The composition for treatment of aircraft, designed to eliminate or prevent it from icing (options) and how you can get
(57) Abstract:Described by the universal aircraft-based liquid of an aqueous solution of glycol or glycerol, or a mixture thereof, gelled polymeric thickener and/or its salt after neutralization, which contains about 40% of one or more glycols or glycerol or mixtures thereof, at least about 0.05% of a thickening agent, a neutralizing agent, representing the sodium hydroxide to achieve a pH of about 7.1, surfactant, forming associat with a thickening agent, a corrosion inhibitor, dye and water - the rest. The thickener includes the following components: 1-99,9 and one more,-unsaturated carboxylic acids with monoethanol communication, 0-98,9% of one or more unsaturated monomers with monoethanol communication, 0.1 to 99% of one or more unsaturated monomers with monoethanol connection, preferably of macromonomer containing at least one hydrophobic side fragment and 0-20% of one or more unsaturated monomers with plastic ties. Described is a method of obtaining songs. The technical result - the fluid has good resistance to viscosity reduction, and other critical parameters under the influence of heat and/or shear forces. 3 S. and 1 is its description in the form of links, Tsatsa patent application U.S. that have the following rooms: 887645, 887646, 887642, 887673, 887672, 887641, 887648, 887647, 887644 and 887671.The present invention relates to compositions based on glycol or glycerol, designed to eliminate or prevent icing of aircraft, hereinafter occasionally collectively referred to under the General title "aircraft fluid" (SG). In these fluids added thickeners in the form of some polymers containing macromonomer bearing hydrophobic fragments, which is infilled above the liquid, and the process of thickening proceeds by an associative mechanism. In particular, the present invention relates to fluids, eliminating or preventing icing of aircraft (hereinafter sometimes in the text, WAR and AFTER, respectively), which have improved thermal stability and therefore are more widespread use as defrosters (which store and use at elevated temperatures). Because aircraft fluid, as claimed in the present invention, have found application in the form of products to eliminate and to prevent icing, hereinafter sometimes mentioned under the General title of the "plane of liquids is Parkovaya there in between flights, able in cold winter weather to accumulate on its surface snow, ice, snow cereal or frost. The presence of such deposits in particular on the aerodynamic surfaces of the aircraft, usually unsafe and creates conditions that hinder the start, or at least very undesirable during takeoff and initial flight period, because even small deposits can lead to serious deterioration of the aerodynamic characteristics of the wing, sometimes causing a crash of the aircraft during takeoff or during launch and leading to loss of life of the people.Glycols long been used in aqueous solutions of different concentrations as defrosters, which is applied by sputtering on the surface of the aircraft for removal of deposits of snow, ice, cereals and frost. Such glycol fluid for de-icing aircraft, usually applied in a heated condition in order to more effectively destroy the adhesion of the surface of the ice or to melt the snow. Typical liquid anti-icer for aircraft consists of mixtures of alkaline glycol (usually ethylene glycol, propylene glycol and/or diethylene glycol) and water (as a solvent), taken approximately equal to OSTO-active substances (surfactants), which promote wetting of the surface of the aircraft during operation of the spray. Instead of glycol in such liquids to remove icing optional use glycerin, and their preparation is carried out in the same way. It is further assumed that any reference to the glycol fluid to remove ice aircraft (WAG) or prevent icing (AMPS) or the so-called aircraft fluid multi-purpose (USE) will also include liquid prepared in glycerol, used instead of or in addition to one or more glycols.Provided that the hot liquid is applied at a sufficiently close distance to the surface, applying a heated liquid minimizes the amount required to remove snow and ice. WAR can also be applied in the stream under high pressure, to a strong jet of fluid to remove snow and ice deposits on the surface of the plane.After this treatment WAS remains on the surface of the aircraft in the form of a film, in order to serve as an anti-icer, which provides a long lasting antifreeze protection and delaying further education or nerasta the hypoxia concentrations can be successfully applied to the removal, and to prevent icing. However, without the thickener WAS able to flow down the inclined surface of the wings or tail, and with a nearly vertical surface of the fuselage and tail fin. Therefore, in the absence of a thickening agent, they provide only limited protection against icing.For more effective protection of aircraft fluids typically contain a thickener and at the same time it is desirable that they possessed the following characteristics (none of which prevents their use for removing ice):
(a) formation of a solid film after application through standard spray device even not horizontal surfaces of the aircraft, which are crucial in relation to its aerodynamic characteristics during launch or takeoff, such as the vertical tail stabilizer, but at the same time, it would not interrupt the smooth contour of the surface of the fuselage;
(6) long deicing protective effect; and
(b) viscosity and rheological characteristics, which accelerate the formation of a strong effective protective film, but nevertheless enable the liquid coating to drain from the surface of the wings is known from the prior art fluids to prevent icing of aircraft (AMPS) is infilled, generally, compounds with very large molecules (e.g., xanthan gum or various organic polymers, such as some acrylics), thickening action which is determined by molecular entanglement and intermolecular friction (adhesion). Such thickeners have shortcomings because they do not provide the optimal non-Newtonian behavior (i.e., their viscosity does not decrease fast enough and/or in a wide extensive under the action of shearing forces of the wind) for use in all weather conditions and for relatively slow turbojet aircraft, such as regular planes. In addition, these thickeners are exposed to excessive viscosity reduction as a result of the high shearing forces from the operation of the spray heads used for applying fluid to the surface plane.An important step forward in the technology of liquids, to prevent icing of aircraft, provided compositions proposed in the U.S. patent 5 461 100 and simultaneously considered and a General purpose application U.S. 08/065237 with a filing date of may 20, 1993. Both these documents are mentioned as references. Yasanmamislari, thickening effect which is due to the Association among the hydrophobic groups have a specific efficiency as thickeners for ECW glycol-based. These fluids have ensured the creation of such liquid products for preventing the formation of ice, which are much more protection compared to previous compositions of this assignment, however, as the last of these newly created products found limited use as a fluid de-icing, as achieved with their help guard time sought to decrease due to prolonged heating at temperatures which are dealing in operations to remove ice.The present invention is based on the surprising discovery that such liquid compositions, warning icing, can be improved in such a way as to significantly improve their thermal stability, making them more useful for application as a liquid material to address (and to prevent) icing.The present invention provides a composition that retains its purpose to protect from freezing and at the same time is much more useful clarina, gelled polymer, preferably containing macromonomer and bearing a hydrophobic group. The content of the polymer is not more than 5 wt.% the total weight of the composition. The polymer is present in an aircraft fluid in sufficient quantity to its density in order to enhance the adhesion of the liquid surface of the fixed plane, but at the same time providing the possibility of its removal caused by the shearing force of the wind during his run up to a full turn. Improved thermal stability is achieved by applying a certain amount of a suitable stabilizing the base, preferably by adding a stabilizing salt and control over the content of the glycol and/or glycerol, and pH of the liquid.Accordingly, the present invention provides a composition for de-icing aircraft with improved thermal stability comprising a mixture of glycol and/or glycerin, water, preferably nabukelevu in alkali polymeric thickener, bearing a hydrophobic group, a thickening agent which runs mainly through intermolecular associative mechanism among these hydrophobic groups, and this fluid has sufficient time remains sufficiently fluid under the influence of shearing forces of the wind, in order to flow with the aerodynamic surface of the aircraft when it reaches the value of velocity of takeoff or near it. Preferably, the thickener included the main chain of the macromolecule to which using the flexible end of the chains were attached hydrophobic groups, and where, in particular, these flexible leaf chain included one or more hydrophilic polymers. In addition, it is desirable that these flexible end of the chains were long enough to hydrophobic groups were located outside of any "carboxyl" environment main polymer chain, i.e. no electronic influence of carboxyl groups attached to the main chain. Although thickeners, as claimed in the present invention, allow for significant variation in molecular weight, depending on their molecular composition (which in fact is one of their advantages), but it is preferable that each repeating section had a molecular weight of not more than 6000, more preferably not more than 3000.Properties of advanced fluids universal destination for de-icing aircraft (above USG) can also be characterized according to the results of standard tests SET), the length of the moving boundary layer (Boundary Layer Displacement Thickness)(BLDT) and viscosity. Thus, in the present invention proposed USE, in which the parameter WSET is at least about 30 minutes, preferably about 80 min, and the parameter BLDT is less than 11 mm, preferably less than 10 mm, and more preferably less than 8 mm at -20oC.In the present invention a method of thickening water-glycol or water-glycerol aircraft fluid, which comprises blending with a thickener. In addition, the invention features a method of de-icing aircraft, providing as a method of prevention and de-icing, and including drawing on the aerodynamic surface of the aircraft liquid containing a thickening agent.Thickeners proposed in the present invention, preferably obtained from the polymerized carboxylic acids, copolymerizable with macromonomers bearing hydrophobic groups. Thus, the preferred micromanometers polymers used in the present invention include:
(A) 1-99,9, preferably 10-70 wt.% one or more -,- unsaturated carboxylic acids with monoethanol communication, usually IU the new connection, usually acrylate;
(C) 0.1 to 99, preferably 5-60 weight. % of one or more unsaturated macromonomers with monoethanol communication; and
(D) 0-20, preferably 0-10 weight. percent or more of one or more unsaturated monomers with monoethanol communication, usually trimethylolpropane.Macromonomer part preferably includes at least about 5 weight. % polymer.Applied fluid preferably is a standard aircraft fluid type II for de-icing, known as the joint product of the society of automotive engineers and transport (USA) and the International organization for standardization (ISO)- (Society of Automotive Engineers (SAE) /International Standards Organization (ISO). This liquid is infilled micromanometers polymer in an amount of not more UES. % It is desirable that the polymeric thickener is present in an amount of from 0.05 to 4 weight. %, preferably from 0.1 to 2 weight. %
Glycol or glycerol component of this composition is preferably a glycol, alone or in combination with other glycols, such as dietilen or propylene glycol and/or glycerine. Glycol or glycerol component is present preferably is in the curves of freezing points of various other glycols and glycerol, their preferred concentrations differ from the concentrations of ethylene glycol, but can be taken from the prior art.The desired alkalinity (pH) is obtained by mixing the neutralizing base is an amine, such as alkylamine or alkanolamine, or preferably a hydroxide of an alkali metal, or a combination of these compounds. Only the use of hydroxides of alkali metals, i.e. in the absence of amine, is preferred, particularly preferably using sodium hydroxide. The amount of neutralizing base should be sufficient to bring the pH of the solution at least to 7.1, preferably 8.5 to 9.5. A higher pH will improve thermal stability of the fluid, however, they are not preferred because such environments are more aggressive towards aluminum.Fluid combat obladnannyam aircraft General purpose (USE) may also contain salt hydroxide of an alkali metal and a weak acid, which serves as a supporting base or stabilizing salt. More effective salts with lower molecular weight. Preferably, but not necessarily to the rest saloon is there together with sodium hydroxide. Low concentrations of salts are preferred because higher concentrations (even if they further improve thermal stability) tend in the direction of decreasing time protection for the liquid used in the mode prevent icing. The preferred concentration of the stabilizing salt are 0-0,10 weight. %, more preferably of 0.0005 to 0.02 weight. %
Accordingly, the present invention features a composition for de-icing aircraft, providing both prevention and elimination of icing with water and glycol or glycerine solution, gelled polymeric thickener and/or its salt after neutralization, taken in an amount sufficient to gel the composition and its coupling with the surface of the plane is at rest, but at the same time ensuring its destruction under the action of shearing forces of the wind during takeoff of the aircraft. When this polymer consists of the following components in weight. % of the total number of polymer:
(A) 1-99,9% of one or more,-unsaturated carboxylic acids with monoethanol communication;
(B) 0-98,9% of one or more unsaturated monomers with monoethanol communication;
(C) 0.1 to 99% of one or more unsaturated monofono group, preferably complex; and
(D) 0-20% or more of one or more unsaturated monomers with a plastic connection;
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) hydroxide, preferably hydroxide monovalent metal, 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) surfactant, which forms associate with a thickener in an amount sufficient to enhance the thickening effect;
(5) optional corrosion inhibitor in an effective amount;
(6) optionally one or more colorants; and
