JPH0224394A - Fuel oil composition - Google Patents

Abstract

PURPOSE: To decrease the tendency of wax cohesion and improve the fluidity at a low temperature, by blending a large amount of liquid hydrocarbon fuel with a small amount of polymer containing plural amino groups.

CONSTITUTION: A large amount of liquid hydrocarbon fuel (example: distilled fuel oil or the like of diesel fuel, aviation fuel, kerosene, jet fuel or the like) is blended with a small quantity of a polymer containing more than one amino groups. At that time, these amino groups are so selected as are primary, secondary or tertiary amine salt or quarternary ammonium salt. This polymer containing more than one amino groups can be prepared by reacting a polymer having plural carboxylic acid groups or acid anhydride groups with a primary, secondary or tertiary amine, also, a quarternary ammonium salt can be prepared by reacting one of the cited polymers with tetrahydrocarvil ammonium halide. Also, the amount of polymers containing amine salts is preferably 0.0001-5.0 wt.% (active material) with the weight standard of the hydrocarbon fuel.

COPYRIGHT: (C)1990,JPO

Description

[Detailed description of the invention] (Field of industrial application of the invention) The present invention relates to fuel oil compositions containing flow improvers.

BACKGROUND OF THE INVENTION Wax separation in crude oil, middle distillate fuels, heavy residual fuels, and lubricating oils limits their flow at low temperatures.

Typical methods for solving these problems include wax crystal modifying compounds (nucleating agents) that make the wax crystals smaller and/or wax crystal modifying compounds (nucleating agents) that make the wax crystals smaller and grow into a more compact configuration. (inhibitor).

Another difficulty is that small wax crystals can stick together to form larger aggregates, and these aggregates as well as individual crystals can block the filter screen through which the individual crystals pass; , which settles faster than smaller crystals.

Means for Solving the Problems The present inventors have discovered that wax crystals can be modified to improve filterability and reduce pour point by the addition of certain amino salts or quaternary ammonium salts. It has been found that the tendency of agglomeration can be reduced.

In accordance with the present invention, the fuel composition comprises a large weight proportion of a liquid hydrocarbon fuel and a small weight proportion of a polymer containing more than one amino group, the amino groups being a primary, secondary or tertiary amine or a quaternary amine. It is an ammonium salt.

Also in accordance with the present invention, polymers containing one or more amino groups in which the amine groups are salts of primary, secondary or tertiary amines or quaternary ammonium salts are used to improve flow in liquid hydrocarbon fuels. used as an agent.

The liquid hydrocarbon fuel oil can be a distilled fuel oil, such as a middle distilled fuel oil, such as diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil, and the like. Generally, suitable distillate fuels are 120°C to 500°C (ASTM D8
6) distillate fuel with a boiling point in the range of 150°C to 4°C, preferably 150°C to 4°C;
It is a distillate fuel with a boiling point in the range of 00°C. Typical heating oil specifications include 10% with a distillation point below about 226°C, 50% with a distillation point below about 272°C, and 90% with a distillation point of at least 282°C.
requires a distillation point below about 338°C to 343°C, although some specifications set 90% distillation points as high as 357°C. Preferably, the heating oil is made from a blend of a virgin distillate, such as gas oil, naphtha, etc., and a thalassoked distillate, such as a catalytic cycle oil.

Polymers containing more than one amine group are classified as primary, polymers with multiple carboxylic acid or acid anhydride groups,
It can be prepared by reacting with a secondary or tertiary amine.

To prepare the quaternary ammonium salt, the polymer may be reacted with a tetrahydrocarbyl ammonium halide. They may also be prepared by reaction of a tertiary amine with a halogenated hydrocarbyl; the polymers from which the desired polymer is thus derived should have halide groups and be reacted with the tertiary amine, respectively.

There are many different types of polymers that can be further reacted to produce the desired polymer containing two or more amine bases.

(1) Examples thereof are polymers of one or more unsaturated monomers containing ester groups and free acid groups and copolymers of unsaturated ester monomers in which at least one heptad also has free acid groups. Particular examples are copolymers of dialkyl fumarates, maleates, citraconates or itaconates, copolymers of vinyl acetate with monoalkyl fumarates, maleates, citraconates or itaconates, copolymers of alkyl acrylates or alkyl methacrylates with monoalkyl fumarates, maleates, citraconates or itaconates. and copolymers of dialkyl fumarates, maleates, citraconates or itaconates and monoalkyl fumarates and vinyl acetate.

A particularly preferred example of a type I polymer is a copolymer of vinyl acetate, monoalkyl fumarate, and dialkyl fumarate, where the alkyl group is a monomer of dodecyl and tetradecyl.
: 1) and vinyl acetate and monododecyl,
It is a copolymer with monotetradodecyl or monohexadecyl fumarate.

