RU2171272C2 - Homogenized composition of waxy depressants of fluidity loss point and method of homogenation of mixture - Google Patents

Abstract

FIELD: chemical industry, more particularly dispersions of waxy depressants of fluidity loss point. SUBSTANCE: depressant composition comprises depressant which is solid at 10 C with average numerical molecular weight of at least 500 and liquid medium in which material of depressant of fluidity loss point is substantially insoluble at room temperature. Depressant component is dispersed in liquid medium. Depressant makes it possible to decrease solidification temperature to desired values using no solvents. EFFECT: improved properties of the homogenized composition. 16 cl, 9 ex

Description

BACKGROUND OF THE INVENTION
The invention relates to dispersions of waxy depressants of the yield point.

 Different types of distillate oil products, such as diesel fuel, various oils with a viscosity that ensures their use as lubricants, gear oils, hydraulic oils, household fuel and crude oil, require the use of additives - depressants of the yield point in order to provide their free flowing at low temperatures. Often kerosene is added to such petroleum products as a solvent for paraffins, in particular for those present in distillate petroleum products. However, the demand for kerosene as a fuel for jet engines has caused a decrease in the amount of kerosene in distillate petroleum products in recent years. This, in turn, required the addition of paraffin crystal modifiers to compensate for the lack of kerosene. Moreover, the need for depressant additives, the point of loss of fluidity of crude oil may be even more important, since the addition of kerosene is not considered economically viable.

 Many pour point depressants themselves are to some extent paraffin-like solid materials due to the presence of relatively long chains of hydrocarbyl groups. It is better to deal with such materials at room temperatures if they are in liquid form, i.e., dissolved or dispersed in a certain environment.

 US Pat. No. 4,435,309 to House, dated March 6, 1984, discloses a method for liquefying materials that are either waxy solid materials or solid or semi-solid mixtures of such waxy materials and their solvents at room temperature. A solution of a waxy material in a solvent is obtained at elevated temperatures, then the solution is cooled to a semi-solid to solid phase, and then the mixture is subjected to shear deformation. Waxy materials include quaternary ammonium compounds and polyoxyethylated alkyl phenols; solvents include mixtures of isopropylamine and water or hexylene glycol.

 US Pat. No. 3,061,544 to Martinek of October 30, 1962, discloses a method for producing colloidal dispersions by simultaneously reducing temperature, pressure and concentration under shear strain. The colloidal phase is dissolved in a minimum amount of the colloidal phase by heating to obtain a solution. The hot concentrated solution is injected under high pressure through a nozzle or spray nozzle into a zone with lower temperature and pressure, where jets or atomized particles meet with the liquid phase, which is also injected under high pressure.

 U.S. Patent No. 3,393,078 to Lockhart et al, July 16, 1968, discloses a car polishing composition prepared by stirring and heating ingredients until the waxy components are dispersed and emulsified as finely molten / or almost molten particles /, and cooling the resulting emulsion composition to room temperature. This emulsion is mixed rapidly while it cools to a temperature that is lower than the melting point of the waxes; then the emulsion is stirred slowly, while it is allowed to flow from the outlet / mixing / container into the containers for trade.

US Pat. No. 1,637,475 to Davis et. al of August 2, 1927, an emulsion is disclosed which is used as an emulsifying agent, a colloidal material which consists of a mixture of hard and soft soaps. Heating and vigorous stirring of the mass is continued until the wax becomes dispersed. After processing the dispersion, the cooling medium circulates in the jacket of the mixer until the mass is rapidly cooled, while stirring is continued. When the temperature of the mass reaches about 65 ^° C., it is forced through a cellular tissue and then allowed to slowly cool to room temperature.

 US Pat. No. 5,039,437 to Martella et al. Of August 13, 1991 (and US Pat. No. 5,082,470 to Martella et. Al of January 2, 1992) disclose alkyl phenol formaldehyde condensate additives to improve the flow properties of hydrocarbon fuels at low temperatures. The number average molecular weight of the polymer composition is at least about 3000, and the molecular weight distribution is at least 1.5; in the alkylated phenolic reagent, the alkyl groups are almost linear and contain from 6 to 50 carbon atoms, and the average number of carbon atoms is from about 12 to 26; and no more than about 10 mol. % of alkyl groups of alkyl phenol contain less than 12 carbon atoms, and not more than about 10 mol. % of alkyl groups of alkyl phenol contain more than 26 carbon atoms.

U.S. 4,564,460 to Dorer, Jr. et. al dated January 14, 1986 (and US Pat. Nos. 4,559,155 dated December 17, 1985; 4,565,550 dated January 21; 4,575,526 dated March 11, 1986; and 4,613,342 dated September 23, 1986) disclosed combinations of additives to improve cold flow properties of hydrocarbon fuel compositions. The composition includes a yield point depressant, which may be a hydrocarbon-substituted phenol of the formula (R ^* ) _a -Ar- (OH) _b , where R ^* represents a hydrocarbyl group selected from the group consisting of hydrocarbyl groups containing from about 8 to about 39 atoms carbon, and polymers containing at least 30 carbon atoms. Ar represents an aromatic moiety, which may include linked multicore aromatic moieties represented by the general formula ar- (Long-ar -) - _w ) Q) _nw , where w represents an integer from 1 to about 20, each Lng represents a bridging bond of the type which includes alkylene bonds (e.g., -CH ₂ , among others).

Summary of invention
The present invention provides a homogenized liquid pour point temperature depressant composition containing a yield point solid at 10 ^° C. with a number average molecular weight of at least 500, and each medium in which the depressant is practically insoluble at 10 ^° C. dispersed form.

In addition, the present invention provides a method for homogenizing a pour point depressant mixture that is solid at 10 ^° C. with a number average molecular weight of at least 500, and
a liquid medium in which the depressant is practically insoluble at 10 ^° C., comprising the steps of heating the liquid medium and the depressant to a temperature at which the depressant is soluble or spread in the liquid medium,
mixing heated components and
cooling the heated mixture to a temperature at which the depressant is practically insoluble in the liquid medium.

DETAILED DESCRIPTION OF THE INVENTION
The present invention is a dispersion of a waxy pour point depressant in a material that is non-solvent for a pour point depressant. This dispersion is usually homogeneous, at least on a macroscopic scale. The waxy pour point depressant is a material with a number average molecular weight of at least 500, preferably at least 700, and more preferably at least 1000, preferably up to 500,000, preferably 50,000, more preferably 5000 This material is a solid (in the absence of solvent additives) at 10 ^° C, preferably also at room temperature, that is, at a temperature of at least up to 20 ^° C, and more preferably up to 30 or 40 ^° C or higher.

 Further, this material relates to materials that act as a depressant for a pour point when added to a paraffin-containing hydrocarbon liquid as determined by ASTMD-97.

 Oligomers are often suitable materials and often they contain at least one hydrocarbyl group per molecule containing at least 12 carbon atoms.

 The present invention encompasses many types of yield point depressants. They include yield point depressants that encompass the reaction product of a hydrocarbyl-substituted phenol with a sufficient number of carbon atoms in the hydrocarbyl substituent, which provides a solid or semi-solid state of the product at room temperature, usually a “waxy” material, and an aldehyde containing from 1 to 12, preferably from 1 to 4 carbon atoms, or its source.

 Hydrocarbyl substituted phenols represent well-known materials, as well as methods for their preparation. In the sense that the term is used here, phenol refers not only to benzene (unless in the context there are specific instructions, for example, in the examples), although benzene may be the preferred aromatic group.

