JP2003528160A - Polymer material - Google Patents

Abstract

  (57) [Summary] A polymer low-temperature flow improver in which a crystalline part and an oil-solubility enhancing part are linked by a functional group.

Description

Detailed Description of the Invention

The present invention relates to an additive for use in an oil composition, mainly a fuel oil composition, especially a fuel oil composition susceptible to wax formation at low temperatures and a method of making the additive. Fuel oils derived from petroleum or vegetable sources contain components (e.g. alkanes) that at low temperatures tend to precipitate as large crystals or wax spherulite as well as form gel structures, whereby the fuel is Lose liquidity. The lowest temperature at which fuel can flow is known as the pour point. When the fuel temperature drops and reaches the pour point, difficulties arise in transporting the fuel through lines and pumps. In addition, wax crystals tend to clog fuel lines, screens and filters above the pour point. These problems are well recognized in the art and various additives have been proposed to reduce the pour point of fuel oils, many of which are used industrially. Similarly, other additives have been proposed and used industrially to reduce the size and shape of the wax crystals that form. To reduce the possibility of clogging the filter,
Smaller size crystals are desirable.

Diesel fuel waxes are predominantly alkane waxes, which crystallize into platelets, some additives suppress this and make the wax acicular habits, and the resulting acicular crystals are platelets. It is easier to pass the filter than is. The additive may also have the effect of maintaining crystals formed in the fuel suspension, resulting in reduced settling and helping to prevent obstructions. Effective wax crystal modification (measured by cold filter plugging point (CFPP) and other feasibility tests, as well as simulated and field tests) is ethylene-vinyl acetate (EVAC) Or by a propionate copolymer-based flow improver. The use of hydrogenated diene copolymers having one or more crystalline or crystallized regions and one or more non-crystallized regions as cold flow improvers has been proposed for a long time (see, for example, U.S. Pat.No. 3,600,311). reference). Although these materials are effective wax crystal modifiers or nucleating agents, their production involves the lithium-containing polymerization catalyst, at least two-step polymerization and subsequent hydrogenation, and the disadvantage of being expensive. Have.

The present invention provides a polymeric material of formula AB, which material has a molecular weight in the range of 400 to 7000 and comprises alkyl or alkylene chains, such that its crystallinity is at least 25%. A portion A having linearity and a portion B that imparts oil solubility to the material, the portion B having a crystallinity of at most 10%, the portions A and B being linked by a bond other than a carbon-carbon bond, or It is linked by the reaction product of a functional group, preferably a nucleophilic group and an electrophilic group. For simplicity, this material is referred to below as the polymeric material of the present invention. In one embodiment of the invention, Part A is (or comprises) an ethylene-based polymer (homopolymer or copolymer). The polymer may be obtained by polymerization of ethylene, optionally not more than 15 mol%, preferably not more than 8 mol%, most preferably not more than 5 mol% of one or more ethylenically unsaturated comonomers, preferably from 3 to 1
An ethylenically unsaturated hydrocarbon compound having 6 and preferably 3 to 8 carbon atoms (
For example olefins). The α-olefin is preferably propene or butene, for example.

The ethylene-based moiety A may be prepared for example by Ziegler-Natta polymerization or metallocene / alumoxane catalyzed polymerization, in which case it is preferably at least 30%, more preferably at least prior to ligation. EP-A containing 50%, preferably at least 60%, most preferably 75 to 95% terminal ethenylidene unsaturation.
-353935 (the disclosure of which is incorporated herein), as well as those of WO 91/11469 and WO 94/13709, and the specification also describes polymer moiety A Describes methods that may be prepared with electrophilic or nucleophilic groups linked to moiety B. Instead, the polymer is a linear diene, especially α-of butadiene.
It may also be obtained by polymerization using the omega chain and subsequent hydrogenation. Linear dienes may be polymerized alone or with a branched comonomer in a manner that provides some α-β linkages, thus some are branched, but need to achieve the required crystallinity. There is. Hydrogenated polybutadiene is preferred.

In a further embodiment, part A is (or comprises) a wax. Suitably, the wax contains a high weight percentage of n-alkanes, preferably with an n-alkane content of at least 30%. The wax preferably contains ethylenically unsaturated groups or some other reactive group, preferably all such groups are terminal groups. Alternatively, a wax may be used to alkylate the phenol, the hydroxyl group of which is linked to the moiety B. A suitable molecular weight range for part A is 1000 to 5000, preferably 1000 to 3000,
Most preferred is about 1500. If part A is a polymer or wax, the molecular weight is Mn
And is measured by GPC. The crystallinity of part A may be determined by X-ray diffraction and DSC. Suitably, the crystallinity is at least 30%, preferably at least 40%.

Considering now section B, which is preferably a polymeric material,
Whether or not it is a polymer, preferably in the range of 1000 to 70,000, more preferably in the range of 2000 to 20000, preferably in the range of 2000 to 10000, most preferably
It has a molecular weight in the range of 5000 to 6000 (Mn in the case of polymers). The molecular weights of the two parts are suitably of the same order, preferably the molecular weight of part B is 1 to 5 times the molecular weight of part A. Part B is preferably an ethylene-based homopolymer or copolymer. Like Part A, it may be obtained by the polymerization of ethylene with one or more ethylenically unsaturated compounds, preferably hydrocarbon comonomers, for example in a proportion of at least 20 mol%, preferably at least 30 mol%. Present and high enough to render the polymer low crystalline. Alternatively, it may be an ethylene homopolymer prepared by a method that gives a high degree of branching, ie having at least 10 CH ₃ groups per 100 CH ₂ groups. As described above with respect to part A, the polymer may be, for example, Zieg
It may be prepared by ler-Natta or metallocene / alumoxane catalyzed polymerization.

Polymers based on one or more olefinic hydrocarbon monomers other than ethylene may also be used, especially containing from 3 to 10 and more especially 3 to 5 carbon atoms. Examples of such a monomer include propene, n- and iso-butene, 1-
Examples include pentene, 1-octene and styrene. Preferred examples of monomers and monomer mixtures are propene, propene / iso-butene, n-butene / iso-butene, especially iso-butene. Further, the polymer may be obtained by 1,2-configuration polymerization of at least partially linear dienes, polymerization of branched dienes or combinations of such polymerizations, and subsequent hydrogenation. Suitable dienes include, for example, butadiene, isoprene and 2,3-dimethylbutadiene. 1,2 and 1,4 mixed polymerization of butadiene prepares hydrogenated ethylene-butene type polymers, while isoprene yields ethylene-propene type materials. Moiety B is suitably a hydrocarbon polymer, preferably predominantly saturated or unsaturated aliphatic chains. Like part A, it is close to the bond with the other parts (
close or adjacent) An aromatic ring may be included. The hydrocarbyl chain may optionally contain one or more kinds of hetero atoms, for example, an oxygen atom, as in the case of a chain containing a polyoxyalkylene group.

The crystallinity of part B is suitably at most 7%, preferably at most 5%. Most preferably, part B is amorphous. Part B is preferably essentially oil-soluble, and is preferably oil-soluble to form a substantially homogeneous composition with which the materials of the present invention are handled, ie stable over time. However, due to its functional nature, it is expected that at least some of the materials of the present invention will come out of solution with respect to the wax crystals when the oil temperature falls near its cloud point.