(II) Other examples are copolymers of unsaturated esters and/or olefins with unsaturated carboxylic acid anhydrides. These copolymers can give half-amide/half-amine salts by reaction with acid anhydride groups upon reaction with primary or secondary amines. Particular examples are (a) copolymers of dialkyl fumarates, maleates, citraconates or itaconates with maleic anhydride, or (b
) a copolymer of vinyl esters such as vinyl acetate or vinyl stearate with maleic anhydride, or (C
) Copolymers of dialkyl fumarates, maleates, citraconates or itaconates with maleic anhydride and vinyl acetate.

Other examples are copolymers of maleic anhydride with styrene or aliphatic olefins such as C1o-C50 olefins such as decene, dodecene, tetradecene, hexadecene, eicosene, tocosene, tetradecyl, oftacocene, propylene tetramer or propylene hexamer.

A particularly preferred example of a type H polymer is a copolymer of didodecyl fumarate and vinyl acetate maleic anhydride, di-
A copolymer of tetradecyl fumarate, vinyl acetate, and maleic anhydride, a copolymer of dihexadecyl fumarate, vinyl acetate, and maleic anhydride, or a similar copolymer in which itaconate is used in place of fumarate.

(II[) The desired polymer can also be prepared by partial hydrolysis of a polymer containing ester groups to obtain carboxylic acid or acid anhydride groups. The partially hydrolyzed polymer is then reacted with an amine to produce the desired polymer containing two or more amine bases.

Thus, polymers of acrylates, methacrylates, alkyl fumarates, alkyl maleates, or copolymers thereof or copolymers thereof with olefins may be hydrolyzed.

Particularly suitable examples of polymers of type II are partially hydrolyzed polymers of alkyl acrylates or methacrylates, such as dodecyl acrylate, tetradecyl acrylate or hexadecyl acrylate.

(IV) Also suitable polymers are polymers of unsaturated carboxylic acids, such as polyacrylic acid or polymethacrylic acid, copolymers of acrylic acid with olefins, such as ethylene or alkyl fumarates, and copolymers of methacrylic acid with olefins, such as evaporated ethylene or alkyl fumarates. It is a copolymer with fumarate.

In all of the above types of suitable polymers (■, ■, ■, and It is obtained by reacting to obtain the corresponding amine salt (if necessary, and when reacting with an alcohol, an ester-amine salt is formed). Very often, for example when reacting polymers containing acid anhydride groups, the resulting amino groups are amine salts and amides. Such polymers may be used provided they contain at least two amine bases.

To prepare quaternary ammonium salts, any of the above polymers (I, Either they are converted to contain halide groups, or they are produced by polymerizing them with unsaturated halides, such as vinyl chloride. They are then reacted with tertiary amines to form quaternary ammonium salts.

(v) Other suitable polymers are obtained by partially hydrolyzing a polymer of unsaturated esters, followed by reaction with a carboxylic acid anhydride, which is then reacted with a primary, secondary or tertiary amine to form the desired amine. Obtained by producing salt.

Suitable polymers of unsaturated esters are homopolymers of acrylates, methacrylates, alkyl fumarates or copolymers of these with olefins such as ethylene or copolymers of vinyl acetate with olefins.

A special example is a copolymer of ethylene and vinyl acetate. After partial hydrolysis, the polymer may be reacted with an acid anhydride, such as succinic anhydride or maleic anhydride, and the resulting product may be reacted with a primary, secondary or tertiary amine to obtain the corresponding amine salt. Alternatively, it may be reacted with a tetrahydrocarbyl ammonium halide to give the corresponding quaternary ammonium salt.

The polymer containing at least two amine or quaternary ammonium bases has at least one hydrogen- and carbon-containing group (the total number of carbon atoms in the one or more groups being at least 10 carbon atoms). ) is not required but highly desirable. It is further preferred that there are 12 to 18 carbon atoms in at least one of the above groups. Such groups, which are preferably linear or branched alkyl groups, may be present attached directly to the main chain of the polymer or via carboxylate groups, or may be present as amine bases or quaternary ammonium bases. It may exist bonded to a nitrogen atom. The polymer may also contain such groups attached both to the nitrogen atom and to the backbone or carboxylate group. Thus the type■,■,■
In the polymers of (1) and (2), the alkyl groups of the mono- and di-alkyl fumarates, alkyl acrylates, or alkyl methacrylates from which the polymers are derived may contain at least 10 carbon atoms. Particularly suitable monomers are therefore didodecyl fumarate, ditetradecyl fumarate, dioctadecyl fumarate and the corresponding monoalkyl fumarates and mixtures thereof. Also particularly suitable are dodecyl, tetradecyl, hexadecyl and octadecyl acrylates and methacrylates. In polymers of type (2), for example didecyl maleate, didodecyl maleate, ditetradecyl maleate can be used.

