 4008202, 3190925, 3794608, 4338239, 4939283 and 3499876. They can also be obtained by the method described in co-pending application US 887645, which is incorporated into this description by reference. Other macromonomers that may be used in the practice of the present invention include oligomers bearing the complex hydrophobic groups described in co-pending application US 887646, which is also referred to here by reference.

The hydrophobic residue R ¹ in the formula I may be a simple or complex hydrophobic group or a mixture thereof. However, complex hydrophobes are preferred. Different hydrophobic groups may be present on the same molecule, or their presence can be ensured through physical mixtures of various polymers. Simple hydrophobes mean products that are currently commercially available, typically consisting of no more than 30 carbon atoms, as shown in Table 1 of US Pat. No. 4,426,485. Complex hydrophobes include products that will be described below and are presented in Tables 2 and 3 of US patent 5,292,828.

Illustrative substituted and unsubstituted divalent R ² hydrocarbon residues in formula I include those described below for substituents of the same type in formulas (i) and (ii). Illustrative substituted and unsubstituted monovalent hydrocarbon residues R ⁴ , R ⁵ and R ⁶ in formula I include those described below for substituents of the same type in formulas (i) and (ii).

Illustrative R ³ substituents include, for example, the organic residue of ethers and esters, urethanes, amides, ureas, anhydrides, etc., including mixtures thereof. The substituent R ³ can be represented in general terms as a bridge between a surfactant carrying a complex hydrophobic group or alcohol and an unsaturated part of a macromonomer compound. Preferred bridges include the following: urethane bridges from the reaction of an isocyanate with a surfactant bearing a hydroxyl group; urea bridges from the reaction of an isocyanate with a surfactant carrying an amine group; unsaturated surfactant esters, such as the product of esterification of surfactants with unsaturated carboxylic acid or unsaturated anhydride; unsaturated esters of alcohols; esters of oligomers of ethyl acrylate, oligomers of acrylic acid and allyl-containing oligomers; half-esters of surfactants, such as those obtained by the reaction of surfactants with maleic anhydride; unsaturated esters obtained by the interaction of vinylbenzyl chloride and a surfactant or by the interaction of allyl glycidyl ether with a surfactant, alcohol or carboxylic acid.

Oxyalkylene fragments included in macromonomer compounds (I) are homopolymers or block copolymers or random copolymers with straight or branched alkylene oxide groups. Mixtures of alkylene oxides such as ethylene oxide and propylene oxide can be used. It is assumed that each group R ² in a separate substituent for all positive values of z can be the same or different. Although ethylene oxide is preferred, it is noted that large amounts thereof can have a negative effect on the index of thermal stability and / or stability when diluting a thickened aircraft liquid.

где R₁ и R₂ - одинаковые или различные и представляют собой водород или замещенный или незамещенный одновалентный углеводородный остаток; R₃ представляют собой замещенный или незамещенный двухвалентный или трехвалентный углеводородный остаток; каждый R₄ - одинаковый или различный и представляет собой замещенный или незамещенный двухвалентный углеводородный остаток; каждый R₅ - одинаковый или различный и представляет собой замещенный или незамещенный двухвалентный углеводородный остаток; R₆ представляет собой водород, замещенный или незамещенный одновалентный углеводородный остаток или ионный заместитель; а и b - одинаковые или различные и представляют собой величину, равную 0 или 1; x и y - одинаковые или различные и представляют собой величину, большую или равную нулю; при условии, что по крайней мере два из R₁, R₂, R₃, R₄, R₅ и R₆ представляют собой углеводородный остаток, содержащий более 2 атомов углерода в случае R₁, R₂ и R₆, или содержащий более 2 боковых атомов углерода в случае R₃, R₄ и R₅.Complex hydrophobic compounds having at least one active hydrogen, useful for preparing the macromonomers used in the present invention, are represented by the following formula:

where R ₁ and R ₂ are the same or different and represent hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue; R ₃ represents a substituted or unsubstituted divalent or trivalent hydrocarbon residue; each R ₄ is the same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; each R ₅ is the same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; R ₆ represents hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent; a and b are the same or different and represent a value equal to 0 or 1; x and y are the same or different and represent a value greater than or equal to zero; with the proviso that at least two of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are a hydrocarbon residue containing more than 2 carbon atoms in the case of R ₁ , R ₂ and R ₆ , or containing more 2 side carbon atoms in the case of R ₃ , R ₄ and R ₅ .

где R₇ и R₈ - одинаковые или различные и представляют собой водород или замещенный или незамещенный одновалентный углеводородный остаток; R₁₁ и R₁₄ - одинаковые или различные и представляют собой водород, замещенный или незамещенный одновалентный углеводородный остаток или ионный заместитель; R₉ и R₁₂ - одинаковые или различные и представляют собой замещенный или незамещенный двухвалентный или трехвалентный углеводородный остаток; каждый R₁₃ - одинаковый или различный и представляет собой замещенный или незамещенный двухвалентный углеводородный остаток; R₁₅ - представляет собой замещенный или незамещенный двухвалентный углеводородный остаток; d и e - одинаковые или различные и равны 0 или 1; f и g - одинаковые или различные и представляют собой величину, большую или равную нулю; при условии, что по крайней мере два из R₇, R₈, R₉, R₁₀, r₁₁, R₁₂, R₁₃, R₁₄ и R₁₅ представляют собой углеводородный остаток, содержащий более 2 атомов углерода в случае R₇, R₈, R₁₁ и R₁₄, или содержащий более 2 боковых атомов углерода в случае R₉, R₁₀, R₁₂, R₁₃ и R₁₅.Other complex hydrophobic compounds having at least one active hydrogen, useful for preparing the macromonomers used in the present invention, are represented by the following formula:

where R ₇ and R ₈ are the same or different and represent hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue; R ₁₁ and R ₁₄ are the same or different and represent hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic substituent; R ₉ and R ₁₂ are the same or different and represent a substituted or unsubstituted divalent or trivalent hydrocarbon residue; each R ₁₃ is the same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; R ₁₅ - represents a substituted or unsubstituted divalent hydrocarbon residue; d and e are the same or different and equal to 0 or 1; f and g are the same or different and represent a value greater than or equal to zero; with the proviso that at least two of R ₇ , R ₈ , R ₉ , R ₁₀ , r ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ represent a hydrocarbon residue containing more than 2 carbon atoms in the case of R ₇ , R ₈ , R ₁₁ and R ₁₄ , or containing more than 2 side carbon atoms in the case of R ₉ , R ₁₀ , R ₁₂ , R ₁₃ and R ₁₅ .

 Illustrative substituted or unsubstituted monovalent hydrocarbon residues contain from 1 to 50 or more carbon atoms and are selected from alkyl radicals, including linear or branched primary, secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, amyl, sec -amyl, tert-amyl, 2-ethylhexyl and the like; aryl radicals such as phenyl, naphthyl and the like; arylalkyl radicals such as benzyl, phenylethyl, triphenylmethylene and the like; alkylaryl radicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyl and the like; and cycloalkyl radicals such as cyclopentyl, cyclohexyl, cyclohexylethyl and the like. Suitable hydrocarbon residues may contain fluorine, silicon, or other atoms other than carbon.

 Preferably, substituted or unsubstituted hydrocarbon residues are selected from alkyl and aryl radicals that contain from 1 to 30 or more carbon atoms. More preferably, alkyl radicals contain from 1 to 18 carbon atoms, while aryl, arylalkyl, alkylaryl and cycloalkyl radicals preferably contain from 6 to 18 or more carbon atoms.

где R₁₆ и R₁₇ имеют значения, определенные выше для R₁, R₂, R₇ и R₈, h и i - одинаковые или различные и равны 0 или 1; R₁₈ имеет значения, определенные выше для R₃. Для соединений формулы (i) и (ii) предполагается, что каждый радикал формулы (iii) в данном соединении может быть одинаковым или различным, и группы R₁₆ и/или R₁₇, как описано ниже, для того, чтобы обеспечить получение сложных гидрофобов дендритной или каскадной природы, сами по себе могут представлять собой радикал (iii). Кроме того, R₄, R₅, R₁₀ и R₁₃ могут индивидуально представлять собой углеводородный радикал формулы
-CH[(OR₁₉)_jOR₂₀]- (iv)
где R₁₉ имеет значения, определенные выше для R₄, R₅, R₁₀ и R₁₃; R₂₀ имеет значения, определенные выше для R₆, R₁₁ и R₁₄; и j представляют собой величину, большую или равную нулю.In a preferred embodiment, R ₁ , R ₂ , R ₇ and R ₈ may individually be a hydrocarbon radical of the formula:

where R ₁₆ and R ₁₇ have the meanings defined above for R ₁ , R ₂ , R ₇ and R ₈ , h and i are the same or different and are 0 or 1; R ₁₈ has the meanings given above for R ₃ . For compounds of formula (i) and (ii), it is contemplated that each radical of formula (iii) in a given compound may be the same or different, and R ₁₆ and / or R ₁₇ groups, as described below, in order to provide complex hydrophobes of dendritic or cascade nature, themselves can be a radical (iii). In addition, R ₄ , R ₅ , R ₁₀ and R ₁₃ may individually be a hydrocarbon radical of the formula
-CH [(OR ₁₉ ) _j OR ₂₀ ] - (iv)
where R ₁₉ has the meanings given above for R ₄ , R ₅ , R ₁₀ and R ₁₃ ; R ₂₀ has the meanings given above for R ₆ , R ₁₁ and R ₁₄ ; and j are a value greater than or equal to zero.

Illustrative ionic substituents for R ₆ , R ₁₁ , R _14, and R ₂₀ include cationic and anionic groups such as sulfates, sulfonates, phosphates, and the like. R ₆ , R ₁₁ , R ₁₄ and R ₂₀ preferably represent an organic residue containing one or more hydroxyl groups and nitrogen-containing derivatives or epoxides or other reactive groups that contain or do not contain unsaturation.

Other illustrative end groups represented by the substituents R ₆ , R ₁₁ , R ₁₄ and R ₂₀ include, for example, hydrocarbon residues that contain allyl or vinyl unsaturation, acrylic or methacrylic, styryl or α-methylstyrene functional group, and the like, such as the reaction product between the terminal alcohol (R ₆ , R ₁₁ , R ₁₄ and R ₂₀ are hydrogen) and gpicidylmethacrylate, isocyanatoethyl methacrylate, α-, α-dimethyl-m-isopropenylbenzylisocyanate (m-TMI) and the like. Other examples of end groups include hydrocarbon residues from alkyl, aryl, aralkyl, alkaryl and cycloalkyl, which are optionally substituted or not substituted with one or more substituents of the following: hydroxyl, carboxyl, isocyanato, amino, mono- or disubstituted amino, quaternary ammonium, sulfate, sulfonate, phosphate, epoxy and the like, and furthermore, may or may not contain other atoms other than carbon, including silicon or fluorine. In addition, divalent siloxy radicals may be included here. Other non-hydrocarbon end groups may include sulfates, phosphates, and the like.

Illustrative divalent hydrocarbon residues represented by the radicals R ₃ , R ₄ , R ₅ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₅ , R ₁₈ and R ₁₉ in the above formulas include substituted or unsubstituted groups selected from alkylene , -alkylene-hydroxy-alkylene-, -arylene-hydroxy-arylene-, arylene, alicyclic radicals, phenylene, naphthylene, -phenylene- (CH ₂ ) _m (Q) _n - (CH ₂ ) _m -phenylene-, -naphthylene - (CH ₂ ) _m (Q) _n (CH ₂ ) _m -naphthylene-, where Q independently represents a substituted or unsubstituted divalent bridging group selected from -CR ₂₁ R ₂₂ -, -O-, -S-, -NR ₂₃ , -SiR ₂₄ R ₂₅ and -CO-, where R ₂₁ and R ₂₂ independently represent a radical selected from hydrogen, alkyl containing from 1 to 12 carbon atoms, phenyl, tolyl and anisyl; R ₂₃ , R ₂₄ and R ₂₅ independently represent a radical selected from hydrogen and methyl; and each type is independently 0 or 1. More specific values for the illustrative divalent radicals represented by R ₃ , R ₄ , R ₅ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₅ , R ₁₈ and R ₁₉ include 1 , 1-methylene, 1,2-ethylene, 1,3-propylene, 1,6-hexylene, 1,8-octylene, 1,12-dodecyken, 1,4-phenylene, 1,8-naphthylene, 1,1 biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl, 2,2'-binaphthyl-1,1'-diyl and the like. Alkylene radicals may contain from 2 to 12 or more carbon atoms, while arylene radicals contain from 6 to 18 or more carbon atoms. Preferably, R ₃ , R ₄ , R ₅ , R ₉ , R ₁₀ , R ₁₂ , R ₁₃ , R ₁₅ , R ₁₈ and R ₁₉ are an alkylene or arylene radical. Suitable divalent hydrocarbon residues may contain fluorine, silicon or other atoms other than carbon.