(7) water - the rest.In its preferred embodiment described above, the composition also contains an effective amount, preferably at least about 0,0005 weight. % auxiliary base, preferably a weak, such as acetate, phosphate and the like.In addition, the present invention includes the above-described composition for fighting the Additionally, the present invention proposes a method of obtaining the above-described composition for de-icing aircraft, includes mixing ingredients according to the recipe above.The composition, as claimed in the present invention, it is not necessarily receive in the form of a concentrate suitable for dilution, to meet any requirements in relation to its actions in the mode of prevention and de-icing of aircraft as separately or together.As previously mentioned, WAS used to remove ice, frost, accumulated snow or slush from the surfaces of the aircraft, while the LATTER prevent the buildup of ice, snow, snow grains, and other forms of ice otlozhenii on the clean surfaces of the aircraft after removal of the ice. Typical liquid for de-icing (WAG) consists of a mixture of alkaline ethylene-, propylene - or diethylene glycol or glycerine and water (as a solvent), taken in approximately equal weight proportions, ready for use, or can be mixed with more than 80 weight. % glycol or glycerol with obtaining a concentrate, which is diluted in the field. If the pH of the mixture is 7.1 to 9.5, preferably of 8.5 to 9.5. The liquid also contains ionic corrosion inhibitors, flame retardants, dyes and surfactants, which contribute to the local from the prior art, provided that they do not interfere with the action of the fluid for its intended purpose.Typical liquid to prevent icing (AMPS) includes the same as those of the above components as a typical WAG, but additionally contains a rheological modifiers. To conventional rheological modifiers used for liquids, to prevent icing of aircraft include cross-linked polyacrylates, carboxypolymethylene and polysaccharides (xanthan gum, and carrageenan). World airlines, which operate at congested airports, requiring longer-term protection from snow, ice, freezing rain, or frost, apply such liquid chemical de-icers.Ideal thickener acts on ECW at the time, until the aircraft is parked to prevent the accumulation of freezing rain, snow, slush or ice on a clean surface after removal of ice and accelerate the adhesion of the composition with the vertical surfaces of the body of the plane. To minimize loss in the lifting force applied after the very liquefies under the action of shearing efforts, resulting in easily flow off the wing during the takeoff the surface plane) is sufficient to so the pilot could fly, which corresponds to a shear force of about 10 PA. Viscosity AFTER should not change greatly with temperature or upon dilution with water: viscosity, which does not change or even increased slightly when the dilution is correlated with the "overtime" - the period of time during which the aircraft is able to survive in bad weather without the need for additional processing for de-icing. One of the important decisions, thanks to which the stated aircraft fluids superior to the prior art, is to obtain a composition, which, although they suffer significant dilution, and still retain satisfactory performance. Data universal aircraft fluid (USG) you can either slightly dilute and apply to prevent icing of large aircraft with fixed wings or scheduled (Charter) aircraft, or to dilute the stronger for the application (hot) as a means for removing ice for all types of aircraft. These compositions differ from previously known defrosters that the proposed formulation was chosen in order to improve their t is the product still had a low freezing temperatures, what makes possible their use in harsh weather conditions.Fluid de-icing (eliminating or preventing the formation of ice), as claimed in the present invention and having the necessary performance characteristics, can be obtained from standard compositions on glycol and/or glycerol-based through the use of micromanometers polymer as a thickener. Micromonosporaceae polymer designed for use as the primary thickener for standard fluids on glycol and/or glycerol-based, used to eliminate or prevent the icing of the aircraft. These compositions for de-icing, called fluids type II Society of automotive engineers and transport (USA) and the International organization for standardization (ISO) contain a thickener, and micromanometers polymers disclosed in the present description, in particular suitable for use as thickeners for these fluids.Composition for removal and prevention of ice formation on glycolic-based well-known and for many decades used to combat allegemeine this purpose, is a water-soluble glycol compound. Liquid glycol based, as a rule, contain one or more glycols selected from ethylene, propylene and diethylenglycol and mixtures thereof. Along with the above products, or instead can be applied, and other glycols, glycerine or polyole properties depressant that lowers the freezing point.The preferred preparative form contains ethylene glycol as a main glycol component, preferably in an amount constituting at least about 80 weight. % Propylene and/or diethylene glycol may also be present in the liquid glycol basis. Diethylene glycol in combination with propylene glycol is another glycolic formulation, which is also suitable for use in the present invention. In addition, the glycol component can be replaced with glycerin and apply it mixed with glycol or other glycols. The choice and relative amounts of specific glycol compounds present in the products glycolic basis, will depend on the particular anti-icing and antifreeze properties that would be desirable possessed this fluid, such as temperature froze the I (hereinafter sometimes referred to simply as a liquid de-icing) is an aqueous solution, i.e. the product obtained upon dilution of ethylene glycol or other suitable glycol or glycerol with water. Glycol or glycerin should be present in aqueous solution in the amount of at least about 40 weight. %, preferably about 50 weight. % up to 95 weight. % The preferred interval of contents glycol or glycerin is 60-75 weight. % Of the combined glycol (or glycerin) and water 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 content of the glycol or glycerol was sufficient to ensure that the freezing point of the fluid lower than -10oC, more preferably below -30oC. For liquids to be applied undiluted and diluted form, it is particularly important that the level of the contents of the glycol or glycerol was maintained high enough in undiluted liquid so that the dilution was also provided for low temperature freezing.As the neutralizing agent can be used Amin, alkanolamine, hydroxide of alkali metal or some combination thereof. Preferably the application that is for example triethanolamine, monoethanolamine, triethylamine and the like, are permitted for use, the use of certain amines (e.g. triethanolamine) is not preferred because such amines, apparently, lower thermal stability. The amount of neutralizing base should be sufficient to bring the pH of the solution at least to 7.1, preferably 8.5 to 9.5. Although the upper limit of the pH is not critical, it is assumed that it must be kept below the value, which may be corrosion of the surface of the body of the plane. In the absence of the intent of the authors to link it to any specific theory, it can be assumed that the high pH is desirable in order to minimize hydrolysis of the hydrophobic groups of the associative thickeners, as claimed in the present invention.Such hydrolysis can lead to loss of hydrophobic Association and, consequently, to a reduced viscosity at low shear.Optional, but highly preferred aspect of the present invention is the use of an auxiliary base, which can also be viewed as a stabilizing salt or buffer. Takanishi molecular weight are more effective. To the preferred weak bases include acetates, phosphates and the like. Preferably, the remainder of the alkali metal in the salt molecule was the same as the cation of a strong neutralizing base, such as sodium acetate works well together with sodium hydroxide; however, in many cases it is possible to effectively use salt or other mixed cations. As a General recommendation accept that the auxiliary base has a pKa of the conjugated acid of less than 10, preferably less than 5.The method of obtaining the claimed compositions is not critical and includes the simple mixing of the various ingredients under stirring for a sufficient time (usually about 15-20 min) to obtain the proper mixture and associative thickening. The preferred method of obtaining the composition comprises the following stages: (a) preparation of the concentrate by adding with stirring to the water-glycol or a water-glycerin mixture used as solvent, surfactant and thickener in the amount of 1-was. % from total quantity of solvent; (b) adding with stirring the concentrate (a) to the remaining part of the solvent followed the user agent to the suspension (b), followed by stirring, sufficient to obtain a homogeneous solution. This preferred method provides a more efficient mixing and thickening compared with simple stirring.Illustrative micromanometers polymers used in the present invention, and methods for their preparation are disclosed in which the joint consideration of the application of the U.S. No.887 647, which is here referred to as links. The polymers used in the present invention, there is a large share of one or more Monomeric -,-unsaturated carboxylic acids with monoethylene links. Can be used for various acids, such as acrylic, metachroma, etakrinova, -goracinova, crotonic, fumaric, Tarakanova, musicanova, Takanawa, maleic and the like, including mixtures thereof. Methacrylic acid is preferred, in particular in a concentration that constitutes at least about 49 weight. % of polymer. A large proportion of carboxylic acid as a monomer is desirable to obtain a polymer structure that is able to swell or dissolve and to provide the necessary thickening agent in the interaction with alkali, for example sodium hydroxide.Polymers, ispynow with monoethanol communication. Preferred monomers give when homopolymerization water-insoluble polymers, and are esters of acrylic and methacrylic acids, such as acrylate, butyl acrylate or the corresponding methacrylate. Other used monomers include styrene, alkylthiol, vinyltoluene, vinyl acetate, vinyl alcohol, Acrylonitrile, vinylidenechloride, vinylketones and similar compounds. Directionspanel monomers are preferred, these include monomers, in which a single ethylene group is the sole reactive group under conditions of polymerization. However, in some cases it is possible to use monomers containing groups which can react under the conditions of heat treatment or to be reactive in relation to ions of bivalent metals (zinc oxide), for example, hydroxyethylacrylate.Other illustrative unsaturated monomers with monoethylene links include, for example, propylbetaine, isopropylacetate, butylmethacrylate, n-amylmetacresol, second-amylmetacresol, vexillarius, laurenmarie, stearyl-methacrylate, ethylhexylacrylate, gratismaterial, cinnamyl-methacrylate, olymethacrylic,Neil-tert-butyrate, minikart, ministart, miniplanet, vinilla, wikipediaby ether, unilateraly ether, vinyl n-propyl ether, inilitary ether, vinyl n-butyl ether, vinyl isobutyl ether, virilization ether, finalfantasy ether-hlorfenilovy ether, vinyl--nattily ether, Methacrylonitrile, acrylamide, methacrylamide, N-alkylacrylate, N-vinyl pyrrolidone, N-vinyl-3-morpholino, N-vinylacetate, N-vinylimidazole and the like, including mixtures thereof.Macromonomer used in the present invention represented by the formula:
< / BR>where R1represents a monovalent residue of a substituted or unsubstituted hydrophobic compounds;
each R2- same or different and represents a substituted or unsubstituted divalent hydrocarbon residue;
R3represents a substituted or unsubstituted divalent hydrocarbon residue;
R4, R5and R6- same or different and represent hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue;
z - value greater or equal to zero.Macromonomer used in the present invention, receive standartisation methods described, for example, in U.S. patents 4514552, 4600761, 4569965, 4384096, 4268641, 4138381, 3894980, 3896161, 3652497, 4509949, 4226754, 3915921, 3940351, 3035004, 4429097, 4421902, 4167502, 4764554, 4616074, 4464524, 3657175, 4008202, 3190925, 3794608, 4338239, 4939283 and 3499876. They can also be obtained by the method described in the joint consideration of the application of the U.S. 887645, which is incorporated into this description by reference. Other macromonomer, which can be used when implementing the present invention include oligomers bearing complex hydrophobic groups, as described in the joint consideration of the application of the U.S. 887646, which is also mentioned here as a reference.Hydrophobic residue R1in the formula I may be a simple or complex hydrophobic group, or their mixture. However, complex hydrophobe are preferred. On the same molecule may have different hydrophobic groups or their presence can be achieved through physical mixtures of different polymers. Under a simple gidrofobny mean products that are currently available in the industry, usually consisting of no more than 30 carbon atoms, as shown in Table 1, are presented in U.S. patent 4 426 485. Under complex Hydra is.Illustrative substituted and unsubstituted divalent hydrocarbon residues R2in the formula I include the remains described below for the substituents of the same type in formulas (i) and (ii). Illustrative substituted and unsubstituted monovalent hydrocarbon residues R4, R5and R6in the formula I include the remains described below for the substituents of the same type in formulas (i) and (ii).Illustrative substituents R3include, for example, the organic residue was simple and esters, urethanes, amides, ureas, anhydrides, and other, including mixtures thereof. Deputy R3can be represented in General form as a bridge between the surface-active substance (surfactant), bearing complex hydrophobic group, or alcohol and unsaturated part macromonomers connection. It is preferable bridges include the following: urethane bridges from the reaction of isocyanate with surfactants bearing a hydroxyl group; urea bridges from the reaction of isocyanate with surfactants bearing amine group; unsaturated esters surfactants, such as the product of esterification of surfactants unsaturated carboxylic acid or an unsaturated anhydride; unsaturated esters of alcohols; esters of oligomers of acrylate, acrylic oligomers what hydride; unsaturated esters obtained by the interaction of vinylbenzoate and surfactants or when interacting allylglycidyl ether surfactants, alcohol or carboxylic acid.Oxyalkylene fragments included in macromonomer compounds (I) are homopolymers or copolymers or random copolymers with straight or branched etkilenecegini groups. You can use a mixture of alkalisation, such as ethylene oxide and propylene oxide. It is assumed that each group R2in a separate Deputy for all positive values of z may be the same or different. Although ethylene oxide is preferred, note that the large quantity can have a negative effect on the rate of thermal stability and/or stability when diluted thickened aircraft fluids.Complex hydrophobic compounds having at least one active hydrogen, is useful for obtaining macromonomer used in the present invention, represented by the following formula:
< / BR>where R1and R2- same or different and represent hydrogen or a substituted or unsubstituted monovalent hydrocarbon any residue; each R4- same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; each R5- same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; R6represents hydrogen, a substituted or unsubstituted monovalent hydrocarbon residue or an ionic Deputy; a and b are the same or different and are a value of 0 or 1; x and y are the same or different and are a value greater or equal to zero; provided that at least two of R1, R2, R3, R4, R5and R6represent a hydrocarbon residue containing more than 2 carbon atoms in the case of R1, R2and R6or containing more than 2 side of the carbon atoms in the case of R3, R4and R5.Other complex hydrophobic compounds having at least one active hydrogen, is useful for obtaining macromonomer used in the present invention, represented by the following formula:
< / BR>where R7and R8- same or different and represent hydrogen or a substituted or unsubstituted monovalent is hydrated or unsubstituted monovalent hydrocarbon residue or an ionic Deputy; R9and R12- same or different and represent a substituted or unsubstituted divalent or trivalent hydrocarbon residue; each R13- same or different and represents a substituted or unsubstituted divalent hydrocarbon residue; R15represents a substituted or unsubstituted divalent hydrocarbon residue, d and e are the same or different and is 0 or 1; f and g are the same or different and are a value greater or equal to zero; provided that at least two of R7, R8, R9, R10, r11, R12, R13, R14and R15represent a hydrocarbon residue containing more than 2 carbon atoms in the case of R7, R8, R11and R14or containing more than 2 side of the carbon atoms in the case of R9, R10, R12, R13and R15.Illustrative of the substituted or unsubstituted monovalent hydrocarbon residues containing from 1 to 50 or more carbon atoms and are selected from alkyl radicals containing a linear or branched primary, secondary or tertiary alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, amyl, sec-Amie radicals, such as benzyl, phenylethyl, triphenylmethyl and the like; alcylaryl radicals, such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyl and the like; and cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cyclohexylethyl and the like. Acceptable hydrocarbon residues may contain fluorine, silicon or other non-carbon atoms.Preferably a substituted or unsubstituted hydrocarbon residues are selected from alkyl and aryl radicals which contain from 1 to 30 carbon atoms. More preferably the alkyl radicals contain from 1 to 18 carbon atoms, while aryl, arylalkyl, alcylaryl and cycloalkyl radicals preferably contain from 6 to 18 or more carbon atoms.In a preferred embodiment of the invention R1, R2, R7and R8can individually represent a hydrocarbon radical of the formula:
< / BR>where R16and R17have the meanings given above for R1, R2, R7and R8, h and i are the same or different and is 0 or 1; R18has the values defined above for R3. For compounds of formula (i) and (ii) it is assumed that each is/SUB> as described below, in order to obtain the complex gidrofonov dendritic or cascading nature, may themselves represent a radical (iii). In addition,4, R5, R10and R13can individually represent a hydrocarbon radical of the formula
where R19has the values defined above for R4, R5, R10and R13; R20has the values defined above for R6, R11and R14; and j represents a value greater or equal to zero.Illustrative ionic substituents for R6, R11, R14and R20include cationic and anionic groups such as sulfates, sulfonates, phosphates and the like. R6, R11, R14and R20preferably is an organic residue containing one or more hydroxyl groups and nitrogen-containing derivatives or epoxy or other reactive groups that contain or do not contain unsaturation.Other illustrative end groups represented by the substituents R6, R11, R14and R20include , for example, hydrocarbon residues, which contain allyl is a second group, and the like, such as the reaction product between the terminal alcohol (R6, R11, R14and R20represent hydrogen) and getitemestimate, isocyanatoacetate, -, -dimethyl-m-isopropylbenzylamine (m-TMI) and the like. Other examples of end groups include hydrocarbon residues from alkyl, aryl, aralkyl, alkaryl and cycloalkyl, that may be substituted or not substituted with one or more Deputy of the following: hydroxyl, carboxyl, isocyanato, amino, mono - or disubstituted amino, Quaternary ammonium, sulfate, sulfonate, phosphate, epoxy and the like, and, in addition, may contain or not contain other atoms other than carbon, including silicon or fluorine. In addition, there may be included and bivalent siloxides. Other non-terminal groups may include sulfates, phosphates and the like.Illustrative of the divalent hydrocarbon residues represented by the radicals R3, R4, R5, R9, R10, R12, R13, R15, R18and R19in the above formulae include substituted or unsubstituted group selected from alkylene-alkylene-hydroxy-alkylene-, -aralen-hydroxy-arylene-allenina-, -naphtalen-(CH2)m(Q)n(CH2)m-naphthylene-, where Q independently represents a substituted or unsubstituted divalent bridging group selected from-CR21R22-, -O-, -S-, -NR23, -SiR24R25and-CO-, where R21and R22independently represent a radical selected from hydrogen, alkyl containing from 1 to 12 carbon atoms, phenyl, talila and anisyl; R23, R24and R25independently represent a radical selected from hydrogen and methyl; and each type independently equal to 0 or 1. More specific values for illustrative divalent radicals represented by R3, R4, R5, R9, R10, R12, R13, R15, R18and R19include 1,1-medicen, 1,2-ethylene, 1,3-propylene, 1,6-hexylen, 1,8-acticin, 1,12-dodecene, 1,4-phenylene, 1,8-naftilan, 1,1-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl, 2,2'-binaphthyl-1,1'-diyl and the like. Alkylene radicals can contain from 2 to 12 or more carbon atoms, while allenbyi radicals contain from 6 to 18 or more carbon atoms. Preferably R3, R4, R5, R9, R10, R12, R13, R15, R18and R19are alkalinity or ariley, other than carbon.Illustrative trivalent hydrocarbon residues represented by the radicals R3, R9, R12and R18in the above formulae include substituted and unsubstituted groups selected from CH, C(R26)-, CR27and the like, where R26represents a substituted or unsubstituted monovalent hydrocarbon residue, and R27represents a substituted or unsubstituted divalent hydrocarbon residue.Of course, in addition assume that hydrocarbon residues in the above formula can be replaced by any acceptable substitute. 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(R28)3and-Si(OR28)3, amino,- N(R28)2; acyl, such as-C(O)R28; acyloxy, such as-OC(O)R28; carbonyloxy,
such as COOR28; amido,- C(O)N(R28)2and-N(R28)R28; sulfonylurea radicals, such as-SO2R28; sulfinyl radicals, such as-SO(R28)2; tional, such as-SR28; FDE each R28can be a monovalent hydrocarbon radical such as alkyl, aryl, aralkyl, alkaryl and cycloalkyl, provided that aminosalicylates, such as-N(R28)2each of R28taken together, able to give a divalent bridging group that forms a heterocyclic radical with the nitrogen atom, imidazolides, such as-C(O)N(R28)2and-N(R28)COR28where each R28associated with the nitrogen atom, is a hydrogen, and postonline substituents, such as -- P(O)(R28)2where one of R28represents hydrogen. I believe that each group R28in a separate Deputy may be the same or different. Such hydrocarbon substituents can be, in turn, replaced by the appropriate Deputy of the above.Preferred alkalinity that ensure the presence of statistical units or block units in complex hydrophobic compounds of formulas (i) and (ii) include alkalinity, such as ethylene oxide, propylene oxide, 1,2-butylenes, 2,3-butylenes, 1,2 - and 2,3-pestilence, cyclohexyloxy, 1,2-exilerated, 1,2-accelerated, 1,2-decelerated and higher olefins, epoxy; aromatic epoxides such as styrene oxide and the oxide of 2-methyl-styrene; and hydroxy - and halogensubstituted alkalinity, such as glycidol, epichlorohydrin and epibromohydrin. For your preferred alkalinized include ethylene oxide and propylene oxide. Here may also be included hydrocarbon residues of substituted or unsubstituted cyclic simple or complex esters such as l'occitane and tetrahydrofuran. Assume that the compounds represented by formulas (i) and (ii) contain statistical and/or block oxyalkylene links, as well as mixtures oxyalkylene links. In addition, suppose that for every R4, R5, R10, R13and R19in a separate Deputy for all positive values of x, y, z, f, g and j respectively can be the same or different.The values of x, y, z, f, g and j are not strictly determinative, and can vary within wide limits. For example, they can range from 0 to 200 and more preferably from 0 to 100 and more, and more preferably from 0 to 50 and more. Alkalinized used in any desired amount, for example, from 0 to 90 wt.% and more, based on the total weight content of complex hydrophobic compounds.Returning to the General the natural balance of the formula (iii), the resulting connection can contain any valid number and combination of hydrophobic groups dendritic or cascade type. Such compounds included in the above General formula, should be easily installed by any specialist in this field.Illustrative complex hydrophobic compounds containing at least one active hydrogen, which are useful for implementing the present invention, and methods for their preparation are described in the joint consideration of the application of the U.S. 887 648, which is mentioned in the present description by reference.In a preferred embodiment of the present invention, the structure represented by formula (iii) represents the balance of the reaction product between epichlorohydrin and alcohol, including spirits, whose remains can be described by the formula (iii), or fooly or mixtures thereof. These patterns can be represented as a complex hydrophobic molecules dendritic or cascading nature in the following graphic:
< / BR>It is preferable macromonomer compounds used in the present invention include compounds of the following formulas:
< / BR>< / BR>(HU)
where R1, R2, R4, R19z and j have Britanie, answers to the following formula:
< / BR>The preferred spacing of contents the components of the Monomeric fragments are as follows: acid monomer X is 10-40%, copolymerizing associative monomer Y is 10-50%, associative monomer Z - 5-30%, and the amount of p that indicates the amount of amoxilonline in moles (or propoxycarbonyl) is 20-80 mol. Hydrophob R can be alkaryl, such as Nonylphenol or dinonylphenol, or to have the following structure:
< / BR>where R1and R2have the meanings given above.Macromonomer compounds used in the present invention, is subjected to additional time transformation(s) in order to obtain their desired derivatives. Such derivatization reactions are carried out by known standard methods. Illustrative derivatization reactions include, for example, a complex esterification, simple esterification, alkoxysilane, amination, alkylation, hydrogenation, dehydrogenation, reduction, acylation, condensation, carboxylation, oxidation, Siciliana and the like, including a valid combination. The present invention is not intended to limit in any way the proposed method is x connections.In particular, macromonomer with terminal hydroxyl groups is subjected to any of the known reactions involving hydroxyl group, an illustration of which are reactions with galoidazinov to form esters; with ammonia, nitrile or cyanide hydrogen with the formation of amines; acid alkyl sulphates with the formation of bisulfate; carboxylic acids and anhydrides of the acids with the formation of esters and polyesters; with alkali metals to form salts; cachename to form esters; with the anhydrides of the acids with the formation of carboxylic acids; with oxygen to form aldehydes and carboxylic acids; reaction with opening cycle lactones, tetragidrofuranom; dehydration with the formation of aldehydes; reactions involving isocyanates to form urethanes and others.Unsaturated macromonomer component with monoethanol connection is subjected to significant change within previously presented formulas. The nature of macromonomer is difficult hydrophob carrying polyethoxylate chain (which may include some polipropilene group) and which ends at least one hydroxy-group. When used on the drive with monoethanol communication, you will, for example, unsaturated urethane with monoethanol communication, in which complex hydrophobic polyethoxylate structure associated with copolymerizable monoethylene group via a urethane bridge.Connection unsaturation which is due to the presence monoethylene communication and which is used to obtain unsaturated macromonomer containing such monoethylene communication, is subjected to a large change. You can use any copolymerizing unsaturation, such as acrylate and methacrylate. You can also use and allylic unsaturation, which is achieved by using allyl alcohol. These compounds, which are preferably present in the form of hydroxyquinoline derivative, obtained by the interaction WITH2-C4-monoepoxide (for example, ethylene oxide, propylene oxide or butilenica) with acrylic or methacrylic acid with obtaining complex hydroxyether, react in equimolar quantities of an organic compound, such as colorvision or isophorondiisocyanate. Preferred monoisocyanates with monoethanol communication is storiestease -,-dimethyl-m-Isopropenyl the e esters, amides, urea, anhydrides, other urethanes and similar compounds containing monoethylene connection.The polymers used in the present invention, receive through a series of well-known polymerization reactions. The technique of polymerization affects the microstructure, the distribution of the sequence of monomers in the polymer chain and the molecular weight of the polymer, which depends on its characteristics. Illustrative methods of polymerization include, for example, standard and stepwise emulsion polymerization by means of a simultaneous loading (batch), semi-continuous or continuous processes, micellar polymerization, reversed emulsion polymerization, polymerization in solution, non-aqueous dispersion polymerization, interfacial polymerization, polymerization in emulsion and suspension polymerization deposition, polymerization attach (polymerization), such as free radical, anionic, cationic, coordination, etc.The thickeners used in the present invention have the structural characteristics of two very different types of connections (connection, which is infilled thanks alkaline swelling or select explains the attainment of excellent thickening properties. However, I believe that in order to ensure non-Newtonian rheology, which is crucial to the performance of thickeners used in aircraft fluids, it is the Association among hydrophobic groups (and deassociate caused by the shearing force of the wind) and determines the dominant reaction mechanism.The aqueous emulsion copolymerization is standard procedure for any specialist in this field of chemistry. In order to assess the effectiveness of the thickening, the product is diluted with water to a solids content of about 1%, and then neutralized with alkali. As the latter, as a rule, use ammonium hydroxide, however, to neutralize you can take sodium hydroxide and potassium and even amines, such as triethylamine. The neutralization product is dissolved in water to increase viscosity. In normal mode the original (neitralizovannykh) the thickener is added to the liquid, and then neutralized. This facilitates handling of the thickener, as in this case, to neutralize it has a lower viscosity. In addition, this methodology requires the use of more water to get the preparative form.The polymers used in nastiamouseforum, necessary for the emulsification of the monomers and maintenance of the obtained polymer in a suitable dispersion medium. As emulsifiers used conventional anionic surfactants, such as nutriceuticals, dodecylbenzensulfonate and sulphates of ethoxylated fatty alcohols. Used emulsifier in an amount of from 0.5 to 6% by weight of monomers.It is preferable to use water-soluble initiators such as persulfate of an alkali metal or ammonium in an amount of from 0.01 to 1.0% by weight of monomers. Gradual additive thermal process at temperatures of 60-100oWith is preferable compared to the redox systems.The polymerization system contains a small amount (0.01 to 5 wt.