Long chain groups may be introduced into the polymer by means of criminal law or as additions by using long chain primary, secondary or tertiary amines or tetrahydrocarbyl ammonium halides or mixtures thereof during salt formation.

Amines have the formulas R' NHz , R' R2NH and R'
R'' R3N, and the tetrahydrocarbyl ammonium halide has the formula R'R2R' R
' can be represented by NX (where R1, R2
, R:l and R4 are hydrocarbyl groups, preferably alkyl groups, and at least one of R1, R2, R3 and R4 has at least 10 carbon atoms, for example 12 to 18
carbon atoms, such as dodecyl, tetradecyl, hexadecyl and octadecyl, and X is halogen, preferably chlorine).

Suitable polyamines are 2 Hz N (RIIN) x H and R' NH (RNR' ) x H, where R1 is a hydrocarbyl group and R is a divalent hydrocarbyl group, preferably alkylene or hydrocarbyl-substituted alkylene; and X is an integer).

Examples of suitable primary amines are hexylamine, octylamine, and primary amines containing at least 10 carbon atoms, such as decylamine, tetradecylamine, octadecylamine, eicosylamine, mixed amines RN Hz
(Armeen C) (wherein R is 0
．． 5 wt.% 06 alkyl, 8 wt.% C1l alkyl, 7 wt.% C1° alkyl, 50 wt.% 01□ alkyl, 18 wt.% C14 alkyl, 8 wt.% C1&
Alkyl, 1.5% by weight Cl11 alkyl and 7.0
wt% CIa/C+ q-unsaturated groups).

Examples of suitable secondary amines are dioctylamine and secondary amines containing alkyl groups with at least 10 carbon atoms, such as didecylamine, cytosylamine, dicocoamine (i.e. di-mixed 01□-CI2 alkyl amines), dioctadecyl Amine, hexacyl, octadecylamine, di-hydrogenated beef tallow amine (Arm
een) 2 HT) (approximately 4 wt% nc+4
Alkyl, 30 wt% nC1a alkyl, 60ffi
ffi% C11+ alkyl, remaining unsaturated groups), n-
Coco-propyldiamine (Ct□/CI4alkyl-propyldiamine-Duomeen) C
), n-tallow-propyldiamine CC+h/CIa alkylpropyldiamine diamine T).

Examples of suitable tertiary amines are trihexylamine, trioctylamine and tertiary amines containing alkyl groups with at least 10 carbon atoms, such as hexyldidecylamine, tridecylamine and trihexadecylamine. .

Examples of suitable quaternary ammonium halides are trioctyl-methylammonium chloride and quaternary ammonium halides containing an alkyl group with at least 10 carbon atoms, such as tridodecyl-methylammonium chloride, tritetradecyl, dodecylammonium chloride, and Hexadecyl, dimethyl, and phenylamine.

Examples of suitable polyamines are N-octadecylpropanediamine, N',N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N,N'-dihexadecylhexanediamine.

The polymer salt of the present invention usually has a molecular weight of 1,000 to 500,
000, for example from 10,000 to 100,000.

Particularly suitable examples of polymers containing amino groups for use in the present invention are as follows.

(11 diCrb/CB n-alkylamine (CIb
ditetradecyl fumarate, acetic acid, reacted with alkyl/C1, where alkyl is about 1=2) to form a half-amide, half-amine salt of carboxylic acid groups derived primarily from the maleic anhydride units of the copolymer. Copolymer of vinyl and maleic anhydride (molar ratio of vinyl acetate: fumarate: maleic anhydride approximately 50:45)
: 5).

(2) 50 mol% vinyl acetate, 45 mol%, reacted with 5 mol% trioctylamine to form a half-amide, half-amine salt of the EMRed carboxylic acid group from the maleic anhydride units of the copolymer; The Clz/
Cl 4 alkyl fumarate (1:l mixture) and 5
Copolymer of mol % maleic anhydride (3) A copolymer similar to (2) above, except that it is produced by the reaction of 10 mol % dicoco(CI 2- C+ aalkyl)amine in place of trioctylamine ( 4) A copolymer similar to (2) above, but produced by the reaction of 5 mol % trioctyl-methylammonium chloride and 5 mol % sodium hydroxide in a minimal amount of water instead of trioctylamine. This results in a quaternary ammonium salt of the polymer.