 Rather, the term should be considered in a broader sense, and it includes hydroxyl aromatic compounds in general, for example, substituted phenols, hydroxynaphthalenes, and the like.

 Thus, the phenol aromatic group may be mononuclear or polynuclear substituted, and may also include other types of aromatic groups.

 The aromatic group of the hydroxyaromatic compound in this way can be such a separate aromatic core as a benzene core, pyridine core, thiophene core, 1,2,3,4-tetrahydronaphthalene core, etc., or a polynuclear aromatic moiety.

 Such polynuclear fragments may be of a condensed type, i.e. such when a pair of aromatic nuclei representing an aromatic group has two common atoms, such as, for example, naphthalene, anthracene, aza-naphthalene, etc. Polynuclear aromatic fragments can also be of a related type, where at least two nuclei (either mononuclear or polynuclear) are bridged to each other. Such bridge bonds can be selected from the group consisting of simple carbon-carbon bonds between aromatic nuclei, ether bonds, keto bonds, sulfide bonds, polysulfide bonds containing from 2 to 6 sulfur atoms, sulfinyl bonds, sulfonyl bonds, methylene bonds, alkylene bonds, di (lower alkyl) methylene bonds, lower alkylene ether bonds, alkylene keto bonds, lower alkylene sulfur bonds, lower alkylene polysulfide bonds containing from 2 to 6 carbon atoms, amino bonds, polyamino bonds and mixtures so x divalent bridging linkages. In some cases, more than one bridging bond may be present in the aromatic group between the aromatic nuclei. Thus, for example, fluorene nuclei contain two benzene nuclei bonded both by a methylene bond and a covalent bond. Such kernels can be considered as containing 3 kernels, but only two of them are aromatic. Typically, an aromatic group contains only carbon atoms in the aromatic nucleus itself, although other non-aromatic substitutions may be present, as in specific short-chain alkyl substituents. So aromatic groups can have methyl, ethyl, propyl and tert.-butyl groups, even if such groups are not represented in the following structures.

и т. д., где М представляет метил, Et - представляет этил или этилен, а Pr представляет пропил. Конкретными примерами конденсированных ароматических колец, являются:

Если ароматический фрагмент является связанным полиядерным ароматическим фрагментом, его можно представить формулой:
ar(--L--ar-)_w,
где w представляет целое число от 1 до около 20, каждый ar представляет отдельное кольцо или ароматические ядра с конденсированными кольцами, содержащими от 4 до около 12 атомов углерода, а каждый L независимо выбирают из группы, состоящей из простых углерод-углеродных связей между ar и ядрами, либо эфирных связей:
(например, -О-), кетосвязей (например,

сульфидных связей (например -S-), полисульфидных связей, содержащих от 2 до 6 атомов серы (например, -S-_2-6), сульфинильных связей (например, -S(O)-), сульфонильных связей /например, -S(O)₂-), низших алкиленовых связей (например, -CH₂,-, -CH₂-CH₂-,

моно(низший алкил(метиленовых связей) например, -CHR⁰-), ди(низший алкил(метиленовых связей), например, -CR₂ ⁰-, низших алкиленэфирных связей (например, -CH₂O-, -CH₂O-CH₂, -CH₂-CH₂O-, -CH₂CH₂OCH₂CH₂-,

и т. д. низших алкиленсульфидных связей (например, таких, где один или более из -О-, находящийся в алкиленэфирной связи, замещен атомом серы), низших алкиленполисульфидных связей (например, таких, где один или более из -O- заменен группой -S_2-6-/, аминосвязей (например,

-CH₂N-, -CH₂NCH₂, -алк-N-, где алк представляет низший алкилен и т.д.), полиаминосвязей (например, -N(алк-N)_1-10, где свободная валентность атома азота занята атомами H или группами R₀), связей, полученных из оксо- или кетокарбоновых кислот, например, таких, которые представлены формулой:

где каждый из R¹, R² и R³ независимо представляет гидрокарбил предпочтительно, алкил или алкенил, более предпочтительно низший алкил или H, R⁶ представляет H или алкильную группу, а x представляет целое число от 0 до около 8, и смесей таких мостиковых связей (причем каждый из R⁰ представляет низшую алкильную группу).The following are specific examples of fragments with one aromatic ring:

and so on, where M is methyl, Et - is ethyl or ethylene, and Pr is propyl. Specific examples of fused aromatic rings are:

If the aromatic fragment is a linked polynuclear aromatic fragment, it can be represented by the formula:
ar (- L - ar-) _w ,
where w represents an integer from 1 to about 20, each ar represents a separate ring or aromatic nuclei with condensed rings containing from 4 to about 12 carbon atoms, and each L is independently selected from the group consisting of simple carbon-carbon bonds between ar and nuclei or ether bonds:
(e.g. -O-), keto bonds (e.g.

sulfide bonds (e.g. -S-), polysulfide bonds containing 2 to 6 sulfur atoms (e.g. -S- _2-6 ), sulfinyl bonds (e.g. -S (O) -), sulfonyl bonds / e.g. -S (O) ₂ -), lower alkylene bonds (e.g., -CH ₂ , -, -CH ₂ -CH ₂ -,

mono (lower alkyl (methylene bonds) e.g. -CHR ⁰ -), di (lower alkyl (methylene bonds), e.g. -CR ₂ ⁰ -, lower alkylene ether bonds (e.g. -CH ₂ O-, -CH ₂ O- CH ₂ , -CH ₂ -CH ₂ O-, -CH ₂ CH ₂ OCH ₂ CH ₂ -,

etc. lower alkylene sulfide bonds (for example, those where one or more of —O— located in the alkylene ether bond is substituted by a sulfur atom), lower alkylene polysulfide bonds (for example, where one or more of —O— is replaced by a group -S _2-6 - /, amino bonds (e.g.

-CH ₂ N-, -CH ₂ NCH ₂ , -alk-N-, where alk represents lower alkylene, etc.), polyamino bonds (for example, -N (alk-N) _1-10 , where the free valency of the nitrogen atom occupied by H atoms or groups R ₀ ), bonds derived from oxo- or ketocarboxylic acids, for example, those represented by the formula:

where each of R ¹ , R ² and R ³ independently represents hydrocarbyl, preferably alkyl or alkenyl, more preferably lower alkyl or H, R ⁶ represents H or an alkyl group, and x represents an integer from 0 to about 8, and mixtures of such bridging bonds (each of R ⁰ being a lower alkyl group).

Обычно все эти Ar группы не содержат заместителей, за исключением тех, которые специально указаны. Исходя из соображений стоимости, доступности и удобства и т. д. , ароматические группы обычно бывают бензольными ядрами, связанными алкиленовыми мостиками или нафталиновыми ядрами. Наиболее предпочтительной ароматической группой являются бензольные ядра.Specific examples of related fragments are:

Typically, all of these Ar groups do not contain substituents, with the exception of those specifically indicated. Based on considerations of cost, availability and convenience, etc., aromatic groups are usually benzene nuclei, linked by alkylene bridges or naphthalene nuclei. The most preferred aromatic group are benzene nuclei.