The nature of the linkage between the moieties is not critical per se and the orientation and position of the moieties is not critical, but is preferably located at each end. But one part is
More than one chain may form the other part, for example if it contains a divalent linking group (eg a dicarboxylic acid group), or if each chain should be linked at its termini. Even the other moieties may be considered linked at non-terminal positions. In any such case it is the sum of the molecular weights of the chains that should be considered within the molecular weight ranges referred to above. Also, polymeric materials that include more than one of moieties A or B, which may be the same or different, are within the scope of the invention. For example, the material may comprise a moiety B at each end, a moiety B on at least one, and preferably moieties B on both, moieties B being linked by a nucleophilic-electrophilic reaction product, or Preferably, the material may comprise, at each end, a moiety B having at least one, and preferably both linkages, moiety A which is a nucleophilic-electrophilic reaction product. Examples of reactive groups include amines, alcohols, amino alcohols, phosphines, thiols or organometallic compounds such as those derived from hydrocarbyllithium. Examples of electrophilic groups include those derived from acids, such as acid chlorides and anhydrides, and other acylating agents.

The electrophilic or nucleophilic group is introduced into the moieties A or B by methods specific to the polar group concerned. For example, a hydroxy group may be reacted in the presence of a basic catalyst (eg, lithium hydroxide) with ethylene oxide or propylene oxide and subsequent reaction with a proton donor (eg, carboxylic acid) to form a hydroxide, or in US Pat. Introduced by the ethylene oxide treatment described in US Pat. No. 3,135,716, the disclosure of which is incorporated herein. A further method of introducing a hydroxy group into the polymer moiety is a peroxide as described in U.S. Pat.No. 3,446,740,
For example, by polymerizing in the presence of hydrogen peroxide, the disclosure of which is incorporated herein. Hydroxy groups provide sites for further reaction to yield other unique groups. Carboxy groups may also be introduced by treating the polymer with CO ₂ as described in U.S. Pat.No. 3,135,716 if it is desired to be used as an additional reaction site in a manner similar to hydroxy groups. Good.

Moieties with ethylenic unsaturation, especially terminal unsaturation, may have nucleophilic groups replaced with other types of nucleophilic groups (eg hydroxy groups). Examples of this method include the addition of phenol to a terminally unsaturated polymer or wax and are described in more detail in the examples below. Each moiety may be functionalized to incorporate functional groups, especially electrophilic or nucleophilic groups, at both ends or as one or more pendant groups on the polymer backbone. Functional groups are typically polar and contain one or more heteroatoms such as P, O, S, N, B or halo. It may be attached to the saturated hydrocarbon portion of the moiety by a substitution reaction or to the olefin portion by an addition reaction or a cycloaddition reaction. Alternatively, functional groups may be incorporated with oxidation or splitting of the partial chain ends (eg ozonolysis). Functionalizations provided include "ene" reactions, especially with unsaturated monocarboxylic acids, unsaturated dicarboxylic acids or unsaturated dicarboxylic acid anhydrides, especially maleic anhydride, followed by one or more carboxylic acid groups. Reacts with nucleophilic reactants such as alcohols, amino alcohols or amines.

Functionalization is provided by other methods such as oxidation, hydroformylation, epoxidation, reaction with hydroxyaromatic compounds or Koch reaction. The provision of functionalization by the Koch reaction is described in International Application WO94 / 13709, the disclosure content of which is incorporated herein. According to the method described in the international application, the terminal ethenylidene group is treated with carbon monoxide in the presence of an acid catalyst and a nucleophilic trapping agent and the resulting acid group is subsequently obtained as described above. Treated by nuclear reactants.

The present invention also provides an additive composition containing the polymeric material of the present invention and a cold flow improver other than the polymeric material of the present invention. Examples of cold flow improvers include (A) ethylenically unsaturated ester compounds, (B) comb polymers, (C) polar nitrogen compounds, (D) hydrocarbon polymers, (E) amine-substituted carboxylic acids. And (F) poly (meth) acrylate esters, (G) polyoxyalkylene compounds, and (H) a mixture of at least some saturated hydrocarbons having a number of carbon atoms in the range of 15 to 60. In a preferred embodiment of the invention, the additional cold flow enhancer is:

(A) In addition to the unit derived from an ethylenically unsaturated ester compound, particularly methylene, it has a unit of the following formula. -CR ³ R ⁴ -CHR ⁵ -In the formula, R ³ represents hydrogen or methyl, R ⁴ represents COOR ⁶ (R ⁶ represents an alkyl group having 1 to 9 carbon atoms (straight chain or 3 or more When it contains a carbon atom, it represents branched)) or OOCR ⁷ (R ⁷ represents R ⁶ or H), and R ⁵ represents H or COOR ⁶ . These may include copolymers of ethylene and ethylenically unsaturated esters or derivatives thereof. Examples include esters of ethylene with saturated alcohols and copolymers of unsaturated carboxylic acids, but preferably the esters are esters of unsaturated alcohols with saturated carboxylic acids. Ethylene-vinyl ester copolymers are preferred, ethylene-vinyl acetate copolymers, ethylene-vinyl propionate copolymers, ethylene-vinyl hexanoate copolymers or ethylene-vinyl octanoate copolymers being preferred.

As disclosed in US Pat. No. 3,961,916, the flow enhancer composition may include a wax growth arrestor and a nucleating agent. Without wishing to be bound by any theory, the user considers that the macromolecules of the present invention act primarily as a nucleating agent, benefiting from the presence of an inhibitor. For example, this may be an ethylenically unsaturated ester as described above, especially at most 14000, preferably at most 10000,
Preferably a molecular weight of 2000 to 6000, more preferably 2000 to 5500 (Mn, measured by gel permeation chromatography against polystyrene standards) and 7.5 to 35
It may be an EVAC with an ester content of mol%, preferably 10 to 20 mol%, more preferably 10 to 17 mol%. Additional nucleating agents, eg number average molecular weights in the range 1200 to 20000 and 0.3 to 10 mol%
It is within the scope of the invention to include ethylenically unsaturated esters, preferably vinyl acetate, copolymers, preferably having a vinyl ester content of 3.5 to 7.0 mol%.

(B) Comb type polymer Such a polymer is “Comb-Like Polymers. Structure and Properties”
, NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8,
It is discussed in p117-253 (1974). Suitably, the comb polymer is at least 25 mol%, preferably at least 40
%, More preferably at least 50 mol% of homopolymers or copolymers with units of side chains containing at least 6, preferably at least 10 atoms. Examples of preferable comb polymers include polymers of the following general formula.