(5) A copolymer similar to (1) above, except that it is produced by the reaction of a mixture of dodecylamine and tetradecylamine in place of the dialkylamine. (6) In place of the dialkylamine, n-coco (C1 Except produced by the reaction of CI alkyl)propyldiamine,
Copolymer (7) similar to (11) above The copolymer is based on equimolar proportions of alkyl fumarate and vinyl acetate, and the amount of maleic anhydride is 10 mol % based on the total weight of fumarate and vinyl acetate. Certain copolymers similar to (11-(6) above) Improved results are often obtained when the fuel compositions of the present invention are incorporated with other additives commonly known to improve the cooling flow properties of distillate fuels. Examples of these other additives are polyoxyalkylene esters, ethers, esters/ethers, amides/esters and mixtures thereof, especially polyoxyalkylene glycols with a molecular weight of 100 to 5,000, preferably 200 to s, ooo. (The alkyl group in the polyoxyalkylene glycol contains 1 to 4 carbon atoms), preferably at least two linear saturated alkyl groups from CIO to C3°.European Patent Public notice number 0
．． No. 061,895A 2 describes some of these additives.

Preferred esters, ethers or esters/ethers are shown structurally by the following formula:

R'-0-(A)-0-R' (wherein R5 and R6 are the same or different, (i)
n-alkyl(ii) n-furkyl-C (iii) n-furkyl-OC(CHz)n
-(IV) n -furkyl -0-C(CHz
) nC, the alkyl group is linear and saturated and contains 10 to 30 carbon atoms, and A is substantially linear, polyoxymethylene, polyoxyethylene or polyoxytrimethylene represents a polyoxyalkylene segment of a glycol, where the alkylene group has 1 to 4 carbon atoms, such that a degree of branching with lower alkyl side chains (as is the case for example in polyoxypropylene glycol) is permissible. (although it is preferred that the glycol is substantially linear).

Suitable glycols are substantially linear polyethylene glycols (referred to as PEG) and polypropylene glycols (referred to as PPG), generally having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000. Esters are preferred, fatty acids containing 10 to 30 carbon atoms are useful for reacting with glycols to produce ester additives, cps to CZ4 fatty acids,
Particular preference is given to using behenic acid. Esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols. A particularly preferred additive of this type is polyethylene glycol dibehenate, in which the glycol moiety has a molecular weight of about 600, often abbreviated as PEG600 dibehenate. Similar polyethylene glycol dibehenates whose glycol moieties have molecular weights of about 200 and 400 are often abbreviated as PEG200 and PEG400, respectively.

Other additives suitable for the fuel compositions of the present invention are ethylenically unsaturated ester copolymer flow improvers. Unsaturated supermers that can be copolymerized with ethylene include unsaturated monoesters and diesters of the formula:

(In the formula, R6 is hydrogen or methyl, R1 is 00C
R+. group (wherein R1° is hydrogen or C3~(/28,
Furthermore, it is usually a linear or branched alkyl group of C, ~Ca1, preferably CI-CIl), or R7 is a -COOR+o group (wherein R1° is as defined above, ) and R1 is hydrogen or C OOR+ as defined above. ) R1 and R are hydrogen and R8 is 0 CRI.

Monomers that are CI""C29, more commonly CI to C
I8 monocarboxylic acid, preferably 02 to C29, more usually 01 to Cl1l monocarboxylic acid, preferably 02
Contains vinyl alcohol esters of ~C5 monocarboxylic acids. Examples of vinyl esters that can be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or vinyl isobutyrate, with vinyl butyrate being preferred. Preferably, the copolymer contains 20 to 40% by weight vinyl ester, more preferably 25 to 35% by weight vinyl ester. Also, they are U.S. Patent No. 3,961,91
It may also be a mixture of two copolymers such as those described in No. 6. Preferably, these copolymers have a number average molecular weight of 1,000 to 6,000, preferably 1,000 to 3,000, as measured by gas phase osmometry.

Other additives suitable for the fuel compositions of the present invention are polar compounds, ionic or nonionic, that have the ability to act as wax crystal growth inhibitors in the fuel. It has been found that polar nitrogen-containing compounds are particularly effective when used in combination with glycol esters, ethers or esters/ethers. These polar compounds are generally in a molar ratio of at least 1 hydrocarbyl-substituted amine and 1
amine salts and/or amides produced by reaction with hydrocarbylic acids having a molar ratio of 1 to 4 carboxylic acids or their acid anhydrides.

