DE2002046A1 - Thickened hydrocarbon preparation and process for its production - Google Patents

Description

This invention relates to thickened aliphatic hydrocarbons and particularly relates to liquid aliphatic hydrocarbons having a low Amount of a polymeric additive are thickened. Besides the invention relates to a method of manufacture such preparations and on the Verdiekungsaittel.

For sahireich® areas of application it is of interest to thicken liquid aliphatic hydrocarbons. A particularly interesting field of application for such thickened hydrocarbons is the use of thickened fuels in internal combustion engines, such as aircraft doors, automobile engines and the like. By using thickened. Fuels are the Fire hazards significantly reduced if a fuel tank is hit by a shock, e.g. B. in a collision or also destroyed by a gunshot. The requirements for such a thickened fuel are contradicting each other to a certain extent, as it is an ideal fuel for such mechanical damage to the Tank should be a bold and cohesive material that does not break apart in the event of a shock, and neither does it in a different way. However, in order to direct the fuel into the engine, it must be pumped and through lines from the tank under the influence of the Gravity springs IMSt. Therefore it should be a suitable one Fuel has a viscous or gelatinous texture have, if it is not subjected to visual stress,

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and but behave essentially like a liquid when a shear force, as it is e.g. B. caused by a propellant off puape is applied. The thickened fuel should expediently under the influence of the Gravity flow like a liquid at a rate sufficient to, among other things, allow the fuel to drain from the fuel tank at a rate at least equal to the rate of fuel consumption. When using thickened In propellants, it is very desirable that minimal amounts of such thickeners be used and that all Components of the fuel mixture are volatile under the combustion conditions and that the system is essentially is free of metal ions that promote sulphide formation in internal combustion engines. Such fuels are la general hydrocarbon preparations and preferably aliphatic hydrocarbon preparations. As used herein, the term "aliphatic hydrocarbons" is inclusive aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and mixtures thereof.

Aliphatic hydrocarbons that can be used in the invention include compounds that are either branched or linear and saturated or unsaturated can be, such as B. propane, butane, pentane, hexane, heptane, Octane, nonane, decane, dod "* ear." Propene, butene, 1,3-butadiene and isoprene. Examples of suitable eye1 © aliphatic Hydrocarbons which can be thickened or gelled according to the invention are cyclopentane, 1,1-dimethylcyclopentane, ljS-diaethylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 2,4-diraethylcyclohexane.

Other substances that can be gelled according to the invention, • ind those who have solubility parameters from about 6.8 to 11 have. Solubility parameters are from Hildebrand and Scott in "Solubility of Non-Electrolytes", Reinhold (1950) and by H. Burrell in "Solubility Parameters", Intercheeical Review, Volume 14, pages 3 and 31 (1955). Solubility parameters of different hydrocarbons substances are given in the following:

009831/1549 bathroom

- 3 - Isobutylene • 6.7 2002046 Scented petroleum ether 6.9 Pentane 7.0 Hexane ■ 7.3 Heptane 7.4 Octane 7.6 Methylcyclohexane 7.8 turpentine 8.1 Kerosene 8.2 Cyclohexane " 8.2 Dipentane 8.5 Pine Cl 8.6 Carbon tetrachloride 8.6 Naphtha (high flash) 8.7 ■ Xthy! Benzene 8.8 Xylene 8.8 toluene 8.9 benzene 9.2 Tetralin 9.5 Monochlorobenzene 9.5

In addition, mixtures can also be used as hydrocarbons which essentially contain one or more substances from the above classes of hydrocarbons. Such mixtures can be obtained by distillation or alkylation of petroleum or crude oil raw materials. Examples are petroleum ether, gasoline, petroleum, ligroin and motor oil. Of particular interest are those petroleum distillates that are commercially available as fuels, such as those obtained under the trade name ^M Jet-A ^st and "Jet-B", both of which can be used with or without anti-icing additives. Other suitable fuels which can be thickened according to the invention are turbine fuels. The hydrocarbons to be thickened should not be dehydrated, but should contain the usual traces of water that occur in commercial products.

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In accordance with the present invention, such hydrocarbon materials are thickened by uniformly adding 0.2 to 10% by weight of a synthetic hydrocarbon material in the hydrocarbon material organic polyaers that are soluble in the hydrocarbon is distributed. This polymer should advantageously be at least 0.2 to 3 percent by weight, based on the weight of the polymer, of an oxygen-containing polar compound from the Contain a group of olefinically unsaturated polymerizable compounds from the following group: (a) acids old up to 6 carbon atoms, such as acrylic acid, methacrylic acid, itaconic acid and citraconic acid; (b) Amides with up to 4 carbon atoms such as acrylamide and mixtures thereof; (c) Hydroxy-acrylic esters, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 3-hydroxypropyl acrylate; (D) sulfonic acids, such as 2-sulfoethyl ethacrylate, 2-sulfoethyl acrylate, 3-vinylbenzenesulfonic acid, 2-benzenesulfonic acid and the like.