[0017]

[Chemical 1]

In the formula, D = R ¹¹ , COOR ¹¹ , OCOR ¹¹ , R ¹² COOR ¹¹ or OR ¹¹ , E = H, CH ₃ , D or R ¹² , G = H or D, J = H, R ¹² , R ¹² COOR ¹¹ , aryl or heterocyclic group, K = H, COOR ¹² , OCOR ¹² , OR ¹² or COOH, L = H, R ¹² , COOR ¹² , OCOR ¹² , COOH or aryl, R ¹¹ ≧ C ₁₀ hydrocarbyl, R ¹² ≧ C ₁ hydrocarbyl or bidrocarbylene, m and n represent a molar ratio, m is in the range of 1.0 to 0.4, and n is in the range of 0 to 0.6. R ¹¹ preferably represents a hydrocarbyl group having 10 to 30 carbon atoms, and R ¹² is
It preferably represents a hydrocarbyl group or a hydrocarbylene group having 1 to 30 carbon atoms. The comb polymer may include units derived from other monomers if desired or required. Including two or more different comb polymers,
It is within the scope of the present invention.

These comb polymers include maleic anhydride or fumaric acid and other ethylenically unsaturated monomers such as α-olefins or unsaturated esters such as vinyl acetate.
). It is preferred, but not essential, to use equimolar amounts of comonomers, with molar ratios ranging from 2 to 1 and 1 to 2 being preferred. For example, examples of the olefin copolymerized with maleic anhydride include 1-decane, 1-dodecane, 1-tetradecane, 1-hexadecane and 1-octadecane. The copolymer may be esterified by any suitable technique, with maleic anhydride or fumaric acid at least 50% esterified being preferred, but not required. Examples of alcohols used include n-decane-1-ol, n-dodecane-1-ol, n-tetradecane-1-ol, n-hexadecane-1-ol and n-octadecane-1-ol. To be The alcohol may also contain up to one methyl branch per chain, for example 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol. The alcohol may be a mixture of straight chain alcohols and branched alcohols of one methyl group. Although it is preferred to use pure alcohols than commercially available alcohol mixtures, where mixtures are used, R ¹² refers to the average number of carbon atoms in the alkyl group and includes branches at the 1 or 2 positions. If an alcohol is used, R ¹² refers to the linear backbone portion of the alcohol.

These comb polymers may especially be fumarate or itaconate polymers and copolymers such as those described in EP-A-153176, 153177 and 225688 and WO91 / 16407. A particularly suitable fumarate comb polymer is a copolymer of fumarate (preferably an alkyl fumarate) and vinyl acetate, the alkyl group of which has 12 to 20 carbon atoms, in particular the alkyl group has 14 carbon atoms. A polymer having or a polymer whose alkyl group is a mixture of C ₁₄ / C ₁₆ alkyl groups (eg copolymerization of an equimolar mixture of fumaric acid and vinyl acetate, the resulting copolymer and an alcohol or two or more alcohols (linear chain Alcohol is preferred) consisting of a solution which reacts with the mixture). If a mixture is used, a mixture of linear C ₁₄ and C ₁₆ alcohols (weight ratio 1: 1) is preferred. Furthermore, a mixture of C ₁₄ ester and C ₁₄ / C ₁₆ mixed ester is also preferably used. In such a mixture, the ratio of C ₁₄ to C ₁₄ / C ₁₆ is suitably in the range 1: 1 to 1: 4 by weight, preferably in the range 2: 1 to 7: 2, most preferably It is about 3: 1. Other preferred comb polymers are polymers and copolymers of α-olefins, esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid, a mixture of two or more comb polymers. May be used in the present invention as described above, and such use is suitable.

[0021] (C) Ionic or nonionic polar nitrogen compound   Such compounds which are oil-soluble are suitably at least one, preferably at least one.
At least two, formula ＞ NR⁸  Including a substituent of⁸Has 8 to 40 carbon atoms
Containing a hydrocarbyl group), one or more of its substituents
It may be in the form. Examples thereof include groups of the following compounds. (A) at least 1 molar ratio of hydrocarbyl-substituted amine and 1 to 4 carboxylic acid groups
Or by reaction with 1 mole ratio of hydrocarbyl acid with its anhydride
Amine salts and / or amides, wherein the one or more substituents are preferably of the formula --NR⁸R ⁹   Is the formula> NR⁸  (Where R⁸Is defined above and R⁹Is hydrogen or
R⁸Represents, but R⁸And R⁹May be the same or different),
The substituent forms part of the amine salt and / or amide group of the compound.   Suitably an ester containing 30 to 300, preferably 50 to 150, total carbon atoms.
/ Amide is used and these nitrogen compounds are described in US Pat. No. 4,211,534.
Has been. Preferred amine is C₁₂To C₄₀Primary, secondary, tertiary or quaternary amines or
A mixture of them, shorter chain amines may be used, but as a result
The nitrogenous compound must be oil soluble. Nitrogen compounds are preferably at least
Also one C₈To C₄₀, Preferably C₁₄To C_{twenty four}Including a linear alkyl part of

[0022]   Secondary amines are preferred, only tertiary and quaternary amines form amine salts. Ami
Examples of amines include tetradecylamine, cocoamine and hydrogenated
Examples include tallow amine. Examples of secondary amines include dioctadecyl
Mention may be made of amines and methyl behenyl amines. Also amine mixed
The product is preferably derived from a natural material, for example. Preferred amines have the formula   HNR¹³R¹⁴  Is a secondary hydrogenated tallow amine of¹³And R¹⁴Is hydrogenated taro
-An alkyl group derived from fat (usually about 4% C₁₄, 31% C₁₆, 59% C ₁₈ Consisting of an alkyl group).

Examples of suitable carboxylic acids and their anhydrides for preparing nitrogen compounds are cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid. Acids and naphthalene dicarboxylic acids and 1,4-dicarboxylic acids including dialkyl spirobislactones. Generally, these acids have 5 to 13 carbon atoms in the cyclic portion. Preferred acids are benzenedicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid. Phthalic acid or its anhydride is particularly preferred. A particularly preferred compound is the amidoamine salt formed by the reaction of 1 mole part phthalic anhydride with 2 mole parts hydrogenated tallow amine, preferably a secondary hydrogenated tallow amine. Another preferred compound is the diamide formed by dehydration of this amidoamine salt. Other examples include long chain alkyl or alkenyl substituted dicarboxylic acid derivatives (
Examples include amine salts of substituted succinic acid monoamides, examples of which are known in the art and are described, for example, in US Pat. No. 4,147,520. Suitable amines are those described above. Other examples are condensates, such as those described in EP-A-327,423.

(B) compounds containing a ring system, compounds having at least two (preferably only two) substituents of the formula A-NR ¹⁵ R ^{16 in} the ring system, in which A is an aliphatic hydrocarbylene group (May optionally include one or more hetero-primitives in the middle), is linear or branched, and R ¹⁵ and R ¹⁶ are the same or different and each independently.
A hydrocarbyl group containing 9 to 40, preferably 16 to 40, preferably 16 to 24 carbon atoms (optionally with one or more heteroatoms)
The substituents may be the same or different, and if necessary, the compounds may be in the form of their salts. Preferably R ¹⁵ and R ¹⁶ are linear, preferably R ¹⁵ and R ¹⁶ are alkyl, alkenyl or alkyl-terminated mono- or polyoxyalkylene groups.