Also, esters/amides containing 30 to 300, preferably 50 to 150 total carbon atoms can be used. These nitrogen compounds are described in US Pat. No. 4,211,534. Suitable amines are usually long chain C+ t -C
4°-class, secondary, tertiary or quaternary amines or mixtures thereof, provided that the resulting nitrogen compound is oil-soluble and typically contains from about 30 to 300 total carbon atoms. Shorter chain amines may be used. The nitrogen compound has at least one straight chain C, -C,. , preferably a CI4 to C24 alkyl segment.

Suitable amines include primary, secondary, tertiary and quaternary amines, with secondary amines being preferred. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecylamine, cocoaamine, hydrogenated tallow amine, and the like. Examples of secondary amines include dioctadecylamine, methyl-behenylamine, and the like. Also suitable are amine mixtures, and many amines derived from natural substances are mixtures. Preferred amines have the formula HNR+ Rz, where R8 and R
2 is almost 4% CI 31% CI 6.59% CI 8
is an alkyl group derived from hydrogenated raw fat containing)
It is a secondary hydrogenated beef tallow amine.

Carboxylic acids (
and their acid anhydrides) are cyclohechitin-1,
These include 2-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclopenkune-1,2-dicarboxylic acid, naphthalene dicarboxylic acid, and the like.

Generally these acids contain about 5 to 13 carbon atoms in the cyclic group. Preferred acids are benzenedicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid. Particularly preferred is phthalic acid or its acid anhydride. A particularly preferred compound is an amido-amine produced by reacting 1 mole fraction of phthalic anhydride with 2 mole fractions of di-hydrogenated tallow amine. Another preferred compound is this amide-
It is a diamide produced by dehydrating an amine salt.

The relative proportions of additives used in the above mixtures are preferably from 0.05 to 20 parts by weight to 1 part of other additives such as polyoxyalkylene esters, ethers, ester/ethers or amide ethers; Preferably, the polymer contains 0.1 to 5 parts by weight of amine salt or quaternary ammonium salt. The amount of polymer containing amine salt or quaternary ammonium salt added to the liquid hydrocarbon fuel is preferably from 0.0001 to 5.0% by weight, based on the weight of the hydrocarbon fuel, such as from 0.001 to 5.0% by weight.
0.5% by weight, in particular 0.01-0.05% by weight (active substance).

The polymer may conveniently be dissolved in a suitable solvent to produce a concentrate of 20 to 90% by weight, such as 30 to 800 to 80 weight mer in the solvent. Suitable solvents include kerosene, aromatic naphthas, lubricating mineral oils, and the like.

In this example, a vinyl acetate, dialkyl fumarate copolymer AA is combined with a copolymer BB containing two amine salts and a copolymer DD containing CC and a quaternary ammonium salt, each having the following properties: A comparison was made when added to two distillate fuel oils F1 and F2.

PI F2 D-86 distillation: IBP 222°C 238°C
20% 275 ℃ 281 ℃90%
336℃ 331'CFBP 36
0 ℃ 352 ℃ Braze precipitation point -
3℃ -3.5℃ base CPPPT”
-3℃ -3℃* Cooling filter plugging point test
o1nt Te5t ) The details of the polymer are as follows.

AA: Equal molar ratio of vinyl acetate and C+Z alkyl/C
Copolymer BB of 14 alkyl (1:1) with dialkyl fumarate: 50 mol% vinyl acetate, 45.0 mol% 01□alkyl/CI4alkyl (1
: Terpolymer of dialkyl fumarate of 1) and 5 mol% maleic anhydride
CIz ” C+ a) reacted with amine, 5
Terpolymer of 0 mol% vinyl acetate, 45.0 mol% dialkyl fumarate of 01□alkyl/CI4alkyl (1:1) and 5 mol% maleic anhydride DD = minimum amount of water (NaCl separated) case) 5 inside
47.5 mol% reacted with mol% trioctylmethylammonium chloride and 5 mol% NaOH
of vinyl acetate, 47.5 mol% of 01□alkyl/C
Copolymer of Ia alkyl (1:1) dialkyl fumarate and 5 mol% maleic anhydride Polymer AA,
BB, CC and DD each with half the weight of PE
G200 behenate, PEG400 behenate and PE
mixed with a mixture of G-behenate in a molar ratio of 1:1:1;
In each case a blend of polymer and PEG behenate was added to the fuel F at an active substance concentration of 0.1% (1000 ppm).
1 and fuel F2 and tested with CFPPT, the results obtained were as follows.

Polymer! Steal F2 AA -11-10 8B -13-12 CC-14-12 DD -14-13 Polymers BB, CC and DD show better results than those shown by polymer AA without amino groups That is clear.

Details of CFPPT are as follows.