 The first reagent is a hydroxyaromatic compound, that is, a compound in which at least one hydroxyl group is directly attached to the aromatic ring. The number of hydroxyl groups per aromatic group can vary from 1 up to the maximum number of such groups that a hydrocarbyl-substituted aromatic moiety can accumulate while at least one and preferably at least two positions remain, at least some of which are preferably adjacent (ortho) with a hydroxyl group, which are suitable for further condensation with aldehydes, is described in detail below. Thus, most reagent molecules must have at least two unsubstituted positions. Such materials may thus include hydrocarbyl-substituted catechols, resorcinols, hydroquinones, and even pyrogallols and phloroglucin. Most often, each of the core nuclei, however, contains one hydroxyl group and, if a hydrocarbyl-substituted phenol is used, the material contains one benzene ring and one hydroxyl group. Naturally, a small fraction of the molecules of the aromatic reagent may not contain hydroxyl substituents. For example, a small amount of hydroxyl-free material may be present as an impurity. However, this does not violate the essence of the invention as long as the starting material is functional and usually contains at least one hydroxyl group per molecule.

 Similarly, a hydroxyaromatic reagent is characterized in that it contains a hydrocarbyl substituent. The term "hydrocarbyl substituent" or "hydrocarbyl group" is used here in the usual sense, well known to specialists. In short, it refers to a group containing a carbon atom, directly bonded to the rest of the molecule, and having primarily a hydrocarbon character.

Examples of hydrocarbyl groups include:
/ 1 / hydrocarbon substituents, i.e. aliphatic / e.g. alkyl or alkenyl /, alicyclic / e.g. cycloalkyl, cycloalkenyl / substituents, and amatically, aliphatically and alicyclic substituted aromatic substituents, as well as cyclic substituents in which the ring is supplemented with another part of the molecule / for example, two substituents together form an alicyclic radical /;
(2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups, which in the context of the present invention do not predominantly violate the hydrocarbon nature of the substituent (for example, halogen, especially chlorine and fluorine), hydroxy, alkoxy, mercapto, alkyl mercapto, nitro, nitroso and sulfoxy );
(3) hetero substituents, that is, substituents which, while retaining a predominantly hydrocarbon character in the context of the present invention, contain atoms other than carbon in the ring or chain. Hetero atoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, preferably no more than one non-hydrocarbon substituents should be present for every 10 carbon atoms in the hydrocarbon group; usually in hydrocarbyl groups there are no non-hydrocarbon substituents.

 Preferably, the hydrocarbyl groups are alkyl groups, preferably, the alkyl group contains: at least 12, more preferably 20, and even more preferably at least 30 carbon atoms, or, if the alkyl group is a mixture of alkyl groups, this mixture preferably contained on average at least 30 carbon atoms, usually from 31 to 400 carbon atoms, preferably from 31 to 60, and more preferably from 32 to 50 or 45 carbon atoms, although this is not required. In a preferred embodiment, the alkyl group in the composition is a mixture of alkyl groups, which may vary in length from one particular molecule to another. Although some of these molecules may contain less than 30 carbon atoms in the alkyl groups, the composition as a whole is usually characterized in that it contains alkyl substituents containing at least 30 carbon atoms. For certain embodiments of the present invention, the alkyl groups may be shorter and may contain less than 30 carbon atoms, for example, preferably from 24 to 28 carbon atoms or from 20 to 24 carbon atoms. In any case, alkyl groups can be obtained from either linear or branched olefin reagents; moreover, linear is somewhat preferable, although materials with longer chains tend to increase branching content. A number of branches seem to be involved in rearrangement mechanisms during the alkylation process.

 In a preferred embodiment, the hydrocarbyl groups used comprise a mixture of alkyls predominantly 30 to 36 carbon atoms long, with a number average carbon number of about 34.4 to about 35.4. This material is characterized in that it has approximately the following distribution along chain lengths:

C ₂₆ - 0.3%
C ₂₈ - 11.9
C ₃₀ - 16.7
C ₃₂ - 11.3
C ₃₄ - 8.6
C ₃₆ - 6.6
C ₃₈ - 5.0
C ₄₀ - 3.8
C ₄₂ - 2.9
C ₄₄ - 2,3
C ₄₆ - 1.8
C ₄₈ - 1.5
C ₅₀ - 1.3
Thus, the hydrocarbyl substituent contains a number of chains with an average of more than 30 carbon atoms. Such substituents are preferably alkyl groups in which the average number of carbon atoms in the alkyl chain is 31-40, more preferably 32-38.

A hydrocarbyl group can be obtained from the corresponding olefin, for example, a C ₂₆ alkyl group is derived from a C ₂₆ alkene, preferably 1 alkene, a C ₃₄ alkyl group is derived from a C ₃₄ alkene, and mixed length groups are obtained from the corresponding olefin mixtures. If the hydrocarbyl group is a hydrocarbyl group containing at least 30 carbon atoms, however, it is often an aliphatic group (or a mixture of such groups) derived from homo- or interpolymers (e.g. copolymers, terpolymers) of mono- and di-olefins containing from 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, etc. For appropriate use as a depressant, the yield points of at least a portion of the alkyl group or groups are preferably a straight chain, i.e. substantially linear. It is believed that this characteristic is preferable since it allows the chain to interact more favorably with the chain structure of wax-forming hydrocarbons. It is known that in many cases there is methyl branching at the point of attachment of the alkyl chain to the aromatic ring, even if an alpha-olefin is used. This situation is considered to be included in the scope of meanings for a straight chain or alkyl groups. Similarly, in some cases, part of the alkyl groups may contain a branching of lower alkyls at the point of attachment (or in the alpha position), mainly associated with the migration of the active center during the alkylation. Commonly used olefins are 1-monoolefins, such as ethylene homopolymers. These aliphatic hydrocarbyl groups can also be obtained from halogenated (e.g., chlorinated or brominated) analogues of such homo- or inter-polymers. However, such groups can be obtained from other sources, such as monomeric macromolecular alkenes (e.g. 1-tetra-conten) and their chlorinated analogues and their hydrochlorinated analogues, aliphatic oil fractions, in particular paraffin waxes and cracked and chlorinated analogs thereof, and their hydrochlorinated analogues, liquid paraffin, synthetic alkenes, such as those obtained in the Ziegler-Natta process (for example, polyethylene lubricants), and other sources known to those skilled in the art. Any unsaturations in hydrocarbyl groups can be restored or eliminated by hydrogenation by methods known to those skilled in the art. The preparation or use of materials that are substantially free of chlorine or other halogens is somewhat preferable for environmental reasons.

 In one embodiment, a portion of the hydrocarbyl groups is derived from polybutene. In another embodiment, part of the hydrocarbyl groups are derived from polypropylene. In a preferred embodiment, the hydrocarbyl groups are prepared from a mixture of substantially unbranched long chain olefins containing predominantly 30-36 carbon atoms, as previously indicated.

 More than one such hydrocarbyl group may be present, but usually no more than 2 or 3 groups for each aromatic nucleus in the aromatic group. Typically, only one hydrocarbyl group is present per aromatic moiety, especially if the hydrocarbyl-substituted phenol is based on one benzene ring.

 The attachment of a hydrocarbyl group to the aromatic moiety of the first reagent of the present invention can be accomplished by a number of methods well known to those skilled in the art. One most suitable method is the Friedel-Crafts reaction, in which an olefin (for example, a polymer containing an olefinic bond) or a halogenated or hydrohalogenated analog thereof is reacted with phenol in the presence of a Lewis acid catalyst. Methods and conditions for carrying out such reactions are well known in the art. See, for example, the discussion in the article entitled “Alkylation of Phenols” in (“Kirk and Othmer Encyclopedia of Chemical Technology” 3Ed, vol. 2, pp. 65-66, Interscience Publishers, John Wiley and Company, N.Y.). Other equally suitable and convenient methods for attaching hydrocarbon groups to an aromatic moiety will be readily apparent to those skilled in the art.