Illustrative trivalent hydrocarbon residues represented by the radicals R ₃ , R ₉ , R ₁₂ and R ₁₈ in the above formulas include substituted and unsubstituted groups selected from CH—, C (R ₂₆ ) -, CR ₂₇ - and the like, where R ₂₆ represents a substituted or unsubstituted monovalent hydrocarbon residue, and R ₂₇ represents a substituted or unsubstituted divalent hydrocarbon residue.

Of course, it is further contemplated that the hydrocarbon residues in the above formulas may be substituted with any suitable substituent. Such illustrative substituents include radicals containing from 1 to 18 carbon atoms, such as alkyl, aryl, aralkyl, alkaryl and cycloalkyl; alkoxy; silyl radicals such as —Si (R ₂₈ ) ₃ and —Si (OR ₂₈ ) ₃ ; amino radicals such as —N (R ₂₈ ) ₂ ; acyl such as —C (O) R ₂₈ ; acyloxy such as -OC (O) R ₂₈ ; carbonyloxy,
such as COOR ₂₈ ; amido such as —C (O) N (R ₂₈ ) ₂ and —N (R ₂₈ ) COR ₂₈ ; sulfonyl radicals such as —SO ₂ R ₂₈ ; sulfinyl radicals such as —SO (R ₂₈ ) ₂ ; thionyl, such as —SR ₂₈ ; phosphonyl, such as —P (O) (R ₂₈ ) ₂ ; as well as halogen, nitro, cyano, trifluoromethyl and hydroxy and the like, where each R ₂₈ may be a monovalent hydrocarbon radical, such as alkyl, aryl, aralkyl, alkaryl and cycloalkyl, provided that in amino substituents such as -N ( R ₂₈ ) ₂ , each of R ₂₈ taken together is capable of producing a divalent bridging group that forms a heterocyclic radical with a nitrogen atom in amido substituents such as —C (O) N (R ₂₈ ) ₂ and —N (R ₂₈ ) COR _28, wherein each R ₂₈ bonded to a nitrogen atom represents hydrogen, and in phosphonyl substituents such as s as -P (O) (R _{28) 2,} wherein one R ₂₈ is hydrogen. It is believed that each R ₂₈ group in a separate substituent may be the same or different. Such hydrocarbon substituents may, in turn, be substituted with an acceptable substituent from the above.

Preferred alkylene oxides that provide the presence of statistical units or block units in complex hydrophobic compounds of formulas (i) and (ii) include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentylene oxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide, 1,2-decylene oxide and higher α-olefin epoxy compounds; epoxidized fatty alcohols, such as epoxidized soy and flaxseed fatty alcohols; aromatic epoxides such as styrene oxide and 2-methyl styrene oxide; and hydroxy and halogen substituted alkylene oxides such as glycidol, epichlorohydrin and epibromohydrin. Preferred alkylene oxides include ethylene oxide and propylene oxide. Hydrocarbon residues from substituted or unsubstituted cyclic esters or ethers such as oxytane and tetrahydrofuran may also be included. It is believed that the compounds represented by formulas (i) and (ii) contain statistical and / or block oxyalkylene units, as well as mixtures of oxyalkylene units. In addition, it is believed that each R ₄ , R ₅ , R ₁₀ , R ₁₃ and R ₁₉ in a separate substituent for all positive values of x, y, z, f, g and j, respectively, may be the same or different.

 The values of x, y, z, f, g, and j are not strictly determinative, but can vary widely. For example, they can range from 0 to 200 or more, preferably from 0 to 100 or more, and more preferably from 0 to 50 or more. Alkylene oxide is used in any desired amount, for example, from 0 to 90 wt.% Or more, based on the total weight content of the complex hydrophobic compound.

Returning to the general formulas (i) and (ii), it is assumed that when R ₁ , R ₂ , R ₇ and / or R ₈ are a hydrocarbon residue of the formula (iii), the resulting compound may contain any acceptable number and combination of hydrophobic dendritic groups or cascading type. Such compounds included in the above general formulas should be readily established by any person skilled in the art.

 Illustrative complex hydrophobic compounds containing at least one active hydrogen useful in the practice of this invention and methods for their preparation are described in co-pending application US 887,648, which is incorporated herein by reference.

К предпочтительным макромономерным соединениям, используемым в настоящем изобретении, относятся соединения следующих формул:

(ХIY)
где R₁, R₂, R₄, R₁₉, z и j имеют значения, определенные выше.In a preferred embodiment of the invention, the structure represented by formula (iii) is the remainder of the reaction product between epichlorohydrin and an alcohol, including those alcohols whose residues can be described by formula (iii), or phonols or mixtures thereof. These structures can be represented as complex hydrophobic molecules of dendritic or cascade nature in the following graphic image:

Preferred macromonomer compounds used in the present invention include compounds of the following formulas:

(Xiy)
where R ₁ , R ₂ , R ₄ , R ₁₉ , z and j are as defined above.

Предпочтительные интервалы содержаний составляющих мономерных фрагментов таковы: кислотный мономер Х - 10-40%, сополимеризуемый неассоциативный мономер Y - 10-50%, ассоциативный мономер Z - 5-30%, причем величина р, обозначающая степень этоксилирования в молях (или пропоксилирования) составляет 20-80 молей. Гидрофоб R может представлять собой алкарил, такой как нонилфенол или динонилфенол, или иметь следующую структуру:

где R₁ и R₂ имеют значения, определенные выше.The preferred polymer thickener proposed in this invention meets the following formula:

Preferred ranges for the content of constituent monomer fragments are as follows: acid monomer X — 10–40%, copolymerizable non-associative monomer Y — 10–50%, associative monomer Z — 5–30%, and the p value indicating the degree of ethoxylation in moles (or propoxylation) is 20-80 moles. Hydrophobic R may be alkaryl, such as nonylphenol or dinonylphenol, or have the following structure:

where R ₁ and R ₂ have the meanings defined above.

 The macromonomer compounds used in the present invention are subjected to additional conversion (s) in order to obtain their desired derivatives. Such derivatization reactions are carried out according to known standard procedures. Illustrative derivatization reactions include, for example, complex esterification, simple esterification, alkoxylation, amination, alkylation, hydrogenation, dehydrogenation, reduction, acylation, condensation, carboxylation, oxidation, silylation, and the like, including a combination thereof. The present invention does not intend to limit in any way the proposed method to the above allowable derivatization reactions or derivatives of macromonomer compounds involved in them.

 In particular, hydroxyl terminated macromonomers undergo any of the known hydroxyl group reactions, illustrated by reactions with haloacyl esters; with ammonia, nitrile or hydrogen cyanide to form amines; with acidic alkyl sulfates to form bisulfates; with carboxylic acids and acid anhydrides to form esters and polyesters; with alkali metals to form salts; with ketenes with the formation of esters; with acid anhydrides to form carboxylic acids; with oxygen to form aldehydes and carboxylic acids; reactions with opening the cycle with lactones, terahydrofuran; dehydrogenation with the formation of aldehydes; reactions involving isocyanates with the formation of urethanes and others.

 The unsaturated macromonomer component with a monoethylene bond is subjected to a significant change within the previously presented formula. The nature of the macromonomer is a complex hydrophobic one carrying a polyethoxylate chain (which possibly includes some polypropoxylate groups) and which ends with at least one hydroxy group. When the hydroxyl-terminated polyethoxylate complex hydrophobic compound used is reacted with an unsaturated monoisocyanate with a monoethylene bond, a result is, for example, an unsaturated urethane with a monoethylene bond, in which the complex hydrophobic polyethoxylate structure is bonded to the copolymerizable monoethylene group by means of.

A compound whose unsaturation is due to the presence of a monoethylene bond and which is used to produce an unsaturated macromonomer containing such a monoethylene bond is subjected to a large change. Any copolymerizable unsaturation, such as acrylate and methacrylate, can be used. Allyl unsaturation, which is ensured by the use of allyl alcohol, can also be used. These compounds, which are preferably present in the form of a hydroxy-functional derivative obtained by reacting a C ₂ -C ₄ monoepoxide (e.g. ethylene oxide, propylene oxide or butylene oxide) with acrylic or methacrylic acid to give the hydroxy ester, react in equimolar amounts with an organic compound such as toluene diisocyanate or isophorondiisocyanate. A preferred monoisocyanate monoisocyanate is a styryl-containing α-, α-dimethyl-m-isopropenipbenzylisocyanate. Other suitable organic compounds include, for example, unsaturated ethers and esters, amides, ureas, anhydrides, other urethanes, and the like compounds containing monoethylene bonds.

 The polymers used in the present invention are obtained through a number of known polymerization reactions. The polymerization technique affects the microstructure, the distribution of the sequence of monomers in the polymer chain and the molecular weight of the polymer, on which its characteristics depend. An exemplary polymerization technique includes, for example, standard and stepwise emulsion polymerization via a batch process (batch process), semi-continuous or continuous processes, micellar polymerization, reverse emulsion polymerization, solution polymerization, non-aqueous dispersion polymerization, interfacial polymerization, emulsion polymerization and suspension precipitation, addition polymerization (A-polymerization), such as free radical, anionic, cationic, coordination, etc.

 The thickeners used in the present invention have the structural characteristics of two completely different types of compounds (compounds that thicken due to alkaline swelling or solubilization of the polymer object, and compounds whose thickening effect is due to association), and this fact explains their excellent thickening properties. However, it is believed that to ensure non-Newtonian rheology, which is crucial for the performance of thickeners used in aircraft liquids, it is the association among hydrophobic groups (and the disassociation caused by the shear force of the wind) that determines the predominant reaction mechanism.

 Aqueous emulsion copolymerization is a standard procedure for any person skilled in the art of chemistry. In order to evaluate the effectiveness of thickening, the product is diluted with water to a solids content of about 1%, and then neutralized with alkali. As a rule, ammonium hydroxide is usually used, but sodium and potassium hydroxide and even amines, for example triethylamine, can be taken to neutralize. The neutralization product dissolves in water to increase viscosity. In normal mode, the original (non-neutralized) thickener is added to the liquid and then neutralized. This facilitates the handling of the thickener, since in this case it has a lower viscosity before neutralization. In addition, this technique involves the use of more water to obtain a formulation.

 The polymers used in the present invention are usually prepared by conventional aqueous emulsion polymerization using the appropriate emulsifiers necessary to emulsify the monomers and maintain the resulting polymer in a suitable dispersion medium. As emulsifiers, conventional anionic surfactants are used, such as sodium lauryl sulfate, dodecylbenzenesulfonate and sulfates of ethoxylated fatty alcohols. An emulsifier is used in an amount of from 0.5 to 6% by weight of the monomers.

It is preferable to use water-soluble initiators, such as alkali metal or ammonium persulfate in an amount of from 0.01 to 1.0% by weight of the monomers. A gradual additive thermal process at temperatures of 60-100 ^{° C.} is preferred over redox systems.

 The polymerization system contains small amounts (0.01-5 wt.% Of the total weight of monomers) of mercaptans as a chain carrier, such as hydroxyethyl mercaptan, β-mercaptopropionic acid and alkyl mercaptans containing from 4 to 22 carbon atoms, and the like. The use of a mercaptan modifier reduces the molecular weight of the polymer and, consequently, the thickening effectiveness of the latter.