% the total weight of monomers) of mercaptans as a carrier chain, such as hydroxyterminated, -mercaptopropionic acid and allylmercaptan containing from 4 to 22 carbon atoms, and the like. The use of the mercaptan modifier reduces the molecular weight of the polymer and, consequently, the thickening efficiency of the latter.The polymers used in the present invention can be further modified by introducing a certain amount of the components is to crosslinking of the polymer, such as diallylphthalate, divinylbenzene, allyl-methacrylate, trimethylolpropane, etilenglikolevye or dimethacrylate, 1,6-hexanediamine or dimethylacrylate, gallivants and the like. Thus, in polymerbased mixture can contain from 0.05% and less than about 20% or more of the above unsaturated compounds, calculated on the total weight of monomer. The resulting polymers are either strongly branched, or present in the form of a spatial (three-dimensional) grids. While in neutralized salt form, these grids swell in the water system, acting as a very efficient thickener.Other illustrative unsaturated copolymerizate the monomers with plastic ties used in the present invention, includes any copolymerizable compound which contains in the structure of two or more unpaired points ethylene unsaturation or two or more unpaired vinylidene group SN2With such as dividercolor, trivinylbenzene, Divinington, trimethylaminuria or dimethacrylate, 2-ethylhexane-1,3-dimethacrylate, divinycell, diphenylethylene, divinely ether, divinylsulfide, allyl esters polivalentny connection is t, diallylmalonate, diallylphthalate, diallylphthalate, diallylamine, diallylmalonate, diallylmalonate, diallylamine, diallylamine, diallylmalonate, diallylether, dealersocket,reallistically, triallylamine, triallyl-citrate, triethylphosphate, N,N,-methylenedianiline, N,N-methylene-dimethacrylate, N,N-ethylendiamine and 1,2-di-(alpha-methyl-methansulfonate)ethylene.Other polymers that may be used in the present invention include the polymers described in the joint consideration of the orders of the USA 887644, 887642, 887673, 887641, 887672, 887646, all of which are mentioned in the present description as a reference. The polymers having primary, which contains urethane linkages, also included in the scope of the present invention.To obtain a thickener or thickened compositions of the present invention there are different ways of applying the polymer component. For example, the polymer being in the form of aqueous dispersions or dry, knead in water system that is subject to thickening, followed by the addition of neutralizing agent. Alternatively the polymer can first be neutralized in the form of an aqueous slurry and then mixed with the water system. PR mixed separately (in the form of dry products or in the form of a disperse system or suspensions in aqueous dispersion, to be thickening, followed by a stage of neutralization.Although you can get water concentrates the acid form of the polymer and surfactant and add them to tugusheva water dispersion, followed by neutralization of the mixture, such concentrates tend to be too viscous in order to ensure easy handling of these products. However, it is possible to prepare a dry mixture or the aqueous composition containing solid particles, which has a sufficiently low viscosity to be capable of pumping the pump or to the filling, and then to additional thickening of the mixture through alkaline product.Polymeric thickener can be obtained in dry form in a variety of ways. For example, non-alkaline polymer can be subjected to spray or drum drying and, if desired, mixed with a surface-active substance used as a thickener. However, you can also dry it by spraying and dehydrating neutralized polymeric thickener that way, and then re-prepare the aqueous slurry thickener, provided that its pH is maintained at level 7 or above.The more trivial the method of use claimed susp is after mixing to introduce alkaline product to neutralize the acid. Mainly thickening reach within a few minutes after neutralization. In the presence of high concentrations of electrolytes increase in viscosity takes much more time. This method of applying the polymer in the aqueous system to the stage of neutralization allows the user to deal with a fairly solid thickener in a non-viscous state, to obtain a homogeneous mixture, and then turn it into a product with high viscosity by adding to the system alkaline compounds to achieve pH 7 and above.Aqueous solutions thickened neutralized polymers, exhibit stable viscosity properties up to pH 13.The polymer can be used for thickening compositions in acidic conditions in the presence of a relatively large amount of surfactant, where the thickened composition, for example, in the form of an aqueous system has a pH of less than 7, reaching even up to 1.Increased thickening (referred to here as "co-zagustevanii") adding surfactant may result in a water system containing the claimed polymer, in the case when the latter is neutralized. In some cases, salustiana increased almost 40-fold compared with the viscosity, which is active substances. Although traces of the surfactant may be present in the product of polymerization (for example, all that can remain is about 1.5% surfactant on the number of monomers), believe that such content surfactants alone do not lead to any appreciable co-salustiano.When calculating the water system containing from 0.1 to 5 wt.% solid polymer, a useful amount of surface-active substances for optimal co-thickening is 0.1-1.0 wt.% of the total mass of the system. As already noted, the content of polymer and surfactant co-thickening agent can vary widely, going even beyond the possible values, depending on the type of polymer and surfactant and other components of the mixture to be thickening. However, co-salustiana can reach a maximum in the process of introducing a surfactant, and then begin to decline as it can be added later. Therefore, the use of surfactants in amounts outside the established concentrations and ratios between the polymer and the surface-active substance, may be uneconomical, but it can be defined in the usual way in each case.The preferred method of applying the polymer and surfactant for water segusini is of alkaline foods to neutralize the acid. This method of applying the polymer and surfactant in the aqueous system before neutralization allows the user to deal with solid thickener in a non-viscous state, to obtain a homogeneous mixture, and then turn it into a high-viscosity product by adding to the system alkaline compounds to achieve pH 7 and above. However, neutralization of the polymer in the aqueous system can be operated before adding surface-active substances.Surfactants that can be used in the method preferably include nonionic and anionic surfactants separately or in combination, and the choice depends on the compatibility with the other ingredients already thickened or intended and capable of salustiano 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 water system, or to take them in such small quantities, so as not to cause such incompatibilities.Suitable anionic surfactants that can be used in the method include sulfates of higher fatty alcohols, such as sulfates of sodium or potassium for alcohols containing from 8 to 18 atoda, sulfonated alcylaryl compounds such as dodecylbenzenesulfonate sodium.Examples of nonionic surfactants include alkylphenolethoxylates with alkyl groups containing from 7 to 18 carbon atoms and from 9 to 40 and more oxyethylene links, such as octylphenoxy-polyethoxyethanol, dodecyltrichlorosilane; ethylenoxide derivatives of long-chain carboxylic acids, such as lauriola, myristic, palmitic, oleic; ethyleneoxide condensates of long chain alcohols, such as lauric or cetyl alcohol, and the like.Examples of cationic surfactants include lauryldimethylamine, activesystemconsole ammonium didecyldimethylammoniumchloride condensates of primary fatty amines and ethylene oxide, and the like.The above and numerous other useful nonionic, anionic, cationic and amphoteric surfactants 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, the solvent (or mixture of solvents, other organic and volatile substances) can be used to control viscosity polymer-containing systems. Here the interest is of rites affects the amount of white spirit, which can be added before the solution will be divided into two-phase system.The amount of polymer that can be dissolved in any of the considered water composition varies widely, depending on the specific viscosity values.Thus, although dissolution is possible to take any effective amount of the polymer used, usually from 0.05 to 20 wt.%, preferably from 0.1 to 5 wt.%, and most preferably from 0.1 to 3 wt.% polymer, calculated on the weight of the final aqueous composition including the polymer.In addition to micromanometers the polymer, which acts as a liquid thickener fluid on glycol or glycerol-based may also contain small amounts of other functional ingredients such as corrosion inhibitors, surfactants, antioxidants, flame retardants, stabilizers, dyes and similar substances. These components are usually present in individual amounts not more than 2 wt.%, typically, in the range of 0.01-1 wt.% for each component.Micromonosporaceae the polymer used as a thickener for universal fluids, zayavleniya icing of aircraft. This polymer is used in amounts that pour in to a significant change in the rheological characteristics of glycol fluids. Claimed in the present invention the liquid to eliminate or prevent icing of aircraft do not show the rheological properties associated with conventional Newtonian fluids.In addition, the proposed universal fluid must differ from liquids that have been thickened by the standard method, since they are associative mechanism. Composition for de-icing airplanes of U.S. patent 4 358 389, gelled crosslinked polyacrylate, with optional addition of xanthan resin are examples of known compositions described in the literature.When applied to exposed surfaces of aircraft fluid is sufficiently viscous and/or sticky, and has an appropriate gel-like structure that provides grip even with not horizontal surfaces. This forms a film of a thickness sufficient to prevent buildup or ice buildup, snow, snow grains, ice, rain or frost on these surfaces when the aircraft is parked or while taxiing. However, as soon as Seely wind. Therefore, the so-called critical surfaces of the aircraft there is no appreciable amount of liquid up to a complete rotation of the plane at the moment when the pilot starts a separation from the earth, being on the runway, and later on the surfaces of the aircraft, when it is already in the air. This result is highly desirable, because the residual layer of liquid anti-icer on aerodynamic surfaces like trails of snow, freezing rain or snow can negatively affect workers lift characteristics of the wing.It should be noted that in the absence of micromanometers polymeric thickener used in the present invention, water glycol fluid would have a relatively low viscosity and are willing to drain off any not horizontal surface under the action of gravity, leaving the film, which is insufficient to effectively act as an anti-icer for a long time.Micromonosporaceae polymeric thickener is used in an amount which increases the viscosity and/or stickiness aircraft fluids, and, in addition, gives them heliogabale thickener in liquid water based should be less than 5% 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 fluids containing such quantities of the above polymeric thickener, applied to the outer surfaces of the fixed plane, the drift of the liquid film with not horizontal surfaces (inclined, vertical, and others ) significantly delayed or completely stopped for a long time.Thickened liquid for de-icing form a coating that when applied to the surface by standard methods gives the coated outer surface of the aircraft de-icing and antifreeze properties and minimizes adhesion or increase it ice, snow, cereals, etc.The apparent viscosity, which is provided micromanometers polymeric thickener in the liquid glycol or glycerol-based, should be in the range of 1000-100000 MPa, preferably 20000-60000 MPa (measurement performed on a Brookfield viscometer at a speed of 0.3 rpm and the temperature 01oWith using the rotating rod #31 (PEFC is on turnover and separation from the earth, the impact force of the wind on the wings and other open surfaces treated with the composition of icing, as well as mechanical vibration in the wings and other structural elements of the aircraft, causes an action sufficient to shift efforts on aircraft fluid razzhizhaya her so that she behaved like a relatively non-viscous material. After that the liquid easily flows out from the wings and other surfaces of the aircraft.During takeoff aircraft and up to a full turn (the point at which the lifting force that acts vertically on the aerodynamic surface of the aircraft, sufficient to ensure that the pilot made the take-off and separation of the aircraft from the ground), the shifting force of the air jet from the wind modifies the rheological properties of the claimed fluid, causing severe liquefaction under the action of shear and a noticeable decrease of the apparent viscosity, which allows the liquid to flow freely from the surface of the wings. Thus, the aerodynamic surface remains free not only from any buildup of snow, but also on thickened liquids, which could have undesirable effects on the lift force.Micromonosporaceae the polymer used is osili may be present minor amounts of other ingredients, including other thickeners, in order to provide additional salustiana or more gel-forming functional group, or for the modification of rheological properties. Micromonosporaceae the polymer used as the required thickening agent is present preferably in amounts of at least about 80 wt.% from the present thickeners; preferably, its content is more than 90 wt.% from the thickener used.Gelling micromanometers polymers used as thickeners, show the necessary low viscosity characteristics, which are caused by shifting effort, and yet resistant to mechanical degradation with shear stresses arising from the use of the pump and nozzle. This special characteristic is very important because fluid designed for de-icing, usually applied using conventional ground-based equipment, which includes a spray system, which is driven by the pump. Water glycol fluids de-icing, thickened micromanometers polymer, are quite fluid (low viscosity) properties to be sposobnost they mentioned earlier in the text of the standard aircraft fluid SAE/ISO Type II, as a rule, sensitive to shear force and therefore must be delivered to the injection piston pumps or pressure.Water liquid glycol or glycerin based mostly designed to eliminate or prevent icing by processing a stationary aircraft, but can also be used for normal removal of ice, for example for processing the windshields of cars and different vehicles, and other outdoor surfaces.The modification of the rheological properties of the object determined by the following parameters:
(1) the structure and concentration of associative macromonomers, including: a) the size and structure of molecules hydrophobe; (b) number of CNS groups (in moles) between the hydrophobic group and a double bond; (C) the chemical nature of the bond between alkoxycarbonyl part and a reactive double bond (e.g., having a single ether, ester or urethane linkages); and (d) the structure actually double bond (acrylic, methacrylic, crotonic, styrene and so on);
(ii) the structure and concentration of the acid monomer in the polymer (for example, acrylic, methacrylic, crotonic, taconova cvut the polymer during the polymerization (for example, trimethylolpropane), as well as those compounds that are left untouched functional groups in an associative polymer, capable of forming crosslinks, not resulting in cross-linking during polymerization (for example, 2-hydroxyethyl-acrylate);