 The second component that reacts with the formation of a pour point depressant, as indicated earlier, is an aldehyde containing from 1 to 12 carbon atoms, or a source thereof. Suitable aldehydes have the general formula RC (O) H, where R preferably represents hydrogen or a hydrocarbyl group, as previously indicated, although R may include other functional groups that do not interfere with the condensation reaction (described below) of the aldehyde with a hydroxyaromatic compound. This aldehyde preferably contains from 1 to 12 carbon atoms, more preferably from 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Such aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyric aldehyde, isobutyric aldehyde, pentanaldehyde, caproaldehyde, benzaldehyde and higher aldehydes. Monoaldehydes are preferred. The most preferred aldehyde is formaldehyde, which can be supplied as a solution, but is more often used in polymer form as paraformaldehyde. Paraformaldehyde can be considered as the reactive equivalent of an aldehyde or as its source. Other reactive equivalents may include hydrates or cyclic trimers of aldehydes.

 Hydrocarbylphenol and aldehyde are reacted in relative amounts ranging from approximately equal equimolar amounts to about 30% molar excess of aldehyde (based on aldehyde monomer). Preferably, the amount of aldehyde is 5-20%, more preferably 8-15% more than molar-based hydrocarbylphenol. The components are reacted under conditions that result in the formation of an oligomer or polymer. The molecular weight of the product will depend on parameters, including equivalent ratios of reactants, temperature and reaction time, as well as on impurities present. The product may contain from 2 to 50 aromatic units repeating in a chain, preferably from 3 to 30 such units, more preferably from 4 to 14 units. If hydrocarbylphenol is specifically an alkyl phenol containing 24-28 carbon atoms in the alkyl chain, and if the aldehyde is formaldehyde, the material will preferably have a number average molecular weight of from 1000 to 24000, more preferably from 2000 to 18000, even more preferably from 3000 to 6000. Molecular the weights of materials based on hydrocarbyl substituents with a chain length of about 34 carbon atoms will be proportionally slightly higher.

Hydrocarbylphenol and aldehyde are reacted by mixing alkyl phenol and aldehyde in an appropriate amount of diluent oil, or optionally another solvent, for example, an aromatic solvent such as xylene, in the presence of an acid such as sulfuric acid, such as sulfonic acid, such as alkyl phenol sulfonic acid, steam -toluene-sulfonic acid or methanesulfonic acid, in an organic acid such as glyoxylic acid or Amberlyst ^TM catalyst solid macroporous, weakly-bonded, a sulfonating annogo polystyrene-divinylbenzene resin catalyst from Rohm and Haas. The resulting mixture is usually heated to 90-160 ^o C, preferably to 100-150 or 100-120 ^o C for a suitable period of time, for example 30 minutes to 6 hours, preferably from 1 to 4 hours, to remove the water formed during condensation. Time and temperature are correlated in such a way that the reaction at lower temperatures usually takes longer, etc. Determining the exact conditions is the responsibility of specialists. If desired, the reaction mixture can then be heated to higher temperatures, for example 140-180 ^o C, preferably 145-155 ^o C to further remove volatiles and move the reaction to completion. The product can be treated with a base such as NaOH, if desired, to neutralize the strong acid catalyst and to obtain the sodium salt of the product, and then isolated by such conventional methods as filtration.

и его изомеры положения. Однако часть формальдегида, который предпочтительно используют, как предполагают, может включаться в молекулярную структуру в форме замещающих групп и групп связи, таких, как те, которые проиллюстрированы следующими типами, включая эфирные связи и гидроксиметильные группы:

Для использования в контексте настоящего изобретения пригодны также другие типы воскообразных депрессантов точки потери текучести. Одним из примерных классов является класс, сополимеров альфа-олефин/ацилирующий агент, эстерифицированных жирными спиртами. Олефин, который является сомономером в таких сополимерах, является одним или более из альфа-олефина/ иногда именуемого как моно-1-олефин/, или изомеризованных альфа-олефинов. Примеры альфа-олефинов включают этилен, пропилен, бутилен, 1-октен, 1-нонен, 1-децен, 1-додецен, 1-тридецен, 1-тетрадецен, 1-пентадецен, 1-гексадецен, 1-гептадецен, 1-октадецен, 1-нонадецен, 1-ейкозен, 1-геникозен, 1-докозен, 1-тетракозен и т.д. Возможные для использования коммерчески доступные альфа-олефиновые фракции включают C_15-18 альфа-олефины, C_12-16 альфа-олефины, C_14-16 альфа-олефины, C_14-18 альфа-олефины, C_16-18 альфа-олефины, C_16-20 альфа-олефины, C_22-28 альфа олефины и т.д. В одном варианте олефинами являются C₁₆ и C_16-18 альфа-олефины. Кроме того, можно использовать C₃₀+альфа-олефиновые фракции, доступные от Gulf Oil Company под торговой маркой Gulftene. В предпочтительном варианте альфа-олефины попадают в круг C_16-30 и тех, что указаны ранее.The product of this reaction can be generally represented as containing polymers or oligomers with the following repeating structure:

and its position isomers. However, the portion of formaldehyde that is preferably used is believed to be incorporated into the molecular structure in the form of substituent groups and bond groups, such as those illustrated by the following types, including ether bonds and hydroxymethyl groups:

Other types of waxy pour point depressants are also suitable for use in the context of the present invention. One example class is the class of alpha olefin / acylating agent copolymers esterified with fatty alcohols. The olefin, which is a comonomer in such copolymers, is one or more of an alpha olefin / sometimes referred to as a mono-1-olefin /, or isomerized alpha olefins. Examples of alpha olefins include ethylene, propylene, butylene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene , 1-nonadecene, 1-neukosen, 1-genicosene, 1-docosen, 1-tetracose, etc. Commercially available alpha olefin fractions for use include C _15-18 alpha olefins, C _12-16 alpha olefins, C _14-16 alpha olefins, C _14-18 alpha olefins, C _16-18 alpha olefins, C _16-20 alpha olefins, C _22-28 alpha olefins, etc. In one embodiment, the olefins are C ₁₆ and C _16-18 alpha olefins. In addition, C ₃₀ + alpha olefin fractions available from the Gulf Oil Company under the trade name Gulftene can be used. In a preferred embodiment, alpha-olefins fall into the circle of C _16-30 and those indicated above.

 Methods for producing olefins are well known in the art and are described in detail in the Olefins section of Encyclopedia of Chemical Technoloqy, 2d Ed. Kirk and Othmer, Supplement, pp 632, 657, Interscience Publishers, Div. of John Wiley and Son, 1971.

 Another component of the copolymer is a copolymerizable acylating agent. An acylating agent is a material that will react with alcohol to form an ester; it is usually an acid, an ester, or preferably a more reactive equivalent, such as an acyl halide or anhydride. Both monocarboxylic and polycarboxylic acylating agents are included. Most preferred are dicarboxylic acylating agents such as succinic acylating agents. They include succinic acid, halides, esters and anhydrides, preferably acids, esters or anhydrides, most preferably anhydrides.