 The polymers used in the present invention can be further modified by introducing a certain amount of component (D), namely one or more unsaturated copolymerizable polyethylene-linked monomers effective for crosslinking the polymer, such as diallyl phthalate, divinylbenzene, allyl methacrylate, trimethylol propane triacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate or dimethyl acrylate, diallyl benzene and the like. Thus, from 0.05% or less to 20% or more of the above unsaturated compound, based on the total weight of the monomer, can be included in the polymer-forming mixture. The resulting polymers are either highly branched or present as spatial (three-dimensional) networks. Being in a neutralized salt form, these nets swell in the water system, acting as a very effective thickener.

Other illustrative unsaturated copolymerizable polyethylene bond monomers used in the present invention include any copolymerizable compound that contains two or more non-conjugated ethylenically unsaturated points in the structure or two or more non-conjugated CH ₂ -C- vinylidene groups such as divinyltoluene, trivinylbenzene, divinylnaphthalene, trimethylene glycol diacrylate or dimethacrylate, 2-ethylhexane-1,3-dimethacrylate, divinylxylene, divinyl ethyl benzene, divinyl ether, divinyl sulfone, allyl ether s polyhydric compounds such as glycerol, pentaerythritol, sorbitol, sucrose and resorcinol, divinyl ketone, divinyl sulfide, allyl acrylate, diallyl maleate, diallilfumarat, diallyl phthalate, diallilsuktsinat, diallylcarbonate, diallilmalonat, dialliloksalat, dialliladipinat, diallilsebatsinat, dialliltartrat, diallilsilikat, trialliltrikarballilat, triallilakonitat, triallyl citrate, triallyl phosphate, N, N, methylene diacrylamide, N, N-methylene dimethacrylamide, N, N-ethylene diacrylamide and 1,2-di- (alpha-methylmethylene sulfonamide) ethylene.

 Other polymers that may be used in the present invention include those described in co-pending applications US 887644, 887642, 887673, 887641, 887672, 887646, all of which are incorporated herein by reference. Polymers having a base that contains urethane units are also included in the scope of the present invention.

 To obtain a thickener or thickened compositions of the present invention, there are various ways of using the polymer component. For example, the polymer, in the form of an aqueous dispersion or in dry form, is kneaded in an aqueous system that is to be thickened, followed by the addition of a neutralizing agent. Alternatively, the polymer can be neutralized first in the form of an aqueous suspension and then mixed with the aqueous system. Preferably, if it is desired to conduct co-thickening with a surfactant (discussed below), the components are mixed separately (as dry products or as a dispersion system or suspensions) in an aqueous dispersion to be thickened, followed by a neutralization step.

 Although it is possible to obtain aqueous concentrates of the acidic form of the polymer and surfactants and add them to the thickening aqueous dispersion, followed by neutralization of the mixture, such concentrates tend to remain too viscous to allow easy handling of these products. Nevertheless, it is possible to prepare a dry mixture or an aqueous composition containing solid particles, which has a sufficiently low viscosity to be capable of pumping or filling, and then further thickening the mixture with an alkaline product.

 The polymer thickener can be obtained dry in various ways. For example, an alkali-free polymer can be spray dried or tumble dried and, if desired, mixed with a surfactant used as a co-thickener. However, you can also dry it by spraying or dehydrate the neutralized polymer thickener in another way, and then re-prepare the aqueous suspension of the thickener, provided that its pH is maintained at 7 or higher.

 A more trivial method of using the claimed suspension in the case of water thickening is to add an aqueous suspension of the polymer to the thickening medium and, after mixing, introduce an alkaline product to neutralize the acid. Thickenings generally reach within a few minutes after neutralization. In the presence of high concentrations of electrolytes, an increase in viscosity takes much longer. This method of applying the polymer in the aqueous system to the stage of neutralization enables the user to deal with a sufficiently solid thickener in an inviscid state, to obtain a homogeneous mixture, and then turn it into a product with a high viscosity by simply adding an alkaline compound to the system to achieve a pH of 7 and above.

 Aqueous solutions thickened with neutralized polymers exhibit stable viscosity properties up to pH 13.

 The polymer can be used to thicken the compositions under acidic conditions in the presence of a relatively large amount of surfactants, where the thickened composition, for example, in the form of an aqueous system, has a pH of less than 7, even reaching 1.

 The enhancement of thickening (referred to herein as “co-thickening”) upon the addition of a surfactant can result in an aqueous system containing the claimed polymer when the latter is neutralized. In some cases, the thickening is enhanced by almost 40 times compared with the viscosity, which is provided only by the addition of a neutralized polymer. A wide variety of surfactants are used for this chain. Although traces of surfactants may be present in the polymerization product (for example, all that can remain is about 1.5% surfactant of the amount of monomers), it is believed that such surfactant contents alone do not lead to any noticeable thickening.

 When calculated on an aqueous system containing from 0.1 to 5 wt.% Solid polymer, a useful amount of surfactant for optimal co-thickening is 0.1-1.0 wt.% Of the total weight of the system. As already noted, the content of the polymer and surfactant co-thickener can vary widely, even going beyond the possible values, depending on the type of polymer and surfactant and other components of the mixture to be thickened. However, co-thickening can reach a maximum during the introduction of surfactants, and then begin to decline as it is further added. Therefore, the use of surfactants in amounts beyond the established concentrations and ratios between the polymer and the surfactant may become uneconomical, but it can be determined in the usual way in each case.

 A preferred method of using the polymer and surfactant for water thickening is to add the polymer and surfactant to the thickening medium in any sequence and to introduce, after mixing, the alkaline product to neutralize the acid. This method of applying the polymer and surfactant in an aqueous system before neutralization enables the user to deal with a solid thickener in an inviscid state, to obtain a homogeneous mixture, and then turn it into a highly viscous product by simply adding an alkaline compound to the system to achieve a pH of 7 and above. However, the neutralization of the polymer in the aqueous system can also be carried out before adding the surfactant.

 Surfactants that can be used in the method preferably include nonionic and anionic surfactants, separately or in combination, the choice depending on the compatibility with other ingredients of the already thickened or intended and thickening suspension, which is claimed in the present invention. You can also use cationic and amphoteric surfactants, provided that they are compatible with the polymer and other ingredients of the aqueous system, or take them in such small quantities so as not to cause such incompatibility.

 Suitable anionic surfactants that can be used in the method include sulfates of higher fatty alcohols, such as sodium or potassium sulfates for alcohols containing from 8 to 18 carbon atoms, alkali metal salts or amine salts of higher fatty acids containing from 8 to 18 atoms carbon, sulfonated alkylaryl compounds such as sodium dodecylbenzenesulfonate.

 Examples of nonionic surfactants include alkylphenoxypolyethoxyethanols with alkyl groups containing from 7 to 18 carbon atoms and from 9 to 40 or more hydroxyethylene units, such as octylphenoxy-polyethoxyethanol, dodecylphenoxyolylethoxyethanol; ethylene oxide derivatives of long chain carboxylic acids such as lauryl, myristic, palmitic, oleic; ethylene oxide condensates of long chain alcohols such as lauryl or cetyl alcohol, and the like.

 Examples of cationic surfactants include lauryl pyridic chloride, octyl benzyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride condensates of primary fatty amines and ethylene oxide and the like.

 The above, as well as many other useful non-ionic, anionic, cationic and amphoteric surfactants are described in the literature, for example, in the book: McCutcheon. Detergents & Emulsifiers 1981 Annual, North America Edition, MC Publishing Company, Glen Rock, NJ 07452, U.S.A.

 Generally speaking, solvents (or mixtures of solvents, other organic and volatile substances) can be used to control the viscosity of polymer-containing systems. It is interesting to note here how white spirit acts as a co-thickener and how the solubility in water of another solvent affects the amount of white spirit that can be added before the solution is separated into a two-phase system.

 The amount of polymer that can be dissolved in any aqueous composition in question varies widely, depending on the specific viscosity required.

 Thus, although any effective amount of polymer can be taken for dissolution, typically 0.05 to 20 wt.%, Preferably 0.1 to 5 wt.%, And most preferably 0.1 to 3 wt. % polymer, based on the weight of the final aqueous composition, including the polymer.

 In addition to a macromonomer-containing polymer that acts as a liquid thickener, a glycol or glycerol-based liquid may also contain small amounts of other functional ingredients, such as corrosion inhibitors, surfactants, antioxidants, flame retardants, stabilizers, dyes, and the like. These components are usually present in individual amounts of not more than 2 wt.%, Typically in the range of 0.01-1 wt.% For each component.

 The macromonomer-containing polymer used as a thickener for the universal liquids of the present invention determines their advantageous properties inherent in compositions for preventing icing of aircraft. This polymer is used in amounts that pour on a significant change in the rheological characteristics of glycol liquids. The fluids claimed in the present invention to eliminate or prevent icing of aircraft do not exhibit rheological properties associated with conventional Newtonian fluids.

 In addition, the proposed universal liquids should be different from liquids thickened by a standard method, since they work by an associative mechanism. Compositions for anti-icing aircraft from US patent 4 358 389, thickened with a crosslinked polyacrylate, with the optional addition of xanthan gum, are examples of known compositions described in the literature.

 When applied to exposed surfaces of an aircraft, the fluid is sufficiently viscous and / or sticky and has a corresponding gel-like structure, which ensures its adhesion even to non-horizontal surfaces. In this case, a film of sufficient thickness is formed to prevent sticking or growth of ice, snow, snow pellets, ice rain or hoarfrost on these surfaces when the aircraft is stationary or during taxiing. However, as soon as the aircraft begins its take-off, the liquid drains easily from its surface before take-off under the influence of the shear force of the wind. Consequently, on the so-called critical surfaces of the aircraft, there are no noticeable amounts of liquid until the aircraft is completely rotated at the moment when the pilot begins to take off from the ground while on the runway, and subsequently on the surfaces of the aircraft when it is already in the air. Such a result is highly desirable, since the residual layer of liquid de-icer on the aerodynamic surface, like traces of snow, ice rain or hoarfrost, can adversely affect the working lift characteristics of the wing.

 It should be noted that in the absence of the macromonomer-containing polymer thickener used in the present invention, the aqueous glycol liquid would have a relatively low viscosity and would tend to drain from any non-horizontal surface by gravity, while leaving a film that is insufficient for its effective acting as an anti-icer for a long time.

 Macromonomer-containing polymer thickener is used in an amount that increases the viscosity and / or stickiness of aircraft fluids, and, in addition, gives them a gel-like structure under conditions of zero or very small shear.

 The amount of macromonomer-containing polymer thickener in a water-based liquid should be less than 5% by weight. in relation to the weight of the liquid. The amount of thickener is preferably in the range of 0.05-3 wt.%, More preferably in the range of 0.05 -1 wt.%.

 In cases where aircraft liquids containing such amounts of the above polymer thickener are applied to the outer surfaces of a stationary aircraft, the gravity of the liquid film from non-horizontal surfaces (inclined, vertical, etc.) is significantly delayed or completely stopped for a long time.

 The thickened anti-icing fluids form a coating that, when applied to the surface by standard methods, gives the treated outer surface of the aircraft anti-icing and antifreeze properties and minimizes the sticking or growth of ice, snow, groats, etc. on it.

The apparent viscosity, which is provided by the macromonomer-containing polymer thickener in glycol or glycerol-based liquids, should be in the range of 1000-100000 mPa, preferably 20,000-60000 mPa (measurement is carried out on a Brookfield viscometer at a rotation speed of 0.3 rpm and a temperature of 0 ± 1 ^o With the use of a rotating rod # 31 (after 20 minutes equilibrium and a measurement time of 10 minutes).

 As soon as the aircraft begins to take off, but until it is completely turned and taken off the ground, the impact force of the wind on the wings and other exposed surfaces treated with an anti-icing composition, as well as mechanical vibration in the wings and other structural elements of the aircraft, causes sufficient shear to be applied to the aircraft liquid , liquefying it in such a way that it behaves like a relatively inviscid material. After that, the liquid drains easily from the wings and other treated surfaces of the aircraft.