(iv) the molecular weight of the polymer, which is controlled during the polymerization using mercaptans.All these parameters affect the viscosity of the liquid under steady shear viscoelastic properties and extending the ability of the polymer, but also on the efficiency of the thickening. Options (ia) and (ib) influence of rheological properties by regulating morphological properties, thermodynamic parameters and kinetics of formation of associative connections. Parameter (ic) controls the hydrolytic stability of connection, which connects the surfactant with the main chain of the polymer, and the simplicity (and therefore cost) synthesis of associative macromonomers. Parameter (id) controls the activation sequence in the polymer macromonomer and the amount of coagulate in the reactor, resulting in the polymerization process, which determines the productive viability of the polymer. Options (ii) and (iii) con polymer chain.Since the viscosity of the liquid should not significantly decrease as dilution water (to increase the "overtime" and time are sewn in the mode of irrigation water spray), associative activity of the polymer must balance the loss of ductility caused by the dilution of the polymer. At the same time because the viscosity of the liquid should not significantly increase when the temperature drops, the hydrodynamic size of the polymer molecules must sufficiently be reduced in order to compensate for the increased viscosity of the mixture of ethylene glycol and water. (The hydrogen bond between water molecules and molecules of ethylene glycol increases 2 times the viscosity of the mixture of ethylene glycol and water at a ratio of components 50/50 with decreasing temperature from 20 to 0oC).Investigated the effects of water dilution and temperature changes on the viscosity model aircraft fluids, consisting of a 0.5% solutions of polymer in mixtures of glycol and water, taken in equal proportions. The results are shown in Table Q.Experiment on water dilution is essentially titration glycol solution containing the polymer, water, i.e. the creation of such conditions, rat less than 50% weight. water, consistent with the experiment "dry out", which simulates the evaporation of water; at the same time, compositions which contain more than 50 wt%. water, consistent with the experiment for determining the time of protection by irrigation water spray that simulates the effect of freezing rain or snow grains hitting the treated surfaces of the aircraft, are waiting on the runway. The viscosity of the solution is measured as adding water to it. Is the fluid viscosity is invariant to the dilution or not, depends on the number of moles of ethylene oxide in macromonomer, as well as the concentration of associative macromonomers and methacrylic acid in the polymer.The degree to which the viscosity model aircraft fluids depends on the temperature also depends on the structure of an associative polymer. The dependence of the solution viscosity of the size of the polymer coil and concentration is often expressed as the main empirical dependencies of type h/ = f(c[h]), such as the Huggins equation:
h/ = 1+c[h]+Kc2[h]2+ ... (1)
where h is the viscosity of the polymer solution, the viscosity of the solvent, c[h] - dimensionless volume of molecular tangle, and constant To' characterizes the Noi 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 similar to equation (1), often combined viscosity data within a wide range of molecular weights and concentrations for the diluted system "polymer-solvent".As the viscosity of the solvent in the form of a mixture of ethylene glycol and water increases with decreasing temperature, the contribution of solvent to total viscosity of the solution, you can exclude and define only increase, which gives a polymer having their own specific viscosity:
< / BR>Characteristic viscosity [h] depends on the hydrodynamic size of the polymer coil, which, in turn, depends on the molecular weight of the polymer, solvent and temperature. Taking the ratio of the characteristic viscosity to the viscosity obtained at an arbitrary reference temperature Trefyou can select the temperature effect for a given molecular weight of the polymer. Temperature correlation for viscosity usually take the form of equation Arrhenius equation:
< / BR>where R is the universal gas constant and LH is the activation energy for the change of viscosity with temperature. Wnie the viscosity of liquid anti-icer: if LH is equal to zero, the viscosity of the solution is changed in exactly the same way as 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 with decreasing temperature. The amount of LH is determined by the subordination of the temperature dependence of the specific viscosity of 0.5% solutions of polymer in mixtures of glycol and water, taken in the ratio of 50/50, equation (3) using standard least-squares method.Is the fluid viscosity is invariant to temperature or not depends on the concentration of associative macromonomer in the polymer, the number of moles of ethylene oxide in macromonomer and the concentration of carboxyl groups in the polymer. If it is determined that the structure of individual micromanometers polymer is unacceptably sensitive to dilution and/or thermal effects (which tend to be inversely proportional to each other), can be taken to compensate changes of water solubility and glass transition temperature of the main chain of the polymer. Thus, an acrylate, for example, can partially replace matlacha liquefaction, however, with almost invariant to the temperature profile of viscosity. In the past, this effect was achieved through the formulation with the inclusion of anionic surfactants. Non-ionic surface-active systems have the advantage that you can use for storage tanks made of carbon steel.Although the prior art describes a standard fluid (SAE/ISO Type II) to prevent icing with increased protection against ice, snow, slush and frost, these fluids have found limited use as a means for de-icing, as the defense had a tendency to decrease due to heating for several days at temperatures 75-95oWith faced in operations to remove ice.At temperatures 75-95oWith thickeners based on polymers with high molecular weight, such as polyacrylates or polysaccharides, as well as xanthan gum, dissolved in a few days, losing viscosity, in particular the viscosity, measured at low shear rates. Since this viscosity helps to protect against icing, time protect these liquids will decrease over time, as their heat when held can break down at elevated temperatures (>60o(C) if to prevent such destruction not to use the basis of the proper type and in the proper concentration. Although the inventors do not aspire to be bound to any theory, it is assumed that this destruction occurs via hydrolysis of macromonomer to this form, which is less efficient for use as a thickener.As mentioned earlier, when using a hydroxide of alkali metal, in particular sodium hydroxide, with the aim to bring the pH of the solution to 7.5, and preferably to a pH of 8.5 to 9.5, it was observed that thermal stability, as measured by the change in viscosity at low shear, increased significantly. Higher pH is actually further improve thermal stability of the composition, but composition having a high pH value, the more aggressive to aluminium and are therefore preferably avoided.When using salt hydroxide of an alkali metal and a weak acid in combination with an appropriate base, it was noted that thermal stability increases additionally. In particular, it was noted that sodium acetate works well in combination with sodium hydroxide. Sodium acetate is even more weak is to one sodium hydroxide. However, low concentrations of the stabilizing salt is preferred because the higher its content (even if they further improve thermal stability) tend to reduce the fluid when it is used in the mode prevent icing. The preferred concentration of the stabilizing salt is from 0 to 0.10 wt.%, more preferably from 0 to 0.02 wt.%.Used in the description of the term "complex hydrophob" is intended to include all permissible hydrocarbon compounds having 2 or more hydrophobic groups, such as bis-dodecylphenyl, bis-nonylphenyl, bis-octylaniline and the like.In the present invention, the term "hydrocarbon" is intended to include all permissible compounds having at least one hydrogen atom and one carbon atom. In a broad aspect, the permissible hydrocarbons include substituted or unsubstituted acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic organic compounds.If not specified, it is used in the description, the term "substituted" is intended to include all permissible substituents of the organization of the data and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic 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 1 to 20 and more preferably from 1 to 12. Permissible substituents of the corresponding organic compounds may be the same or different and to be present in the amount of one or more. The present invention is not intended in any way to limit the above allowable organic substituents.In more detail, the present invention is illustrated by the following examples.Example 1. Obtain 1,3-bis(nonylphenoxy)-2-propanol
In pathology round bottom flask 2 l, equipped with addition funnel, thermometer, nitrogen dispergating tube, a mechanical stirrer and a nozzle for decanting water from the fridge, add 220 g (1.00 mol) of Nonylphenol and 250 ml of cyclohexane. The solution is heated to education phlegmy and slowly added to the flask 2.8 g (1.3 wt.% in terms of nonylphenyl) of potassium hydroxide in 10 ml of water. After all the water extracts the CSOs ether. While adding pilgramage ether the reaction temperature support between 60 and 80oC. After the addition of ether, the solution is refluxed for 4 hours the Contents of the flask are washed with 5% aqueous solution of phosphoric acid, the organic layer is separated from the water and washed twice with deionized water. After that the reaction mixture is transferred into a round bottom flask of 1 l and unreacted Nonylphenol and the remaining cyclohexane is removed by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Od. During distillation prevent the temperature in the flask was exceeded 180oTo prevent discoloration of the product. The concentrated solution is filtered twice, getting 425 g of liquid pale yellow color. Analysis of end groups gives the molecular weight 506,8 (theoretical value MV=496,8). The IR and NMR spectra were identical to the previously cleared spectra of this compound.Example 2. Obtain 1,3-bis(nonylphenoxy)-2-propanol
In pathology 2-liter round bottom flask equipped with addition funnel, thermometer, nitrogen dispergating tube, a mechanical stirrer and a nozzle for decanting water from the fridge, add 451,7 g (2.05 could (of 1.05 mol) of potassium hydroxide in 60 ml of water. After all the water is extracted in dicontinuous the nozzle (60 ml + 19 ml formed), the reaction mixture is cooled to 40oC and slowly added of 92.5 g (1.00 mol) of epichlorohydrin. During the operation of addition, the reaction temperature kept lower than 60oWith by adjusting the rate of addition of epichlorohydrin. After adding the last solution is stirred for one hour and then heated under reflux for another 3 hoursThe reaction mixture is filtered under vacuum through a Buchner funnel with a steam jacket to remove the potassium chloride formed as a by-product. The filtering carried out three times to remove most of the salts. After that the reaction mixture is transferred into Crumpton flask of 1 l and unreacted Nonylphenol and the remaining cyclohexane is removed by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Od. During distillation prevent the temperature in the flask was exceeded 180oTo prevent discoloration of the product. The concentrated solution is filtered twice, getting 275 g of liquid pale yellow color. Analysis of end groups gives the molecular weight 459,7 (theoretical value MV-496,8). IR and NMR spectratone)-2-propanol
In a high pressure autoclave of stainless steel, 500 ml load of 200 g (x 0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol containing a catalytic amount of potassium salt of the alcohol as described in Example 1. After purging the reactor with nitrogen, the alcohol is heated to 130oWith stirring for 2 h add 86,9 g (2,0 mol) of ethylene oxide. The reaction temperature and pressure support, respectively, at 130-140oWith 4.2 kg/cm2. After the addition of ethylene oxide, the mixture was incubated additionally for one hour at a temperature of 140oWith and give all the ethylene oxide to Vivarais. The reaction mixture is discharged in a hot condition in a nitrogen atmosphere and neutralized with acetic acid, getting 285 g of liquid pale yellow color.Example 4. Getting adduct nonspermicidal ether and 5 M ethoxylate 1,3-bis(nonylphenoxy)-2-propanol
In pathology 1-liter round-bottom flask equipped according to Example 1 was added 5 M ethoxylate 1,3-bis-(nonylphenoxy)-2-propanol and 100 ml of cyclohexane. The mixture is boiled (100o(C) under reflux for one hour to remove residual amounts of water, and then cooled to 50oC in nitrogen atmosphere by adding 0.5 g F3/Et2oWith to facilitate separation of both layers. Water and cyclohexane organic layer is evaporated in a vacuum, getting 145 g of a viscous liquid pale yellow color. Analysis of end groups gives the molecular weight of 880 (theoretical value MV-993).Example 5. Obtaining poly(Nonylphenol)pilgramage ether
In a round bottom flask of 500 ml, equipped with a top stirrer, inlet for nitrogen, reflux condenser, addition funnel and temperature controller, load 1.9 ethanol (22 mmole) and 200 g of cyclohexane and bring the solution to 50oC. after heating using a 2 ml syringe to inject 0.5 ml (4 mmole) F3/Et2Acting as soon As the introduction of acid, are added dropwise 100 g noninteroperable ether (362 mmole) in such a way that the temperature was maintained in the range of 45-55oC. After addition of ether, the solution is refluxed for 3 h is the PMC and washed with 100 ml of 5% sodium bicarbonate solution. The aqueous layer was separated, the organic layer washed twice demonizirovannyj water (2 x 100 ml). Water layers decentered, the organic layer is dried on magnesium sulfate not less than 1 h For alchanii drying the magnesium sulfate and the organic solvent is removed on a rotary evaporator, obtaining 100 g of a viscous polymer. Analysis by gel permeation chromatography (GPC) gave values of Mw-2600 (srednevekovaja molecular weight) and mn-1700 (srednekislye molecular weight) with respect to standard monodisperse polystyrene.Example 6. Amoxilonline poly(Nonylphenol)pilgramage ether
In an autoclave of stainless steel Zipperclave) 500 ml add 60,0 g (0,035 mol calculated by the estimated value of the MV-1700) resin obtained in Example 5, together with 0.5 g of potassium hydroxide. The vessel attached to the auto setting for amoxilonline and heated to 50oC. the Vessel is continuously rinsed with nitrogen for 15 min, and then heated to 100oWith and implement continuous purging with nitrogen addition within 15 minutes After the reaction vessel is heated to 140oWith and conduct a series of 6 tests with crimping approximately 12.7 kg/cm2(80 psi), followed blower adjust is the turn of ethylene oxide overlook two valves with electric and together with the main supply pipe to the autoclave. Filing carry out continuously, the pressure in the vessel to regulate the amount of about 4 kg/cm2(55 psi) at a temperature of 140oC. Automatic design so that adding ethylene oxide through the valve with the actuator to maintain the temperature and pressure within safe operating limits. The flow continues until, until you have entered 60,0 g (1,362 mole) of ethylene oxide (based on the difference in weight of the feed cylinder). After filing the reaction continued for another hour, after which the vessel is cooled to 60oC, rinsed 4 times with nitrogen up to a pressure of about 5.6 kg/cm2and then the reaction mixture is discharged into the container. The weight of the finished product is 115 g with theoretical output 123, Analysis by gel permeation chromatography gives the values of Mw=2600 (srednevekovaja molecular weight) and mn=1700 (srednekislye molecular weight) with respect to standard monodisperse polystyrene.Example 7. Obtaining poly(phenyl)Glendalough ether