 The copolymer is esterified with one or more of the fatty alcohols. Fatty alcohols are synonymous with alkyl hydroxy compounds, especially straight chain alkyl hydroxy compounds, and especially those containing at least 6, preferably at least 12 or 18 carbon atoms. Preferred fatty alcohols contain from 16 to 30 carbon atoms. Examples of fatty alcohols include capryl alcohol, pelargonyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, margaril alcohol, stearyl alcohol, arachidine alcohol, behenyl alcohol, cerotyl alcohol, commercial alcohols and mixtures of alcohols containing, for example, 8-12 16-20 carbon atoms, etc.

One example of a pour point depressant of the type described above is a behenyl alcohol diester of a copolymer of C ₂₀ -C ₂₄ alpha-olefin and maleic anhydride (1: 1, mol).

Other types of waxy pour point depressants that can be used in the method of the present invention include ether-containing polymers or oligomers, including ethylene / vinyl acetate copolymers, especially those with a melt index less than 100 (ASTM 1238, condition E), and also include polymers, which contain acrylate or methacrylate monomers; fatty alcohol ether polymers, such as copolymers of vinyl carboxylate (dialkyl fumarate, in particular vinyl acetate) C _16-30 alkyl fumarates derived from fatty alcohols; poly (methyl acrylate) or poly (methyl methacrylate) transesterified with fatty alcohols containing from 16 to 30 carbon atoms to form esters with long chains: similar polymers obtained by esterification of acrylic acid with C _16-30 alcohols, and then polymerized; and styrene / maleic acid copolymers esterified with C _16-30 fatty alcohols. Certain poly-alpha olefins can also be used as depressants for pour points. Alkylated naphthalenes are also included, including those obtained by the reaction of chlorovax and alpha olefins with naphthalenes. Both types of waxy pour point depressants are well known in the art and are usually available as commercial products.

The pour point depressant of the present invention is supplied as dispersions in a liquid medium in which it is usually insoluble at 10 ^° C, and preferably also insoluble at room temperature, i.e. at a temperature of about 20 ^° C. or even 30 or 40 ^° C. That is, the medium is, firstly, a liquid at room temperature (about 20 ^° C.) and preferably has a freezing point of 10 ^° C. or lower. Some preferred media, in particular mixtures, have a freezing point as low as 0, -20, -30, -40 ^o C or lower. Moreover, the medium does not dissolve a significant amount of a yield point depressant at such temperatures, preferably at room temperatures. More specifically, the medium preferably dissolves less than 4%, preferably less than 2%, or even 1% of the depressant, pour point or moderately elevated temperatures. (In some cases, a small soluble part may contain impurities and unreacted materials, so that the actual amount of depressant that is dissolved will be correspondingly even less, for example 0.5 wt.%). Preferably, the medium remains non-solvent up to 30 ^o C, or preferably up to 40 ^o C or 50 ^o C or higher.

 In order for the liquid medium to remain a solvent for the waxy depressant of the pour point, the medium should usually have a suitable degree of polarity. Polarity can be defined or expressed in various ways. Thus, in one embodiment, the solvent molecules preferably contain from 10 to 80 wt.% Heteroatoms, such as oxygen or nitrogen, more preferably from 20 to 70% and even more preferably from 25 to 60 wt.%. In another embodiment, the medium may have a dielectric constant of at least 3, preferably at least 10. The above parameters generally refer to the medium as a whole, including, if it is a mixture, all components as mixed.

Suitable liquid media include acetates (e.g., 2-ethoxyethyl acetate, also known as Cellosolve ^™ acetate), ketones (e.g., acetone, butanone, pentanone, hexanone), or aqueous mixtures of glycols (e.g., ethylene glycol / water mixtures). Among the materials that can be used alone or in combination with water are ethylene glycol and its derivatives, such as monomethyl ether (Methyl Cellosolve ^TM ), monoethyl ether (Cellosolve ^TM ), monopropyl ether, monobutyl ether and monohexyl ether; diethylene glycol and its derivatives, such as monomethyl ether (Methyl Carbitol ^TM ), monoethyl ether (Carbitol ^TM ), monopropyl ether, monobutyl ether and monohexyl ether; propylene glycol and its derivatives, including monomethyl ether (Methyl Propanol ^TM ), monopropyl ether and monobutyl ether; and dipropylene glycol and its derivatives, such as monomethyl ether (Methyl Dipropanol ^TM ), monopropyl ether) and monobutyl ether.

Other suitable materials include butyrolactone and alcohols such as butanol, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2,6-dimethyl-4-heptanol (Diisobyityl Carbinol ^TM ), hexanol, isopropanol, 2-ethylhexanol and 1-pentanol.

The liquid material may also be a mixture of any of the above materials, including mixtures with water, although the waxy depressants of the pour point should be practically insoluble at the same time in such a mixture. If the liquid material is a mixture of glycol and water, the relative amounts of materials are such that the aqueous component will not freeze even at such low temperatures as from 0 to -40 ^° C. Weight ratios of about 1: 1 are often preferred for such aqueous mixtures, more usually a ratio of 1: 2 to 2: 1, preferably a ratio of 1: 1.5 to 2.5: 1 are satisfactory.

Many waxy depressant pour points are supplied in the form of concentrates containing various amounts of aromatic solvents such as xylenes, or a commercial mixed aromatic solvent with a boiling point of about 179 ^° C. The presence of a moderate amount of such solvents (e.g. 10 to 50%, e.g. 25% based on the weight of the mixture, the yield point depressant / solvent), as it turned out, is sometimes involved in the dispersion of the yield point depressant dispersion in the medium, although its presence is not required. If such an aromatic solvent is present, it can be considered as a component of a liquid medium, and it contributes to the total amount and nature of the solvent (polarity) of the medium.

 The dispersed composition preferably also contains a dispersant to participate in the formation and maintenance of the dispersion. Dispersants, also known as surface active agents, can be divided into anionic, cationic, zwitterionic or nonionic. Anionic surfactants include substances containing a long lipophilic tail linked to a water-soluble (hydrophilic) group on the other hand, the hydrophilic group containing an anionic fragment such as carboxylic acid, sulfonic acid or phenolic group, neutralized by a cation such as an alkali metal or ammonium. The lipophilic tail preferably represents an alkyl group, usually containing from about 8 to about 21 carbon atoms.

Typical anionic surfactants include carboxylic acid salts such as fatty acid salts of the formula R ₁ COOR ₂ , where R ₁ is a straight or saturated, unsaturated hydrocarbon radical containing from about 8 to about 21 carbon atoms, and R ₂ is a base forming radical, such as Li, Na, K, or NH ₄ , which makes the detergent-like surface active agent soluble in water, or increases the affinity of the surface active agent for water. In another embodiment, R ₂ may be a divalent or polyvalent metal, in which case an appropriate number of acid groups are present in order to provide a neutral salt. Metals forming ions include Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb and others. Typical fatty acid salts include sodium stearate, sodium palmitate, ammonium oleate and triethanolamine palmitate. Carboxylic acid addition salts suitable as anionic surfactants include salts and especially sodium and potassium salts, coconut oil fatty acids and tallow acids, as well as other compounds, including amine salts such as triethanolamine salts, acylated polypeptides and such salts N-laurylsarcosyl, as the sodium salt of N-dodecanoyl-N-methylglycine.