 During the take-off run of the aircraft and to a full revolution (the moment at which the lifting force, which acts vertically on the aerodynamic surface of the aircraft, is sufficient for the pilot to take off and take off the aircraft from the ground), the shear force of the air stream from the wind changes the rheological properties of the declared liquid , causing a strong liquefaction under the action of shear and a noticeable decrease in apparent viscosity, which allows fluid to flow freely from the surface of the wings. Thus, the aerodynamic surface remains free not only from any sticking of snow, but also from the thickened fluid, which could have an undesirable effect on the lifting force.

 Macromonomer-containing polymer is used as the main thickener in icing fluids. However, as noted above, minor amounts of other ingredients, including other thickeners, may be present in the composition in order to provide additional thickening or an additional gelling function, or to modify rheological properties. The macromonomer-containing polymer used as the necessary thickening component is preferably present in an amount of at least about 80% by weight of the thickeners present; preferably, its content is more than 90% by weight of the thickener used.

 The gel-forming macromonomer-containing polymers used as thickeners exhibit the necessary low-viscosity characteristics, which are caused by shear, and are nevertheless resistant to mechanical degradation under shear stresses arising from the use of a pump and nozzle. This particular characteristic is very important, since anti-icing fluids are usually applied using standard ground equipment, which includes a pump-driven spray system. Aqueous glycol de-icing fluids thickened with a macromonomer-containing polymer exhibit sufficiently fluid (low viscosity) properties to be capable of pumping on standard ground equipment to eliminate icing on aircraft. In contrast to them, SAE / ISO Type II standard aircraft fluids mentioned earlier in the text are typically sensitive to shear and must therefore be delivered by pressure piston pumps or pressurized.

 Glycol or glycerin-based aqueous fluids are primarily intended to eliminate or prevent icing by treating fixed planes, but can also be used for routine ice removal, for example for treating car windshields and various vehicles and other open surfaces.

The modification of the rheological properties of the considered object is determined by the following parameters:
(1) the structure and concentration of the associative macromonomer, including: a) the size and structure of the hydrophobic molecule; b) the number of alkoxyl groups (in moles) between the hydrophobic group and the double bond; c) the chemical nature of the bond between the alkoxylated moiety and the reactive double bond (for example, the presence of ether, ester or urethane bonds); and d) the structure of the double bond itself (acrylic, methacrylic, crotonic, styrene, etc.);
(ii) the structure and concentration of the acid monomer in the polymer (for example, acrylic, methacrylic, crotonic, itaconic acid, etc.);
(iii) the structure and concentration of the associative macromonomer, including monomers that crosslink the polymer during polymerization (for example, trimethylolpropanetriacoylate), as well as those compounds that leave intact functional groups in the associative polymer that are capable of crosslinking, without resulting in cross-linking into polymerization time (e.g. 2-hydroxyethyl acrylate); and
(iv) the molecular weight of the polymer, which is regulated during the polymerization using mercaptans.

 All these parameters affect the fluid viscosity at steady shear, the viscoelastic properties and the elongation ability of the polymer, as well as the thickening efficiency. Parameters (ia) and (ib) influence the rheological properties by controlling the morphological properties, thermodynamic parameters, and kinetics of the formation of associative compounds. The parameter (ic) controls the hydrolytic stability of the bond, which connects the surfactant with the main polymer chain, as well as the simplicity (and therefore cost) of the synthesis of the associative macromonomer. The parameter (id) controls the sequence of incorporation of macromonomer into the polymer and the amount of coagulate in the reactor formed during the polymerization, which determines the productive viability of the polymer. Parameters (ii) and (iii) control the phase transition temperature (i.e., chain stiffness), hydrophobicity, and water solubility of the main polymer chain.

Since the viscosity of the liquid should not decrease significantly with dilution with water (to increase the “overtime” and the time it is sewn up in the spraying regime), the associative activity of the polymer should balance the viscosity loss due to the dilution of the polymer. At the same time, since the viscosity of the liquid should not increase significantly with a drop in temperature, the hydrodynamic size of the polymer molecule should be sufficiently reduced in order to compensate for the increase in the viscosity of the mixture of ethylene glycol and water. (The hydrogen bond between water molecules and ethylene glycol molecules doubles the viscosity of a mixture of ethylene glycol and water at a ratio of 50/50 components as the temperature decreases from 20 to 0 ^o C).

 The effect of aqueous dilution and temperature change on the viscosity of model aircraft fluids, consisting of 0.5% polymer solutions in ethylene glycol and water mixtures, taken in equal proportions, was studied. The results are shown in Table Q.

 The water dilution experiment essentially consists in titration of a glycol solution containing the polymer with water, that is, the creation of conditions such that the polymer concentration is 0.5% when the glycol concentration reaches 50%. Compositions that contain less than 50% weight. water, correspond to the experiment "dry out", which simulates the evaporation of water; at the same time, compositions that contain more than 50% weight. water, correspond to the experiment to determine the time of protection by spraying with water spray, which simulates the effect of ice rain or snow pellets striking on the treated surface of an aircraft, which is waiting on the runway. The viscosity of a solution is measured as water is added to it. Whether the viscosity of the liquid is dilution invariant or not depends on the number of moles of ethylene oxide in the macromonomer, as well as the concentration of the associative macromonomer and methacrylic acid in the polymer.

The degree to which the viscosity of model aircraft fluids depends on temperature also depends on the structure of the associative polymer. The dependence of the viscosity of the solution on the size of the polymer coil and concentration is often expressed as the main empirical dependences of the type h / = f (c [h]), such as the Huggins equation:
h / μ = 1 + c [h] + K′c ² [h] ² + ... (1)
where h is the viscosity of the polymer solution, μ is the viscosity of the solvent, c [h] is the dimensionless volume of the molecular coil, and the constant K 'characterizes the primary effect of polymer interaction on viscosity. The Huggins parameter K 'is usually independent of the molecular weight of the polymer in the case of long polymer chains and has a value of about 0.4 for polymers in good solvents where there are no interaction effects, and a value of about 0.8 for polymers in theta solvents. Equations like Equation (1) often combine viscosity data over a wide range of molecular weights and concentrations for a given diluted polymer-solvent system.

Характеристическая вязкость [h] зависит от гидродинамического размера полимерного клубка, который, в свою очередь, зависит от молекулярной массы полимера, качества растворителя и температуры. Взяв отношение характеристической вязкости к вязкости, полученной при произвольной стандартной температуре Т_ref, можно выделить температурное влияние для данной молекулярной массы полимера. Температурные корреляции для вязкости обычно принимают вид уравнения Аррениуса:

где R представляет собой универсальную газовую постоянную и LH -энергию активации на изменение вязкости с температурой. Величина энергии активации дает количественную оценку для того, чтобы сравнить влияние температуры на изменение вязкости жидкого антиобледенителя: если LH равен нулю, вязкость раствора изменяется точно таким же образом, как и растворителя; если LH больше нуля, тогда полимерный клубок расширяется и вязкость раствора возрастает по мере возрастания температуры; если LH меньше нуля, тогда полимерный клубок сжимается и вязкость раствора уменьшается по мере снижения температуры. Величину LH определяют путем подчинения температурной зависимости удельной вязкости для 0,5%-ных растворов полимера в смесях этиленгликоля и воды, взятых в соотношении 50/50, уравнению (3) посредством стандартного метода наименьших квадратов.Since the viscosity of the solvent in the form of a mixture of ethylene glycol and water increases with decreasing temperature, the contribution of the solvent to the total viscosity of the solution can be eliminated and only the increase that the polymer gives due to its own specific viscosity can be determined:

The intrinsic viscosity [h] depends on the hydrodynamic size of the polymer coil, which, in turn, depends on the molecular weight of the polymer, solvent quality and temperature. Taking the ratio of intrinsic viscosity to viscosity obtained at an arbitrary standard temperature T _ref , we can distinguish the temperature effect for a given molecular weight of the polymer. Temperature correlations for viscosity usually take the form of the Arrhenius equation:

where R is the universal gas constant and LH is the activation energy for a change in viscosity with temperature. The value of the activation energy gives a quantitative estimate in order to compare the effect of temperature on the change in viscosity of a liquid de-icer: if LH is zero, the viscosity of the solution changes in exactly the same way as the solvent; if LH is greater than zero, then the polymer coil expands and the viscosity of the solution increases with increasing temperature; if LH is less than zero, then the polymer coil is compressed and the viscosity of the solution decreases as the temperature decreases. The value of LH is determined by subjecting the temperature dependence of the specific viscosity for 0.5% polymer solutions in mixtures of ethylene glycol and water taken in a ratio of 50/50 to equation (3) using the standard least squares method.

 Whether the viscosity of the liquid is temperature-invariant or not depends on the concentration of the associative macromonomer in the polymer, the number of moles of ethylene oxide in the macromonomer, and the concentration of carboxyl groups in the polymer. If it is established that the structure of a single macromonomer-containing polymer is unacceptably sensitive to dilution and / or thermal effects (which tend to be inversely proportional to each other), compensation can be made by changing the solubility in water and the glass transition temperature of the polymer main chain. Thus, ethyl acrylate, for example, can be partially replaced by methyl acrylate.

 The co-thickening interaction of the polymer thickener with a non-ionic surfactant can provide shear thinning, nevertheless with a viscosity profile that is almost temperature-invariant. In the past, this effect was achieved through the formulation with the inclusion of anionic surfactants. Nonionic surfactant systems have the advantage of being able to use carbon steel tanks for storage.

Although the prior art describes standard liquids (SAE / ISO Type II) for preventing icing with an extended protection time against ice, snow, slush and hoarfrost, these liquids have found limited use as anti-icing agents, since the protection time tended to decrease. due to heating for several days at temperatures of 75-95 ^o C, which are encountered in operations to remove ice.

At temperatures of 75-95 ^o With thickeners based on polymers with a high molecular weight, such as polyacrylates or polysaccharides, as well as xanthan gum, are destroyed within a few days, losing the viscosity, in particular the viscosity measured at low shear rates. Since this viscosity helps provide protection against icing, the protection time of these fluids decreases over time, as they are heated during ice removal work.

Even the macromonomer thickeners of the present invention are capable of degrading at elevated temperatures (over 60 ^{° C.} ) unless a base of the proper type and concentration is used to prevent such breakdown. Although the inventors do not seek to associate themselves with any theory, it is assumed that this destruction occurs by hydrolysis of the macromonomer to a form that is less effective for use as a thickener.

 As mentioned previously, when using an alkali metal hydroxide and, in particular, sodium hydroxide, in order to bring the pH of the solution to 7.5, and preferably to a pH of 8.5 to 9.5, it was noted that thermal stability, as measured by the change viscosity at low shear, increased significantly. Higher pH actually actually further improve the thermal stability of the composition, however, compositions having a high pH are more aggressive towards aluminum and therefore it is preferable to avoid them.

 When using an alkali metal hydroxide salt and a weak acid in combination with an appropriate base, it was noted that thermal stability is further enhanced. In particular, it was noted that sodium acetate works well in combination with sodium hydroxide. Sodium acetate is an even weaker base and therefore, based on theoretical considerations, it tends to cause less hydrolysis than just one sodium hydroxide. However, low concentrations of the stabilizing salt are preferred since higher contents (even if they further improve thermal stability) tend to reduce the liquid protection time when used in the anti-icing mode. Preferred concentrations of stabilizing salt are from 0 to 0.10 wt.%, More preferably from 0 to 0.02 wt.%.

 As used herein, the term “complex hydrophobic” is intended to include all permissible hydrocarbon compounds having 2 or more hydrophobic groups, for example, bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl and the like.

 In the present invention, the term “hydrocarbon” is intended to include all valid compounds having at least one hydrogen atom and one carbon atom. In a broad aspect, acceptable hydrocarbons include substituted or unsubstituted acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic organic compounds.

 Unless otherwise indicated, the term “substituted” as used herein is intended to include all acceptable substituents of organic compounds. In a broad aspect, acceptable substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkoxyl, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, amino-alkyl, halogen and the like, in which the number of carbon atoms is from 1 to 20 or more, preferably from 1 to 12. Permissible substituents corresponding organic compounds may be the same or different and be present in an amount of one or more. The present invention is not intended to be limited in any way by the above admissible organic substituents.