In a round bottom flask of 500 ml, equipped with a top stirrer, inlet for nitrogen, reflux condenser, addition funnel and temperature controller, load 47,6 phenol (500 mmol) and 100 g of toluene and bring the solution to ending the introduction acid, added dropwise 68,18 g phenylglycidyl ether (454 mmole) in such a way that the temperature was maintained in the range of 45-55oC. After adding pilgramage ether solution is refluxed for 3 h, and then cooled to 50oC.Hot (below 60oC) the mixture is transferred into a separating funnel and washed with 100 ml of 5% sodium bicarbonate solution. The aqueous layer was separated, the organic layer washed twice demonizirovannyj water (2100 ml). Water layers decanted, the organic layer is dried on magnesium sulfate not less than 1 h after drying, the magnesium sulfate and the organic solvent is removed on a rotary evaporator, obtaining 100 g of a viscous polymer. The final yield a viscous polymer is of 90.3 g (with 11% unreacted phenol). Analysis by gel permeation chromatography (GPC) gave values Mw=470 (srednevekovaja molecular weight) and MP-310 (srednekislye molecular weight) relative to the standard samples of monodisperse polystyrene.Example 8. Obtain 1,3-bis(phenoxy)-2-propanol using CSS technology of polyols
In a round bottom flask of 1 l, equipped with a top stirrer, inlet ammerstol), 12,86 g of iodide of tetraethylammonium (0.05 m), 3.00 g of water (to 0.17 mol), 42,08 g of potassium hydroxide (to 0.75 mole) and 250 g of toluene. In an addition funnel 100 ml placed 23,13 g of epichlorohydrin (0,25 mol) and 50 g of toluene. The solution was adjusted to 65oTo add the epichlorohydrin in toluene for 15 min while maintaining the temperature in the interval 655oC, and the mixture is left for 48 h for the reaction.After 48 h the solution is cooled to room temperature. Toluene solution is washed with deionized water (2250 ml), the aqueous layers are separated, the toluene together with unreacted phenol is removed on a rotary evaporator. The weight of the final product and 64.5 g, which is 106% of theoretical (balance - phenol), the purity of the final product is about 95% (by GPC results).Example 9. Dimerization of 1.3-bis(phenoxy)-2-propanol using CSS technology of polyols
In a round bottom flask of 250 ml, equipped with a top stirrer, inlet for nitrogen, reflux condenser, addition funnel and temperature controller, load 20,03 g of 1,3-bis-(phenoxy)-2-propanol obtained in Example 8 (82 mmole), of 2.06 g of the iodide of tetraethylammonium (8 mmol), 0,49 g of water (27 mmol), 6,51 g of potassium hydroxide (116 mmol) and 125 g of toluene. In drip italalian in toluene for 15 min, while maintaining a temperature in the range of 655oC, and the mixture is left for 48 h for the reaction.After 48 h the solution is cooled to room temperature. Toluene solution is washed with deionized water (2250 ml), the aqueous layers are separated, the toluene together with unreacted phenol is removed on a rotary evaporator. The weight of the final product is 21.6 g, which is 101% of theoretical. The GPC analysis shows that the product consists of two main components. The first component starting material in an amount of about 41% (MP=220) and second - dimer in an amount of about 59% (Mw=520).Example 10. Obtain 1,3-bis(hexadecylamine)-2-propanol using CSS technology of polyols
In a round bottom flask of 500 ml, equipped with a top stirrer, inlet for nitrogen, reflux condenser, addition funnel and temperature controller, load 60,61 of hexadecanol (0,25 mol), 16,18 g of iodide of tetraethylammonium (0,024 mol), 1.44 g of water (0,082 mol), 20,20 g of potassium hydroxide (of 0.36 mol) and 125 g of toluene. In an addition funnel 100 ml placed 11,10 g of epichlorohydrin (0.12 moles) and 25 g of toluene. The solution was adjusted to 65oTo add the epichlorohydrin in toluene for 15 min while maintaining the temperature howl temperature. Toluene layer is washed with deionized water (2x250 ml), the aqueous layers are separated and the toluene is removed at a rotary evaporator. The weight of the final product - to 70.9 g, which is 109% of theoretical (balance - hexadecanol).Example 11. Sulfonation 1,3-bis(nonylphenoxy)-2-propanol-block-(propylene oxide)10-block-(ethylene oxide)10< / BR>In a round bottom flask of 500 ml, equipped with a top stirrer, temperature controller and a vacuum adapter, loads of 75.0 g of the product from Example 13 (49 mmol). The vacuum vessel to a pressure less than 20 mm Od and heated to 100oWith removal of water. After one hour, the reactor is cooled to 60oAlso under vacuum. When reaching the 60oWith the vacuum removed with nitrogen and added to 5.3 g of sulfamic acid (54 mmole), after which the reactor is heated to 110oC and pumped to a vacuum of less than 20 mm Od. The mixture is left to react for 3 hoursAt the end of the reaction the reactor is cooled to 85oWith, the vacuum is removed with hydrogen, and then added slowly under hydrogen shell 1.2 g diethanolamine (11 mmol) and the solution stirred for 30 minutes In a reactor, add 10 g of ethanol and the temperature is brought to 55oAnd the solution is stirred for another 30 min Heat removed is of 15 min or until as the temperature is reduced to room (less than 35oC).The pH value of the solution is checked by dissolving 2 g of a solution of the product in 18 ml of deionized water. If when checking the pH is below 6.5, add diethanolamin portions 0.2 g up until the pH is set in the range of 6.5-7.5.Example 12. Getting 1.3-bis(nonylphenoxy)-2-propanol-unit-(propyleneoxide)10< / BR>In an autoclave of stainless steel Zipperclave) 500 ml load of 100 g (0,202 mole) of 1,3-bis(nonylphenoxy)-2-propanol obtained in Example 1, together with 0.7 g of potassium hydroxide. The reactor is combined with automatic installation and heated to 50oC. Then the reactor was continuously rinsed with nitrogen for 15 min, and then heated to 100oC, then rinsed with nitrogen continuously for 15 minutes Then the reaction vessel is heated to 140oWith and conduct a series of 6 tests with moulding up to about 5.6 kg/cm2and subsequent ventilation. At the end of the ventilation vessel pressurized with nitrogen to about 1.4 kg/cm2.Line of propylene oxide, is connected to the feed cylinder pre-filled 117,0 g of propylene oxide (2,02 mol), go on valves with electric and together with the main petousis kg/cm2and temperature 140oC. Automatic design so that when the introduction of ethylene oxide by a pair of electrically-driven valves to maintain the temperature and pressure within safe operating limits. The flow continues until, until you have entered all the propylene oxide. After filing the reaction continued for another hour, after which the vessel is cooled to 60oC, rinsed 4 times with nitrogen up to a pressure of about 5.6 kg/cm2and the reaction mixture is discharged into the container. The weight of the final product is 211 g and theoretical yield 277, Analysis by gel permeation chromatography gave Mw=650 (srednevekovaja molecular weight) and mn=490 (srednekislye molecular weight) relative to the standard samples of monodisperse polystyrene.Example 13. Getting 1.3-bis(nonylphenoxy)-2-propanol-block-(propylene oxide)10-block-(ethylene oxide)10< / BR>In an autoclave of stainless steel Zipperclave) 500 ml load (75 g (0,070 mole) of propoxylate from Example 12 together with 0.3 g of potassium hydroxide. The reactor is combined with automatic installation for amoxilonline and heated to 50oC. Then the reactor was continuously rinsed with nitrogen for 15 min, and then heated to 100oAnd again prodamauto with moulding up to about 5.6 kg/cm2and subsequent ventilation. At the end of the ventilation vessel pressurized with nitrogen to about 1.4 kg/cm2.Line of ethylene oxide, is connected to the feed cylinder, overlook valves with electric and together with the main supply pipe to the autoclave. Filing operate continuously and parameters in the vessel to regulate the pressure of about 4 kg/cm2and temperature 140oC. Automatic design so that when the introduction of ethylene oxide by a pair of electrically-driven valves to maintain the temperature and pressure within safe operating limits. The flow continues until, until you enter a 30.7 g (0,696 mole) of ethylene oxide (based on the difference in weight of the feed cylinder). After filing the reaction continued for another hour, after which the vessel is cooled to 60oC, rinsed 4 times with nitrogen up to a pressure of about 5.6 kg/cm2and the reaction mixture is discharged into the container. The weight of the final product is 99 g and theoretical yield 106 gExample 14. Obtaining bis(nonylphenoxy) adduct of 1,4-butanediol-diglycidylether ether
In pathology round bottom flask 2 l, equipped with addition funnel, thermometer, nitrogen dispergating tube, mechanical mesalina. The solution is heated to education phlegmy and slowly added 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 extracted in dicontinuous nozzle (15 ml + 2 ml formed), are added dropwise to 220 g (1,09 mole) of 1,4-potentialapplications ether. While adding pilgramage ether the reaction temperature support between 60 and 80oC. After the addition of ether, the solution is refluxed for 4 hours the Contents of the flask are washed with 5% aqueous solution of phosphoric acid, the organic layer is separated from the water and washed twice with deionized water. After that the reaction mixture is transferred into a round bottom flask of 1 l and unreacted Nonylphenol and the remaining cyclohexane is removed by distillation, first at atmospheric pressure and then under vacuum at 0.2 mm Od. During distillation prevent the temperature in the flask was exceeded 180oTo prevent discoloration of the product. The concentrated solution is filtered twice, getting 710 g of a liquid pale yellow color. The molecular mass determined by the method of analysis of end groups is 689,9 (theoretical value MV= 643,0). The IR and NMR spectra Soroki)-2-propanol
In the Zipperclave reactor of 500 ml load in a stream of nitrogen 200,1 g (of 0.43 mole) of 1,3-bis-(nonylphenoxy)-2-propanol obtained in Example 2, and 0.20 g (0.1 weight. % ) F3/Et2O. thereafter, the reaction mixture is heated to 80oC and for 2 h injected into the reactor with 55.1 g (1.25 mol) of ethylene oxide. After doing the whole product, the reaction mixture is boiled for 1 h, and then unload hot in nitrogen atmosphere in a vessel containing 160 ml of 1% aqueous solution of sodium hydroxide. The organic layer is separated from the water and washed twice with deionized water. Washing is carried out at a temperature of 90oWith to facilitate separation of both layers. The resulting product is dried by azeotropic removal of water using cyclohexane (300 ml) as azeotropically. Cyclohexane is evaporated under vacuum, obtaining a viscous liquid pale yellow color, molecular weight, determined by analysis of end groups is 601,7 (theoretical value MV= 629). The IR and NMR spectra correspond to the expected structure of the compound.Example 16. Getting 8 M ethoxylate bis(nonylphenoxy) adduct of 1,4-potentialization ether
In the Zipperclave reactor of 500 ml load in a stream of nitrogen to 150.2 g (0.22 m is/Et2O. thereafter, the reaction mixture is heated to 80oC and for 2 h injected into the reactor to 77.5 g (1,76 mole) of ethylene oxide. After doing the whole product, the reaction mixture is boiled for 1 h, and then unload hot in nitrogen atmosphere in a vessel containing 160 ml of 1% aqueous solution of sodium hydroxide. The organic layer is separated from the water and washed twice with deionized water. Washing is carried out at a temperature of 90oWith to facilitate separation of both layers. The resulting product is dried by azeotropic removal of water using cyclohexane (300 ml) as azeotropically. Cyclohexane is evaporated under vacuum, obtaining a viscous liquid pale yellow color, molecular weight of which, determined by the method of analysis of end groups is 1047 (theoretical value MV=995). The IR and NMR spectra correspond to the expected structure of the compound.Example 17. Getting macromonomers connection
In a round-bottom reaction flask of 1 l, equipped with a heating jacket, trap Dean-stark, refrigerator, thermometer, nitrogen bubbler, nitrogen purge, and stirrer, a load of 300 g of toluene and 63 g of surfactant, denoted as S-1 in the Pref is re about 110oWith and dryness to remove traces of water by the method of azeotropic removal. The solution is then cooled to 90oTo download 1.5 bismuth in the form of 28% accolate bismuth as a catalyst (firm Mooney Chemical, Inc., Cleveland, Ohio, US), mix well, and then add a stoichiometric amount of 95% of aliphatic isocyanate t-TMI (company American Cyanamid) (American Cyanamid Co. , Stamford, CT, US). After 1.3 h after start of the reaction, reaching 90oWith the obtained product is cooled to 70oWith and add 0.03 g of 2,6-di-tert-4-METHYLPHENOL (EIT) as a preservative. The mixture is then poured into a bath of stainless steel with a large surface area to facilitate drying. The final product is a waxy material, referred to as macromonomer M-1.Examples 18-34. Getting macromonomer compounds
Other macromonomer obtained by methods similar to those described in Example 17, using stoichiometric amounts of surface-active compounds and unsaturated compounds identified in Table Century.Example 35. Getting thickener, alkali-soluble
Monomer mixture (300 g) obtained by loading into the vessel acrylate (Aldrich), methacrylic acid (Aldrich), macromonomer M-the water and dispersing the contents of intense shaking. The acrylate, methacrylic acid and macromonomer M-1 is added in amounts shown in Table C. the Catalytic mixture comprising of 0.53 g sodium persulfate (Aldrich) and 52,47 g of water, is prepared in another container. In a plastic flask for 2 years, immersed in a thermostated water bath and equipped with a four-bladed mechanical stirrer stainless steel connecting tube Clausen, refrigerator water, nitrogen trap bubbling type, thermometer, inlet for the monomer and the catalyst, is placed 1.20 g of sodium salt of vinyl sulfonic acid and 658,5 g of water. Monomeric mixture is loaded into a graduated feed cylinder 1 l monomer, and the catalyst solution in a graduated feed cylinder 125 ml of catalyst. Under the current of nitrogen, the reactor is heated to 70oWith, then 33 ml of monomer mixture and 3 ml of the catalytic mixture is loaded into the reaction vessel and then heated to 80oC. After the reaction of the monomers for 20 min with the formation of polymer seed mixture of the monomer and the catalyst is transferred into the reaction vessel using FMI pumps by Teflon tubing with a diameter of 1/8 inch with a speed of 1.94 and 0.27 ml/min, respectively, under continuous stirring and podilchuk through nylon cloth with a pore size of 200 mesh. The coagulate is collected from the reaction vessel and filter cloth. Salustiano the ability of the resulting product is controlled by the Brookfield viscometer at a speed of 6 rpm by dilution of the latex to 0.25, 0.50 and 0.75% in terms of solid substance, followed by neutralization of the product to a pH of 9.0 using 95% aqueous solution of 2-amino-2-MetOp-1-propanda (AMR-95 company Angus chemical company, USA). The results are shown in Table C.Examples 36-131. Getting thickeners, alkali-soluble