Suitably A contains from 1 to 20 carbon atoms and is preferably a methylene or polymethylene group. Ring systems may include homocyclic, heterocyclic or fused polycyclic ring assemblies or systems in which two or more such ring assemblies are linked together, the ring assemblies being the same or different. May be. If there are two or more such ring aggregates, the expression-
The substituents of A-NR ¹⁵ R ¹⁶ may be the same or different aggregates, but are preferably the same aggregates. Preferably one or each ring assembly is an aromatic ring, more preferably a benzene ring. When the substituent is preferably in the ortho or meta position, the ring system is most preferably one benzene ring,
If necessary, the ring may be further substituted. The ring atoms of one or more ring assemblies are preferably carbon atoms, but may, for example, contain one or more ring N, S or O atoms. Examples of the ring assembly include a condensed benzene structure (for example, naphthalene, anthracene, phenanthrene and pyrene), a condensed ring structure containing a ring other than benzene (for example, azulene, indene, hydroindene, fluorene and diphenylene oxide),
Ring-bonded "end-on" (eg diphenyl), heterocyclic compounds (eg quinoline, indole, 2,3-dihydroindole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazole and thiodiphenylamine), non-aromatic or Partially saturated ring systems (eg decalin (decahydronaphthalene), α
-Pinene, cardinene and bornylene) and bridged ring structures such as norbornene, bicycloheptane (ie norbornane), bicyclooctane and bicyclooctene.

(C) A long-chain primary or secondary amine condensate having a carboxylic acid-containing polymer. Specific examples include the polymers described in GB-A-2,121,807, FR-A-2,592,387 and DE-A-3,941,561, the esters of telomeric acid and alkanolamines described in U.S. Pat.No. 4,639,256 and U.S. Pat. And the reaction products of amine-containing branched carboxylic acid esters, epoxides and monocarboxylic acid polyesters described in US Pat.

(D) Hydrocarbon Polymers These are preferably copolymers of ethylene with at least one α-olefin and have a number average molecular weight of at least 30,000. Preferably, the α-olefin has at most 20 carbon atoms. Examples of such olefins include propylene, 1-butene, isobutene, n-octene-1, isooctene-1, n-decene-1 and
n-dodecene-1 is mentioned. Also, small amounts of copolymers (eg up to 10% by weight)
Other copolymerizable monomers of (eg, olefins other than α-olefins) and non-conjugated dienes may also be included. The preferred copolymer is an ethylene-propylene copolymer. It is within the scope of this invention to include two or more different ethylene-α-olefin copolymers of this type. The number average molecular weight of the ethylene-α-olefin copolymer is, as indicated above, at least 30,000 (measured by GPC relative to polystyrene standards), suitably at least 60,000, preferably 80,000. No functional upper limit arises, but mixing difficulties result from viscosity increase at molecular weights above about 150,000, with preferred molecular weight ranges of 60,000 and 80,000 to 120,000.

Suitably the copolymer has an ethylene content in the range 50 to 85 mol%. More suitably the ethylene content is in the range of 57 to 80%, preferably 58 to 73%,
More preferably it is in the range of 62 to 71%, most preferably 65 to 70%. Preferred ethylene-α-olefin copolymers are ethylene-propylene copolymers having an ethylene content of 62 to 71 mol% and a number average molecular weight in the range of 60,000 to 120,000, and particularly preferred copolymers are ethylene contents of 62 to 71% and 80
It is an ethylene-propylene copolymer having a molecular weight of 1,000 to 100,000. The copolymer may be prepared by any method known in the art (eg, using a Ziegler type catalyst). Since highly crystalline polymers are relatively insoluble in fuel oils at low temperatures, the polymers should be substantially amorphous. Also preferably, the additive composition is an ethylene-α-olefin copolymer having a number average molecular weight (by vapor phase osmometry) of at most 7,500, preferably 1,000 to 6,000, preferably 2,000 to 5,000. May be further included. Suitable α
-The olefin is as indicated above or is styrene, with propylene being more preferred. Preferably the ethylene content is from 60 to 77 mol%, but for ethylene propylene copolymers a maximum of 86 wt% ethylene is preferably used.

(E) Hydrocarbyl Esters Preferred materials of this type include C ₈ to C ₃₂ hydrocarbyl esters of tertiary amine substituted aliphatic carboxylic acids. In particular, the compound of the following formula may be mentioned. In _{^{(R 21 R 22 N) e}} -G- (NR 21 R 23) f or JNR ²¹ ₂ formula, G is (e + f) represents a value, oxygen in the middle by J is a monovalent hydrocarbon radical (required And optionally at least one heteroatom selected from nitrogen), each R ²¹ independently represents —CHR ²⁴ (CHR ²⁵ ) _p COOR ²⁶ , and R ²² and R ²³ are each Independently R ²¹
, H or an alkyl group containing 1 to 8 carbon atoms, R ²⁴ and R ²⁵ each independently represent H or an alkyl group containing 1 to 8 carbon atoms, and R ²⁶ is 8 to 32. Represents a hydrocarbyl group containing a carbon atom of (optionally having at least one hetero atom selected from oxygen and nitrogen in the middle), and e and f represent an integer of 0 or 0 at the maximum, and R ²¹ The total number of groups is at least 2, and p represents 0 or an integer in the range of 1 to 4. Further details of such compounds are described in International Application WO98 / 03614, the disclosure content of which is incorporated herein. Suitably G or J represents a group containing 1 to 200, preferably 2 to 65 carbon atoms. G or J may represent a saturated aliphatic group or a group of the following formula. -[CH (CH ₃ ) CH ₂ O] _a- [CH ₂ CH ₂ O] _b- [CH ₂ CH (CH ₃ ) O] _c -CH ₂ CH (CH ₃ )-where a + c is 2 Range from 4 to 4 and b ranges from 5 to 100. A preferred example of this group is the C ₁₈ to C ₂₂ mixed alkyl tetraester of hexanediaminetetrapropionic acid.

(F) Poly (meth) acrylate Esters Preferably, these materials are acrylates and methacrylates (hereinafter collectively referred to as (meth) acrylates) homo and copolymers. Examples of such polymers include varying numbers of carbon atoms (eg 6 to 40),
Copolymers of (meth) acrylic acid esters of at least two linear or branched alkanols, especially C ₁₈ to C ₂₂ linear alkanols (optionally olefin monomers (eg ethylene) or nitrogen-containing monomers (eg N-vinyl pyridine or dialkyl). Aminoalkyl (meth) acrylates) together with methacrylic acid ester copolymers. The weight average molecular weight of the polymer (as measured by GPC) is preferably in the range of 50,000 to 500,000. Currently, the preferred polymer of this type is a copolymer of methacrylic acid and a methacrylic acid ester of a C ₁₄ / C ₁₅ saturated alcohol (molar ratio 1: 9), the acid groups of which are neutralized with di (hydrogenated tallow) amine. .

