JPH07500620A - Oil and fuel oil compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Oil and fuel oil compositions The present invention relates to additive compositions and their use in improving the properties of oil and fuel oil compositions. Regarding use.

It is known that waxes separate from oils and fuel oils at low temperatures, thereby impairing certain properties. It is being to improve their properties, e.g. to improve cold flow properties Additives may also be used to inhibit wax settling under gravity during storage. Also known. Additives for the former are sometimes referred to as cold flow improvers; These additives are sometimes referred to as anti-wax settling agents.

Examples of patent specifications describing such additives and their uses are: US Patent 3 048 479; 3 961 916; 3 252 771. 2 542 542; 3 444 082; 4 211 53S; 4 375 973 and 4 402 708; UK Patent 1 263 152; I 469 016. + 468 588. 2 1.29 012B 2 923 645; and I 209 678; a National patent publication 56 54 038. 56 54 037. and 5540 640.

EP-A-0225688 covers oils (crude oil or lubricating oils) and fuel oils e.g. for improving the cold flow properties of residue fuels, middle distillate fuels and jet fuels, or Itaconic acid ester and citraconic acid ester polymers are used as dewaxing aids in lubricating oils. Describes the use of remers and copolymers, and describes the use of polymers and copolymers in It can be formulated to be suitable for side oils or fuel oils. It is a gel penetrating black It also has a number average molecular weight of 1,000 to 500,000 as determined by chromatography. Polymers and copolymers with molecular weights of 20,000 and above are described. Examples include polymers and copolymers.

Polymers such as those included within E P-A-0 255 688 are The problem with using them in fuel oils and fuel oils is that they affect the low temperature flow properties of flow improvers. It is possible to degenerate Noh. The present invention describes this degeneration below, and for example This can be overcome by using a combination of certain comb polymers, as shown in can be done.

International application PCT/GB91100622 (Publication No. WO91/16407 ) is used as a low temperature flow improver for distillate fuels. Examples of polymers with a number average molecular weight of 1,000 to 20,000 included in Other additives, such as comb polymers, are mentioned but not specifically exemplified. It describes the use in combination with no.

In a first aspect, the present invention provides (i) Unit or [Wherein, X is an integer, y is 0 or an integer, and the sum of X and y in the polymer is at least 2, the ratio of unit (II) to unit (1) is 0 to 2, and the unit The ratio between (11) and the unit (III> is 0 to 2, and R1 and R2 are the same or different. , respectively represent (C,, ~C3゜)alkyl, and R'1tH1-00CR', ( C+ -Cso) furkyl, -COOR', -OR', aryl or alkal Represents a lyl group or halogen, R4 represents H or methyl, R'I; tHl(CI-C3o) Furkyl 1. ! ; display t-coOR' and R6 represents (C, ~Cff2) alkyl, optionally groups R1, R4, R 2, R1, R, b and R6 are inertly substituted] a polymer comprising, and (ii) From the polymer main chain, it has an aryl group and a hydrocarbyl group, and its Dragon-type polymers in which the drocarbyl groups have 10 or more carbon atoms.

An additive composition comprising a combination of the following is provided. Preferably component (ii) has the general formula : [In the ceremony, D = R', C(0), OR, QC(0), R', R''C(0), OR' or OR'E = H or CH, or D or Rl G = H or D m = 1.0 (homopolymer) ~ 0.4 (molar ratio) J = H, R', 7'J -R or C complex] 1 group, R"CO, OR'=l(, C(0), OR@, QC(0 ), R’, OR”, C(0)Of(L=H,R”, C(0), OR”, QC(0), R', aryl, C(0)OHn = 0 to 0.6 (molar ratio) R7 is a hydrocarbyl group with 10 or more carbon atoms and R8 is C 1 or higher hydrocarbyl group, with the proviso that at least one of J and L is aryl group].

Advantageously, R7 has 10 to 30 carbon atoms and R8 has 1 to 30 carbon atoms. have.

In a second aspect, the present invention provides the additive composition of the first aspect of the present invention for crude oil, lubricant Use as a flow improver in oil or fuel oil or as a dewaxing acid in lubricating oils provide law.

In a third aspect, the invention provides main weight proportions of crude oil, lubricating oil or fuel oil and fresh weight A crude oil, lubricating oil or fuel oil composition comprising the additive composition of the first aspect of the invention in proportions provide.

In a fourth aspect, the invention provides for Additive concentrate comprising a dispersed mixture of the additive composition of the first aspect of the invention provide support.

In a fifth aspect, the present invention provides for mixing the additive composition of the 1111th aspect of the present invention into oil. for improving the flow properties of crude oil, lubricating oil or fuel oil, including provides a method for promoting dewaxing of lubricating oils.

Next, individual features of the invention will be described in more detail.

Ingredient (i) Polymer (i) is a homopolymer of dialkyl itaconate or dialkyl ntraconate. or dialkyl itaconate or dialkyl ntraconate and aliphatic olefin vinyl ethers, vinyl esters of alkanoic acids, alkyl esters of unsaturated acids aromatic olefins, vinyl halides or dialkyl fumarates or It can be a copolymer with dialkyl leate or polymer (i) is dialkyl itaconate or noalkyl ntraconate and aliphatic olefin, (C .