 In more detail, the present invention is illustrated by the following examples.

Example 1. Obtaining 1,3-bis (nonylphenoxy) -2-propanol
220 g (1.00 mol) of nonylphenol and 250 ml of cyclohexane are added to a 2 L five-necked round bottom flask equipped with a dropping funnel, a thermometer, a nitrogen dispersion tube, a mechanical stirrer and a decantation head with a water cooler. The solution was heated to reflux and slowly added to the flask 2.8 g (1.3 wt.% In terms of nonylphenyl) potassium hydroxide in 10 ml of water. After all the water is extracted into the decanter nozzle (10 ml + 1 ml formed), 250.7 g (0.91 mol) of nonylphenyl glycidyl ether are added dropwise. During the addition of glycidyl ether, the reaction temperature was maintained between 60 and 80 ^° C. After the completion of the addition of ether, the solution was refluxed for 4 hours. The contents of the flask were washed with a 5% aqueous solution of phosphoric acid, the organic layer was separated from the aqueous and washed twice with deionized water. After this, the reaction mixture was transferred to a 1 L round-bottom flask and the unreacted nonylphenol and the remaining cyclohexane were recovered by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Hg. During the distillation, the temperature in the flask is not allowed to exceed 180 ^{° C.} to prevent discoloration of the product. The concentrated solution was filtered twice, obtaining 425 g of a pale yellow liquid. Analysis of the end groups gives a molecular weight of 506.8 (theoretical value MV = 496.8). IR and NMR spectra are identical to previously recorded spectra of this compound.

Example 2. Obtaining 1,3-bis (nonylphenoxy) -2-propanol
451.7 g (2.05 mol) of nonylphenol and 300 ml of cyclohexane are added to a five-necked 2-liter round-bottom flask equipped with a dropping funnel, a thermometer, a nitrogen dispersion tube, a mechanical stirrer and a decantation head with a water cooler. The solution is heated to reflux and 58.9 g (1.05 mol) of potassium hydroxide in 60 ml of water are slowly added to the flask. After all the water is extracted into the decanter nozzle (60 ml + 19 ml formed), the reaction mixture is cooled to 40 ^{° C.} and 92.5 g (1.00 mol) of epichlorohydrin are slowly added. During the addition operation, the reaction temperature is kept below 60 ^{° C.} by controlling the rate of addition of epichlorohydrin. Upon completion of the addition of the latter, the solution was stirred for one hour, and then heated under reflux for another 3 hours.

The reaction mixture was filtered under vacuum through a Buchner funnel with a steam jacket to remove the potassium chloride formed as a by-product. Filtration is carried out three times to remove most salts. After this, the reaction mixture was transferred to a 1 L round-bottom flask, and the unreacted nonylphenol and the remaining cyclohexane were recovered by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Hg. During the distillation, the temperature in the flask is not allowed to exceed 180 ^{° C.} to prevent discoloration of the product. The concentrated solution was filtered twice, obtaining 275 g of a pale yellow liquid. Analysis of the end groups gives a molecular weight of 459.7 (theoretical value MV-496.8). IR and NMR spectra are identical to previously recorded spectra of this compound.

Example 3. Obtaining 5 M ethoxylate 1,3-bis (nonylphenoxy) -2-propanol
In a 500 ml stainless steel high pressure autoclave, 200 g (0.40 mol) of 1,3-bis (nonylphenoxy) -2-propanol containing a catalytic amount of the potassium salt of alcohol are charged as described in Example 1. After purging the reactor with nitrogen, alcohol heated to 130 ^{° C.} with stirring, and 86.9 g (2.0 mol) of ethylene oxide were added over 2 hours. The reaction temperature and pressure are maintained, respectively, at 130-140 ^{° C.} and 4.2 kg / cm ² . Upon completion of the addition of ethylene oxide, the mixture was incubated for an additional hour at a temperature of 140 ^o C and allow all ethylene oxide to boil. The reaction mixture is discharged hot in a nitrogen atmosphere and neutralized with acetic acid to give 285 g of a pale yellow liquid.

Example 4. Obtaining the adduct of nonylphenylglycidyl ether and 5 M ethoxylate 1,3-bis (nonylphenoxy) -2-propanol
To a five-necked 1-liter round bottom flask equipped in accordance with Example 1, 5 M of 1,3-bis- (nonylphenoxy) -2-propanol ethoxylate and 100 ml of cyclohexane were added. The mixture was refluxed (100 ^° C) for one hour to remove the residual amount of water, and then cooled to 50 ^° C in a nitrogen atmosphere by adding 0.5 g of BF ₃ / Et ₂ O. After that, it was left in the flask for 1 h nonylphenyl glycidyl ether (46 g, 0.17 mol) is added and the mixture is heated to reflux. After three hours at reflux, the hot mixture was transferred to a separatory funnel and washed with saturated aqueous sodium bicarbonate. The organic layer was separated from the aqueous layer and washed twice with hot deionized water. Washing is carried out at a temperature of 50 ^o With to facilitate the separation of both layers. Water and cyclohexane from the organic layer are evaporated in vacuo to give 145 g of a pale yellow viscous liquid. Analysis of the end groups gives a molecular weight of 880 (theoretical value MV-993).

Example 5. Obtaining poly (nonylphenol) glycidyl ether
1.9 ethanol (22 mmol) and 200 g of cyclohexane are added to a 500 ml round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, dropping funnel and temperature controller and the solution is adjusted to 50 ^° C. After heating, using a 2 ml syringe, 0.5 ml (4 mmol) of BF ₃ / Et ₂ O is injected. As soon as the acid administration is completed, 100 g of nonylphenol glycidyl ether (362 mmol) is added dropwise so that the temperature is maintained in the range of 45-55 ^{° C.} After adding ether, the solution is refluxed. refluxed refrigerator for 3 hours, and then cooled to 50 ^o C.

In hot form (below 60 ^o C), the mixture is transferred to a separatory funnel and washed with 100 ml of 5% sodium bicarbonate solution. The aqueous layer was separated, the organic layer was washed two more times with deionized water (2 x 100 ml). The aqueous layers are deactivated, the organic layer is dried on magnesium sulfate for at least 1 hour. After drying, magnesium sulfate is filtered off and the organic solvent is removed on a rotary evaporator to obtain 100 g of a viscous polymer. Gel permeation chromatography (GPC) analysis gave values of Mw-2600 (weight average molecular weight) and Mp-1700 (number average molecular weight) relative to standard monodispersed polystyrene.

Example 6. Ethoxylation of poly (nonylphenol) glycidyl ether
To a 500 ml stainless steel autoclave (Zipperclave) add 60.0 g (0.035 mol based on the approximate value of MV-1700) of the resin obtained in Example 5, together with 0.5 g of potassium hydroxide. The vessel is connected to an automatic plant for ethoxylation and heated to 50 ^° C. The vessel is continuously purged with nitrogen for 15 minutes, then heated to 100 ^{° C.} and a continuous nitrogen purge is carried out for an additional 15 minutes. After that, the reaction vessel is heated to 140 ^o C and spend a series of 6 purges with pressure testing to about 12.7 kg / cm ² (80 psi), followed by ventilation. At the end of ventilation, the vessel is pressurized with nitrogen to approximately 1.5 kg / cm ² (20 psi).

The ethylene oxide lines go to two electrically actuated valves and, together with the main feed line, to the autoclave. The feed is carried out continuously, the pressure in the vessel is regulated by a value of about 4 kg / cm ² (55 psi) at a temperature of 140 ^o C. Automation is designed so that when ethylene oxide is added through an electrically actuated valve, temperature and pressure are maintained in safe working conditions limits. The feed is continued until 60.0 g (1.362 mole) of ethylene oxide is added (based on the difference in weight of the feed cylinder). At the end of the feed, the reaction is continued for another hour, after which the vessel is cooled to 60 ^o C, purged 4 times with nitrogen to a pressure of about 5.6 kg / cm ² and then the reaction mixture is unloaded into a container. The weight of the finished product is 115 g with a theoretical yield of 123 g. Gel permeation chromatography analysis gives Mw = 2600 (weight average molecular weight) and Mn = 1700 (number average molecular weight) relative to standard monodispersed polystyrene.

Example 7. Obtaining poly (phenyl) glinidyl ether
47.6 phenol (500 mmol) and 100 g of toluene are charged to a 500 ml round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, dropping funnel and temperature controller, and the solution is brought to 50 ^° C. After heating, Using a 2 ml syringe, 1.0 ml (8 mmol) of BF ₃ / Et ₂ O is injected. Once acid administration is complete, 68.18 g of phenyl glycidyl ether (454 mmol) is added dropwise so that the temperature is maintained in the range of 45- 55 ^o C. After the addition of the glycidyl ether solution was refluxed olodilnikom for 3 hours and then cooled to 50 ^o C.

In hot form (below 60 ^o C), the mixture is transferred to a separatory funnel and washed with 100 ml of 5% sodium bicarbonate solution. The aqueous layer was separated, the organic layer was washed two more times with deionized water (2 • 100 ml). The aqueous layers are decanted, the organic layer is dried on magnesium sulfate for at least 1 hour. After drying, magnesium sulfate is filtered off and the organic solvent is removed on a rotary evaporator to obtain 100 g of a viscous polymer. The final yield of the viscous polymer is 90.3 g (at 11% unreacted phenol). Analysis by gel permeation chromatography (GPC) yielded values of Mw = 470 (weight average molecular weight) and Mn-310 (number average molecular weight) relative to standard samples of monodispersed polystyrene.

Example 8. Obtaining 1,3-bis (phenoxy) -2-propanol using cascade technology of polyols
94.11 phenol (1 mol), 12.86 g of tetraethylammonium iodide (0.05 mol), 3, 00 g of water (0.17 mol), 42.08 g of potassium hydroxide (0.75 mol) and 250 g of toluene. 23.13 g of epichlorohydrin (0.25 mol) and 50 g of toluene are placed in a 100 ml dropping funnel. The solution was brought to 65 ^° C, epichlorohydrin in toluene was added over 15 minutes, while maintaining the temperature in the range of 65 ± 5 ^° C, and the mixture was allowed to react for 48 hours.

 After 48 hours, the solution was cooled to room temperature. The toluene solution is washed with deionized water (2 x 250 ml), the aqueous layers are separated, the toluene together with unreacted phenol is removed on a rotary evaporator. The mass of the final product is 64.5 g, which is 106% of theoretical (the residue is phenol), the purity of the final product is about 95% (according to the results of GPC).

Example 9. Dimerization of 1.3-bis (phenoxy) -2-propanol using cascade technology of polyols
In a 250 ml round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, dropping funnel and temperature regulator, 20.03 g of the 1,3-bis (phenoxy) -2-propanol obtained according to Example 8 (82 mmol), 2.06 g of tetraethylammonium iodide (8 mmol), 0.49 g of water (27 mmol), 6.51 g of potassium hydroxide (116 mmol) and 125 g of toluene. 3.61 g of epichlorohydrin (39 mmol) and 25 g of toluene are added to a 100 ml dropping funnel. The solution was brought to 65 ^° C, epichlorohydrin in toluene was added over 15 minutes, while maintaining the temperature in the range of 65 ± 5 ^° C, and the mixture was allowed to react for 48 hours.

 After 48 hours, the solution was cooled to room temperature. The toluene solution is washed with deionized water (2 x 250 ml), the aqueous layers are separated, the toluene together with unreacted phenol is removed on a rotary evaporator. The mass of the final product is 21.6 g, which is 101% of the theoretical. GPC analysis shows that the product consists of two main components. The first component is the starting material in an amount of about 41% (Mn = 220) and the second is a dimer in an amount of about 59% (Mw = 520).