Other anionic surfactants include aryl and alkylaryl sulfonates, such as alkylbenzenesulfonate, linear alkylbenzenesulfonates, sodium tetrapropylenebenzenesulfonate, sodium dodecylbenzenesulfonate, tensol-, toluene, sulfonates, petroleum sulfonates, petroleum sulfonates, sulfonates, sulfonates , alpha-olefin sulfonates, alkylnaphthalene sulfonates, n-acyl-n-alkyl sulfonates, sulfosuccinate esters, isethionates, sulfates of formula R ₁ OSO ₃ R ₂ where R ₁ and R ₂ are as defined above The values, such as litiydodetsilsulfat, sodium dodecyl sulfate, kaliydodetsilsulfat and natriytetradetsilsulfat, alkylsulfonates of the formula R ₁ SO ₃ R ₂ wherein R ₁ and R ₂ have the meanings as sodium lauryl, sulfurized and sulfonated amides and amines, sulfurized and sulfonated esters as defined above, such as lauric monoglyceryl sodium sulfate, sodium sulfoethyl oleate and sodium lauryl sulfoacetate, layers of sulfuric acid esters such as sulfated linear primary alcohols, sulfated polyoxyethyl linear straight chain alcohols and sulfated triglyceride oils, phosphoric and polyphosphoric esters, perfluorinated carboxylic acids and polymeric anionic surfactants such as alginic acids.

 Also included are polymeric anionic surfactants, such as salts of polymers of alkyl acrylates and / or alkyl methacrylates and acrylic and / or methacrylic acids, as well as salts of partial esters of copolymers of maleic anhydride and styrene.

 Other groups of materials that can be classified as anionic surfactants include those that are known as ultra-alkaline or extra-alkaline materials. These are salts of base metals, preferably alkali or alkaline earth metals, salts of acidic organic compounds (carboxylic acids, sulfonic acids, phosphonic acids, phenols, etc.). Superbasic materials usually represent a single phase, homogeneous Newtonian systems, which are characterized by an excess metal content compared with that which must be present for neutralization in accordance with the stoichiometry of the metal and the specific organic compound that reacts with this metal. Superbasic materials are prepared by reacting acidic materials (usually an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture containing an acidic organic compound in a reaction medium containing at least one inert organic solvent (mineral oil, naphtha, toluene , xylene, etc. for the indicated organic material, a stoichiometric excess of the metal base, and a promoter such as phenol or alcohol. typically contains enough carbon atoms to provide solubility in oil and to impart a certain degree of surface activity to the product. The amount of excess metal is usually expressed in units of metal ratio. The term "metal ratio" represents the ratio of total metal equivalents to equivalents of acidic organic compound: neutral salt metal has a metal ratio of 1; a salt in which the amount of metal is 4.5 times the amount present in a normal salt will be et metal excess of 3.5 equivalents, and the ratio of 4,5.

 Superbased materials are commonly used as lubricants and are well known to those skilled in the art. Although they are useful for some applications, their scope of application may differ from other surfactants. That is, it is sometimes observed that they are precipitated and, apparently, as calcium carbonate after exposure to an electric field. However, in situations where this is not a problem, their use may be satisfactory and, accordingly, should be considered within the scope of the present invention. Patents describing methods for preparing the basic salts of sulfonic acids, carboxylic acids, and mixtures of any two of them or more, include US patents 2501731, 2616905, 261691, 2616925, 2777874, 3256186, 3384585, 3365396, 3320162, 3318809, 3488284 and 3629109.

Cationic surfactants are similar to anionic surfactants, except that the surface-active part of the molecule carries a positive charge. Examples of cationic surfactants include long chain amines and their salts, such as primary amines derived from animal and vegetable fatty acids and tall oil, and synthetic C ₁₂ -C ₁₈ primary, secondary or tertiary amines; diamines and their salts, quaternary ammonium salts, including tetraalkylammonium salts and imidazolinium salts, obtained, for example, from tall or hydrogenated tall oil, or N-benzyl-N-alkyl dimethylammonium halides; long chain polyoxyethylene amines; long chain quaternized polyoxyethylene amines; and amine oxides such as N-alkyl dimethyl amine oxides (which are actually zwitterions), such as cetyl dimethyl amine oxide or stearyl dimethyl amine oxide.

 Zwitterionic surfactants include amino acids such as β-N-alkylaminopropionic acid, N-alkyl-β-iminodipropionic acid, imidazoline carboxylates, N-alkyl betaines, sulfobetaines and sultaines.

 Non-ionic surfactants preferred for the purposes of the present invention are similar materials in which the polar functionality is not provided by the anionic or cationic group, but due to such a neutral polar group, which is typical for alcohol, amine, ether, ester, ketone or amide function. Typical non-ionic surfactants include polyoxyethylated alkyl phenols such as polyoxyethylated r-nonylphenol, p-octylphenol or r-dodecylphenol, straight chain polyoxyethylated alcohols derived from coconut oil, hard fat or synthetic materials, including oleyl derivatives; polyoxyethylated polyoxypropylene glycols (block copolymers of ethylene oxide and propylene oxide) usually with a molecular weight of from 1,000 to 30,000; polyethylene glycol, polyoxyethylated mercaptans; long chain carboxylic esters, including glyceryl and polyglyceryl esters of natural fatty acids, propylene glycol esters, sorbitol esters, polyoxyethylated sorbitol esters; polyoxyethylene glycol esters and polyoxyethylated fatty acids; alkanolamine "condensates", for example, condensates obtained by reacting methyl or triglyceride fatty acid esters with equimolar or doubly equimolar amounts of alkanolamine; tertiary acetylene glycols; polyoxyethylated silicones; obtained by reacting a reactive silicone derivative with a “closed” / capped / allyl polyalkylene oxide such as propylene oxide or a mixed copolymer of ethylene oxide (propylene oxide; N-alkyl pyrrolidones; and alkyl polyglycosides (long chain polysaccharide acetals). Many of these and other ionic and nonionic surfactants are described by Rosen "Surfactants and Interfasial Phenomena" John Wiley and Sons, pp. 7-31, 1989.

Some materials that are typically characterized as non-ionic surfactants may resemble some of the liquid media described previously. If a distinction needs to be made between these compounds, the material can be classified as a non-ionic surfactant for the purposes of the present invention, if it exhibits the characteristics of a non-ionic surfactant, and is also solid at room temperature, preferably even at 30 ^° C or 40 ^o C. Materials that are liquids at these temperatures, especially at room temperature and below, can soon be classified as a component of a liquid medium.

 Further, nonionic surfactants more specifically include ethoxylated coconut amides, oleic acid, tert-dodecyl mercaptan, modified polyester dispersants, esters, amides or mixed esteramide dispersants based on polyisobutenyl succinic anhydride, dispersants based on polyisobutylphenol, non-acrylic polymers grafted copolymers, octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, alkylaryl ethers, alkylaryl polyethers, amine condensates oliglycols, modified polyethoxy adducts, modified alkylaryl ethers, modified polyethoxylated straight chain alcohols, linear primary alcohols finished with ethoxylates, high molecular weight tertiary amines such as 1-hydroxyethyl-2-alkylimidazolines, oxazolines, perfluoroalkyl ethersulfonates, fatty acids aliphatic and aromatic phosphate esters. Also included are the reaction products of hydrocarbyl-substituted succinic acylating agents and amines. These reaction products and methods for their preparation are disclosed in US Pat. Nos. 4,234,435, 4,952,328, 4,938,881 and 4,957,649.