~C11) Co-co-production with vinyl ester or alkyl-substituted vinyl ester of alkanoic acid It can be a polymer.

R1 and R2 are each preferably linear, but they are branched be able to. If it is branched, the technique is preferably a single methyl in the 1st or 2nd position.

Examples of R1 and R2 are decyl, to-decyl, hexadecene and eicosyl.

R+ and R' are each a single (CIo-C3G) alkyl group or a mixture of alkyl groups. It can be a compound. R' and R2 are each (C1, ~ C2°) alkyl Polymers that are polymers of the radicals are particularly useful as flow improvers in middle distillate fuel oils. be. Polymers in which R1 and R2 are each (C, 6 to C72) are particularly suitable for heavy fuels. Useful in feed oils and crude oils, where R1 and R2 are each (C+.~C+s). These polymers are particularly useful in lubricating oils. Such particularly useful polymers are homogeneous It can be a polymer or a copolymer.

When dialkyl itaconate or noalkyl citraconate is a comonomer, formula (wherein R3, R4 and R1' are as defined above). Como like that Nomers can be mixtures.

When such comonomer is an aliphatic olefin, R3 and R6 are hydrogen or (C, ~Cso) represents an alkyl group, preferably an n-alkyl group, which is the same or is different. Therefore, when R3, R' and R5 are each hydrogen, the olefin is ethylene, R3 is methyl, R' and R5 are hydrogen, oleph The fin is n-propylene. When R+ is an alkyl group, R4 and R5 are preferably Or hydrogen. Examples of other suitable olefins are butene-1, butene-2, iso Butylene, pentene-1, hexene-11 tetradecene-1, hexadecene-1 and octadecene-1, and mixtures thereof.

Other such comonomers are (c,~c!l) vinyl esters of alkanoic acids or It is an alkyl-substituted vinyl ester: In the vinyl ester, R3 is R'C OO-, R4 is for power, R5 is H, alkyl substituted vinyl ester in which R3 is R'COO-, R4 is methyl, and/or R 5 is (CI-C3°)alkyl. Unsubstituted vinyl esters are preferred, examples being Vinyl acetate, vinyl propionate, butyl butyrate, vinyl decanoate, hexadecane vinyl acid and vinyl stearate.

Other types of comonomers are alkyl esters of unsaturated acids, i.e. R1 is R600. C-, and R5 is H or (C, ~C1°) alkyl.

When R4 and R5 are hydrogen, the comonomer is an alkyl ester of acrylic acid. be. When R4 is methyl, the comonomer is methacrylic acid or (C+~C1° ) is an ester of alkyl-substituted methacrylic acid. Alkyl ester of acrylic acid Examples are methyl acrylate, n-hexyl acrylate, n-decyl acrylate, n-hexadecyl acrylate, n-octadecyl acrylate and 2-methacrylate It's chillhexadenle. An example of an alkyl ester of methacrylic acid is methacrylic acid Propyl, n-butyl methacrylate, n-octyl methacrylate, methacrylic acid n-tetradecyl, n-hexadecyl methacrylate and n-octa methacrylate It's decile. Other examples include R3 being alkyl such as methyl, ethyl, n-hexyl, With the corresponding esters being n-decyl, n-tetrazonol and n-hexadecyl be.

Another type of comonomer is one in which R3 and R5 are both R"0OC-, i.e. That is, they are (C, ~C2-) dialkyl esters of fumaric acid or maleic acid. and the alkyl group is n-alkyl or branched alkyl such as n-octyl. n-decyl, n-tetrazonol, n-hexadecyl or n-octadecyl Something can happen.

Other examples of comonomers are those in which R5 is an aryl group. R4 and R5 are hydrogen and when R3 is phenyl, the comonomer is styrene and R4 and R When one of 5 is methyl, the comonomer is methylstyrene, e.g. It is tyrene. Another example when R3 is aryl is vinylnaphthalene.

Other examples when R1 is alkaryl include, for example, substituted styrenes such as vinyl Luene or 4-methylstyrene.

Other comonomers are those in which R' is a halogen, such as chlorine, such as vinyl chloride. That is, R4 and R5 are hydrogen).

As mentioned above, some or all of the groups R1, R2, R1, R4, R5 and Ra are inert. Examples include one or more halogen atoms, e.g. salts. Based on elemental or fluorine. For example, the comonomer may be vinyl trichloroacetate. can. Alternatively, the inert substituent can be alkyl, such as methyl.

The ratio between unit (II) and unit (+) and the ratio between unit (II) and unit (Ill) are 0 When the polymer is an itaconic acid ester or a citraconic acid ester homopolymer - and when the ratio is 2, the polymer is a copolymer. The ratio is preferably 0. 5-1. It is 5. Usually, copolymers contain only units (1) and (II) or only units (1) and (II). It consists only of positions (II) and (III), but other units are not excluded. death of units (1) and (11) or of units (II) and (II) in the copolymer. The weight percentage of I) is desirably at least 60%, preferably at least It is 70%.