Example 10. Obtaining 1,3-bis (hexadecyloxy) -2-propanopol using cascade technology of polyols
60.61 hexadecanol (0.25 mol), 16.18 g of tetraethylammonium iodide (0.024 mol) are charged into a 500 ml round bottom flask equipped with an overhead stirrer, nitrogen inlet, reflux condenser, and dropping funnel. 44 g of water (0.082 mol), 20.20 g of potassium hydroxide (0.36 mol) and 125 g of toluene. 11.10 g of epichlorohydrin (0.12 mol) and 25 g of toluene are placed in a 100 ml dropping funnel. The solution was brought to 65 ^° C, epichlorohydrin in toluene was added over 15 minutes, while maintaining the temperature in the range of 65 ± 5 ^° C, and the mixture was allowed to react for 48 hours.

 After 48 hours, the solution was cooled to room temperature. The toluene layer is washed with deionized water (2x250 ml), the aqueous layers are separated and the toluene is removed on a rotary evaporator. The mass of the final product is 70.9 g, which is 109% of theoretical (the remainder is hexadecanol).

Example 11. Sulfonation of 1,3-bis (nonylphenoxy) -2-propanol-block- (propylene oxide) _10- block- (ethylene oxide) ₁₀
In a 500 ml round bottom flask equipped with an overhead stirrer, a temperature controller and a vacuum adapter, 75.0 g of the product from Example 13 (49 mmol) was charged. The vessel is evacuated to a pressure of less than 20 mm Hg and heated to 100 ^o With to remove water. After an hour, the reactor was cooled to 60 ^{° C.} also under vacuum. Upon reaching 60 ^{° C., the} vacuum was removed with nitrogen and 5.3 g of sulfamic acid (54 mmol) was added, after which the reactor was heated to 110 ^{° C.} and pumped to a vacuum of less than 20 mm Hg. The mixture was allowed to react for 3 hours.

At the end of the reaction, the reactor is cooled to 85 ^° C, the vacuum is removed with hydrogen, and then 1.2 g of diethanolamine (11 mmol) are slowly added under the hydrogen shell and the solution is stirred for 30 minutes. 10 g of ethanol was added to the reactor and the temperature was adjusted to 55 ^° C and the solution was stirred for another 30 minutes. The heat is removed and 30 g of water and 20 ethanol are added to the reactor with constant and good stirring. The solution is stirred for 15 minutes or until the temperature drops to room temperature (less than 35 ^{° C.} ).

 The pH of the solution is checked by dissolving 2 g of a solution of the product in 18 ml of deionized water. If the pH check is less than 6.5, diethanolamine is added in 0.2 g portions until the pH is in the range of 6.5-7.5.

Example 12. Obtaining 1.3-bis (nonylphenoxy) -2-propanol-block- (propyleneoxyl) ₁₀
In a 500 ml stainless steel autoclave (Zipperclave), 100 g (0.202 mol) of the 1,3-bis (nonylphenoxy) -2-propanol obtained in Example 1 are charged together with 0.7 g of potassium hydroxide. The reactor is connected to an automatic installation and heated to 50 ^° C. Next, the reactor is continuously purged with nitrogen for 15 minutes, and then heated to 100 ^{° C.} , after which it is continuously purged with nitrogen for another 15 minutes. Next, the reaction vessel is heated to 140 ^o C and spend a series of 6 purges with pressure testing to about 5.6 kg / cm ² and subsequent ventilation. At the end of ventilation, the vessel is pressed with nitrogen to about 1.4 kg / cm ² .

Lines of propylene oxide connected to a feed cylinder pre-filled with 117.0 g of propylene oxide (2.02 mol) go to the electrically operated valves and, together with the main feed line, to the autoclave. The feed is carried out continuously, the parameters in the vessel are regulated to a pressure of about 4 kg / cm ² and a temperature of 140 ^° C. The automation is designed so that when ethylene oxide is introduced by means of a pair of electrically operated valves, the temperature and pressure are kept within safe operating limits. The flow is continued until all propylene oxide has been introduced. At the end of the feed, the reaction is continued for another hour, after which the vessel is cooled to 60 ^o C, purged 4 times with nitrogen to a pressure of about 5.6 kg / cm ² and the reaction mixture is unloaded into a container. The mass of the final product is 211 g with a theoretical yield of 277 g. Analysis by gel permeation chromatography gave Mw = 650 (weight average molecular weight) and Mn = 490 (number average molecular weight) relative to standard samples of monodispersed polystyrene.

Example 13. Obtaining 1.3-bis (nonylphenoxy) -2-propanol-block- (propylene oxide) _10- block- (ethylene oxide) ₁₀
In a 500 ml stainless steel autoclave (Zipperclave), 75 g (0.070 mol) of propoxylate from Example 12 are charged with 0.3 g of potassium hydroxide. The reactor is connected to an automatic plant for ethoxylation and heated to 50 ^° C. Next, the reactor is continuously purged with nitrogen for 15 minutes and then heated to 100 ^° C, and again purged with nitrogen continuously for another 15 minutes. Next, the reaction vessel is heated to 140 ^o C and spend a series of 6 purges with pressure testing to about 5.6 kg / cm ² and subsequent ventilation. At the end of ventilation, the vessel is pressed with nitrogen to about 1.4 kg / cm ² .

The ethylene oxide lines connected to the feed cylinder exit to the electrically operated valves and, together with the main feed line, to the autoclave. The feed is carried out continuously and the parameters in the vessel are adjusted to a pressure of about 4 kg / cm ² and a temperature of 140 ^° C. The automation is designed so that when ethylene oxide is introduced through a pair of electric valves, the temperature and pressure are kept within safe operating limits. The flow is continued until 30.7 g (0.696 mol) of ethylene oxide are added (calculated on the difference in weight of the feed cylinder). At the end of the feed, the reaction is continued for another hour, after which the vessel is cooled to 60 ^o C, purged 4 times with nitrogen to a pressure of about 5.6 kg / cm ² and the reaction mixture is unloaded into a container. The mass of the final product is 99 g with a theoretical yield of 106 g.

Example 14. Obtaining bis (nonylphenoxy) -adduct 1,4-butanediol-diglycidyl ether
506.8 g (2.30 mol) of nonylphenol and 350 ml of cyclohexane are added to a 2-liter five-necked round-bottomed flask equipped with a dropping funnel, a thermometer, a nitrogen dispersion tube, a mechanical stirrer and a decantation head with a water cooler. The solution is heated to reflux and slowly add to the flask 6.5 g (1.3 wt.% In terms of nonylphenol) of potassium hydroxide in 15 ml of water. After all the water is removed into the decanter nozzle (15 ml + 2 ml formed), 220 g (1.09 mol) of 1,4-butanediol diglycidyl ether are added dropwise. During the addition of glycidyl ether, the reaction temperature was maintained between 60 and 80 ^° C. After the completion of the addition of ether, the solution was refluxed for 4 hours. The contents of the flask were washed with a 5% aqueous solution of phosphoric acid, the organic layer was separated from the aqueous and washed twice with deionized water. After this, the reaction mixture was transferred to a 1 L round bottom flask, and the unreacted nonylphenol and the remaining cyclohexane were recovered by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Hg. During the distillation, the temperature in the flask is not allowed to exceed 180 ^{° C.} to prevent discoloration of the product. The resulting concentrated solution was filtered twice, obtaining 710 g of a pale yellow liquid. The molecular weight determined by the analysis of the end groups is 689.9 (theoretical value MV = 643.0). IR and NMR spectra correspond to the intended structure of the compound.

Example 15. Obtaining 3 M ethoxylate 1,3-bis (nonylphenoxy) -2-propanol
In a 500 ml Zipperclave reactor, 200.1 g (0.43 mol) of 1,3-bis- (nonylphenoxy) -2-propanol obtained according to Example 2 and 0.20 g (0.1 wt.) Are charged under a stream of nitrogen. %) BF ₃ / Et ₂ O. After this, the reaction mixture is heated to 80 ^° C and 55.1 g (1.25 mol) of ethylene oxide are introduced into the reactor over 2 hours. At the end of the entire product, the reaction mixture is boiled for 1 h, and then discharged hot in a nitrogen atmosphere into a vessel containing 160 ml of a 1% aqueous solution of sodium hydroxide. The organic layer was separated from the aqueous and washed twice with deionized water. Washing is carried out at a temperature of 90 ^o With to facilitate the separation of both layers. The resulting product was dried by azeotropic removal of water using cyclohexane (300 ml) as an azeotropically. Cyclohexane is evaporated under vacuum, obtaining a pale yellow viscous liquid, the molecular weight of which, determined by analysis of the end groups, is 601.7 (theoretical value MV = 629). IR and NMR spectra correspond to the intended structure of the compound.

Example 16. Obtaining 8 M ethoxylate of bis (nonylphenoxy) -adduct 1,4-butanediol glycidyl ether
150.2 g (0.22 mol) of the bis (nonylphenoxy) adduct of the 1,4-butanediol diglycidyl ether obtained in Example 14 and 0.30 g (0.2% by weight) are charged into a 500 ml Zipperclave reactor ) BF ₃ / Et ₂ O. After this, the reaction mixture is heated to 80 ^{° C.} and 77.5 g (1.76 mol) of ethylene oxide are introduced into the reactor over 2 hours. At the end of the entire product, the reaction mixture is boiled for 1 h, and then discharged hot in a nitrogen atmosphere into a vessel containing 160 ml of a 1% aqueous solution of sodium hydroxide. The organic layer was separated from the aqueous and washed twice with deionized water. Washing is carried out at a temperature of 90 ^o With to facilitate the separation of both layers. The resulting product was dried by azeotropic removal of water using cyclohexane (300 ml) as an azeotropically. Cyclohexane is evaporated under vacuum, obtaining a pale yellow viscous liquid, the molecular weight of which, determined by the analysis of the end groups, is 1047 (theoretical value MV = 995). IR and NMR spectra correspond to the intended structure of the compound.

Example 17. Obtaining macromonomer compounds
300 g of toluene and 63 g of surfactant, designated S-1 in Table A below, are charged into a 1 L round bottom reaction flask equipped with a heating jacket, a Dean-Stark trap, a refrigerator, a thermometer, a nitrogen bubbler, a nitrogen purge line and a stirrer. When purging with nitrogen, the resulting solution is heated to reflux at a temperature of about 110 ^o C and traces of water are removed to dryness by the method of azeotropic removal. The solution was then cooled to 90 ^{° C.} , 1.5 bismuth was charged as 28% bismuth octolate as a catalyst (Mooney Chemical, Inc., Cleveland, Ohio, US), mixed well, and then a stoichiometric amount of 95% was added. aliphatic isocyanate t-TMI (American Cyanamide company) (American Cyanamid Co., Stamford, CT, US). 1.3 hours after the start of the reaction at 90 ^{° C.} , the resulting product was cooled to 70 ^{° C.} and 0.03 g of 2,6-di-tert-4-methylphenol (BHT) was added as a preservative. The mixture is poured into a stainless steel bath with a large surface to facilitate drying. The final product is a waxy material designated as macromonomer M-1.

Examples 18-34. Obtaining macromonomer compounds
Other macromonomers are prepared by methods similar to those described in Example 17, using stoichiometric amounts of surfactants and unsaturated compounds identified in Table B.

Example 35. Obtaining a thickener soluble in alkali
A monomer mixture (300 g) is obtained by loading ethyl acrylate (Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 g of a 75% solution of Aerosol ^R surfactant (American Cyanamide, USA) and 3 g of distilled deionized water into a vessel and dispersing the contents by vigorous shaking. Ethyl acrylate, methacrylic acid and macromonomer M-1 are added in the amounts indicated in Table C. A catalyst mixture comprising 0.53 g of sodium persulfate (Aldrich) and 52.47 g of water is prepared in a different container. In a 2-liter plastic flask immersed in a thermostatic water bath and equipped with a four-blade stainless steel mechanical stirrer, Klaisen connecting tube, water cooler, nitrogen bubble trap, thermometer, monomer and catalyst inlet, put 1.20 g of vinyl sodium salt -sulfonic acid and 658.5 g of water. The monomer mixture is loaded into a 1 L graduated feed cylinder for the monomer, and the catalyst solution is loaded into a 125 ml graduated feed cylinder for the catalyst. Under a stream of nitrogen, the reactor is heated to 70 ^{° C.} , after which 33 ml of the monomer mixture and 3 ml of the catalytic mixture are loaded into the reaction vessel and then heated to 80 ^° C. After the monomers have reacted for 20 minutes to form a polymer seed, the mixture of monomer and catalyst is transferred to the reaction vessel using FMI pumps through a Teflon pipe with a diameter of 1/8 inch at a speed of 1.94 and 0.27 ml / min, respectively, with continuous stirring and maintaining the reaction temperature in the range of 76-82 ^o C. the Reaction is carried out for another 1 h, after which the product is cooled and filtered through nylon cloth with a pore size of 200 mesh. The coagulate is collected from the reaction vessel and from the filter cloth. The thickening ability of the obtained product is monitored using a Brookfield viscometer at a rotation speed of 6 rpm by diluting the latex to 0.25, 0.50 and 0.75% by solid, followed by neutralization of the product to pH 9.0 with 95% a solution of 2-amino-2-metip-1-propanop (AMP-95 from Angus Chemical Company, USA). The results are shown in Table C.