Suitable oil soluble polymers that can be used in the present invention include alkyl styrene polymers a, which can easily be prepared by copolymerization of alkylstyrene ■ onoaeren old the oxygen-containing polar compounds, the alkylstyrenes having alkyl groups with 3 to 20, preferably 4 to 12, carbon atoms. Polyaers made from mixtures of styrene monomers are also suitable, which contain an average of at least 3 and not more than 20, preferably 4 to 12, aliphatic carbon atoms per aromatic ring. Examples of thickening polymers of alkyl styrenes include the following polymers: Polymers of tertiary alkyl styrenes such as p-tertiary butyl styrene, p-tertiary ayl styrene, p-tertiary hexyl styrene, p-tertiary octyl styrene, p-tertiary dodecyl styrene, p-tertiary octadecyl styrene and p-tertiary eicosylstyrene; Polyaers of n-alkylstyrenes, such as n-butyletyrene, n-arylstyrene, n-hexylstyrene, n-octyl- • tyrene, n-dodecylstyrene, n-octadecylstyrene and n-eicosylstyrene; Polyaere of sec-alkylstyrenes like sec # -butylstyrene, • ek.-hexylstyrene, sec.-octylstyrene, sec.-dodecylstyrene, • ek-octadecyl styrene and sec-eicosyl styrene; Polyaere of Isoalkylstyrenes, such as isopropylstyrene, isobutylstyrene, isohexylstyrene, isooctylstyrene, isododecylstyrene, isooctadecylstyrene and isoeicosylstyrene and copolymers of such monoesters and also copolymers of such alkylstyrenes with Styrene and / or vinyl toluene, e.g. B. a copolyester of

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p-tert-butyl styrene and styrene in a molar ratio of at least 75-25, which contains 1% acrylic acid polymerized; a copolymer of n-amylstyrene and styrene in a ratio of at least 60:40, which contains 1% polymerized itaconic acid; a copolymer of n-hexylstyrene and styrene in a molar ratio of at least 50:50, containing 1% of incorporated citraconic acid < a copolymer of sec-dodecylstyrene and styrene in a molar ratio of at least 25:75, containing 1% of polymerized acrylamide; a copolymer of isoeicosylstyrene and styrene in a molar ratio of at least 15:85, which contains 1% of copolymerized itaconic acid; a copolymer of p-tert-butylstyrene and vinyltoluene in a molar ratio of at least 67:33, which contains 1% acrylic acid polymerized into it; a copolymer of sec-amylstyrene and vinyltoluene in a molar ratio of at least 50:50, which contains Tk polymerized-in methacrylic acid; a copolymer of n-octylstyrene and vinyltoluene in a molar ratio of at least 29:71, which contains 3% methacrylic acid incorporated as a polymer; a copolymer of n-dodecylstyrene and vinyltoluene la molar ratio of at least 19:81, which contains 0.5% acrylic acid and a copolymer of sec.-octadecylstyrene and vinyltoluene in a molar ratio of at least 12§88 and 1.5X citraconic acid, alkyl acrylates such as lauryiacrylate, Di-2-ethylhexyl acrylate, stearyl acrylate either as homopolymers or copolymerized with an alkyl styrene. When alkylstyrenes are used, it is particularly convenient to include therein up to 500 parts of isopropenylvinylbenzene per million parts of the alkylstyrene, preferably 300 parts of isopropenylvinylbenxene per million parts of the alkylstyrene. The presence of the isopropenyl vinyl benzene in the alkyl styrene prior to polymerization increases the gelatinizing and thickening properties of the resulting polymer.

Suitable polar compounds include acrylic acid, methacrylic acid, Acrylamide and itaconic acid, which are present in amounts of about 0.2 to 3% by weight of the polymer introduced into the reactor isicrharic components can be used. If less used as 0.2% of such monomers with the alkylstyrene. no suitable thickeners are created. If the If the content of polar compounds is higher than 3%, the thickening effect suffers. The best results will be in the field from 0.5 to 1.5% by weight of polar compounds.

009031/1849

The polymers used in the invention are conveniently prepared by enulsion polymerization, wherein Usual procedures for emulsion polymerization are used will. However, it is essential that in manufacturing such polymers do not use surfactants, catalysts or other additives Introduce MetalHonen into the system. Therefore ammonium or amine salts of sulfonated fatty alcohols are preferred, Alkyl aryl sulfonates, long chain fatty acids such as lauric acid, palmitic acid and stearic acid are used.