The molecular weight of the polymer of component (1) is 1.00, whether it is a homopolymer or a copolymer. 0-500,000, preferably I, 000-20,000, more preferably I , 000 to 10,000, more preferably 2,200 to 5,000 The molecular weight can be determined by gel permeation chromatography (G PC) and is the number average molecular weight.

Homopolymers and copolymers generally include monomers alone or in hydrocarbon solvents, e.g. Generally in solution in e.g. heptane, benocene, cyclohexane or white oil. At a temperature in the range of 20 to +50'C, an inert gas such as nitrogen is added to exclude oxygen. Usually a peroxide or azo type catalyst e.g. by promoting polymerization with benzoyl or azone isobutyronitrile. Manufactured. Polymers are produced under pressure in autoliaves or by reflux. be able to.

To produce the copolymer, the polymerization reaction mixture contains up to 2 moles of comonomer (e.g. Contains dialkyl itaconate or dialkyl citraconate per mole (vinyl acetate) be able to.

More than one component (i) can be used in the practice of this invention.

The ratio of component (1) and component (ii) is, for example, in the range of lO1 to 1.10 (weight weight). can be within the range.

Ingredients (+1) Comb polymers are intermediate in structure between linear and branched polymers, with interrupted A long fatty acid from the polymer backbone, e.g. a polymethylene backbone, can be It has a group side chain. For example, Piate et al. V, P, 5hibaev).

Glossy of Polymer Science (J, Polymer 5cien ce) Macromolecular-Reviews (Macromolecular R reviews), Vol. 8. pps, 117-253 (1974) , John Wiley and Sons Comb-1ike Polymer, Structure and Properties (Comb-1ike Polymer, Structure and Properties) ers, 5structure and Properties) described in J. has been done.

"Hydrocarbyl" means a group containing hydrogen and carbon, such as an aliphatic group; Examples of one or more heteroatoms that are insufficient for modification of the hydrocarbyl properties of For example, it can be interrupted by O, N, S.

Preferably, the polymer has the general formula (In the formula, D, E, m and n are defined as above, and J is unsubstituted or substituted. is an aryl group that can be present) It is something that has.

More particularly, component (ii) is preferably a copolymer of monomers (a) and (b). Ma is (a) is an ester; fumaric acid has an alkyl group or 8 to 23 carbon atoms; maleic acid, itaconic acid, citraconic acid, mesaconic acid, trans- or nsug mono- or non-alkyl ester of lutaconic acid, (b) is a mono- or non-alkyl ester of lutaconic acid; For example, the formula Ar CH=CHt (where Ar is an aromatic is an aromatic substituted olefin (which is a substituent).

It is a copolymer of

(a) is preferably a noalkyl ester, such as a fumarate ester, but Monoalkyl esters such as fumaric acid esters are suitable. The alkyl group is , preferably straight chain, although branched chain alkyl groups can be used if desired. I can do it. Examples of suitable alkyl groups are decyl, todecyl, tetradecyl, hexadecyl Decyl, octadecyl, eicosyl, behenyl, or mixtures thereof. good Preferably, the alkyl group has 10 to 18 carbon atoms, e.g. 10 to 14 carbon atoms. Motsu. When the ester is a noalkyl ester, such as a dialkyl fumarate, 2 The two alkyl groups can be different.

In (b), the aromatic substituent is preferably a phenyl substituent, particularly preferably a phenyl substituent. New monomers include styrene and α- and β-alkyl styrenes such as α-methyl styrene and β-methylstyrene, which contain e.g. one or It can be substituted with more alkyl groups or halogen atoms. like that Alkyl substituents can have, for example, 1 to 20 carbon atoms.

The molar ratio of (b) and (a) is, for example, 1:1. 5-1. 5:L preferably 1 :1.2-1.2:L can be, for example, about 1-1. (a) and (b) The number average molecular weight of the copolymer was determined by gel permeation chromatography with respect to polystyrene standards. Fee (GPC) i: 2,000 to 100,000, preferably 5 ,000 to so,ooo.

Preferred examples of component (11) are styrene-maleate copolymer or styrene-maleate copolymer. ren-fumaric acid ester copolymers, which are used in the present invention as component (i ) as a polyitaconate ester with a number average molecular weight of 1,000 to 20,000. It is preferable to use it in combination with.

One or more components (11) can be used in the practice of this invention.

Other cold flow improvers The additive compositions of the present invention may contain one or more other cold flow improvers as co-additives. For example, it can be used in combination with those known in the art.

Examples include comb polymers other than those constituting component (i) or component (11): polio Quinalkylene ester, ether, ester/ether, amide/ester, and mixtures thereof, ethylenically unsaturated ester copolymers, polar compounds, ions whether ionic or non-ionic (as described in EPA-0225688)2 Sulfur carboxy compounds as well as hydrocarbon polymers.

Other low temperature flow improvers will now be described in more detail.