(G) Polyoxyalkylene compounds Examples include polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof, in particular at least one, preferably at least 2
One C ₁₀ to C ₃₀ linear alkyl group and a polyoxyalkylene glycol group having a molecular weight of up to 5,000, preferably 200 to 5,000, wherein the alkyl group of the polyoxyalkylene glycol has 1 to 4 carbon atoms. Contains atoms. These materials are the subject of EP-A-0,061,895. Other such additives are described in US Pat.
It is described in No. 1,455. Preferred esters, ethers or esters / ethers are represented by the following general formula. R ³¹ -O (L) -OR ^{32 In the} formula, R ³¹ and R ³² may be the same or different, and (a) n-alkyl-, (b) n-alkyl-CO-, (c) n- alkyl _{-O-CO (CH 2) x} -, or (d) n-alkyl -O-CO (CH ₂₎ represents the _x -CO-, x is for example 1 to a 30, the alkyl group in linear Where L is a polyalkylene moiety of a glycol having 10 to 30 carbon atoms and an alkylene group having 1 to 4 carbon atoms (for example, polyoxymethylene, polyoxyethylene or a substantially linear polyalkylene moiety). Oxytrimethylene moiety), some degree of branching of the lower alkyl side chains (eg of polyoxypropylene glycol) may be present, but it is preferred that the glycol is substantially linear. Further, L may contain nitrogen. Examples of suitable glycols include substantially linear polyethylene glycol (PEG) and polypropylene glycol (PPG) having a molecular weight of 100 to 5,000, preferably 200 to 2,000. Esters are preferred, fatty acids containing 10 to 30 carbon atoms are useful for reaction with glycols, forming ester additives, it is preferred to use C ₁₈ to C ₂₄ fatty acids, especially behenic acid . The ester may also be prepared by esterifying a polyethoxylate fatty acid or polyethoxylate alcohol.

Polyoxyalkylene diesters, diethers, ethers / esters and mixtures thereof are suitable as additives, including small amounts of monoethers and monoesters (
Diesters are suitable for use in narrow boiling distillates when they may be present). It is preferred that a large proportion of dialkyl compound is present. Particularly preferred are stearic acid or behenic acid diesters of polyethylene glycol, polypropylene glycol or a polyethylene / polypropylene glycol mixture. Other examples of polyoxyalkylene compounds are disclosed in Japanese Examined Patent Publication No. 2-51477 and Japanese Examined Patent Publication No. 3
-34790 and the esterified alkoxylate amines described in EP-A-117,108 and EP-A-326,356.

(H) Mixture of Saturated Hydrocarbon Compounds Suitably a mixture of saturated hydrocarbon compounds, component (H) comprises straight chain alkanes.
Suitably, the mixture has a boiling range of about 230 to 510 ° C. Suitably, the mixture is
The lowest carbon number to the highest oxygen number contains a spread of at least 16 carbon atoms. Preferably, the mixture comprises a C ₂₄ to C ₃₂ , more preferably a C ₂₄ to C ₂₈ hydrocarbon in a substantial weight ratio. Suitably, the number average molecular weight is in the range of 350 to 450. Suitably the mixture is a wax. Waxes, in terms of the size and varying number of hydrocarbon components they contain and the difficulty of separating such closely related (often homogeneous) hydrocarbon molecules,
Conventionally, it is defined with reference to its physical characteristics. “Industrial Waxes”, H.
Bennett, 1975 describes different types of petroleum waxes and shows that melting point and refractive index properties prove useful in the classification of various waxes available from different sources. Also, waxes are typically described by their n-alkane content. Component (H) is a mixture, in particular a mixture of two or more linear and non-linear alkanes, which is evident from the chromatographic characteristics and exhibits a bimodal or multimodal distribution of carbon numbers. In general, n-alkane waxes have a maximum in the carbon number distribution with lower carbon numbers than non-n-alkane waxes.

The wax may be an n-alkane wax or a non-n-alkane wax. The term "n-alkane wax" is used herein to mean a wax containing 40% by weight or more of an n-alkane, based on the total weight of the wax. Similarly, the term "non-n-alkane wax" is used herein to mean a wax that contains less than 40% by weight of n-alkane, based on the total weight of the wax. Preferably, the n-alkane wax comprises at least 55% by weight, more preferably at least 60% by weight n-alkane. Preferably, the non-alkane wax is less than 35% by weight, more preferably less than 30% by weight, for example less than 20% or 15% by weight n-.
Including alkane.

More preferably, the n-alkane wax is a wax wax (eg, 90 neutral (ne
sewage from a heavy gas oil having a viscosity equal to the lubricating viscosity range of 100 to 400 neutral (eg 90 slack wax, 130 slack wax, 150 slack wax and 400 slack wax). Is. Such waxes typically contain a range of hydrocarbon components containing from 15 to 60 carbon atoms and the distribution of n-alkanes is typically nC ₁₅ to nC ₅₀ (e.g. nC ₁₅ to nC ₄₅ ). Is. Further examples of n-alkane waxes suitable for use in the present invention include various grades of "Shell waxes", especially shell waxes 130/135 and 12
For example, 5/130. The non-n-alkane wax may be a heavy wax stream (eg, crude wax 600 neutral) or a crude wax derived from petroleum or wax oil materials.

The non-n-alkane waxes preferably have a melting point of 42 to 59 ° C. and a refractive index of 1.445 to 1.458. (The refractive index used herein is ASTM D1747 at a temperature of 70 ° C.
-Measured according to 94. ) The melting point of the non-n-alkane waxes useful in the present invention is preferably 44 ° C to 55 ° C.
, Preferably from 45 ° C to 53 ° C, more preferably from 47 ° C to 53 ° C. The melting points used in the present invention are measured according to ASTM D938. The refractive index of waxes useful in the present invention is preferably in the range 1.445 to 1.455, more preferably in the range 1.447 to 1.454, most preferably in the range 1.445 to 1.453, especially in the range 1.451 to 1.453. Particularly suitable non-n-alkane waxes have the following combinations of melting point and refractive index measured according to the test defined above. (I) Preferably, a melting point in the range of 42 ° C to 59 ° C and a refractive index in the range of 1.445 to 1.455,
(Ii) preferably a melting point in the range of 44 ° C to 55 ° C and a refractive index in the range of 1.447 to 1.454, (iii) more preferably a melting point in the range of 45 ° C to 53 ° C and a refractive index in the range of 1.445 to 1.453 And (iv) most preferably a melting point in the range of 47 ° C to 53 ° C and a refractive index in the range of 1.451 to 1.453.

It has been surprisingly found that mixtures of different petroleum waxes have properties which are particularly useful for improving the cold flow properties of oils, especially fuel oils (eg middle distillate fuel oils). Without wishing to be bound by any particular theory, the wax mixture preferably interacts with the precipitating n-alkane present in the oil and any further cold flow enhancers also present in the oil. It is expected that the detrimental effect of the wax's inherent settling properties on oils will be reduced and prevented. Mixtures of two or more such waxes may perform better than a single wax in cold flow improver applications. A preferred wax mixture is one in which at least one wax is an n-alkane wax and at least one wax is a non-n-alkane wax. Additives comprising one or more n-alkane crude waxes having one or more of the above forms of waxes (i) to (iv) are particularly suitable as flow improvers. More than one of each type of wax may effectively be used in the mixture of waxes. The different waxes used are typically obtained by suitable separation and fractionation of different wax-containing distillate fractions and are also available from wax suppliers.