In making the thickened propellants of this invention, it is essential that non-volatile components are strictly avoided. "Non-volatile components" are those components which, as components or as thermal decomposition products, boil ^{above 400 ° C. during the oxidation.} For example, it is essential that effective amounts of materials are excluded which may contain e.g. B. contain sodium, calcium, or iron, which, when oxidized , tend to form solid deposits. The gelling or Verdickyagseigenschaften of the polymer are indeed increased ions forming materials by the addition of but form the cation and the anion of the ionizable material is to be · vei fluchtigbar in the oxidation of the fuel. As a result, basic Kata Ulicui such as ammonium hydroxide and organic bases are very well suited for the formation of such ionizable materials. Examples of suitable organic lasers are tetramethylammonium hydroxide or other organic bases such as amines with up to 10 carbon atoms, including primary, secondary and tertiary amines, and high ammonium salts of compounds such as methyl amine, ethylamine, butyiamine, diethylamine, ethyleneamine, n-octylamine, Aniline, N-methylaniline and guanidine. By adding the basic materials to polymers having acid or hydroxyl groups, the change in viscosity over time is generally prevented or substantially reduced. If the addition of de-icing agents, such as ethylene glycol, is desired, maximum thickening characteristics are achieved by adding the basic * material. As a rule, the base is added in such amounts that a concentration of 2.5 × to 0.5 molar solution is obtained. ^ as & is obtained in the thickened hydrocarbon. In general, optimum thickening is achieved when the concentration of the base is about 10 ^-3 to 10 ** ⁴ molar, if aqueous ammonia is used as the base.

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BATH ORIGINAL

By adding such materials as sodium hydroxide and sodium lauryl sulfonate will indeed cause gelation and thickening of hydrocarbons with satisfactory rheological. , Merkaalen, but such fuels tend to in an engine with an internal combustion turbine, such as in a jet engine, to form deposits, and according to a'relative short period of time the engine has occurred because of Sulphidation, often referred to as "Black Plague", unusable and needs to be overhauled. Small amounts of water, added to the thickened hydrocarbon and polymer preparations increase the thickening. However, such an increase in thickening disappears within a certain period of time, usually around 24 hours.

The catalysts used for the polymerization reaction are substances such as ammonium persulfate, which form volatile oxidation products when they oxidize in the presence of a hydrocarbon which is liquid under normal conditions. will. For this reason, ammonium persulfates and ammonium perborates, hydrogen peroxide, organic peroxides and hydroperoxides, such as benzoyl peroxide, t-butyl peroxide and t-butyl perbenzoate, are expediently used as catalysts in the polymerization. Azo catalysts such as azobisisobutyronitrile are also suitable. The catalysts are generally used in an amount of 0.05 to 1%, based on the weight of the monomer; amounts of 0.1 to 0.5% are preferred. Qie emulsion polymerization is advantageously carried out by using a suitable mixture of mono- 'mers, catalyst and water is heated temperature to the desired polymerization, wherein used is usually from 40 to 1o0 ° G and preferably from ^ SCT to 100 ⁰ C. The solids content of the latex * that forms becomes J | expediently kept at 30 to 50% by weight and preferably at about 40% by weight. The polymerization is preferably carried out in an aqueous medium at a pH of 3 to 6. In general: it is advantageous to adjust the pH to a value of 4.2 by adding a volatile base such as aqueous or anhydrous ammonia. Alternatively, quaternary ammonium compounds, such as tetramethylammonium hydroxide, or ammonium salts, such as ammonium carbonate and ammonium bicarbonate, can be used with good results. -

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The polymers of the present invention are used with particular advantage for the thickening of liquid hydrocarbon fuels. Movable and volatile hydrocarbon fuels, such as fuels for jet or turbine engines, diesel fuels and gasoline, can thereby be converted into viscous liquids by incorporating 0.2 to 5% by weight of the polymers according to the invention in these fuels. It is expedient to use 0.5 to 3% by weight and advantageously 0.75 to 2.5% by weight of the polymers according to the present invention. By increasing the viscosity of such fuels, the flammability of the fuels is significantly reduced in the event of a crash or other damage to the fuel tank. The exact mechanism of such a reduction in flammability is not known and it is not clear whether this effect occurs because of the high viscosity of the liquid and its resistance to the formation of small droplets or whether this is due to the lowering of the vapor pressure of the liquid fuel, a lowering of the Evaporation rate or a combination of all of these factors or a combination of all of these factors with other unknown factors. It appears that the flash point of the fuel formulation is increased by the thickeners of this invention. The thickened propellants of the present invention are liquids which can be pumped and which can be transported in conventional fuel containers and delivery means of vehicles and stored in conventional fixed storage containers. The more thickened propellants of the present invention are propellants that are thixotropic, clear to slightly cloudy liquids. When subjected to shear, they show an almost instantaneous reduction in viscosity and, when the shear is removed, almost instantaneous restoration of the measured apparent viscosity. The higher thickened propellants of this invention appear as gels, which are often tough, sticky and coherent in nature. If the thickened solutions show the structure of a real gel, they have a yield point that is too low to withstand gravity for long periods of time. When a more thickened solution according to the invention moves e.g. B. if it is shaken in a closed container, it shows a restless, lumpy surface afterwards, with parts of the fuel sticking irregularly to the rare walls of the container. The solution also has features that can be assigned to a gel, like a certain graininess. However, if the solution is for relatively short periods of time, it generally has the characteristics