(Shield polymer Example is a general formula [During the ceremony, D = R, CO, OR, OCO, R, R'CO, OR or ORE =) I or is CH3 or D or R1G=H or D m = 1.0 (homopolymer) ~ o, 4 (molar ratio) J-11, R', 7'J-le Also, C [subcyclic group, also LJ R'CO, ORK = H, CD, OR', OCO, R ’, OR’ or HACOtHL = H, R’, CO, OR’, OCO, R’, 71J -/I/ Also C0tHn = 0.0 -0.6 (molar ratio) It is something that has.

Other monomers can be terpolymerized if desired.

Examples of suitable comb polymers are fumaric acid ester/vinyl acetate copolymers, especially European As described in state patent applications 0153176 and 0153177; olefin/maleic anhydride copolymer, α-olefin/maleic anhydride Polymers and copolymers of acid copolymers: Polymers and copolymers of alpha-olefins esterified copolymers of methylene and maleic anhydride; and itaconic acid or is a polymer of alkyl ester of citraconic acid, for example, 16 to 18 alkyl groups. carbon atoms and the polymer has a number average molecular weight of 1,000 to 20,000. It is something.

Polyoxyalkyleno compound Examples are polyoquinoalkylene esters, ethers, esters/ethers and their in particular at least one, preferably at least two (C,.~C1° ) linear saturated alkyl groups and up to 5,000, preferably from 200 to 5,000 having a molecular weight of polyoquine alkylene glycol groups, The alkyl group in the recall has 1 to 4 carbon atoms. these substances forms the subject of European Patent Publication No. 0061895 A2. other such additives is described in US Pat. No. 4,491,455.

Preferred esters, ethers, or esters/ethers that can be used are structurally of the formula %formula%) [In the formula, R and R2 are the same or different, and (a) n-alkyl.

, n is for example 1-3o, the alkyl group is linear, saturated and , having 10 to 30 carbon atoms, and A is the alkylene group having 1 to 4 carbon atoms. Polyalkylonone segments of glycols, such as substantially linear polyols. Xymethylene, polyoxyethylene or polyoxytrimethylene moiety, represents: Some degree of branching due to lower alkyl side chains (e.g. polyoxypropylene glyco ) can be tolerated, but the glycol must be substantially linear. is preferable. A can also contain nitrogen.

Suitable glycols generally have a molecular weight of about 100 to 5,000, preferably about 200 to 2. Substantially linear polyethylene glycol (PEG) with a molecular weight of Lipropylene glycol (PPG). Ester is preferred, 10 to 30 Fatty acids with carbon atoms of The use of (Ct to C54) fatty acids, especially behenic acid, is preferred. beauty salon It is also an ester of polyethoxylated fatty acids or polyesters and xylated alcohols. It can be manufactured by chemical reaction.

Polyoxyalkylene diesters, diethers, ethers/esters and the like are suitable as additives; diesters are suitable as additives; Noesters (they are often formed during the manufacturing process) may also be present. Preferred for use in narrow boiling cuts when possible. Large amounts of dialkyl compounds are present. This is important for additive performance. In particular, polyethylene glycol, Spread of propylene glycol or polyethylene/polypropylene glycol mixture Tearic acid or behenic acid diesters are preferred.

Examples of other compounds within this general category are Japanese Patent Publication No. 2-51477 and and 3-34790 [both Sanyo], and] EP-A- 117.108 and EP-A-326, 356C are both manufactured by Nippon Oil & Fats. Oil and Fats)).

Ethylene/unsaturated ester copolymer An example is ethylene and the general formula [In the formula, R6 is hydrogen or methyl, and R8 is an 10OCR' group (in the formula, R1' is Hydrogen formate or (C, ~C,,), more generally C3~C,t), preferred or (c+ -Cs) is a straight chain or branched chain alkyl group), or R11 is a -COOIze group (wherein R' is as described above, but is not hydrogen). I) and R? is hydrogen or -COOR” as above] one or more oil-soluble copolymers.

The monomer is (C+ ~C,,,), more generally (C, ~C3) monocarboxylic acids, preferably (Ct~ C2-), more generally (C, ~Cs) monocarboxylic acids, preferably (Cz~Cs) ) Contains vinyl alcohol esters of monocarboxylic acids. copolymerize with ethylene Examples of vinyl esters that can be used include vinyl acetate, vinyl propionate, and vinyl esters. Vinyl acids or isobutyrates are included, with vinyl acetate being preferred. These copolymers 1.000 to 10,000, preferably 1.2 as measured by vapor phase osmotic pressure method.　 It is preferable to have a number average molecular weight of 000 to s, ooo. If you wish, Kopo Remer can be derived from additional comonomers, e.g. If the isoolefin is, for example, no isobutene, then for example it is a terpolymer. - or a tetrapolymer or more.

Polar organic, nitrogen compounds Examples include one or more of F compound compounds (a,) to (ci).