The terms “hydrocarbyl” and “hydrocarbylene” as used herein refer to a group having a carbon atom directly attached to the remainder of the molecule and having a hydrocarbon or predominantly hydrocarbon character. Among these, the hydrocarbyl group includes an aliphatic group (eg, alkyl or alkenyl), an alicyclic group (eg, cycloalkyl or cycloalkenyl), an aromatic group, an aliphatic and alicyclic-substituted aromatic group, and an aromatic group. Included are substituted aliphatic and alicyclic groups. Aliphatic groups are preferably saturated. These groups may contain non-hydrocarbon substituents, but their presence should not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. When the hydrocarbyl group is substituted, a single substituent is preferred. Examples of substituted hydrocarbyl groups include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The group may also include, or instead of, atoms other than carbon on the chain or ring of carbon atoms. Suitable heteroatoms include, for example, nitrogen, sulfur, preferably oxygen. Suitably, the hydrocarbyl groups are at most 30, preferably at most 15, more preferably at most
It contains 10 and most preferably at most 8 carbon atoms.

The composition may comprise more than one polymeric material of the present invention and / or more than one other cold flow enhancer, which may be of the same category from A to H or of different categories. . The present invention also provides an oil comprising the polymeric material or additive composition of the present invention, wherein the additive concentrate is a polymeric material or additive composition of the present invention in admixture with an oil or an oil-miscible solvent. Including things. Further, the present invention provides the use of the polymeric material or additive composition of the present invention to improve the low temperature properties of oils. The oil may be a mineral oil, ie an oil obtained directly from drilling and an oil after refining, the composition of the invention being suitable for use as its flow improver. The oil may be a lubricating oil and is an animal, vegetable or mineral oil (eg naphtha or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oil or petroleum fractions in the range of oxidized mineral oils, etc.). May be. Such oils may contain additives depending on their intended use, examples being viscosity index improvers (eg ethylene-propylene copolymers), succinic acid based dispersants, metal-containing dispersants and zinc dialkyls. Examples include dithiophosphate antiwear agents. The compositions of the present invention are suitable for use in lubricating oils as flow improvers, pour point depressants or dewaxing aids.

The oil may be a fuel oil, especially a middle distillate fuel oil. Such distillate fuel oils typically boil in the range of 110 ° C to 500 ° C, such as 150 ° C to 400 ° C. The present invention is directed to a wide boiling range distillate, namely 90% to 20% boiling temperature difference (ASTM D-8
(According to 6) above 100 ° C and all types of middle distillate fuel oils including FBP-90% above 30 ° C, and especially from 90% below 100 ° C, especially below 85 ° C to 20%
Applicable to those that are more difficult to handle narrow boiling distillates with a boiling range of%. Fuel oil is atmospheric distillate or vacuum distillate, or cracked gas oil or straight run and heat and / or
Alternatively, it may comprise a blend of any proportion of catalytic cracking distillate. The most common petroleum distillate fuels are kerosene, jet fuel, diesel fuel, heating oil.
And heavy fuel oil. The heating oil may be a direct atmospheric distillate and may contain small amounts, for example up to 35% by weight, of vacuum gas or cracked gas oil or both. The invention is also applicable to plant-based fuel oils (eg rapeseed oil) used alone or mixed with petroleum distillates. In addition, the additive and fuel oil compositions may include additives for other purposes, such as reducing particulate emissions or preventing color formation and sediment formation during storage. The fuel composition of the present invention may suitably comprise the polymeric material or additive of the present invention in a total proportion of 0.0005% to 2.5% by weight, preferably 0.01% to 0.25% by weight, based on the weight of the fuel. Good. The polymeric materials and other cold flow enhancers of the present invention are preferably 1:15 to 1: 1,
It is preferably present in a weight ratio of 1:10 to 1: 3. In the following examples, parts and percentages are by weight unless otherwise stated,
The acid value is expressed in mg KOH / g, and the present invention is specifically shown.

Examples 1-18 Preparation of Polymeric Materials Example 1 Part A 500 parts phenol and 153 parts Amberlyst-15® catalyst, equipped with inlet, nitrogen purge, stirrer and thermometer. Placed in a reaction vessel. The mixture was heated to 75 ° C. and 506.1 parts of crystalline C ₃₀₊ wax, Gulfteen 30 + ® with terminal olefin groups and Mn of 478, was added over 1.5 hours with stirring. The temperature was then raised to 90 ° C. and maintained at that temperature for 5 hours with stirring. The reaction mixture was filtered and unreacted phenol was distilled under high vacuum. The FTIR spectrum of the product did not show the signals of the terminal olefin peaks at 1644, 910 and 887 cm ⁻¹ present in the spectrum of the wax reactant, but 3615 and 3615 assigned to the phenolic hydroxy group.
It showed a new peak at 3387 cm ^-1 .

Example 2 Transesterification 3 parts (molar ratio 53) of the product of Example 1 and 11 parts (molar ratio 48) of a carboxy-terminated ethylene-butadiene copolymer chloromethylphenol ester (ethylene content 45%, molecular weight approx. 2200) is heated to 80 ° C and 0.0148 parts (molar ratio 2) of boric acid and 0
0.0235 part (molar ratio 2) of sulfuric acid was added. Raise the temperature to 110 ℃ and under reduced pressure (0.1mmHg)
It was stirred for 3 hours. The IR spectrum showed a shift of the ester carbonyl peak from 1959 cm ^-1 to 1953 cm ^-1 on transesterification. Chlorine content dropped from 1.39% (for initial ester) to 0.088%. Example 3 The procedure of Example 2 was repeated except that the boric acid and sulfuric acid catalysts were used in a transesterification ratio of 4 mol each, and the reaction was carried out at 120 ° C for 30 minutes. It showed a similar IR shift and the product had a chlorine content of 0.195%.

Example 4 Koch reactive esterification 75 parts (molar ratio 1316) of the product of Example 1 and 347.4 parts (molar ratio 1579) of a terminally unsaturated ethylene-butene copolymer (ethylene content 45%, Mn 2200) are used. It was placed in a pressure reactor containing 13.4 parts (1974 molar ratio) of BF ₃ and 500 psi of carbon monoxide. The carbon monoxide pressure was increased to 1500 psi (about 10.3 MPa) and the reactor was maintained at 110 ° C for 1 hour. After removing BF ₃ and CO, the ester product was collected and showed an ester IR peak at 1751 cm ⁻¹ . Example 5 15 parts of hydroxy terminated amorphous ethylene-butene copolymer (Kraton L-1203 (
Trademark and Shell product), 52.8% (68.4% mol%) ethylene, 46.52% (30.1
3 mol%) butene, 0.68% (1.64 mol%) hydroxy groups) and 1.5 parts of linear saturated carboxylic acid terminated crystalline ethylene polymer (Unicid 425 Acid, registered trademark and Petro
The lite product, molecular weight 425 by VPO, acid number 94) was placed in a vessel equipped with an inlet, nitrogen purge, stirrer and thermometer. The mixture was heated to 160 ° C, 0.35 parts of p-tosylic acid was added and the temperature was maintained at 160 ° C for 16 hours. Product details are shown in the table of Example 7 below.