The cold filter properties of the filter plugging blends were determined by the cold filter plugging point test (CFPPT). This study was published in the “Journal of the Institute
ofPetroleum” 5 Volume 2, No. 510,
(June 1966) pages 173-185. Briefly, a 40-degree sample of the oil to be tested is cooled in a bath maintained at about -34°C. Periodically (starting at a temperature of 2° C. above the cloud point and every 1° C. decrease in temperature), the cooling oil is tested for its ability to pass through a fine screen during a predetermined period of time. This cooling property is tested using a device consisting of a pipette fitted with an inverted funnel at its lower end, which is placed below the surface of the oil to be tested.

A 350 mm screen having an area of approximately 0.45 square inches (0.20 cal) is stretched across the mouth of the funnel. Vacuum pressure is applied to the top of the pipette, which forces the oil through the screen to reveal a 20 mm oil. Begin each periodic test by pulling up into the pipette up to the mark. Repeat the test for each 1°C temperature decrease until the oil no longer fills the pipette within 60 seconds. ), which is the difference between the failure temperature of the untreated fuel (CFPP, ) and the failure temperature of the flow improver treated fuel (CFPPI), i.e., △C
FPP=CFPPO-CFPPI Point-1 In this example, polyethylene glycol dibehenate (PE) in which the glycol moiety has a molecular weight of about 600
Polymers containing various amine salts based on alkyl fumarate vinyl acetate maleic anhydride mixed with G600 behenate (referred to as G600 behenate) were mixed into a distillate fuel oil blend known as F3 having the properties shown in Table 1. Added.

The various polymers blended with PEG 600 dibehenate at a weight ratio of 4 parts of polymer per 1 part of PEG 600 dibehenate in each case were as follows:

Half amide, half amine salt of a copolymer of Ejoeni salt ditetradecyl fumarate vinyl acetate-10 mol% maleic anhydride (amine is R2NH, where R is as described above for Armeen C) ditetradecyl fumarate vinyl acetate - 10 mol % half amide, half amine salt of maleic anhydride (the amine is n-tallow probyl diamine) ditetradecyl fumarate vinyl acetate - 10 mol % 50 mol % of a maleic anhydride copolymer was reacted with R2NH (wherein R=CI6/C18 alkyl) in a 1:1 molar ratio to produce a mono-trioctylamine salt half-amide-half amine salt. Copolymer of vinyl acetate 45 mol% di-tetradecyl fumarate and 5 mol% maleic anhydride Half amide-half amine salt of di-tetradecyl fumarate-vinyl acetate-5 mol% maleic anhydride copolymer is R2NH (where R is as described above for Armeen C) Mono-trioctylamine salt G of a copolymer of di-tetradecyl fumarate-vinyl acetate-5 mole % maleic anhydride G di- Tetradecyl fumarate-vinyl acetate-5
Di-trioctylamine salt of a copolymer of mol % maleic anhydride H di-tetradecyl fumarate-vinyl acetate - Half amide, half amine salt of a copolymer of 5 mol % maleic anhydride (where the amine is R2NH R=C+h/C+a alkyl) ■ Di-tetradecyl fumarate-vinyl acetate-5
Half-amide, half-amine salt of maleic anhydride copolymer in mole % where the amine is R2-NH where R is as described above for Armeen C. The blend was also subjected to PCT (Programmed Cooling Test). Details of PCT are as follows.

Programmed Cooling Test (PCT) This is a slow cooling test designed to correlate with the pumping of stored heated oil.

The cooling flowability of the above fuel containing additives is measured by PCT as follows. 300 ml of fuel 1'
Cool linearly to the test temperature at C/hour and then keep the temperature constant. After 2 hours at the test temperature, the surface summary'lQm
1 is removed by suction to prevent the test from being affected by unusually large wax crystals that tend to form at the oil/air interface during cooling. Disperse the settled wax in the bottle by gentle agitation and then insert the CFPPT filter assembly. Open the tap and apply a vacuum of 500 mr of mercury and close the tap when 200 d of fuel passes through the filter and into the calibrated receiver. If 200 ml is collected within 10 seconds through a given mesh size,
A pass is recorded, and a fail is recorded if the flow rate is too slow indicating that the filter becomes blocked.

The mesh number that passes the test temperature is recorded.

The results obtained were as follows.

1 4.5 40 100 * Separate measurements with test temperature CFPPT and P in a weight ratio of 4:1 respectively
Polymer B- blended with EG600 dibehenate
The F3 blend containing I was tested. Copolymer X, included for comparison purposes, is a copolymer of vinyl acetate and ditetradecyl fumarate. The results are as follows.