(a) at least 1 molar proportion of H(-Localhylic-substituted amine) and a molar proportion of 1 ~By reaction with hydrocarhylic acid having 4 carboxylic acid groups or its acid anhydride Amine salt and/or amide formed; 30-300, preferably 50-15 Esters/amides with 0 total carbon atoms can be used. These nitrogen The elementary compound is described in US Pat. No. 4,211,534. Suitable amines are usually Long chain (Cs.) primary, secondary, tertiary or quaternary amines or the like However, the shorter chain amines are a mixture of If present, therefore usually having about 30 to 300 total carbon atoms, use Can be done. The nitrogen compound preferably has at least one straight chain (C, ~c4°), preferably Preferably, it has a (014-C□) alkyl segment.

Suitable amines include primary, secondary, tertiary or quaternary, but are preferred. In other words, it is second class. Tertiary and quaternary amines can only form amine salts. can. Examples of amines include tetrazodinogenine, cocoamine, and hydrogenated tallow amide. Includes Examples of secondary amines include dioctadecylamine and methyl-behenylamine. Contains rumin. Amine mixtures, such as those derived from natural substances, are also Appropriate. Preferred amines have the formula HNR'R'', where R1 and R2 are about Acid derived from hydrogenated beef tallow consisting of 4% CI 4.31% CI 8.59% C+a It is a secondary hydrogenated beef tallow amine (which is a lukyl group).

Examples of carboxylic acids and their acid anhydrides suitable for the production of nitrogen compounds include cyclot\ Xane 1,2 dicarboxylic acid, cyclohexene 1,2 dicarboxylic acid, cyclopenta 2 dicarboxylic acids and naphthalene dicarboxylic acids. Generally these The acids have about 5 to 13 carbon atoms in the ring portion. Preferences useful in the present invention Acids include benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. Particularly preferred is phthalic acid or its acid anhydride. Particularly preferred compounds are 1 mole Formed by the reaction of 2 moles of phthalic anhydride with 2 moles of dihydrogenated beef tallow. It is an amidoan salt. Other preferred compounds are for dehydration of this amide-amine salt. It is a diamide formed by

Another example 1jl is a condensate as described in EP~A-327,423.

(b) A compound containing or including a cyclic ring system, a compound having the following general formula (1) on the ring system )-A-NR' R' (+) -A-NR' R' (1) (wherein A is directly interrupted, optionally interrupted by one or more heteroatoms) an aliphatic hydrocarbyl group that is a chain or a branched chain, and R1 and R2 are the same or different, each independently optionally intermediated by one or more heteroatoms. truncated hydrocarbyl group with 9 to 40 carbon atoms), the substituents are the same. - or at least two different substituents, and the compound optionally has a salt thereof. It is a form.

Preferably A has 1 to 20 carbon atoms, preferably methylene or polymethyl It is a ren group.

"Hydrocarbyl J" in this specification means an organic moiety consisting of hydrogen and carbon; unless the context clearly states otherwise: aliphatic (including cycloaliphatic); aromatic; It can be any combination of these. It can be substituted or unsubstituted alkyl, Can be aryl or aralkyl and can optionally contain unsaturation. Ru. Examples where it is substituted are oxy-, halogeno- and hydroxy-hydrocarbons. It's Rubil.

Cyclic systems are homocyclic, heterocyclic, or fused polycyclic assemblies, or bicyclic assemblies. The more such annular assemblies are connected to each other, the more annular assemblies become It can include systems in which two can be the same or different. two or more such When there is a cyclic assembly such as on the same assembly, preferably on the same assembly. Preferably, The or each ring assembly is aromatic, more preferably a benzene ring . Most preferably the cyclic ring system is a single benzene ring, when the substituents are ortho or It is preferably in the meta position, and the benzene ring may optionally be further substituted. I can do it.

The ring atoms in the cyclic assembly or assemblies are preferably carbon atoms, but , but can contain e.g. one or more N, S or O atoms, the In some cases the compound is a heterocyclic compound.

Examples of such polycyclic assemblies include - fused to/then structures such as naphthalene. anthracene, phenanthrene and pyrene.

・Fused ring structures in which all or not all rings are non-Hensen, e.g. azulene, Indene, hydroindene, fluorene and diphenylene; (end-on) J-linked ring e.g. diphenyl; Heterocyclic compound e.g. quinoline, indole, 2/3 dihydroindole, benzofuran, coumarin, Isocoumarin, benzothiophene, carbazole and thiodiphenylamine.

・Non-aromatic or partially saturated ring systems such as decalin (i.e. decahydronaphthalene) ), α-pinene, caldinene and bornylene: and three-dimensional structures such as nor Bornene, vinclohebutane (i.e. norbornane), bicyclooctane, and Contains bicyclooctene and bicyclooctene.

Each hydrocarbyl group constituting R1 and R2 (Formula 1) in the present invention is, for example, or alkylene group or mono- or poly-alkoxyalkyl group Can be done. Preferably, each hydrocarbyl group is a straight alkyl group.

The number of carbon atoms in each hydrocarbyl group is preferably from 16 to 40, more preferably is 16-24.

It is also possible that the ring system is substituted with just two substituents of general formula (1) and that A is methylene. It is preferable that it is an ion group.