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paint a liquid. When you have a container, the one such a thickened solution contains repeatedly in such a way that the underside of the container turns or rotates kooat upwards so that air bubbles appear in the solution, gives the impression that the material is a gel; the bubbles slowly rise to the surface of the liquid and the contents of the container do not increase over time Appearance of a liquid. A rapid rotation of the container about a quarter and one turn stopping quickly indicates that the material is viscoelastic is. A generally circular oscillation of the liquid occurs after the container moves to the Has been brought to a standstill. A bubble that rises in the thickened material often moves with one irregular speed, suggesting that coherent areas exist within the solution. When you get parts of the thickened liquid out of the container When you remove them and place them on a flat surface, they appear as a gel at first, but transform when you stand into a liquid mass within a few minutes. Such Appearances depend on concentration and time; as the concentration decreases, the means that it approaches 1%, the gel-like features recede and tend to disappear; if against As the concentration of the polymer in the hydrocarbon is increased, such features appear more pronounced. if the viscosity of such solutions with a "Brookfield Viekometer "measures and against the logarithm of the shear rate plots, a linear curve is obtained from which it can be seen that the solution is a liquid and not is a gel, less thickened liquids according to this invention range from viscous to liquid, if Concentrations of the polymer used can vary approach the minimum values, and generally have the appearance and characteristics of a real gel. To that extent how to increase the concentration of the thickener, there is a gradual transition from the state that a pure liquid seems to be up to a stronger one thickened solution with the properties already described here.

00983171549

Of particular interest and advantage are thickened, liquid and combustible fuels which contain a higher proportion of an oxidizable liquid hydrocarbon by uniformly a polymeric agent is dispersed or distributed, this preparation having a viscosity in the range given in Table I. Has. The viscosity is measured using a “Brookfield Viscometer model RVT "measured at 22.78 ± 0.8 <> C.

TABEL I. RPM 5 Spindle No. 6 maximum minimum Spindle No. 4 5 viscosity viscosity RPM Maximum minimum centipoise centipoise Viscosity viscosity O, 500,000 10,000 centipoise centipoise 2, IJO 000 5,000 5 50,000 2,000 10 50,000 2,500 20th 20,000 8,000 100 5,000 100

For use in internal combustion engines, in particular Turbine-jet engines are particularly advantageous formulations that have an apparent viscosity of 7,500 to 20 centipoise h & bsn, measured at lORPM with a spindle no. in a "Brookfield Viscometer Model RVT" at 22.78 <> C - 0.8 ° C. These preparations are able to flow under the influence of gravity and are also substantial free of ionizable materials which lead to the formation of non-gaseous combustion products when the Preparation is oxidized or burned with air. The fuel preparation advantageously contains 0.5 to 5% by weight of the polymeric thickener and especially preferably 0.75 to 2.5 wt.

The thickened hydrocarbons according to this invention Le * • I can easily be prepared by dispersing the specific polymers * according to the invention in the hydrocarbon. in the In general, it is desirable to incorporate the polymer into the liquid hydrocarbon using agitation to disperse high shear, e.g. B, in a colloid mill or high shear stirrer such as one Centrifugal pump, gear pump, propeller mixer or disc mixer with fluted edges. If necessary · there · can · solve

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BATH

al ■ - ^: ■■■. -. ■■ ■■■■ · ■■■■ ■■

⁵ '- ii -. ■ "20020A6

or dispersing can be accelerated by heating. Under the influence of movement, the dispersion or solution appears fluid. But when the movement is ended, they kick gel-like features in appearance. It is therefore advantageous for numerous applications to use the thickening polymer in In the form of fine particles or of fine agglomerations of particles, such as those obtained by spray drying or Drying a latex * or an aqueous suspension of the Polymers at a temperature below the film formation temperature of the polymer can be obtained in a cabinet dryer, drum dryer and the like.

If in a particular application for the thickened hydrocarbon the presence of a small amount of water is permissible, the latex of the polymer can be incorporated directly into the hydrocarbon with stirring or other agitation. Such a measure does not significantly impair the thickening effect. When a latex of the thickening polymer is incorporated into a hydrocarbon, it is generally advantageous to use vigorous stirring at high speed. The water-containing mixture usually has a clearly recognizable turbidity, which is different from the clear to slightly cloudy appearance of solutions or dispersions which have been prepared with a dry, thickening polymer. If necessary, such a water-containing thickened preparation can be freed from water if the dispersion of the latex and the hydrocarbon is subjected to a reduced pressure and the water is fractionally distilled off from the system. In general, it is desirable not to increase the temperature above 80 ⁰ C .to, otherwise the thickening effect can be lowered to. may be based on the dehydration of the system to remove traces of water which can normally be found in such hydrocarbons of commercial purity.

Usually an optimal thickening is achieved by a concentrated dispersion of the polymer in a Hydrocarbon produces and then through Add more hydrocarbon material as desired Solids content diluted - by adding alcohols, such as methanol, butanol, and ethylene glycol, become the apparent Viscosity of the thickened hydrocarbons and their flow characteristics changed. Usually the addition of alcohols results in a gel-like thickened hydrocarbon Newton's view or almost Newton's view flow behavior.