By the way, is similar to that described in Example 35, get other thickeners, soluble in alkali, using the monomers shown in Tables C-J with indication of their numbers. The table illustrates the effect of the concentration of macromonomer containing m-TMI, and amoxilonline on the effectiveness of the thickening. Table D illustrates the effect of mixing m-TMI-containing macromonomers varying degrees of amoxilonline on the effectiveness of the thickening. Table E illustrates the influence of the type of unsaturation orlandersmith of macromonomers on the effectiveness of the thickening. Table F illustrates the influence of structure macromonomers of ester and amoxilonline on the effectiveness of the thickening. Table G illustrates blechlawine polymer and the solubility in water efficiency thickening. Table I illustrates the effect of the concentration of the monomer capable of crosslinking on the efficacy of Auguste. Table J shows the effect of mercaptan on the efficiency of thickening.In Tables C-J used the following abbreviations: MM - macromonomer; EA - acrylate; MAA is methacrylic acid; AA, acrylic acid; MA - methyl acrylate; t-BA - tert-butyl acrylate; n-BA - n-butyl acrylate; MMA - methyl methacrylate; 2-ENR - 2-ethylhexyl-propionate mercaptan; and 2, NEA - 2-hydroxyethylacrylate.Examples 132-187. Co-thickening in the presence of surfactants
The addition of certain surfactants to the solution of the associative polymer provides co-tastically effect. The results are shown in Table L, illustrate this effect, obtained from adding at careful hashing some surfactants from the Table as Their number is listed in Table L with respect to a 0.5% increase to an alkaline solution of thickening agent, soluble in alkali, which identified ibid. The effect estimate for the viscosity measured on a Brookfield viscometer at a speed of 6 rpm and a pH of 9.0.Examples 188-232. Co-thickening in the presence of surfactants
The degree of amoxilonline surfactant added to the solution of the associative polymer, pokazyvaet added with thorough stirring of some surfactants from Table M. Their number is listed in the Table N compared to 0.3% (Examples 172-189), 0,5% (Examples 190-215) or 0.75% (Example 216) to an alkaline solution of thickening agent, soluble in alkali, which is identified in the same Table. The effect estimate for the viscosity measured on a Brookfield viscometer at a speed of 6 rpm and a pH of 9.0.Examples 233-245. Co-thickening in the presence of solvents and nerastvorimaya
Solvents and herstorical added to the solution of the associative polymer can affect the thickening effect, the Results in Table R, illustrate this effect, obtained from adding at careful hashing some LOVE from Table 0. Their number is listed in the Table R with respect to a 0.75% increase to an alkaline solution of thickening agent, soluble in alkali, which is identified in the same Table F. the Effect estimate for the viscosity measured on a Brookfield viscometer at a speed of 6 rpm and a pH of 9.0.Example 246. The study of polymer solutions for songs, ispolzuemykh to prevent icing of aircraft
The polymer solutions titrated with water and then measure the viscosity Brookfield (centipoise) at 30 rpm and room temperature the polymer without the addition of water (0 g) containing 0.5% of 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 are modeling the evaporation of water (the so-called phenomenon of "dry out").Example 247. The sensitivity to temperature of the polymers in the compositions used to prevent icing of aircraft
Solutions of the polymers are heated and measure their viscosity Brookfield at 30 rpm at different temperatures in the temperature-controlled bath. The activation energy determined by the change of viscosity on temperature. In particular, the amount of LH is determined by the subordination of the temperature dependence of the specific viscosity of 0.5% solutions of the polymer from the Table R in water-etilenglikolevye mixture (50/50) equation (3) using the method of least squares. The results obtained are presented in Table R.Example 248. Co-thickening in the polymer solution
Study for the liquids used to prevent icing of aircraft
The polymer solutions titrated with water and then measure the viscosity Brookfield (centipoise) at 30 rpm and room temperature (20oC) and at 0oWith in thermostatic bath. The results are shown in Table S. the polymer Solutions without DBSA mass solution) non-ionic surfactant TergitolR15-S-5, as 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 are modeling 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
Solutions of the polymers are heated and measure their viscosity Brookfield at 30 rpm at different temperatures in the temperature-controlled bath. The activation energy determined by the change of viscosity on temperature. LH determine the subordination of the temperature dependence of the specific viscosity of 0.5% solutions of the polymer from the Table T in the presence of a certain amount (in weight. % by weight solution) non-ionic surfactant TergitolR15-S-5 (table T) in the water-etilenglikolevye mixture (50/50) equation (3) using the method of least squares. The results obtained are presented in Table I.Surfactant affects not only the viscosity, but also on how this viscosity is sensitive to temperature changes.Example 250. The effect of temperature and surfactant on the profile of viscosity at constant shear liquids to prevent icing of aircraft
Viscosity profile at steady shift get a hundred what eometrie shift Mooney-Couette. The polymer solutions containing 0.4% of solid polymer defined in Table U, a certain amount (in wt.% from the total mass of solution) nonionic LOVE TergitolR15-S-5, as defined in Table U, and a mixture of glycol and water (1:1). The results are presented in Table U. Viscosity is expressed in centipoise (SP).Example 251. The effect of water dilution, temperature, shear rate, the type of LOVE and concentration on the viscosity profile at steady shift v fluids to prevent icing of aircraft
Profile of viscosity in steady shear receive on a standard device Bohlin VOR to study the rheological properties of polymers (realmature) with temperature control and geometry shift Mooney-Couette. Source liquids contain 49,75 g of ethylene glycol (class of complex polyester), 38,90 g of distilled water, 0.85 grams of latex containing 30 wt.% solid polymer P-8, and some amount of non-ionic surfactant TergitolRNP-6 defined in Table V. the Liquid is brought to a pH of about 8.5 with a 45% solution of potassium hydroxide. The results are presented in Table V. the Viscosity is expressed in centipoise (SP).Example 252. The influence of the type of polymer on the viscosity profile at steady shift v fluids to Ave the m device Bohlin VOR to study the rheological properties of polymers (realmature) with temperature control and geometry shift Mooney-Couette. Liquids contain of 54.0 g of ethylene glycol (class of complex polyester), to 46.0 g of distilled water, a certain amount of latex containing 30 wt.% solid polymer P-8 or P-31 defined in Table W, some amount of non-ionic surfactant TergitolR15-S-5, as defined in Table W, 0.25 g corrosion inhibitor Sandocarin 8132C and 0.01 g of corrosion inhibitor Sag 7133 liquid is brought to a pH of about 8.5 with a 45% solution of potassium hydroxide. The results are presented in Table W. the Viscosity is expressed in centipoise (SP).Example 253. Stability of shear and time are sewn compositions for preventing icing of aircraft under irrigation by sprinkling water
Tests to determine the stability of shear and time protection (durability) of the songs by irrigation water sprinkling is carried out in accordance with the methodology of carrying out such tests, described in the Technical specifications of the Association of European airlines for liquids used for de-icing aircraft (AEA Material Specification of De-/Anti-Icing Fluid for Aircraft, 6807 G/R). Liquids contain 49,75 g of ethylene glycol (class of complex polyester), 38,90 g of distilled water, 0.85 grams of latex containing 30 wt.% solid polymer P-8, and 0.4 g of non-ionic surfactant TergitolRExamples 254-293 illustrate the effect of neutralizing base on thermal stability of plane 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 antifoam firms Axis, USA (OSi Inc., Danbury. CT). The product, referred to as "Ingredient S (Ingredient S), is a 5-molar ethoxylate of op, known by the trade name "Triton X-45" (TritonRX-45) of the company Union carbide, USA (Union Carbide Corp. Danbury. CT). The product, referred to as "Sandocorin LF", is a patent-protected corrosion inhibitor/flame retardant containing acrylic terpolymer and about 10 wt.% triethanolamine supplied by the company Clariant (Clariant Corp. Charlotte. NC). The product, referred to as "thickener" (Thickener), is a polymer obtained in Example 76 U.S. patent 5 399 618. (In the above Example 43 described getting close product, which by assumption the applicant should seek the reamers).Following the General method given the following four liquid.In the container (1) with a capacity of 1.14 l (1 quart) add g:
The glycol - 550,96
Water - 355,73
In a glass with a magnetic stirrer, add 1, g:
The glycol - 11,57
Water - 10,36
Then under stirring to the contents of the Cup 1 slowly add in the following order:
SAG 2001 - 0,17
Thickener - 5,00
Sandocorin LF - 1,50
Ingredient S - 2,50
After mixing (at least 20 min to obtain a homogeneous slurry mixture from the Cup 1 is transferred under stirring in a container (1).Prepare the Cup 2 with exactly the same content as in the Cup 1. Produce similar add and continue mixing.In a glass add 3, g:
The glycol - 14,47
Water - 12,96
SAG 2001 - 0,17
Triethanolamine (tea) - 2,50
45% solution of potassium hydroxide - 1,00
The contents of the Cup 3 is stirred and slowly transferred into the container (1) with stirring, continuing until the formation of a homogeneous suspension (at least 15 min). According to the described method can get 1000 grams of aircraft fluid.Example 254 corresponds exactly to the one described above. In Example 256 instead of a mixture of KOH/treetalk triethanolamine (19,17 g). In Example 257 instead of a mixture of KOH/triethanolamine use of 1.11 g of 45% sodium hydroxide solution.The initial viscosity at low shear (Brookfield Viscometer LVT, rotating the rod 1, of 0.3 rpm 0oWith a holder for the sample of small mass and a 10-minute time for reading) is determined for each of the liquids, and then two samples each placed in an oven at 70oWith 30 days. Then the liquid is cooled to room temperature and re-measure the viscosity at low shear. Using the data obtained, calculate the viscous losses from heating for four neutralizing bases.The results show that when used as a neutralizing base hydroxide of an alkali metal, preferably sodium hydroxide, get a liquid with a much higher thermal stability. In addition to the low loss of viscosity, the test time protection by irrigation water spray test (WSET) for liquids, neutralized by sodium hydroxide, shows a very high initial rate (150 min), which is reduced for 30 days at a temperature of 70oWith only 9%. On the other hand, potassium hydroxide gives significantly lower pokazatel the/P> Examples 258-275 correspond delivered at the same time the computational experiments in order to determine the influence of five variables on thermal stability of the formulations used as aircraft fluids. In using 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) the content of the product Sandocorin LF; (d) the content of the Ingredient S; (e) the content of sodium hydroxide, referred to in Table II as XI, x2, and so on, respectively. The plan of the experiment and the results are also shown in table II.The number in the column denoted by EG/W, represents the ratio of ethylene glycol and water, and the numbers in the columns "sages."(thickener), LF and S represent the amount (in g) of the components included in each of the first two mixtures prepared in the respective glasses (prescription at 1000 g experienced a mixture). The numbers in the column labeled "NaOH", correspond to the number of (d) component included in the mix (per serving 1000 g). The designation "Early" and "Load" (Htd) corresponds to the liquid before and after heating.The results show that the improved thermal stability (measured either by the magnitude of the viscosity field and water use more thickener, fewer Sandoconn LF and Ingredient S and more NaOH (through preparation of liquids with higher pH). The liquid of Example 261 meets all the given instructions and provides high initial protection (WSET), as well as excellent thermal stability for preservation or indicator WSET, or value of viscosity on Brookfield.Examples 276-281 illustrate the effect of pH on thermal stability. In these Examples repeat the Example 261, except that the amount of NaOH adjusted so as to achieve pH values specified in section "Before heating" Table III. Data on thermal stability is also presented in Table III. In this Table, the viscosity is expressed in centipoise and measured on the Brookfield viscometer. The term "oBrix is a refractive index, measured on the instrument AO 10431 company Misco Products Division, Cleveland, Ohio. The refractive index is very important because it provides a simple and affordable determining the ratio of glycol and water in the fluid (which, in turn, determines the freezing point and other important performance characteristics). To measure pokazati convenient when measuring in the field.Examples 282-285 study the influence of the ion of an alkali metal at a constant pH. The following compositions were obtained by adding the specified amount of sodium acetate to the liquid of Example 261. Immediately after that, add the specified amount of sodium hydroxide. All Examples involve bringing the pH of the mixtures to 9.5 by adding the specified 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 subjected to thermal aging at 95oC for 6 days. The results before and after ageing are presented in Table IV.The results suggest that small doses of sodium acetate (0,025%) provide additional improvement in thermal stability (however, when using it in a sufficiently large amount of influence on the properties before heat aging will be too large).In the Examples 282-285 it was noted that a few more you want to add NaOH to achieve a pH of 9.5 to those liquids that contain sodium acetate. Therefore, the Examples 286-289 repeat Examples 282-285, except that the order of adding the components of the mixture is reversed, so th is 261 (NaAc missing)
Example 287 - 0.25 g NaAc (post-dobalina)
Example 288 - 0.50 g NaAc (post-dobalina)
Example 289 - 0.75 g NaAc (post-dobalina)
All samples subjected to thermal aging at 95oC for 6 days. The results before and after ageing are presented in Table V.Additional experiments performed similarly to Examples 282-289, confirm that within experimental error there is no significant difference between the add whether the first alkaline hydroxide or neutralizing salt, and also that the universal aircraft fluids do not show a noticeable decrease in the viscosity or protective time WSET by heating at 95oC for 6 days.Examples 290-293 relate to assessing the additional impact of sodium salt on thermal stability depending on the pH. As before, the liquid of Example 261 is used as a standard. In each case, the pH was adjusted to 8.5 with NaOH, and then add the specified amount of sodium acetate.Example 290 - Example 261 (NaAc missing)
Example 291 - 0.25 g NaAc (post-addition)
Example 292 - 0.50 g NaAc (post-addition)
Example 293 - 0.75 g NaAc (post-addition)