Examples of salts of compounds are acetate and hydrochloride.

The compounds are conveniently prepared by reacting secondary amines with suitable acid chlorides. It can be produced by reduction of

(C) Specific example of condensate of long-chain primary or secondary amine and carboxylic acid-containing polymer GB-A-2,121,807, FR-A-2,592,387 and DE- A-3゜941,. 561 and also as described in US-A -4,639,256. id) with alkanolamines and US-A-4,631,07 Branched carboxylic acid esters, epoxides and monocarboxylic esters as described in 1. reaction products of amines containing phosphoric acid polyesters.

hydrocarbon polymer An example is the following general formula [In the formula, T=H or RI U=H, T or aryl v=1. (J-0,0 (molar ratio) w = 0.0 to 1.0 (molar ratio), and R1 is alkyl] It is expressed by

These polymers can be produced directly from ethylenically unsaturated monomers or from monomers such as It can be made indirectly by hydrogenation of polymers made from soprene, butadiene, etc. I can do it.

Particularly preferred hydrocarbon polymers preferably contain 20 to 60% (w/w) ethylene. A copolymer of ethylene and propylene with a carbon content, usually produced using a homogeneous catalyst. be done.

Examples of hydrocarbon polymers are described in WO-A-911,1488.

sulfur carboxy compound An example is that described in E.P.A.O., 261,957, which uses the general formula : [In the ceremony, -Y-R' is -3O3'-'CountryNR'sR2,-5O,l-1+HNR3,R ', -5o,'-'　"H2NR'R'　　-SO,'-'　"'H,NR', -5Ox'-'"NR33RI or -3O3R'.

-X-R' is -Y-R' or -COIJR3R', -CD,'-'"NR" , R', -CO,'-'" HN R'!R', -R'-COOR,, -N R33RI, -R'OR', -R'0COR', 4Jl, -N(COR")R 'or 7. i-1++l is NR33RI;, -2+-ゝ is SOs” or -co, "; R' and R2 have at least 10 carbons in the main chain Alkyl, alkoxyalkyl or polyalkoxyalkyl containing elementary atoms ; R3 is hydrocarbyl, each R3 can be the same or different; R4 is nothing; or (C, ~C0) alkylene, in which the carbon-carbon (C-C) bond is a) when A and B are alkyl, alkenyl or substituted hydrocarbyl groups; or b) aromatic, polyaromatic or cyclo-aliphatic. is a part of a cyclic structure in which X-R' and Y-R2 are at least may also contain three alkyl, alkoxyalkyl or polyalcokynealkyl groups. and is preferred.

Multi-component additive systems can be used, with the ratio of additives used depending on the oil being treated. It will depend.

oil and fuel oil The oil can be crude oil, i.e. oil obtained from drilling, before refining, and then The compositions of the invention can be used as flow improvers or dewaxing aids.

The oil can be a lubricating oil, it can be an animal, vegetable or mineral oil such as naphtha or steel. Petroleum distillates from pindle oil to lubricant grade, castor oil, fish oil or oxidized ores It can be oil. The additive composition of the present invention provides flow improvers, pour point It can be used as a depressant or dewaxing aid. Other additives in the final lubricant Examples include viscosity index improvers such as ethylene-propylene copolymer. mer, succinic acid group dispersants, metal-containing dispersing additives and zinc noalkyl dithiophores. Suphate is an anti-wear additive.

Examples of fuel oils are middle distillate fuel oils, i.e. fuels obtained during the refining of crude oil, e.g. They are kerosene to jet fuel fractions and heavy fuel oil fractions. An example is diesel fuel fuel oil, aviation fuel, kerosene, fuel oil and heating oil. generally appropriate Distillate fuel is one that boils within the range of 120 to 500°C (ASTM D1160 ), preferably one that boils within the range of 150 to 400°C, such as about 360°C It has a relatively high end point (FBP). Fuel oil is animal, vegetable or mineral It can be oil. Fuel oils may also contain other additives such as stabilizers, dispersants, antioxidants, etc. Inhibitors, corrosion inhibitors and/or demulsifiers may be included.

Heating oils are straight-run distillates, such as gas oil, naphtha, etc., and cracked fractions, such as contact oil. Can be made with a blend of recycled oils. The typical standards for diesel fuel are 3. Includes a minimum flash point of 8°C and a 90% distillation point of 282-338°C (ASTM Instruction D -396 and D-975).

The total amount of additive composition provided in the fuel in the present invention is based on the weight of the fuel. , preferably o,ooot to 5.0% by weight, e.g. 0.001-0.5% by weight ( active substance).

When the present invention is a concentrate, the additive composition may be 20 to 90% by weight of the concentrate. For example, it can be 30 to 80% by weight. Fluid used during concentrate Examples of body carriers are solvents such as kerosene, aromatic naphtha and mineral lubricating oils.

example The invention will now be described in detail, by way of example only, as follows. As shown, the example is from the book Inventive examples plus comparative examples, Mn was determined by GPC on polystyrene standards. Means the measured number average molecular weight.