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The invention is explained in more detail in the following examples.

example 1

A reactor equipped with a stirrer and a jacket is charged with 82 parts by weight of deionized water and 0.0264 parts by weight of Ethyiendiarain-tetraacetic acid. The reactor is closed and the gases contained in it are evacuated until an absolute pressure of about 127 mm of mercury has been established. While stirring is continued, normal pressure is restored by adding nitrogen. This displacement procedure is repeated to remove the air from the reactor. 0.164 parts by weight of a 28% strength aqueous ammonium hydroxide solution are then introduced into the reactor and nitrogen is added until an overpressure of 0.35 kg / cm 2 has been established. The contents of the reactor are heated to 98 ° C. and 56 parts by weight of a monomer mixture are added. The monomer mixture is prepared by mixing 65.4 parts by weight of t-butyl styrene and 0.1 part by weight of methacrylic acid. A catalyst mixture is produced by dissolving 0.154 parts by weight of ammonium persulfate in 6 parts of water. Two parts of the catalyst mixture are added to the reaction mixture. The reaction mixture is maintained at 98 ° C by introducing steam and water into the jacket of the reactor. An exothermic reaction can be recognized by a rise in the temperature in the water in the mantle. After a period of 45 minutes, when the temperature of the water in the jacket has risen to 98 ° C, 0.5 parts by weight of the ammonium persulfate solution are added to the reaction mixture and the reaction continued until the cooling water in the jacket and the reaction mixture both have one Show temperature of 98 ° C. The reactor is then vented to the atmosphere. The reaction mixture is a latex with a solids content of 40% by weight and a particle size of about 2,600 angstroms. The reaction mixture is cooled to J0 ° C., filtered to remove the coagulate and the polymer obtained by drying in a drying cabinet Worked up at a temperature of 60 ° C. The dried material is an easily breakable cake that can easily be; crushed to a fine powder. Parts of this FoJymr-ion are dissolved in a "Kohi enwasbt'rsLoi ί 'mixture, which is commercially available as fuel for 1.Hi ε Ott ί.lug; - * υΐ', ο under the name"Jt't-A"receives hay irt. F. ine ? ¹ " Λγα. solution of rolynia

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BAD OBlGiNAL

In this fuel there is a tough, fibrous, gel-like solution with a viscoelastic appearance. With a "Brookfield Viscometer" is made using the spindle No. 6 at 10 revolutions per minute has a viscosity of 15,000 to 25,000 measured. If you have a 3% solution of the Polymers in the fuel, the solution has one. Viscosity from 40,000 to 50,000 centipoise. The viscosity ranges indicate the ranges that are obtained at Use of different batches of fuel.

Example 2

The polymerization procedure of Example 1 is repeated with the exception that 2 parts of the catalyst solution was added to the reactor just before the addition of the 56 parts of the monomer mixture be admitted. The polymer is worked up by drying and its thickening ability is increased Dissolving the polymer in different samples of "Jet-A" Jet fuel determined. There are viscosities of 15,000 to 20,000 centipoise measured, the procedure characterized in Example 1 with a spindle no. used at 10 RPM.

The latex is divided into a variety of samples. Table 2 provides information on the type of material that was added to the latex, the amount and weight percent of the polymer in ^M Jet-A "fuel and the viscosity of the solutions obtained ° C. for a period of 18 hours The dry polymer obtained is comminuted in a mortar and added to the fuel.

% More active TABLE II viscosity additive Additive (!) % Polymer Cp, (2) control in fuel 60 none 0.05 1.25 100 NH ₄ OH 0.14 1.25 100 NH ₄ OH 0.28 1.25 400 NH ₄ OH 0.56 1.25 300 NH ₄ OH 0.10 1.25 2,000 TNAH (J) 0.20 1.25 2,000 TMAH 0.40 1.25. 7,000 TMAH 0.60 1.25 7,000 TMAH 1.25 009031/1549

(1) »based on polymer

(2) - Spindle # 6 at 10 RPM

(3) »Tetramethylammonium hydroxide

Parts of the polymer are used to make 3% solutions using the various solids. The results are shown in Table III.

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solvent on (I) TABLE III Description . Trimethylpentane 6.85 Viscosity (2) * like gelatinous applesauce tt-Peiatan 7.0 4,000 Solid gel n-hexane 7.3 6 500 Solid gel n-haptam 7.45 27,000 Solid gel n-Qctan ■ 7.55 36,000 Solid gel ■ ISQ octane 7.55 48,000 Solid gel Ne can 7.7 22,000 Solid gel Cyclohexane 8.2 35,000 Solid gel- wetted viscoelastic ■ ^: "; O
^: 'O toluene 8.93 55,000 · *
viscoelastic ' ¹ CD
CO benzene 9.15 3b 000 viscoelastic ■, o-dichlorobenzene 10.0 35 000 ^f viscoelastic Nitromethane ; 12.7 70,000 Polymer does not disperse • cn no thickening · ■ -to

ta

(1) = solubility parameters

(2) - Brookfield Viscometer Model LVF No. 4 spindle at 6 RPM

*. = Appearance of a commercial apple sauce, (apple sauce gel)