8CPPP 1500 ppm 3000 ppm1
+Jt-1 (Shield 2 light) B
1.5 2.5CI
2D-2” 5.5E
0.5 3F
0 3G
O2,5 HO,53,5 10,53 X 1.5 3.5*
A negative sign indicates an increase in CFPP.

PCT (+2° C.) was also performed on F3 blends containing each of polymers D, E, F, G, H and I blended with PEG600 dibehenate in a weight ratio of 4:1. The results obtained were as follows.

PCT Mesh Polymer Salt Passed at 2°C 150099m Active Ingredients 3000ppm
Active ingredient D 60 E 30 F゛40 G 30 H100

In this example, the polymer salts used in Example 2, E, F, G, H and! was added to F4, a high-boiling distillate fuel, and CFPP (F4 alone) and ΔCPPP were measured in each case.

Details of the ASTM D86 distillation of F4 are as follows.

IBP172℃D20 228℃D50
276℃D90
362°C FBP 389°C fuel base oil with 300 ppm and 500 ppn+ (active ingredients),
The results are shown below for the respective polymer salts added at 0.03% and 0.05% by weight as compared to untreated fuel oil.

Flash AIJ Polymer salt concentration 19m CFPP +3 + 1 + 1 +3 +4 +5 +2 +4 8CPPP In addition, polymer salts E, F, GXH and I were each blended with copolymer Y at a molar ratio of 4, and then 300
ppm (0.03% by weight) and 500ppm (0.0% by weight)
5% by weight) to F4. Copolymer Y is an ethylene/vinyl acetate copolymer with a molecular weight of approximately 2000 containing 36% by weight of vinyl acetate and 13% by weight of vinyl acetate.
in a weight ratio of 3=1 with an ethylene/vinyl acetate copolymer having a molecular weight of about 3000.

As described above, CFPP (processed fuel oil) and 8C
PPP was measured in each case.

The results are as follows.

+4 +3 Polymer i-凰 [- Polymer salt Y (ppm) (ppm) FPP △CPPP It can be seen that in all cases there is a significant decrease in pour point when the polymer salt is added to the fuel base oil. .

1'' [-1 Various polymer salts, alone or in combination with Polymer Y (see second table below), can be used in accordance with the ASTM
Added to distilled fuel oil F5 with D86 distillation characteristics.

IBP 188℃D20
236°C D50 278°C D90 348°C FBP 376°C The results of CFPPT and PCT were as follows.

Polymer concentration salt (ppm) FPP △CPPP PCT at 9°C Concentration ppm Y Polymer FPP FPP = PCT at 9°C (used) and another polymer salt J were added to distillate fuel F6 having the following 086 distillation characteristics.

IBP 173℃D
20 222℃D50
297℃D90
356℃FBP
371℃ Polymer salt J is di-tetradecyl fumarate-vinyl acetate-10 mol%
half amide, half amine salt of a copolymer of maleic anhydride (amine is RzNH (where R is CI6/CI
8 alkyl).

These polymer salts C and J can also be mixed with an ethylene-vinyl acetate copolymer mixture (see Example 3).
The mixture was blended at a molar ratio of 1 to 1.

Polymer salts and mixtures of them with Y in a 1=1 molar ratio were added at 300 ppm and 600 ppm (active ingredient) (0
, 03% and 0.06% by weight) to fuel oil and the resulting blend was subjected to PCT and CFPPT. The results are as follows.

Concentration i++? --Hani [1 rimmer fυw)-m-Z3
00 Z600 C300 Z300 Z600 PCT (-8'C) CF 40 +3 80 →・2 <20 +3 20 +3 S1 super Li In this example, polymer salts A and B (used in Example 2) and J (used in Example 5),
Added to distilled fuel oil F6 of Example 5. Furthermore, the following polymer salts were added to this fuel oil. Each polymer salt was blended with copolymer mixture Y used in Example 3 in a 1:1 molar ratio.

12 melons with ichihiro sword to ditetradecyl fumarate vinyl acetate Nyl-10 mol% maleic anhydride Half amide, half copolymer of Famine salt (amine is RNH, (formula (R=CI6/C+s alkyl) ditetradecyl fumarate vinyl acetate Nyl-10 mol% maleic anhydride Half amide, half copolymer of Famine salt (amine is n-cocope lopyldiamine) R is mentioned above with respect to Armeen C. Same as L except that Ru.

The respective polymer salts blended with copolymer mixture Y were added to the fuel oil at two different concentrations, namely 300 ppm (0.03% by weight) and 600 ppm (0.06% by weight) (active ingredient), and PCT and CFPPT. The results obtained were as follows.