Examples 36-131. Preparation of alkali soluble thickeners
In a manner analogous to that described in Example 35, other alkali soluble thickeners were prepared using the monomers shown in Tables CJ and their quantities. Table C illustrates the effect of the concentration of macromonomer containing m-TMI and ethoxylation on the thickening efficiency. Table D illustrates the effect of mixing m-TMI-containing macromonomers of varying degrees of ethoxylation on the thickening efficiency. Table E illustrates the effect of the type of unsaturation of urethane-containing macromonomers on the thickening efficiency. Table F illustrates the effect of the structure of macromonomer ester and ethoxylation on the thickening efficiency. Table G illustrates the effect of acid type and concentration on the thickening efficiency. Table H illustrates the effect of the glass transition temperature of the polymer and the solubility in water on the thickening efficiency. Table I illustrates the effect of the concentration of the crosslinkable monomer on the eagening efficiency. Table J illustrates the effect of mercaptan on the thickening efficiency.

 The following abbreviations are used in Tables C-J: MM - macromonomer; EA - ethyl acrylate; MAA - methacrylic acid; AA is acrylic acid; MA is methyl acrylate; t-BA is tert-butyl acrylate; p-VA - n-butyl acrylate; MMA - methyl methacrylate; 2-ENP - 2-ethylhexyl propionate mercaptan; and 2-HEA - 2-hydroxyethyl acrylate.

Examples 132-187. Co-thickening in the presence of surfactants
Adding some surfactants to the associative polymer solution provides a co-thickening effect. The results shown in Table L illustrate the effect obtained by adding, with thorough stirring, some of the surfactants from Table K. Their amount is indicated in Table L with respect to the 0.5% alkaline solution of the alkali-soluble thickener that was identified there. . The effect is evaluated by the viscosity measured on a Brookfield viscometer at a rotation speed of 6 rpm and a pH of 9.0.

Examples 188-232. Co-thickening in the presence of surfactants
The degree of ethoxylation of the surfactant added to the associative polymer solution has an effect on the co-thickening effect. The results shown in Table N illustrate the effect obtained by adding, with thorough mixing, some surfactants from Table M. Their amount is indicated in Table N with respect to 0.3% (Examples 172-189), 0.5% (Examples 190 -215) or 0.75% (Example 216) of an alkaline solution of an alkali soluble thickener that is identified in the same Table. The effect is evaluated by the viscosity measured on a Brookfield viscometer at a rotation speed of 6 rpm and a pH of 9.0.

Examples 233-245. Co-thickening in the presence of solvents and non-solvents
Solvents and non-solvents added to the associative polymer solution have an effect on the thickening effect. The results shown in Table P illustrate the effect obtained by adding, with thorough mixing, some LAB from Table 0. Their amount is indicated in Table P with respect to 0. The 75% alkaline solution of the alkali soluble thickener identified in the same Table F. The effect is evaluated by the viscosity measured on a Brookfield viscometer at a rotation speed of 6 rpm and a pH of 9.0.

Example 246. The study of polymer solutions for compositions used to prevent icing of aircraft
Polymer solutions are titrated with water and then Brookfield viscosity (in centipoises) is measured at 30 rpm and room temperature (20 ^° C) and at 0 ^° C in a thermostatic bath. The results are shown in Table Q. Polymer solutions without the addition of water (0 g) contain 0.5% of the solid polymer identified in Table Q, a mixture of ethylene glycol and water (1: 1) and have a pH of 9.0. Negative values in the table simulate the evaporation of water (the so-called "dry out" phenomenon).

Example 247. Temperature sensitivity of polymers in compositions used to prevent icing of aircraft
The polymer solutions are heated and their Brookfield viscosity is measured at 30 rpm at various temperatures in a thermostatic bath. The activation energy is determined by the change in viscosity from temperature. In particular, the LH value is determined by subordinating the temperature dependence of the specific viscosity for 0.5% polymer solutions from Table R in a water-ethylene glycol mixture (50/50) to equation (3) using the least squares method. The results obtained are presented in Table R.

Example 248. Co-thickening in a polymer solution
Study for liquids used to prevent aircraft icing
Polymer solutions are titrated with water and then Brookfield viscosity (in centipoises) is measured at 30 rpm and room temperature (20 ^° C) and at 0 ^° C in a thermostatic bath. The results are shown in Table S. Polymer solutions without the addition of water (0 g) contain 0.5% of the solid polymer defined in Table S, a certain amount (in wt.% Of the total solution weight) of the non-ionic surfactant Tergitol ^R 15-S-5 defined in Table S, in a mixture of ethylene glycol and water (1: 1) and have a pH of 9.0. Negative values in the table simulate the evaporation of water (the phenomenon of "dry out").

Example 249. The effect of added surfactant on the temperature sensitivity of the compositions to prevent icing of aircraft
The polymer solutions are heated and their Brookfield viscosity is measured at 30 rpm at various temperatures in a thermostatic bath. The activation energy is determined by the change in viscosity from temperature. LH is determined by subordinating the temperature dependence of the specific viscosity of 0.5% polymer solutions from Table T in the presence of a certain amount (in wt.% Of the solution weight) of Tergitol ^R 15-S-5 nonionic surfactant (Table T) in a water-ethylene glycol mixture ( 50/50) to equation (3) using the least squares method. The results are presented in Table T.

 Surfactants affect not only the value of viscosity, but also how this viscosity is sensitive to temperature changes.

Example 250. The effect of temperature and surfactant on the viscosity profile at constant shear in liquids to prevent icing of aircraft
The steady-state viscosity profile is obtained on a standard Bohlin VOR instrument for studying the rheological properties of polymers (rheometer) with temperature control and Mooney-Couette shear geometry. The polymer solutions contain 0.4% of the solid polymer defined in Table U, a certain amount (in wt.% Of the total weight of the solution) of Tergitol ^R 15-S-5 non-ionic LAV, defined in Table U, and a mixture of ethylene glycol and water (1: 1). The results are presented in Table U. Viscosity is expressed in centipoises (cP).

Example 251. The effect of dilution with water, temperature, shear rate, type of LOVE and concentration on the viscosity profile at a steady shear v of liquids to prevent icing of aircraft
The steady-state viscosity profile is obtained on a standard Bohlin VOR instrument for studying the rheological properties of polymers (rheometer) with temperature control and Mooney-Couette shear geometry. The starting liquids contain 49.75 g of ethylene glycol (polyester class), 38.90 g of distilled water, 0.85 g of latex containing 30 wt.% Solid polymer P-8, and a certain amount of non-ionic surfactant Tergitol ^R NP-6, defined in Table V. Fluids were adjusted to a pH of about 8.5 with a 45% potassium hydroxide solution. The results are presented in Table V. Viscosity is expressed in centipoises (cP).

Example 252. The effect of the type of polymer on the viscosity profile at a steady shear v of liquids to prevent icing of aircraft
The steady-state viscosity profile is obtained on a standard Bohlin VOR instrument for studying the rheological properties of polymers (rheometer) with temperature control and Mooney-Couette shift geometry. The liquids contain 54.0 g of ethylene glycol (polyester class), 46.0 g of distilled water, some latex containing 30 wt.% Solid polymer P-8 or P-31, as defined in Table W, a certain amount of non-ionic surfactant Tergitol ^R 15-S-5, as defined in Table W, 0.25 g of Sandocarin 8132C corrosion inhibitor and 0.01 g of Sag 7133 corrosion inhibitor fluid were adjusted to a pH of about 8.5 with a 45% potassium hydroxide solution. The results are presented in Table W. Viscosity is expressed in centipoises (cP).

Example 253. Shear stability and protection time of the compositions to prevent icing of aircraft during irrigation by spraying water
Tests for determining the shear stability and protection time (durability) of the compositions by spraying with water are carried out in accordance with the methodology for such tests described in the Technical Specifications of the Association of European Airlines for Liquids used to combat icing aircraft (AEA Material Specification of De- / Anti-Icing Fluid for Aircraft, G 6807 / R). Liquids contain 49.75 g of ethylene glycol (polyester class), 38.90 g of distilled water, 0.85 g of latex containing 30 wt.% Solid polymer P-8, and 0.4 g of non-ionic surfactant Tergitol ^R 15-S- 5. The fluids were adjusted to a pH of about 8.5 with a 45% potassium hydroxide solution. The results show less than 5% for the change in viscosity and 70 min when assessing the healing time (durability). To test for shear stability, the rotation speed and mixing time are 2 times higher than these values from the technical conditions (7000 rpm for rotation speed and 10 min for mixing time).

 Examples 254-293 illustrate the effect of a neutralizing base on the thermal stability of an aircraft fluid as claimed in the present invention.

In these Examples, the product referred to as Sag 2001 is a patent protected organic emulsion used as an antifoam agent from Axis, USA (OSi Inc, Danbury. CT). The product, referred to as "Ingredient S", is a 5 mol octylphenol ethoxylate known by the trade name "Triton X-45" (Triton ^R X-45) from Union Carbide, USA (Union Carbide Corp. Danbury. CT). The product, referred to as "Sandocorin LF", is a patented corrosion inhibitor / flame retardant containing an acrylic terpolymer and about 10 wt.% Triethanolamine, supplied by Clariant (Clariant Corp. Charlotte. NC). The product, referred to as "thickener" (Thickener), is a polymer obtained according to Example 76 of US patent 5 399 618. (Example 43 described above describes the preparation of a similar product, which, according to the applicant, should not differ greatly in their properties or the results achieved from the thickener used in the examples below).

 According to the following General method receive the following four liquids.

In a container (1) with a capacity of 1.14 l (1 quart) add, g:
Ethylene glycol - 550.96
Water - 355.73
In a glass with a magnetic stirrer 1 add, g:
Ethylene Glycol - 11.57
Water - 10.36
Then, with stirring, to the contents of the glass 1 is slowly added in the following order, g:
SAG 2001 - 0.17
Thickener - 5.00
Sandocorin LF - 1.50
Ingredient S - 2.50
After stirring (at least 20 minutes) to obtain a homogeneous suspension, the mixture from the beaker 1 is transferred with stirring to the container (1).

 Prepare beaker 2 with exactly the same contents as in beaker 1. Make the same additions and continue stirring.

In a glass of 3 add, g:
Ethylene Glycol - 14.47
Water - 12.96
SAG 2001 - 0.17
Triethanolamine (TEA) - 2.50
45% potassium hydroxide solution - 1.00
The contents of the glass 3 are mixed and slowly transferred to the container (1) with stirring, continuing until a homogeneous suspension is formed (at least 15 minutes). According to the described method receive 1000 g of aircraft liquid.

 Example 254 exactly matches the above. In Example 256, instead of the KOH / triethanolamine mixture, only KOH (1.35 g of a 45% solution) is used. In Example 255, instead of the KOH / triethanolamine mixture, only triethanolamine (19.17 g) was used. In Example 257, instead of the KOH / triethanolamine mixture, 1.11 g of a 45% sodium hydroxide solution was used.