Other nonionic surfactants include functionalized polysiloxanes. These materials contain functional groups such as amino, amido, imino, sulfonyl, sulfoxyl, cyano, hydroxy, hydrocarbyloxy, mercapto, carbonyl (including aldehydes and ketones), carboxy, epoxy, acetoxy, phosphate, phosphonyl and haloalkyl groups. These polysiloxanes can be linear or branched and usually have a molecular weight of more than 800, i.e. up to 10,000 or 20,000. Functionality may be randomly distributed along the polymer chain or may be present in blocks. Functionality may be present in the form of alkyl or alkaryl groups, as well as in the form of groups such as - (C ₂ H ₄ O) _a - (C ₃ H ₆ O) _b -R, where a and b independently represent numbers from 0 to about 100, provided that at least one of a or b is at least 1, a R is H, acetoxy or a hydrocarbyl group. Other suitable substituent groups may include C ₃ H ₆ X, where X is OH, SH, or NH ₂ . Examples of such materials include Silwet ^™ surface active agents from Union Carbide and Tegopre ^™ surface active silicones from Goldschmidt Chemical Corp., Hopewell, YA. Non-ionic surfactants include polyoxyalkenylalkyl alcohols or phenols, such as ethoxylated nonylphenol, alkanoates (preferably partial alkanoates) of polyalcohols, such as glyceryl monooleate, glyceryl monolaurate, sorbitan monooleate, sorbitan-heptesulfonate-2-decenethyl uronate-2-decenethyl-uron-2-decenethyl-benzene-2-decenol-2-decenethyl-benzene -2-oxazoline. Preferred materials include tall oil fatty acid neutralized with diethanolamine, Triton ^™ surface active agents (from Rohm and Haas), including a series of octyl phenols with 1-70 units of ethylene oxide and a series of nonylphenols with 4-40 units of nonylphenol, surface active Neodol ^TM ethoxylates ( from Shell Chemical Co.) with 2-13 ethylene oxide units, Igepal ^TM surface active agents (from Rhone-Poulenc) containing 7 to 50 ethylene oxide, and Tergtitol ^TM surface active agents (from Union Carbide) containing 4 to 41 ethylene oxide units. The above commercial materials are typically linear primary alcohol ethoxylates or, in the case of Triton materials, branched alkyl phenol ethoxylates.

 The relative amounts of the pour point depressant, liquid medium and optional surfactant can vary widely, but preferably in the range of / 20-60 /: / 40-80 /: / 0-10 /, preferably / 30-50 /: / 50-70 /: / 1-7 /, more preferably, / 35-45 /: / 55-65 /: / 2-6 /, and particularly preferably about 38: 58: 4 parts by weight

The dispersion composition of the present invention is prepared by first heating the components to a temperature at which the waxy material can be dispersed by appropriate methods in a liquid medium plus an optional surfactant, if present. This condition can be fulfilled at appropriate elevated temperatures when the waxy material is soluble in a liquid medium. Typically, such solubility can be determined not only by the characteristic solubility of the waxy material and the properties of the medium, but also by the boiling point of the liquid medium. The preferred combination of the liquid medium and the waxy material should be such that in this embodiment a suitable degree of solubility, for example 80 g per 100 g of medium, is achieved at a normal boiling point of the medium, or at a lower temperature, although if desired, greater solubility can be achieved by combining the components at elevated pressure to increase the boiling point of the medium. In another embodiment, an increased dispersibility of the waxy material can be obtained by heating the mixture to a temperature above the melting point of the waxy material, even if this waxy material does not dissolve in the medium. More often the mixture is heated until the composition goes into a liquid state. And finally, in some cases, it is possible to obtain a suitable dispersibility of materials that neither dissolve nor melt at elevated temperatures, provided that appropriate mechanical means are used to obtain the dispersion. Heated components, especially if they are in a liquid state (molten or dissolved), are then mixed until a dispersion is obtained. This mixture is then treated under high shear or cavitation conditions. The term "high shear" generally refers to shear conditions of at least 10 ³ s ^-1 , preferably 10 ⁵ s ^-1, and more preferably at least 10 ⁶ s ^-1 . Cavitation conditions are also considered as high shear conditions; cavitation usually involves the formation of microscopic bubbles inside the liquid, which expand under the influence of ultrasound energy and then an inward explosion occurs, which has a strong shear effect. Installations capable of providing sufficiently high shear or cavitation conditions include Sonicator ^™ , a high-intensity ultrasonic processor in which a high-frequency voltage (e.g. 20 kHz) is converted into mechanical vibration energy that is sent to a liquid sample, for example, using a probe. High shear dispersing devices (such as Dispersator ^TM ) are also suitable, in which the high-speed rotor is very close to the fixed stator, which creates extremely high shear conditions due to mechanical and hydraulic forces as fluid enters the rotor and passes through it at high speed through a stator, or Microfluidizer (from Microfluidics Intl. Inc.), where two high-pressure streams interact with high speeds in certain microchannels, due to which shear, shock and cavitation forces usually provide the formation of submicron particles. The temperature to which it is necessary to heat the composition depends on the melting characteristics, solubility and volatility of the materials used; it is usually sufficient to heat to 40-100 ^o C, preferably to 50-90 ^o C, and more preferably to 70-8, ^o C. Then the heated mixture is cooled to a temperature at which the waxy material is practically insoluble, and usually exists in solid or semi-solid state while maintaining the mixing conditions. The resulting mixture is a stable dispersion.

 In one embodiment, the depressant pour point is melted, then an appropriate amount of surfactant is added to the melt with stirring. Then, an appropriate amount of a liquid medium heated to the same temperature (for example, a mixture of water and glycol) is added, and all components are mixed. Then, the resulting mixture is processed by mixing with high shear or by ultrasound while it is in the hot state, as well as during the cooling process or in another embodiment, after the mixture is cooled.

 Materials obtained by any of the above methods can also be described as homogenized materials. That is, they are materials in which, due to the above processing, the particle sizes of the suspended material are relatively reduced and preferably relatively homogeneous, and the suspended particles are relatively evenly distributed in the medium and remain in a dispersed state for a commercially reasonable period of time.

Dispersions of the present invention can be used to supply depressants with yield points in the form of concentrates for wax / paraffin-containing hydrocarbon materials such as crude oil or crude oil fractions such as residual oil, vacuum distillation oil or residual vacuum distillation oils (Bunker C crude oils ), that is, natural sources and partially refined oils, including partially processed oils derived from oil. The amount of yield point depressant used in the paraffin-containing liquid should be an amount that is capable of lowering its yield point temperature by a measurable number of degrees, i.e., at least 0.6 ^o C, preferably at least 2 ^o C, more preferably 3 ^° C., and even more preferably 6 ^° C. Such a reduction in pour point is readily determined by those skilled in the art according to ASTM D-97. Typically, the amount of the pour point depressant used (without the liquid medium in which it is dispersed) is from 50 to 10,000 ppm by weight (ppm), preferably from 100 to 5,000 ppm, more preferably 200 to 2000 ppm based on the liquid to which it is added. The total amount of concentrate needed will be proportionally higher, depending on the concentration of the depressant, the temperature of the yield stress in the concentrate.

EXAMPLES
Example 1
571.5 g of ethylene glycol, 571.5 g of distilled water are combined with stirring and heated to about 50 ^° C. Separately, 1143.0 g of a condensation product of formaldehyde and alkyl phenol are mixed and heated to form a p-alloy (about 82 ^° C.), the alkyl substituent being predominantly is a chain with a length of C _30-36 carbons, as previously indicated (50% of the active ingredient in 50% of a diluent mineral oil), and 114.3 g of a dispersant composition of 75.6 wt.% tall oil fatty acid and 24.4 weight .% diethanolamine, after which all this is mixed with sufficient m shear for approximately 10 minutes to obtain a homogeneous mixture. The heated mixture of ethylene glycol and water is added to another mixture using sufficient (shift for about 20 minutes. The resulting mixture is allowed to cool, then passed twice through Micronizer ^™ , which is equipped with a 3669 interaction chamber / to obtain 75 micron particles / and a back pressure module 3839/200 μm / at a pressure of 170 MPa / 25000 psi /. Completely processed material is collected.