All samples subjected to thermal aging at 95oC for 6 days. Achiev the ion of an alkali metal significantly improve thermal stability of the liquid at pH 8.5, effectively making it the same stable as the liquid with a pH of 9.5 (without alkali metal ion).Examples 294-296 relate to the evaluation of thermal stability of the fluid at colouring, and evaluating the dilution water. A portion of the liquid in 2000, prepared in accordance with Example 261 at pH of 9.5, stained with 0.2 g of Cartasol yellow (Cartasol Yellow 3GF) and 0.05 g Blue 6825-2 (Blue 6825-2). Diluted net liquid water in ratios of 75/25 and 50/50 by volume and conduct the test on the stability in an oven at 95oWith within 30 days. For pure (undiluted) liquid test stability is carried out in an oven at 70oWith within 30 days. The results are shown in Table VII.With regard to Table VII, the undiluted liquid of Example 294 would be useful for use either as an aircraft fluid type II (Type II), or as a fluid type IV (Type IV) to prevent icing. (Test SAE - test of the American society of automotive industry and transportation provides viscous losses are not more than 20% in 30 days at a temperature of 70oC). The 75/25 dilution would be useful for its application as a liquid de-icing I type. (Requirement SAE test for time Yu more effective surfactants in comparison with the used in the previous Examples, namely "Ingredient S". To do this, prepare a control composition (see table. 1).Additional compositions are prepared according to the recipe of Example 303, as shown in the Examples 297-302. Tests are normal and the results are presented in Table VIII.In the Examples 297-303 surfactant N represents a 5-6-molar ethoxylate of Nonylphenol supplied by the company Union carbide, USA, under the trade name Triton (TritonRN-57).Although the invention is illustrated by several examples, it does not restricted by them. Rather, the invention covers the General area, as it is disclosed in the present description. Can be carried out various modifications of the invention and examples of its implementation, however, without deviating from the essence and scope. 1. The composition for treatment of aircraft, designed to eliminate or prevent it from icing with water glycol or glycerine solution, gelled polymeric thickener and/or its salt after neutralization, taken in an amount sufficient to gel the composition to conditions, to ensure its adhesion to the surface of the aircraft, nahodyawegosya, moreover, the specified thickener includes the following components (wt.% the total weight of the latter): (A) 1-99,9% of one or more -,- unsaturated carboxylic acids with monoethanol communication; (C) 0-98,9% of one or more unsaturated monomers with monoethanol communication; (C) 0.1 to 99% of one or more unsaturated monomers with monoethanol connection, preferably of macromonomer containing at least one hydrophobic side fragment; and (D) 0-20% of one or more unsaturated monomers with plastic ties; and the said composition comprises the following components in wt.% 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 the thickener; (3) a neutralizing agent comprising sodium hydroxide, in a quantity sufficient to provide a pH of at least about 7.1; (4) a surfactant, which forms associate with a thickener in an amount sufficient to enhance the thickening effect of the thickener; (5) optional corrosion inhibitor in an effective amount; (6) optionally one or more colorants; and (7) water the rest.2. The composition according to p. 1, characterized in that the pH possessing octyl or nonylphenolethoxylate.4. The composition according to p. 1, characterized in that it further includes a weak auxiliary base in a quantity at least, of 0.0005 wt.% the total weight of the composition.5. The composition according to p. 4, characterized in that the auxiliary base is a salt of an alkali metal.6. The composition according to p. 5, characterized in that the alkali metal salt is an acetate or phosphate.7. The composition according to p. 1, characterized in that the hydrophobic fragment is a complex hydrophobic group.8. The composition for treatment of aircraft, designed to eliminate or prevent it from icing with water glycol or glycerine solution, gelled polymeric thickener and/or its salt after neutralization, taken in an amount sufficient to gel the composition to conditions, to ensure its adhesion to the surface of the plane is at rest, but at the same time ensuring its destruction under the action of shearing forces of the wind during takeoff, and the specified thickener includes the following components, wt.% the total weight of the latter: (A) 1-99,9% of one or more -,- unsaturated carboxylic acids with one or more unsaturated monomers with monoethanol communication, preferably macromonomer containing at least one hydrophobic side fragment; and (D) 0-20% of one or more unsaturated monomers with plastic ties; and the specified composition is produced by mixing the following components, taken in wt.% 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 a quantity sufficient to provide a pH of at least about 7.1; (4) a surfactant, which forms associate with a thickener in an amount sufficient to enhance the thickening effect of the thickener; (5) optional corrosion inhibitor in an effective amount; (6) optionally one or more colorants; and (7) water the rest.9. The composition according to p. 8, characterized in that the pH is 8.5 to 9.5.10. The composition according to p. 9, characterized in that the surfactant is octyl - or Nonylphenol-ethoxylate.11. The composition according to p. 8, characterized in that it further includes a weak auxiliary base in a quantity at least, of 0.0005 wt.% the total weight of the composition.13. The composition according to p. 11, characterized in that the alkali metal salt is an 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, wherein 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 includes Amin.18. The composition according to p. 17, wherein the amine is monoethanolamine.19. The composition according to p. 8, characterized in that it further includes Amin.20. The composition according to p. 19, characterized in that the amine is monoethanolamine.21. The method of obtaining the composition of p. 1, comprising the following stages: (a) preparation of the concentrate by adding, with stirring, surfactant and thickener for water-glycol or a water-glycerin mixture used as solvent, taken in an amount of 1-20 weight. % of total required number is receiving, sufficient to obtain a homogeneous suspension; (C) adding with stirring a neutralizing agent to the suspension (b), followed by stirring, sufficient to obtain a homogeneous solution.
FIELD: road servicing industry.
SUBSTANCE: the invention is dealt with the road servicing industry, in particular with the methods of extirpation of ice covering on motorways, bridges, flyovers, and also aerodromes. The method of the roadway covering slipperiness prevention provides for application of a roadway ice covering suppressing reactant based on acetate, in the capacity of which use a solution with pH=7-9.5, containing components in the following ratio (in mass %): magnesium acetate 13-17, potassium acetate 8-16, potassium hydrocarbonate 5-8, potassium carbonate 2-6, water-insoluble impurities 0-6, water - the rest. The roadway ice covering suppressing reactant may additionally contain a fired limestone in amount of 3-5 mass % in terms of calcium oxide. The method of production a roadway ice cover suppressing reactant for a roadway covering slipperiness prevention provides for mixing of a component containing a magnesium compound, iced acetic acid and water, in the capacity of the component containing the magnesium compound is used brucite, the stirring is exercised in two stages: first they continuously agitate brucite with water and a part of iced acetic acid in a stoichiometric ratio at the temperature of 50-70°C within 50-80 minutes, then, not terminating mixing at the same temperature in the produced mix with pH=5-6 add the rest of ice acetic acid and then add potash in amount exceeding by 0.1 - 6 % the stoichiometric ratio and continue agitation till production of the roadway ice cover suppressing reactant - a solution with pH = 7-9.5 with the above indicated composition. The used roadway ice cover suppressing reactant has composition mentioned above. The technical result consists in - maintenance of the low temperature at the reactant usage, ensuring the passing ice covered roadways motor vehicles metal corrosion protection and at use as the airfield runways coatings - the corrosion protection of metals used in aircraft designs as well. The roadway coating treated with the reactant has a high coefficient of adhesion, that reduces the accident rate on the roadways.
EFFECT: the invention ensures, that the roadway coating treated with the reactant decreases the accident rate on the roadways.
6 cl, 2 tbl, 4 ex
FIELD: chemical industry.
SUBSTANCE: invention relates to preparations used for prevention and removal of snow-ice formations in roads. An anti-glaze of ice preparation comprises the following components, wt.-%: calcium chloride, 15-50; sodium chloride, 48.5-83.5; potassium ferricyanide, 0.2-0.5, and sodium dihydrogen phosphate, 0.3-1.0. Anti-glaze of ice preparation in granulated form is resistant against caking, inhibits corrosion of metals and reduces inhibitory effect of chloride on plants.
EFFECT: improved and valuable properties of preparation.
FIELD: special reagents.
SUBSTANCE: invention relates to substances for applying on surface to prevent or diminish adhering ice, mist or water on it, for prevention of icing, in particular, to anti-glaze of ice reagents. The composite comprises the following components, wt.-%: calcium chloride, 25-32; urea, 2-7; sodium nitrite, 0.03-1.0, and water, the balance. Invention provides preparing the composite harmless for environment that doesn't show harmful effect on environment, doesn't corrode road coatings, and inhibits corrosion of metals. Agent shows economy and high effectiveness.
EFFECT: improved and valuable properties of reagent.
2 cl, 1 tbl
FIELD: road-transport industry.
SUBSTANCE: method includes applying substance on asphalt-concrete mixture. As substance silicon-organic modifier is used, loss of which at 1 m2 of area of pre-placed on road asphalt-concrete mixture at temperature 80-100°C is no less than 0,3-0,5 kg. After applying modifier, asphalt-concrete mixture is rolled.
EFFECT: higher efficiency, no corrosive effect on metals, effective at temperature above -20°C.
2 cl, 3 tbl, 3 ex, 1 dwg
FIELD: domestic chemistry.
SUBSTANCE: invention relates to agents using against misting and icing windshields in transports, sight glasses in agent of individual protection and can be used in living conditions for prevention showcase glasses icing. The composition comprises the following components, wt.-%: polyoxyethylene glycol ester of synthetic primary higher alcohols of (C12-C14)-fraction as a surface-active substance, 6-25; urea or thiourea, or mixture of urea and thiourea, 1-20; glycerol, 5-25; ethylene glycol, 5-41; dye, 0.0005-0.02, and a solvent, the balance. Propyl alcohol as propanol-1 or propanol-2 can be used as a solvent. The composition elicits an anti-misting and anti-icing properties, provides two-sided protection of sight glasses of transport agents and agents of individual protection in cooling the protecting glass surface up to -40°C, elicits the prolonged protective effect, it doesn't solidify at the environment temperature below -40°C and doesn't require the special technical devices for its applying.
EFFECT: valuable properties of composition.
3 cl, 1 tbl, 10 ex
FIELD: Composition of an anti-icing water solution for roads surface treatment.
SUBSTANCE: the invention is pertaining to production of composition of an anti-icing water solution for roads surface treatment against a winter slipperiness (snow rolling-ups, a glaze ice, black ice) n the roads and streets in cities and settlements. The composition contains, in mass %: 20-27 calcium chloride, 5-30 ethyl alcohol, 0.3-5 corrosion inhibitors (borax or sodium nitrite or their mixture), the rest - water. The technical result is - an increase of effectiveness of the composition application, an increase of friction coefficient due to a decrease of the ice density, a raise of the composition ice melting capacity.
EFFECT: the invention ensures an increase of effectiveness of the composition application, an increased friction coefficient and a decreased ice density, a raise of the composition ice melting capacity.
1 cl, 1 ex, 2 tbl
FIELD: materials for miscellaneous applications.
SUBSTANCE: grain mixture comprise, in mass %, 15-45% of compressed first salt of alkaline or alkaline-earth metal and 85-55% of the second salt of alkaline or alkaline-earth metal. The first salt is a waterless hygroscopic salt.
EFFECT: reduced cost.
14 cl, 4 dwg
FIELD: preventive means against freezing and sticking of loose materials to walls of mining and transport equipment; prevention of dusting on interim roads, open-cut mining; protection of rolling stock against freezing and blowing-off of loose materials, coal and peat for example.
SUBSTANCE: preventive means is made in form of mixture of solvent and thickening additive of oil nature. Used as solvent are distillation residues of coke and by-product process and/or by-products of production of butadiene, isoprene, isobutylene, ethylene both independently and in mixture with distillation residues of production process of polymers, pyrolysis residues, benzene, styrene and distillation residues of production of butanol, isobutanol, 2-ethyl hexanol acid and 2-ethyl hexanol. Solvent may additionally contain gas oils of thermal and catalytic cracking and gas oils of coking process. Used as thickening additives are mineral and synthetic oils of all kinds, mixture of used oils, oil sludge, oil residues and oil fuel. Components of thickening additive and solvent are used at any combination. Novelty of invention is use of wastes of various processes of oil and petroleum chemistry products.
EFFECT: extended field of application; cut costs; enhanced ecological safety.
5 cl, 1 dwg, 2 tbl, 17 ex
FIELD: suppression or reduction of icing on surfaces by means of antiicing compounds.
SUBSTANCE: proposed anti-icing compounds contain succinic acid and/or succinic anhydride and neutralizing base, sodium hydroxide, potassium hydroxide or ammonium hydroxide in particular. When mixed with water anti-icing compounds form succinates in the course of reaction which causes fast liberation of heat sufficient for melting ice on surface. According to other versions, anti-icing compounds contain glycol which inhibits repeated icing on cleaned surface. Specification gives description of sets of compounds for melting snow and ice.
EFFECT: enhanced efficiency of melting snow and ice on aircraft and territories of their operation.
29 cl, 11 dwg, 7 tbl, 2 ex
FIELD: motor-car industry; other industries; methods of production of the anti-icing reactant.
SUBSTANCE: the invention is pertaining to the method of production of the anti-icing reactants for maintenance of roads in winter. The method of production of the anti-icing reactant based on sodium chloride and calcium chloride provides for mixing of the sodium chloride with calcium chloride and their heating and drying. Sodium chloride crystals are coated with the atomized solution of calcium chloride and dried in the "boiling bed" kiln with production of the double-layer granules, the outer layer of which is composed out of calcium chloride. Sodium chloride crystals are coated with calcium chloride in two phases. The forming small particles of calcium chloride are fed into the cyclone, whence the cyclone dust of the calcium chloride is fed into the mixer for intermixing with the wet crystals of sodium chloride. The produced anti-acing reactant has the improved physicochemical thermodynamic properties.
EFFECT: the invention ensures, that the produced anti-acing reactant has the improved physicochemical thermodynamic properties.
3 cl, 1 ex, 2 tbl