Example 6 The procedure of Example 5 was repeated except that 2 parts of Unicid 550 Acid polymer (molecular weight 550, acid number 72.5) were used. Example 7 The procedure of Example 5 was repeated except that 2.5 parts of Unicid 700 Acid polymer (molecular weight 700, acid number 63) was used.

[0045]

[Table 1]

Example 8 3 parts (1 mol ratio) of substantially terminally unsaturated crystalline ethylene-1-butene copolymer (Mn 1300, 12 mol% butene) and 2.76 parts (1 mol ratio) of phenol end-free. A crystalline ethylene propene polymer (Mn 1100, low ethylene content) was placed in a round bottom flask equipped with a condenser and dropping funnel, 100 parts by volume of chlorobenzene and 30 parts of Amberlyst 15
I put it with. The reaction mixture was stirred under nitrogen and the vessel was placed in an oil bath preheated to 120 ° C and kept at that temperature for 4 hours. After cooling to room temperature, the reaction mixture was filtered, the solvent was evaporated from the filtrate on a rotary evaporator and the reaction was collected. The terminal olefin peak in the FTIR spectrum of the initial ethylene-butene polymer disappeared from the spectrum of the product and new peaks appeared at 3614 and 3362 cm ^-1 .

Example 9 3 parts (1 molar ratio) of the crystalline ethylene-1-butene copolymer used in Example 8 and 2.5 parts (1 molar ratio) of the substantially terminally unsaturated non-crystalline ethylene-propene. The copolymer (Mn 1100, low ethylene content) was placed in a round bottom flask equipped with a condenser and dropping funnel, along with 60 parts by volume of chlorobenzene. To this mixture was added 0.868 parts (4 molar ratio) of phenol and 3 parts of Amberlyst 15 dissolved in 15 parts by volume of chlorobenzene and the reaction mixture was stirred under nitrogen. The vessel was placed in an oil bath preheated to 120 ° C., maintained at that temperature for 4 hours, and the product was recovered as described in Example 8. FTI
R analysis showed that the terminal olefin peaks at 1650 and 887 cm ^-1 of the initial polymer disappeared from the product and new peaks at 3614 and 3356 cm ^-1 appeared.

Example 10 92.12 parts (molar ratio 13.16) of crystalline aliphatic hydroxy-terminated polyethylene (Mw 700) prepared as in the procedure of Example 1, 347.4 parts used in Example 4 (molar ratio 1579).
) Ethylene-butene copolymer, 13.4 parts (molar ratio 1974) BF ₃ and 1414 psig (approximately
Repeat the procedure of Example 4 except using pressurized carbon monoxide at 9.75 MPa
An och-linked PE-PEB ester was obtained. Example 11 347.4 parts (molar ratio 1579) of amorphous ethylene-butene polymer (Mn 2200)
, 75 parts (molar ratio 1316) of phenol-terminated crystalline C ₃₄ wax and BF ₃ (13.4 parts, 1974 molar ratio) as a coupling agent instead of Amberlyst 15.
The procedure of Example 8 was repeated to give the C ₃₄ -PEB ester. Example 12 2.5 parts (36 molar ratio) of pre-made carboxy-terminated polyethylene (Mn 700) in crystalline mass and 6.4 parts (43 molar ratio) of phenol-terminated ethylene-butene polymer (low ethylene in amorphous mass) The procedure of Example 4 was repeated using the content of Mn 1500) and the coupling was catalyzed by sulfuric acid (0.175 parts, molar ratio 2) to give the PE-EB ester.

Example 13 In a round bottom flask equipped with a condenser and dropping funnel, 2 parts of substantially end-unsaturated crystalline ethylene-butene copolymer (Mn 1577, 18.3 mol% 1-butene) and 4 parts Hydroquinone-terminated ethylene-propene copolymer (Mn 3050, low ethylene content) 1
Charged with 00 parts chlorobenzene and 15 parts Amberlyst-15. The mixture was stirred under nitrogen and the vessel was placed in an oil bath preheated to 120 ° C and maintained at that temperature for 4 hours. After cooling to room temperature, the reaction mixture was filtered and the solvent was evaporated from the filtrate on a rotary evaporator to recover the product. Reactant ethylene-butene copolymer F
The terminal olefin peaks at 1650 and 887 cm ^{-1 in} the TIR spectrum disappeared from the spectrum of the product (EP-EB ester).

Example 14 In a round bottom flask equipped with a condenser and dropping funnel, 2.8 parts of the crystalline ethylene-butene copolymer used in Example 13, 5.4 parts of substantially end-unsaturated amorphous ethylene-propene. Copolymer (low ethylene content, Mn 3050) and 60 parts by volume of chlorobenzene were added. The resulting solution contained 0.79 parts hydroquinone and 3 parts Amver.
lyst-15 was added. The procedure of Example 13 was repeated. The terminal olefin peaks at 1650 and 887 cm ^{-1 in} the FTIR spectrum of the initial material disappeared from the spectrum of the product (EP-EB ester), the product showing new peaks at 3615 and 3478 cm ^-1 . Example 15 5.04 parts of phenol terminated ethylene-propene copolymer (Mn
1100, prepared by the procedure of Example 1) and 1 part of a terminally unsaturated ethylene-butene copolymer (Mn 5000) was used as the amorphous mass and the procedure of Example 8 was repeated. 0.75 parts of Amberlyst-15 and 50 parts by volume of chlorobenzene were used.

Example 16 1.65 parts of crystalline ethylene-propylene polymer (Mn 1100) and 8.4 parts of phenol terminated amorphous ethylene-butene copolymer (Mn 5000, prepared using the procedure of Example 1) were used. The procedure of Example 8 was repeated. 0.75 parts of Amberlyst-15 and 25 parts by volume of chlorobenzene were used. Example 17 37.5 parts (molar ratio 658) of the crystalline product of Example 1 and 434.2 parts (molar ratio 789) of the terminally unsaturated amorphous ethylene-butene copolymer were prepared according to the procedure of Example 4 with 6.6 parts (molar ratio). The ratio was 987) and BF ₃ and 1500 psi (about 10.3 MPa) carbon monoxide were used for bonding. Example 18 20.4 parts of the product of Example 17 were post-treated with boric acid (0.05 parts) and sulfuric acid (0.8 parts) at 150 ° C for 24 hours.

Comparative Examples A to E Polyethylene-polyethylene butene (PEPEB) and polyethylene-polyethylene propene (PEPEP) block polymers were prepared by a two step conventional method of polymerization followed by hydrogenation. The polymers are shown below.

[0053]

[Table 2]

In all samples, the polyethylene block was crystalline and contained 2% C ₂
Has a branch. In all samples, the other blocks are oil-soluble, PEP block has about 25% methyl branching, PEB block has a C ₂ branching of about 14%. In the following examples, BS 2869 and Journal of the Institute of Petroleum
, 52 (1966) 173, by testing the products of the invention, by their CFPPs measurements, to evaluate their ability to improve the low temperature properties of three fuels and compare them to conventional materials. did. The characteristics of the fuel are as follows.