Example 2
A 70.57 g / a / pour point depressant consisting of a styrene-maleic anhydride copolymer (1: 1 molar ratio, reduced intrinsic viscosity of about 0.42) esterified with 2.2 moles of behenyl alcohol was charged into a stainless steel glass, and (b) 105.86 g of 2-ethoxyethyl acetate (Cellosolve ^™ acetate). All chemicals were mixed using a laboratory Dispersator ^TM, equipped with a homogenizing head. Continuing to carry out the shift, the mixture is heated to 77 ^o C, and at this moment the mixture becomes transparent. Heating was continued to 82 ^° C. Then it was stopped and the mixture allowed to cool, continuing to carry out shear deformation, to room temperature.

Example 3
0.05 g of the yield point depressant composition of Example 2 was added to a 50 ml sample of crude oil with an unmodified pour point of -18 ^° C.

The pour point of the resulting mixture is -46 ^o C.

Example 4
In a Pyrex ^™ beaker on a hot plate, 28.0 weight is placed. hours / a / depressant pour point of example 2, and / b / 65.0 weight. hours t. propylene glycol butyl ether (Arcosolve ^™ PTB from Arco). These chemicals are heated and mixed using a laboratory stirrer while continuing to heat the mixture until the pour point depressant is completely dissolved. Heating was stopped and the resulting mixture was allowed to cool while stirring to room temperature.

 The particle size of the depressant, the pour point in the mixture is further reduced by placing the mixture in a rod mill consisting of a steel tube and a cylindrical rod corresponding to it, together with the mixture, and grinding it for 1 hour.

Example 5
Example 4 is repeated, except that the mixture contains / a / 120 g of the yield point depressant of Example 1, and / b / medium of 60 g of propylene glycol, monobutyl ether, 60 g of Cellosolve ^™ acetate and 60 g of propylene glycol. Initial heating is carried out until the depressant of the pour point melts.

Example 6
In a Pyrex ^™ beaker, a / a / 15 weight is placed. including depressant pour point containing the condensation product of formaldehyde and alkyl phenol, and the alkyl substituents mainly have a length of C _30-36 carbon atoms, as previously indicated (50% of the active ingredient in a 50% diluent medium - mineral oil), and / b / 1.5 weight. including the composition of the dispersant of 75.6 wt.% fatty acid tall oil and 24.4 wt.% diethanolamine. The resulting mixture was heated to 82 ^o C, while continuing to mix on a hot plate, and the mixture / s / 7.5 weight was slowly added to this mixture. including ethylene glycol and 7.5 weight. including water that has been preheated to 50-70 ^o C. After completion of the addition, the mixture is passed through Microfluidizer ^TM and allowed to cool to room temperature.

Example 7
Example 6 is repeated, except that instead of the condensation product of alkyl phenol, 15 parts by weight are used as component (a). pour point depressant of Example 1.

Example 8
In a Pyrex ^™ beaker, a / a / 15 parts by weight is placed. a pour point depressant containing a copolymer of ethylene and vinyl acetate (Elvax ^™ 150 from Dupont, 33% vinyl acetate, melt index 43 (ASTM D-1238-E)), and / b / 1.5 weight. including dispersant consisting of 75.6 wt.% fatty acid tall oil and 24.4 wt.% diethanolamine. The resulting mixture was heated to 82 ^° C. with stirring on a hot plate, and to this mixture was initially added 7.5 weight. including ethylene glycol, heated to 82 ^o C, and then 7.5 weight. h of water heated to 71 ^o C. After completion of the dilution, the resulting mixture was passed through Microfluidizer ^TM , allowed to cool to room temperature.

Example 9
Example 2 is repeated except that instead of a copolymer of styrene and maleic anhydride, a copolymer of C ₁₈ alpha olefin and maleic anhydride (molar ratio 1: 1) esterified with 2.2 moles of behenyl alcohol is used.

 Each of the documents presented above is hereby incorporated by reference. With the exception of examples or other indications given by way of example, all numerical amounts in this specification characterizing specific amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like. should be understood as defined by the word "about." Unless otherwise indicated, each of the chemical compounds or compositions indicated herein should be considered as commercial grade materials that may contain isomers, by-products, derivatives, and other such materials that are normally present in commercial grade materials. However, an amount of each of the chemical components is present, with the exception of any solvents or diluent oils that may normally be present in commercial materials, unless otherwise indicated. In the sense, as used here, the expression "consisting mainly of" allows you to include substances that do not significantly affect the basic and new characteristics of the considered compositions.

Claims (15)

1. A homogenized liquid composition of a yield point depressant containing a solid at 10 ^° C. a yield point depressant with a number average molecular weight of at least 500 and a liquid medium characterized in that it contains a medium in which the depressant is practically insoluble at 10 ^o C and is dispersed.  2. The composition according to p. 1, characterized in that the pour point depressant contains the reaction product of a hydrocarbyl-substituted phenol and an aldehyde containing from 1 to 12 carbon atoms or its source.  3. The composition according to claim 2, characterized in that the aldehyde is formaldehyde or its source.  4. The composition according to claim 4, characterized in that the yield loss depressant contains a copolymer of alpha-olefin and an acylating agent esterified with a fatty alcohol containing an ester, polymer or oligomer, a copolymer of vinyl carboxylate and dialkyl fumarate, an alkyl naphthalene or polyalphaolefin. 5. The composition according to claim 1, characterized in that the freezing point of the liquid medium is 10 ^o C or lower.  6. The composition according to claim 1, characterized in that the liquid medium contains from about 10 to 80 wt.% Heteroatoms.  7. The composition according to claim 1, characterized in that the dielectric constant of the liquid medium is at least about 3.  8. The composition according to p. 1, characterized in that the liquid medium is selected from the group consisting of acetates, ketones, alcohols and aqueous glycol mixtures.  9. The composition according to claim 1, characterized in that the weight ratio of depressant to liquid medium is from 20: 80 to 60: 40.  10. The composition according to claim 1, characterized in that it contains a dispersant in an amount sufficient to create and maintain a depressant in the form of a dispersion in a liquid medium. 11. The method of homogenization of a mixture of depressant pour point, which is solid at 10 ^o C, with a number average molecular weight of at least 500 and a liquid medium, characterized in that the medium in which the depressant is practically insoluble at 10 ^o C, including heating the liquid medium and the depressant to a temperature at which the depressant is soluble or melted in the liquid medium, mixing the heated components and cooling the heated mixture to a temperature at which the depressant is practically insoluble in liquid medium. 12. The method according to claim 11, characterized in that the depressant and the liquid medium are heated to a temperature of from 40 to 100 ^o C.  13. The method according to claim 11, characterized in that the heated components are mixed under conditions of high shear or cavitation.  14. The method according to claim 11, characterized in that the cooling of the heated mixture is carried out under stirring conditions.  15. A method of reducing the point of fluidity loss of a paraffin-containing liquid, comprising adding to the liquid a reducing point of fluidity the amount of composition according to claim 1. Priority on points:
11.29.1995 - according to claims 1 - 8 and 10 - 15;
04/08/1996 - according to claims 1, 9 and 11.