The initial viscosity at low shear (Brookfield viscometer LVT, rotating rod 1, 0.3 rpm. 0 ^o With a holder for a sample of small mass and 10 minutes for reading) is determined for each of the liquids, and then two samples each is placed in an oven at 70 ^{° C.} for 30 days. After this, the liquids are cooled to room temperature and the low shear viscosity is re-measured. Using the data obtained, the viscosity loss due to heating is calculated for four neutralizing bases.

The results show that when alkali metal hydroxide, preferably sodium hydroxide, is used as a neutralizing base, a liquid with significantly higher thermal stability is obtained. In addition to low losses for viscosity, the test for protection by spraying with water (WSET test) for a liquid neutralized with sodium hydroxide shows a very high initial value (150 min), which decreases by 30% at 30 ^° C only by 9%. On the other hand, potassium hydroxide gives a significantly lower WSET (127 min) and a higher drop (12.6%) from heating for 30 days at a temperature of 70 ^o C.

 Examples 258-275 correspond to the set-up experiments performed at the same time in order to determine the effect of five variables on the thermostability of formulations used as aircraft liquids. They use the methods and materials described in Example 257, and the studied parameters are the following: a) the ratio of ethylene glycol and water; b) the content of the thickener; c) Sandocorin LF product content; d) the content of Ingredient S; e) the content of sodium hydroxide, indicated in Table II as XI, X2, etc. respectively. The experimental design and results are also illustrated in Table II.

 The number in the column labeled EG / W is the ratio of ethylene glycol to water, and the numbers in the “zag.” (Thickener), LF and S columns are the number (in g) of the components added to each of the first two mixtures prepared in appropriate glasses (recipe for 1000 g of the experimental mixture). The numbers in the column labeled “NaOH” correspond to the amount (in g) of the component added to the mixture (per 1000 g portion). The designation "Begin" and "Heat" (Htd) corresponds to the liquid before and after heating.

 The results show that improved thermal stability (measured either by viscosity loss or WSET loss due to reduced protection time) is achieved by increasing the ratio of ethylene glycol to water, using more thickener, less Sandoconn LF and Ingredient S and more NaOH (by preparing a liquid with a higher pH). The fluid of Example 261 meets all of the proposed instructions and provides a high initial protection time (WSET), as well as excellent thermal stability in preserving either the WSET or Brookfield viscosity.

Examples 276-281 illustrate the effect of pH on thermal stability. In these Examples, Example 261 is repeated, except that the amount of NaOH is adjusted so as to achieve the pH values indicated in the "Before Heating" section of Table III. Thermal stability data is also presented in Table III. In this Table, viscosity is expressed in centipoises and measured on a Brookfield viscometer. The term “ ^o Brix” is a refractive index value measured on an AO 10431 instrument from Misco Products Division, Cleveland, Ohio. The value of the refractive index is very important because it provides a simple and affordable determination of the ratio of glycol to water in the liquid used (which, in turn, determines the freezing point and other important performance characteristics). Other instruments can also be used to measure the refractive index, however, the type of refractometer mentioned above is particularly convenient when measuring in the field.

Examples 282-285 study the effect of an alkali metal ion at constant pH. The following compositions were prepared by adding the indicated amount of sodium acetate to the liquid of Example 261. Immediately thereafter, the indicated amount of sodium hydroxide was added. All Examples involve adjusting the pH of the mixtures to 9.5 by adding the indicated amount of NaOH:
Example - NaOH, g (post-addition)
282 Example 261
283 0.25 g NaAc - 1.29
284 0.50 g NaAc - 1.34
285 0.75 g NaAc - 1.40
All samples are subjected to heat aging at 95 ^o C for 6 days. The results before and after aging are presented in Table IV.

 The results suggest that small doses of sodium acetate (of the order of 0.025%) provide an additional improvement in thermal stability (however, if it is used in a sufficiently large amount, the effect on the properties before heat aging will be too great).

 In Examples 282-285, it was noted that a slightly larger amount of NaOH needs to be added to achieve a pH of 9.5 in those liquids that contain sodium acetate. Therefore, Examples 286-289 are repeated Examples 282-285, except that the order of addition of the components of the mixture is reversed, so that sodium hydroxide is added first (to pH 9.5), and then sodium acetate is introduced.

Example 286 - Example 261 (no NaAc)
Example 287 - 0.25 g of NaAc (post-addition)
Example 288 - 0.50 g NaAc (post-addition)
Example 289 - 0.75 g NaAc (post-addition)
All samples are subjected to heat aging at 95 ^o C for 6 days. The results before and after aging are presented in Table V.

Additional experiments performed similarly to Examples 282-289, confirm that within the experimental error there is no noticeable difference between whether alkaline hydroxide or neutralizing salt is added to the first, and in addition to the fact that universal aircraft fluids do not show a noticeable decrease in viscosity or protective time according to WSET from heating at 95 ^o C for 6 days.

 Examples 290-293 relate to evaluating the additional effect of sodium salt on thermal stability as a function of pH. As before, the fluid of Example 261 is used as a standard. In each case, the pH was adjusted to 8.5 with NaOH, and then the indicated amount of sodium acetate was added.

Example 290 - Example 261 (no NaAc)
Example 291 - 0.25 g of NaAc (post-addition)
Example 292 - 0.50 g of NaAc (post-addition)
Example 293 - 0.75 g of NaAc (post-addition)
All samples are subjected to heat aging at 95 ^o C for 6 days. The results before and after aging are presented in Table VI
From these results it is seen that small amounts of an alkali metal ion significantly improve the thermal stability of the liquid at pH 8.5, actually making it as stable as a liquid with a pH of 9.5 (without an alkali metal ion).

Examples 294-296 relate to evaluating the thermal stability of a liquid during staining and to evaluating dilution with water. A 2000 g portion of the liquid prepared in accordance with Example 261 at pH 9.5 was stained with 0.2 g of Cartazol Yellow (Cartasol Yellow 3GF) and 0.05 g of Blue 6825-2 (Blue 6825-2). Dilute the pure liquid with water in ratios of 75/25 and 50/50 by volume and carry out a thermal stability test in an oven at 95 ^o C for 30 days. For a clean (undiluted) liquid, the thermostability test is carried out in an oven at 70 ^o C for 30 days. The results are shown in Table VII.

As for Table VII, the undiluted fluid of Example 294 would be useful either as an aircraft type II fluid (Type II) or as a type IV fluid (Type IV) to prevent icing. (Test SAE - test of the American Society of Automotive Industry and Transport provides for a viscosity loss of not more than 20% after 30 days at a temperature of 70 ^o C). A dilution of 75/25 would be useful for its use as a liquid to eliminate type I icing. (The SAE test requirement for WSET protection time is at least 3 minutes for type I fluid).

 Examples 297-303 relate to the study of a more effective surfactant compared to that used in the previous Examples, namely, "Ingredient S". To do this, prepare the control composition (see tab. 1).

 Additional compositions are prepared according to the recipe of Example 303, as shown in Examples 297-302. The tests performed are routine and their results are presented in Table VIII.

In Examples 297-303, surfactant N is a 5-6 mole nonylphenol ethoxylate marketed by Union Carbide, USA, under the trade name Triton (Triton ^R N-57).

 Although the invention is illustrated by a number of examples, it is by no means limited to them. Rather, the invention encompasses the general field as disclosed herein. Various modifications of the invention and examples of its implementation can be made, however, without deviating from its essence and scope.

Claims (21)

 1. The composition for processing aircraft designed to eliminate or prevent icing, including aqueous glycol or glycerin solution, thickened with a polymer thickener and / or its salt after neutralization, taken in an amount sufficient to thicken this composition to a state that ensures its adhesion to the surface the aircraft is at rest, and, in addition, ensuring its removal under the action of shear forces of the wind during take-off, and the specified thickener includes the following e components (wt.% of the total weight of the latter): (A) 1-99.9% of one or more α-, β-unsaturated carboxylic acids with a monoethylene bond; (B) 0-98.9% of one or more unsaturated monomers with monoethylene bond; (C) 0.1-99% of one or more mono-ethylenically unsaturated monomers, preferably macromonomers containing at least one side hydrophobic moiety; and (D) 0-20% of one or more unsaturated monomers with polyethylene bonds; and this composition includes the following components, in weight. % of the total weight of the composition: (1) at least about 40% of one or more glycols or glycerol, or mixtures thereof; (2) at least about 0.05% of said thickener; (3) a neutralizing agent comprising sodium hydroxide in an amount sufficient to provide a pH of at least about 7.1; (4) a surfactant that forms an associate with a thickener in an amount sufficient to enhance the thickening effect of the thickener; (5) an optional corrosion inhibitor in an effective amount; (6) optionally one or more dyes; and (7) the rest is water.  2. The composition according to p. 1, characterized in that the pH is 8.5-9.5.  3. The composition according to p. 2, characterized in that the surfactant is an octyl or nonyl phenol ethoxylate.  4. The composition according to p. 1, characterized in that it further comprises a weak auxiliary base in an amount of at least 0,0005 weight. % of the total weight of the composition.  5. The composition according to p. 4, characterized in that the auxiliary base is an alkali metal salt.  6. The composition according to p. 5, characterized in that the alkali metal salt is acetate or phosphate.  7. The composition according to p. 1, characterized in that the hydrophobic fragment is a complex hydrophobic group.  8. A composition for treating an aircraft designed to eliminate or prevent icing, including an aqueous glycol or glycerin solution, thickened with a polymer thickener and / or its salt after neutralization, taken in an amount sufficient to thicken this composition to a state that ensures its adhesion to the surface an aircraft at rest, but at the same time ensuring its removal under the action of shear forces of the wind during take-off, the specified thickener includes the following s components, in wt. % of the total weight of the latter: (A) 1-99.9% of one or more α-, β- unsaturated carboxylic acids with a monoethylene bond; (B) 0-98.9% of one or more unsaturated monomers with monoethylene bond; (C) 0.1-99% of one or more mono-ethylenically unsaturated monomers, preferably macromonomers containing at least one side hydrophobic moiety; and (D) 0-20% of one or more unsaturated monomers with polyethylene bonds; and the specified composition is obtained by mixing the following components, taken in weight. % of the total weight of the composition: (1) at least about 40% of one or more glycols or glycerol, or mixtures thereof; (2) at least about 0.05% of a thickener; (3) a neutralizing agent comprising sodium hydroxide in an amount sufficient to provide a pH of at least about 7.1; (4) a surfactant that forms an associate with a thickener in an amount sufficient to enhance the thickening effect of the thickener; (5) an optional corrosion inhibitor in an effective amount; (6) optionally one or more dyes; and (7) the rest is water.  9. The composition according to p. 8, characterized in that the pH is 8.5-9.5.  10. The composition of claim 9, wherein the surfactant is octyl or nonylphenol ethoxylate.  11. The composition according to p. 8, characterized in that it further comprises a weak auxiliary base in an amount of at least 0,0005 weight. % of the total weight of the composition.  12. The composition according to p. 11, characterized in that the auxiliary base is an alkali metal salt.  13. The composition of claim 11, wherein the alkali metal salt is acetate or phosphate.  14. The composition according to p. 8, characterized in that the hydrophobic fragment is a complex hydrophobic group.  15. The composition according to p. 4, characterized in that the auxiliary base is added to the composition before the addition of hydroxide.  16. The composition according to p. 11, characterized in that the auxiliary base is added to the composition before the addition of hydroxide.  17. The composition according to p. 1, characterized in that it further comprises an amine.  18. The composition according to p. 17, wherein the amine is monoethanolamine.  19. The composition according to p. 8, characterized in that it further comprises an amine.  20. The composition according to p. 19, wherein the amine is monoethanolamine.  21. The method for producing a composition according to claim 1, comprising the following stages: (a) preparing a concentrate by adding, with stirring, a surfactant and a thickener to a water-glycol or water-glycerin mixture used as a solvent, taken in an amount of 1 -20 weight. % of its total required amount; (b) adding with stirring the concentrate (a) to the remainder of the solvent, followed by stirring sufficient to obtain a homogeneous suspension; (c) adding with stirring a neutralizing agent to suspension (b), followed by stirring sufficient to obtain a homogeneous solution.

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