l-O CD

IV) 'CD 4> CD

Example 3

The reactor, equipped with a stirrer and jacketed, is charged with 856 parts of deionized water. The reactor is closed and absolutely evacuated to a pressure of about IJO milliliters of mercury, filled with nitrogen up to the level of atmospheric pressure and this cleaning operation with nitrogen was repeated twice more. The water in the reactor is heated to 98 ° C. with stirring heated and there are 1.2 parts by weight of ammonium persulfate and 1.8 parts by weight of a 28% aqueous ammonia solution admitted. The monomer is immediately introduced into the reactor. The monomer mixture consists of 596 parts by weight t-butyl styrene and 0.67 parts by weight methacrylic acid. Of the Reactor contents are held at 98 ° C for a period of 15 minutes after the jacket temperature has increased to 98 ° C has risen. The reaction mixture is cooled and vented to the atmosphere. The reaction mixture has the Form of a latex * with a particle size of about 1,400 angstroms. The conversion of the monomer to the polymer is 95%. The polymer is worked up by drying in a drying cabinet. A 3% strength solution of the polymer obtained in "Jet-A" fuel is prepared, the solution forms a tough-fibrous, gel-like liquid with a viscosity of 31,000 centipoise using a Spindle No. 6 at 10 RPM.

Example 4

The procedure of Example 3 is repeated with the exception that, after the water has been heated to 98 ° C., 0.6 part of a 14% strength by weight solution of ammonium lauryl sulfate in water is added. The tertiary butyl styrene contains 300 parts per million of isopropenyl vinyl benzene. The conversion of the monomer to the polymer is 95 %. The latex particles are about 1,400 angstroms in diameter. The viscosity of solutions containing various concentrations of the polymer in "Jet-A ^M Fuel" is determined on a Brookfield Model RVT Viscometer using Spindle No. The results are shown in Table IV.

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20 Q'2 0 4 6

concentration

TABLE IV viscosity RPM in centipoise 40,000 0.5 29,000 1.0 14 600 2.5 9,000 5 5,500 10 3,200 20th 1,500 50 950 100 64,000 0.5 52,000 1 28 500 2.5 17 500 5 10 500 10 6,000 20th 2 900 50 1,800 100 116,000 0.5 82,000 1 43 200 j 2.5 27 200 5 15,000 10 8 500 20th 4,300 50 2,300 100 124,000 0.5 80,000 1 50,000 2.5 30 400 5 18 600 10 10 300 20th 4 440 50 2,450 100

099 * 3-1 / 1549

Example 5

In a jacketed vessel equipped with a stirrer 1,800 parts by weight of deionized water are added. A flush pipe is placed at the bottom of the vessel, and the vessel is purged with nitrogen for 10 minutes. The vessel is closed and heated to 80 ° C. It will be 3.6 Parts by weight of ammonium persulfate added. Then one will Monomer mixture of 10.8 parts by weight of acrylic acid and 1,789 Parts by weight of t-butyl styrene at constant rate in the vessel pumped over the course of about 1-1 / 2 hours. The reaction mixture is stirred at a temperature of about Maintained 80 ° C for an additional period of about 1-1 / 2 hours. The conversion of the monomer to the polymer is 95%. The particle size of the latex obtained is 7,000 angstroms. The polymer is in a drying cabinet dried and it is a 3% solution in "Jet-A" Propellant prepared that is gel-like and has a viscosity of 18,000 centipoise using a spindle Has # 6 at 10 RPM.

The experiment is repeated with the exception that 10.8 parts by weight of acrylamide are used instead of acrylic acid will. The viscosity of the 3% strength by weight solution is in this case 6,000 centipoise using a # 6 spindle at 10 RPM.

The experiment is repeated again with the exception that the monomer mixture is a 1: 1 mixture of 2-ethylhexyl acrylate and is t-butyl styrene. A J% igc solution of this polymer in "Jet-Α" fuel has a viscosity of 4,000 centipoise with a # 6 spindle at 10 RPM.

Example 6

To the effect of various non-metallic cations To point to the thickening characteristics of the polymers made in accordance with the invention will use a variety of solutions manufactured using a special thickener. The solutions are created by adding the thickener to the fuel with stirring. When a Deicing agent is used, the additive is thickened with a predetermined amount of the "Jet-A" fuel mixed. The solutions are then left to stand for 24 hours and the Viscosity is measured with a "Brookfield Viscoaeter Model LVF"

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at 6 RPM using the iis Table V given Spindle razed. The asterisks behind the numbers in the Refer to the column entitled "Polymer-Probe" Footnote, where it is indicated from which example the polymer was chosen for the test. The chemical composition of the additive is indicated in the "Additive type" column. In the "Additional amount" column is the percentage of the additive, based on the amount of thickening polymer. In the "Percent Polymer" column is the content given on the thickening polymer in percent by weight in the "jet A" fuel.