Additive The additives used were indicated by the code code as follows:

A For tests on Fuels I and 11 (see below), A is two ethylene / Vinyl acetate copolymer Contains 36.5% by weight vinyl acetate, every 3 to 4 methyl groups A copolymer of Mn 2500 containing 100 methylene groups and 13.5% by weight vinyl acetate. Copolymer of Mn 5000 containing 100 methylene groups per 6 methyl groups , and the ratio of the two copolymers is 937 (weight: weight): the remainder For testing on fuel (see below), A uses 29.0% by weight vinyl acetate. ethylene/vinyl acetate copolymer containing 100 methylene groups for every 4 methyl groups. there were.

B. 1 mole of phthalic anhydride and 2 moles of phthalic anhydride to form a half-amide/half-amine salt Reaction product with dihydrogenated tallow amine.

D. A linear alkali made by polymerizing monomers using a free radical catalyst. homopolymers of esters of itaconic acid in which the kill group has 16 carbon atoms; Rimmer has an Mn of 3,500.

G-K A number from 15,000 to 30,000 in which the alkyl group has the following number of carbon atoms: A family of styrene/fumarate copolymers with average molecular weights, fuels The test fuels used were Fuels ■~Vl, their characteristics are shown in Figure 1, and the temperature was The temperature is ℃.

Diagram 1 fuel fuel Properties I II III IV V Vl-based CFPP -8-8-9-7- 40D-861BP 166 168 135 136 178 17920% 231 24B 213 200 261 25750 Hiki 276 279 277 248 291 29390% 325 327 332 329 3 41 350FBP 348 358 361 364 368 373 Test temperature Degree -17-15-17-17-15-9 General operations Additives (individual additives 01 identified by juxtaposition of additive code letters in the results below) (containing combinations of single components) into the test diesel fuel (1-Vl) according to standard methods. 200ppm (active ingredient) for A, 200ppm (active ingredient) for B and 200 ppm (active ingredients) of each of the other additive components if used. minutes) was added to the additive concentration. Then the following test was carried out on fuel No. 2 I went against it.

Clogging point test (or CFPP test) [Journal of the Institute of Petroleum nalof the In5 position of Petroleum) J, Vol, 52. No, 510. June 1900. +1P1.173 ~ 285, the test is carried out in accordance with the procedures detailed in 285. Designed to correlate to cold flow of inter-distillates.

Briefly, a 40ml sample of the oil to be tested is placed in a bath maintained at approximately -34°C. to provide non-linear cooling at approximately 0°C/min. Start periodically (upper blade at cloudy point) (approximately 1°C each), the cooled oil is placed in an inverted leakage tube placed below the surface of the oil being tested. Doo through a fine screen using a testing device that is a pipette connected to the bottom end. It was tested for its ability to flow within a specified period of time. ■2mm in the mouth of the funnel A 350 mesh screen is stretched over the area defined by the diameter of the Ru. Each periodic test begins by applying a vacuum to the top of the pipette. The oil is then passed through the screen and into the pipette until it reaches the 20ml oil mark. It is drawn by After each satisfactory pass, the oil is immediately returned to the CFPP pipe. The exam is For each 1 degree decrease in temperature, oil fills the pipette within 60 seconds (repeat until oil fills the pipette). The temperature at which failure occurs is reported as the CFPP temperature.

Wax Sedimentation Prevention (WAS) Test The degree of sedimentation layer (WAS) is determined by leaving the treated fuel in the volumetric flask. Measured visually as percent of fuel volume. A large amount of wax sedimentation is caused by a low number while non-settling fluid fuels are indicated by 100%. game with big wax crystal Inferior samples of purified fuel almost always show higher values, so such results are , is recorded as a "gel" if it occurs.

Measurement of crystal size The average grain size of wax crystals was determined by analyzing optical micrographs of fuel samples and using predetermined grids. It was measured by measuring the longest axis of up to 50 crystals above.

result Additives or combinations thereof were tested in each of the 1-Vl fuels. CFPP , ~VAS and crystal size are shown in the following three tables, respectively, Table 1. 2 and 3, and the following explanation is given.

Table 1 (CFPP) All results are below 0°C, that is, negative values.

Table 2 (WAS) All results are percentages of variance, 100 is perfect variance and the observations were made after 2-3 hours at the test temperature.

Table 3 (crystal size), all values are on a scale of 1 to IO, where IO is <10 micron, 9 is 10 microns, 8 is 10 to 20 microns, 7 is 20-50 microns, 6 is 50 to 100 microns, 5 is 100-200 microns, 4 is 200-300 microns, 3 is 300-500 microns, 2 is 500-700 microns, 1 is 700 microns.

The following general conclusions can be drawn from the results presented in Tables 1-3.

・Additive AB<comparative example) gave good overall CFPP performance but inconsistent WAS and and crystal size performance.

・Additive ABD (comparative example) showed good WAS and crystal size performance, but C gave a regression in FPP performance.

・The above deterioration is reduced by either additive G- in combination with ABD. Both were partially reduced.