[0055]

[Table 3]

In addition to the Comparative Products A to E, the following materials were used in the tests. Additive F, ethylene-vinyl acetate copolymer, 36% vinyl acetate, Mn 3300, inhibitor. Additive G, 1 mole phthalic anhydride and 2 moles di (hydrogenated tallow) amine half amide, half amine salt reaction product, inhibitor. Additive H, ethylene-vinyl acetate copolymer, 13% vinyl acetate, Mn 6500, nucleating agent.
Additive J, polyethylene glycol ester (PEG ester), nucleating agent.

Examples 19-33 and Comparative Examples K-P In these tests, the polymeric product "inv." Of the invention and the comparative products A-E (generally regarded as nucleating agents) were tested at 4: Used in various total treatment ratios shown below, in combination with inhibitor additive F at a ratio of F: inv. Of 1 and in combination with inhibitor additive G at a ratio of G: inv. Of 3: 1 did.

[0058]

[Table 4]

The results showed that the polymeric materials of the present invention provided CFPP reduction comparable to that achieved with the PEPEP and PEPEB materials produced by conventional methods.

Example 34 and Comparative Examples Q and R As shown above, a typical cold flow improver composition comprises a nucleating agent and a retarder, and in many industrial products they are both ethylene. -Vinyl acetate (EVA) copolymer. Additives F and H are typical deterrents and nucleating agents, respectively.
In other industrial products, the nucleating agent is a PEG ester and additive J is a typical P
EG ester nucleating agent. For Fuel A (Fuel that is difficult to process), the following CFPP results show a combination of Additives F and H and a combination of Additives F and J (both 4: 1 ratio)
, And the use of additive F and the product combination of Example 7 (equal ratios).

[0061]

[Table 5]

The results show that Fuel A is more sensitive to additives that include the polymeric material of the present invention as a nucleating agent than additives that include a conventional EVA copolymer nucleating agent and that includes a PEG ester as a nucleating agent. Showed to be much more sensitive.

Examples 35 and 36 The products of Example 7 were evaluated in Fuel B alone and in combination with Additives F and G. The results of CFPP are shown below.

[0064]

[Table 6]

The results showed that in Fuel B, the polymeric material of the present invention had substantially CFPP inhibitor activity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10L 1/18 C10L 1/18 Z 1/22 1/22 B C C10M 143/00 C10M 143/00 145 / 02 145/02 145/06 145/06 145/14 145/14 145/16 145/16 145/26 145/26 149/02 149/02 // C10N 20:04 C10N 20:04 30:02 30:02 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), AE, AL, A M, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Payfer Dennis George New Jersey 08801 Anandale John Drive 33 ( 72) Inventor Dornis Panagiotis UK Oxfordshire O-Ex 13 6 Beeby Irvingon Milton Hill Pea O Box 1 (72) Inventor Brod Lamar Jessica Oxford Oxfordshire O-Ex 13 6 Cudy Oxford Irvine Don Marcham The For Things 13 (72) Inventor Shurdinski Georgia Earl United States New Jersey 07932 Florham Park Park Avenue 180 PEO Box 390 Exxon Research and Engineer Ring F Term (reference) 4H013 CB01 CC01 CE03 4H104 CA01C CB01C CB03C CB08C CB09C BB09BB02BB02 BB02BB05BB2BB0520204220422AE04J20204AE22AE042204022AE2 EA006 EH086 EH096 EN016 4J031 AA12 AB02 AC05 AD01 AE19 CD12 CD25 CD26 CD27

Claims (22)

[Claims] 1. A polymeric material of formula AB, wherein the polymeric material is 400 to 7000.
A part A having an alkyl chain or an alkylene chain and having a linearity such that its crystallinity is at least 25%, and a part B which imparts oil solubility to the material, Has a crystallinity of at most 10% and the moieties A and B are linked by bonds other than carbon-carbon bonds, or by functional groups. 2. A material according to claim 1 wherein part A is an ethylene-based homopolymer or copolymer. 3. A material according to claim 2 in which the polymer is obtained by the polymerization of ethylene, optionally in the presence of at least one other ethylenically unsaturated monomer. 4. A material according to claim 2, wherein the polymer is obtained by α-ω chain of linear dienes and subsequent hydrogenation. 5. The material of claim 1 in which part A is wax. 6. A material according to claim 1, wherein part B is an ethylene-based homopolymer or copolymer. 7. A material according to claim 6 wherein part B is obtained by the polymerization of ethylene optionally in the presence of at least one other ethylenically unsaturated monomer. 8. A material according to claim 6, wherein the polymer is obtained by 1,2 chain polymerization of linear dienes, polymerization of branched dienes or a combination of such polymerizations and subsequent hydrogenation. 9. Moieties A and B are linked by a reaction product of a nucleophilic group and an electrophilic group or a reaction product of an electrophilic group having an ethylenically unsaturated bond. The material according to any one of paragraphs. 10. The material of claim 9 in which the bond is derived from a phenol or hydroquinone residue. 11. A material according to claim 10 wherein the acid groups are attached to the moieties by the Koch reaction. 12. A material other than (i) the material according to any one of claims 1 to 11 and (ii) the material according to any one of claims 1 to 11 An additive composition comprising a cold flow improver. 13. The component (ii) is (A) an ethylenically unsaturated ester compound, (B) a comb polymer, (C) a polar nitrogen compound, (D) a hydrocarbon polymer, (E) a hydrocarbyl of an amine-substituted carboxylic acid. 1 selected from esters, (F) poly (meth) acrylate esters, (G) polyoxyalkylene compounds, and (H) mixtures of at least some saturated hydrocarbon compounds having a number of carbon atoms in the range from 15 to 60 1 13. The composition of claim 12 which is a seed. 14. The composition of claim 12 in which component (ii) comprises an ethylenically unsaturated ester copolymer. 15. A composition according to claim 14 wherein the copolymer is a terpolymer of ethylene, vinyl acetate and a vinyl ester of a C ₂ to C ₁₀ alkanecarboxylic acid. 16. The composition according to claim 15, wherein the alkanecarboxylic acid is 2-ethylhexanoic acid. 17. Copolymer having a molecular weight of at most 20,000 and at least 7.5 mol%.
A composition according to any one of claims 14 to 16 having an ester content of. 18. Component 12 to 1 wherein component (ii) comprises a mixture of at least some saturated hydrocarbon compounds having a number of carbon atoms in the range 15 to 60.
Item 7. The composition according to any one of items 7. 19. A composition according to any one of claims 12 to 18 in which component (ii) comprises a mixture of ethylene-vinyl acetate copolymer and a saturated hydrocarbon compound. 20. A fuel or lubricating oil composition comprising the polymer material or the additive composition according to any one of claims 1 to 19. 21. An additive concentrate comprising a polymeric material or composition as defined in any one of claims 1 to 19 in an oil or oil miscible solvent. 22. Use of a polymeric material or composition as defined in any one of claims 1 to 19 for improving the cold flow properties of oils.