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O O (D OO

cn co

% Additive- TABEL Additive- V 000 spindle polymer Type Amount: 1) viscosity 500 No. polymer 1.25 no control Cp 000 3 sample 1.25 NH4OH 0.11 5 000 J I) 1.25 NH4OH 0.22 8th 000 J 2 1.25 NH4OH O, jiJ 15th 000 J 3 1.25 NH4OH 0.36 14th 100 4th 1.25 NH4OH 0.72 15th 000 4th 1.0 no control 14th 000 1 ^4th 1.0 NH4OH 0.6 000 3 ⁵ V * 2.0 no control 5 50 6 f 2.0 NH4OH 0.50 18th 50 4th 7th 1.25 no control 32 000 1 ^8th 1.25 water 1.8 000 1 ⁹ 1.25 NH ₄ OH 0.50 000 4th 10 y 1.25 flushed 12th 000 J ¹¹ I. 1.5 no control 6th 000 4th 12> ** 1.5 TMAH (2) 0.16 2 000 4th U) 1.5 TMAH 0, SA 14th 000 1A> * 1.5 TMAH 0.64 16 4th ¹⁵ I. 1.5 TMAH 0.80 17th ¹⁶ V ** 22nd 17 [ 18 I. 19 / I.

(D •

(2)

K>

% By weight based on the thickening polymer from example 1 from example 2 tetramethylammonium hydroxide (as a 60% solution of the pentahydrate)

CD NJ CD

CD

polymer polymer Additive- TABLE V (Continuation) 15,000 on thickening polymer spindle sample 1.5 Type Additive- viscosity 6,000 No. 20] 1.5 TMAH (2) Quantity (1) cp 13,000 4th , 21 1.25 TMAH 1.28 3,000 4th 22nd 1.25 TMAH 1.60 10,000 4th 23 1.25 TMAH (3) 0.50 10,000 (2) * Tetramethylammonium hydroxide (as 60% 4th 1.25 TMAH 0.5 y 60 (3) - Teti 4th 1.25 TMAH 1.06 120 advise thy lamme 4th 1.25 NaOH 1.59 10,000 jniumhydroxi < 1 1.25 H2O 2.7 1,000 i-pentahydrate 1 2 «[™ 1.25 NaOH 1.8 50 4th 25th 1.25 L ₁ OH 0.9 600 2 O ■■■ 2.6 / 1.25 H2O 2.7 200 · 1 O 27 / 1.25 Ca (OH) 2 1.8 50 1 CD
OO, 28> 1.25 Mg (OH) ₂ 2.7 50 2 29 1.25 CaCi ₂ 2.7 2,000 1 JO 1.25 Al (0H) 3 1.0 1 ^^ 31 Al (OH) j '2.7 j cn -% based 2.7 «Ο example 1 Example 2 32f Solution of pentahydrate) 3Jl (fixed) 34 357 (1) - wt * = off ** «= off

In the above examples, the jet fuels do not contain any additives for deicing. When the polymers alone are added to jet fuels that contain de-icing agents, thickening initially occurs but viscosity decreases rapidly over time. So has z. B. after one hour a 2% solution of the polymer of Example 1 has a viscosity of 800 centipoise and after 2 days a viscosity of 300 centipoise. A 2% strength by weight solution of the polymer according to Example 1 in "Jet-B ¹¹ propellant" (which contains an additive for de-icing) is prepared, which is an additional 0.5% by weight, based on the polymer a 28% ammonium hydroxide solution. After 2 days this solution has a viscosity of 14,000 centipoise; after 7 days a viscosity of 15,000 centipoise. When tetramethylammonium hydroxide pentahydrate is added, the viscosity after 7 days is 16,000 centipoise. A 2% Solution in "Jet-B" fuel without deicer has a viscosity of 12,000 centipoise Similar results are obtained when diesel fuel and gasoline are thickened with or without deicer in accordance with the invention.

Example 7

An apparatus for determining flammability is used. The device contains a gun with a barrel 12.19 m long and 20.3 cm in diameter. The sample to be examined is placed in a cylinder made of expanded polystyrene with walls 2.54 cm thick. The fuel to be tested is in turn placed in a double-walled polyethylene bag and placed in the foam cylinder. The fuel to be tested and the foam cylinder are then placed in the loading port of the gun. The gun is aimed in the horizontal direction at a vertically arranged latticework, which is 6.2 ro from the muzzle of the gun. Located away from the gun and adjacent to the latticework are 5 pans 0.3 m wide, 0.6 m long and 10.3 cm deep; these pans are filled with "Jet-B ^M fuel. The pans are arranged in a rectangle with a pan in the center; one edge of the rectangle runs parallel to the lattice work. The next pan is 3.1 m from the lattice work. The" Jet-B "fuel is ignited. Then the foam container is set into the latticework with a muzzle

009831/1549

speed of 40.23 m / sec. fired and the inflammatory characteristics of the resulting fuel spray are visually observed and rated as follows:

(1) 100% reduction in explosion none Inflammation;

(2) 80 to 90% reduction in explosion, very little ignition;

(3) 5.0 to 60% reduction in explosion slight Inflammation; ;

(4) 20 to 30% reduction in explosion -

a clearly perceptible explosion occurs with a small ball of fire;

(5) 0 to 20% reduction in explosion. it occurs, a great explosion, and in big ball of fire.