Table 1 (CFPP) fuel Additive I If If IV V Vl Average AB 13 19 20 14 18 13 16.2ABD 8 18 15 16 7 3 11.2AB DG 11 19 17 15 15 7 14ABD)-111181915 14714ABDI 11 18 20 15 14 To +4.7ABDJ 10 17 20 16 15 9 14.5 ABDK il 15 16 +7 13 10 13.7 Table 2 (WAS) fuel Additive I II Ill IV V VI MAB 70 80 10 15 80 40 49.2ABD 100 100 80 100 75 100 92.5 ABDG 95 do 100 100 100 20 75.8A BDH95501001001002077,5ABD+ 95 50 100 100 100 20 77.5ABDJ 95 50 95 100 10 0 80 86.7ABCK 95 100 +5 100 100 90 8 8.3 Table 3 (crystal size) smoked wood Additive l l l l I 11 1 V V V I Average country a! l-1F Sardine Beef , +a, N+ PCT/EP 92102329 Front page continuation (51) Int, C1,' Identification symbol Internal office reference number C10M 14510 8 9159-4H // C10N 20:04 30:02 I

Claims (1)

[Claims] 1. An additive composition comprising the following components (i) and (ii) in combination: (i) Place: ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein, X is an integer, y is o or a number, and in the polymer, the sum of X and y is at least 2, the ratio of unit (II) to unit (I) is from 0 to 2, and the unit The ratio of (II) to units (III) is 0 to 2; R1 and R2 are the same or different each represents a (C10-C30) alkyl group, R3 is H, -OOOCR5, (C1-C30)alkyl, -COOR8, -OR 6, represents an aryl or alkaryl group or a halogen, R4 is H or methyl represents, R5 represents H, (C1-C30) alkyl, or -COOR6, and R6 represents (C1 ~C22) represents alkyl, optionally the groups R1, R2, R3, R4, R5 and R6 is inactively substituted] a polymer comprising, and (ii) From the poly main group, it has an aryl group and a hydrocarbyl group, and its hydrocarbon Dragon-type polymers in which the lupyl group has 10 or more carbon atoms. 2. Component (ii) or general formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [During the ceremony, D=R7, C(O), OR, OC(O), R7, R8C(O), OR7 or OR 7E=H or CH3 or D or R8 G=H or D M=1.0 (homopomer) to 0.4 (molar ratio) J=H, R8, aryl or complex Ring group, R6CO, OR7K=H, C(O), OR8, OC(O), R8, OR9 , C(O)OHL=H, R8, C(O), OR8, OC(O), R6, Aryl , C(O)OHn=0 to 0.6 (molar ratio) R7 is a hydrocarbyl group with 10 or more carbon atoms and R8 is C 1 or higher hydrocarbyl group, with the proviso that at least one of J and The composition according to claim 1, wherein the composition has an aryl group. 3. The polymer defined in component (ii) has a general formula: ▲ Numerical formula, chemical formula, table, etc. I'm here▼ (wherein D, E, K, m and n are defined as described in claim 2, and J is a substitution or is an unsubstituted aryl group) The composition according to claim 1 or 2, having the following. 4. Polymer is styrene-maleate ester copolymer or styrene-fumaric acid ester copolymer 4. The composition of claim 3, which is an acid ester copolymer. 5. The maleate or fumarate esters also contain 10 to 18 carbon atoms. 5. The composition according to claim 4, having two alkyl groups. 6. The composition contains other cold flow improvers for distillate fuels in combination. The composition according to any one of claims 1 to 4. 7. The polymer defined in component (i) is dialkyl itaconate or citracone. A homopolymer of dialkyl itaconate or dialkyl itaconate or citracone Dialkyl acids and aliphatic olefins, vinyl ethers, vinyl esters of alkanoic acids alkyl esters of unsaturated acids, aromatic olefins, vinyl halides, fumaric acid 2. A copolymer with dialkyl maleate or dialkyl maleate. 6. The composition according to any one of 6. 8. one or both of the polymers defined in components (i) and (ii) is 1.00 Any one of claims 1 to 7 having a number average molecular weight within the range of 0 to 50.000. The composition described in . 9. 9. The composition of claim 8, wherein the range is 1.000-20.000. 10. Claims 1 to 9 have a main weight proportion of crude oil, lubricating oil or fuel oil and a minor quantity proportion. A crude oil, lubricating oil or fuel oil composition comprising an additive composition according to any one of the claims. 11. Claims 1 to 9 dispersed in a liquid medium compatible with crude oil, lubricating oil or fuel oil. An additive concentrate comprising a mixture of the compositions according to any one of the preceding claims. 12. As a flow improver in crude oil, lubricating oil or fuel oil, or as a dewaxing aid. 10. A method of using an additive composition according to any one of claims 1 to 9. 13. The method according to claim 10 or claim 12, wherein the method is oil or middle distillate fuel oil. is a composition. 14. Mixing the additive composition according to any one of claims 1 to 9 into oil. to improve the flow properties of crude oil, lubricating oil or fuel oil, including how to promote