It can be seen that the addition of polymer salts generally improves the flow properties of fuel base oils.

In PCT and CFPPT, a copolymer of styrene and maleic anhydride partially esterified with tetradecanol (referred to as copolymer XX) is used, and the unesterified groups of XX are hydrolyzed, and then carboxylic acid A comparison was made with a polymer salt (N) obtained by reacting a copolymer containing groups with triotadecylamine.

N is more effective than xX due to CFPP at 2°C and 6 meshes of PCT at -14°C, i.e. the fuel oil F5 used in Example 4 with N and xX at a concentration of 500 ppm. N is 60μm when added to
It was found that XX passed at 250 μm.

In this example, the diamine R2NH (wherein R is n
distilled fuel alone and with copolymer Y (see Example 3) Comparisons were made with prior art copolymers also added to the same fuel by adding PCT (at -10°C), CFPPT and DSC tests.

Distilled fuel oil F7 with added copolymer at concentrations of 175 ppm and 300 ppm was prepared as follows:
It had D86 characteristics.

IBP 184℃D20
226°C D50 272°C D90 368°C FBP 398°C Comparisons were also made with other prior art copolymers BB and CC. Details of those copolymers (including copolymer AA) are as follows.

Copolymer AA: Copolymer of octadecene and maleic anhydride Copolymer BB: Copolymer AA copolymer reacted with hexadecanol to form an ester CC: Copolymer AA reacted with octadecanol to form an ester. ΔWAT (wax deposition temperature 2° C.) is measured using a DSC (differential scanning calorimeter). This is the difference between the temperature at which waxes precipitate for the distillate base oil alone (W A T o ) and the temperature at which waxes precipitate for the treated distillate fuel oil (wAT+) when the calorimeter is cooled at 2°C/min. It is. DS
In the C test, results were obtained for only one concentration, 300 ppm using a 25 μl fuel sample. That is, ΔWAT=WATO-WAT+ The results obtained were as follows. The first number is 1
The second number (excluding DSC) is for 300 ppm.

B CC PCT alone + Y0 60/60 80/80 30/30 100/100 40/40 250/250 CFPP alone 0/△1 010 △l/△
1+Y1 △ 18/△19 △15/△16
Δ15/Δ19SC Δ−8 4.2 2.8 2.2 When Y is present, the molar ratio of Y to BB, CC or N is 4:1.

Claims (1)

[Scope of Claims] 1. A polymer containing a large proportion by weight of a liquid hydrocarbon fuel and a small proportion by weight of a polymer containing more than one amino group, wherein the amino group is a salt of a primary, secondary or tertiary amine or A fuel composition characterized in that it is a quaternary ammonium salt. 2. The composition of claim 1, wherein the fuel is a distilled fuel oil. 3. The polymer according to claim 1 or 2, wherein said polymer is derived from a polymer of one or more unsaturated ester monomers which also contain free acid groups or a copolymer of unsaturated ester monomers in which at least one monomer has free acid groups. Composition. 4. Composition according to claim 1 or 2, wherein said polymer is derived from a copolymer of unsaturated esters and/or olefins and unsaturated carboxylic anhydrides. 5. A composition according to claim 1 or 2, wherein said polymer is derived from a polymer containing ester groups which have been partially hydrolyzed to obtain carboxylic acid groups. 6. Composition according to any one of claims 1 to 5, wherein the amount of polymer containing amine salt is from 0.0001 to 5.0% by weight (active substance) based on the weight of the hydrocarbon fuel. 7. Use of polymers containing more than one amino group in which the amino group is a salt of a primary, secondary or tertiary amine or a quaternary ammonium salt as a flow improver in liquid hydrocarbon fuels. 8. The use according to claim 7, wherein the fuel is distilled fuel oil. 9. Use according to claim 7 or 8, wherein said polymer is derived from a polymer of one or more unsaturated ester monomers which also contain free acid groups or a copolymer of ester monomers in which at least one monomer has free acid groups. 10. Use according to claim 7 or 8, wherein said polymer is derived from a copolymer of unsaturated esters and/or olefins and unsaturated acid anhydrides. 11, solvent and 20 to 90% by weight of 1 based on the solvent
Concentrate comprising a polymer containing more than three amino groups, characterized in that the amino groups are salts of primary, secondary or tertiary amines or quaternary ammonium salts. 12. The concentrate according to claim 11, wherein said polymer also contains free acid groups, or is derived from a polymer of one or more unsaturated ester monomers or at least one monomer is derived from a copolymer of unsaturated ester monomers having free acid groups. thing. 13. The concentrate of claim 11, wherein said polymer is derived from a copolymer of unsaturated carboxylic anhydrides.