"Jet-A" fuel and "Jet-B ^H fuel" are tested with the polymer prepared according to Example 1 and the results obtained are summarized in Table VI below.

TABLE VI Polymer concentration
"Jet-A ^M fuel -
Weight-7o ^: Brookfield
viscosity
at 10 RPM Explosion
value 1 . '■ · ■ · ■
1.5
1.75
2
2.5 3,500 cp
5,000.cp
14,000 cp
22,000 cp 5
4th
3
2-1
1 Polymer concentrate
"Jet-B" fuel -
Wt% 2
2.5 10 200 cp
14,000 cp 4 *
3

009831715 ^ 9

"Jet-A" fuel is less volatile than "Jet-B" fuel. The test is repeated using a polymer prepared according to Example 4. It A 2% solution of the polymer in "Jet-Α" fuel is made and portions of this solution are diluted to concentrations of 1, 1.25 and 1.5%. The results are shown in Table VII.

TABLE VII Explosion
value Polymer concentration
"Jet-Α" fuel -
Wt% Brookfield
viscosity
at 10 RPM 5
4th
3
2
1 0
1 *
1.25 *
1.5 *
2 2,000 cp
4,500 cp
12,000 cp
23,000 cp

* produced by diluting the 2% solution with fuel

Example 8

A plurality of 150 g samples of a 1.25 wt% solution of the polymer of Example 1 are treated with different amounts of aqueous ammonium hydroxide and the the observable effect on the viscosity is measured. There is no noticeable change in viscosity 2 microliters per 150 g to 200 microliters at 10 RPM observed with a # 6 spindle. 2.5 microliters of a 28% aqueous ammonium hydroxide solution appears to be optimal and amounts of 0.2 microliters and higher appear to be highly satisfactory. The increase in viscosity will most observed at low shear stresses; that means 5 revolutions in the case of shear stresses per minute and less, at which maximum viscosities at a concentration of 3 microliters per 150 g of 1.5 wt .-% igpi Solution of the polymer in the "Jet-Α" fuel can be observed.

009831/1549

2002Ό46

Similar results are obtained when the working methods these examples are repeated using p-tertiary amyl styrene, ro, -n-hexyl styrene, p-tertiary hexyl styrene and mixtures thereof in place of p-tertiary buttyl styrene.

009831/1549

Claims (1)

Patent claims: 2. Preparation according to claim 1, characterized in that the oxygen-containing, polar, olefinically unsaturated and a monomer selected from the following group is used as a copolymerizable compound: (a) acids with up to 6 carbon atoms, (b) amides with up to 4 carbon atoms, (c) hydroxyalkyl acrylic esters and (d) sulfonic acids. 3. Preparation according to Claims 1 and 2, characterized in that the polymer is a polymer of an alkylstyrene is used. 4. Preparation according to one of claims 1 to 3, characterized in that that it also contains ammonia. 5. Preparation according to one of claims 1 to 4, characterized in that that the polymer is present in amounts of 1 to 4% by weight, based on the weight of the preparation. 6. Preparation according to one of claims 1 to 4, characterized in that that the polymer is present in amounts of 1.25 to 2.5% by weight, based on the weight of the preparation is. 7. Preparation according to one of claims 1 to 6, characterized in that the polymer is a polymer of t-butyl styrene. 8. Preparation according to one of claims 1 to 6, characterized in that that the polymer is a copolymer of t-butyl styrene and methacrylic acid. 009831 / 1SAd 9y thickened fuel preparation for internal combustion engines, which is a viscoelastic fluid, thereby marked that they can be used as fuel under normal conditions liquid, combustible hydrocarbon and 0.2 to 5% by weight, based on the weight of the preparation, contains a polymeric thickener, the polymeric thickener 0.5 to 3 wt .-%, based on the weight of the polymeric thickener, one oxygen-containing, polar compound polymerized and the polar compound contains an acid with up to 6 carbon atoms or an amide with up to 4 carbon atoms and the preparation is essentially free of substances that may cause sulphidation in a turbine jet engine cause with internal combustion. 10. Fuel preparation according to claim 9, characterized in that that the liquid hydrocarbon is a jet fuel is. 11. Preparation according to one of claims 9 or 10, characterized in that the polymeric thickener is a Copolymer of an alkyl styrene and a carboxylic acid is. 12. Preparation according to one of claims 9 or 10, characterized in that that the polymeric thickener is a copolymer of t-butyl styrene and methacrylic acid. 13. Preparation according to one of claims 9 or 10, characterized characterized in that the polymeric thickener is a copolymer of t-butyl styrene and acrylic acid. 14. Preparation according to one of claims 9 to 13, characterized indicated that it also contains a volatile base. 15. Preparation according to one of claims 9 to 13, characterized in that that the preparation also contains ammonia contains. 00 98 31 / 15AÖ