CN1818038B - Additives for oil compositions - Google Patents

Additives for oil compositions Download PDF

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CN1818038B
CN1818038B CN2006100074477A CN200610007447A CN1818038B CN 1818038 B CN1818038 B CN 1818038B CN 2006100074477 A CN2006100074477 A CN 2006100074477A CN 200610007447 A CN200610007447 A CN 200610007447A CN 1818038 B CN1818038 B CN 1818038B
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polyoxyalkylene
alkyl
additives
described compositions
carbon atom
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CN1818038A (en
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C·莫顿
R·D·泰克
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)

Abstract

An additive composition comprises at least one polyoxyalkylene compound and at least one ethylene polymer, wherein the at least one ethylene polymer, in addition to units derived from ethylene, comprises units of the formula (I) and optionally, units of the formula (II) wherein each R<1> group independently represents hydrogen or methyl; wherein each R<2> group independently represents an alkyl group having 5 or more carbon atoms; where in each R<3> group independently represents hydrogen or methyl; wherein each R<4> group independently represents an alkyl group having between 1 to 4 carbon atoms; wherein the proportion of units of formula (I) in the ethylene polymer is between 16 and 30mol%; and wherein the total proportion of units of formula (I) and formula (II) in the ethylene polymeris between 19 and 30mol%. The composition is particularly suitable for improving the low temperature properties of fuels having sharp distillation tails and low final boiling points.

Description

Additives for oil compositions
The present invention relates to additives for oil compositions, relate generally to the fuel oil composition additive, and the fuel oil composition additive that relates more particularly to be easy at low temperatures form wax.
Oil fuel (no matter being derived from oil or plant-derived) comprises the composition of normal paraffin for example or N-alkanes acid methyl ester, and these compositions tend to as big wax disk(-sc) crystalline substance or wax spherocrystal precipitation at low temperatures and make formation can cause described fuel to lose the gel structure of its flow capacity.Described fuel still can the mobile minimum temperature be called as pour point.
Along with the temperature decline of described fuel and near pour point, can encounter difficulties by pipeline and pump delivery fuel.In addition, described wax crystalls tends to block burning line, screen cloth and strainer in the temperature that is higher than pour point.Prior art has been fully recognized that these problems, and has proposed multiple additives, wherein many pour points that are used to reduce oil fuel in commercial applications.Similarly, having proposed other additives and its is used to reduce the size of formed wax crystalls and changes its shape in commercial applications.The crystal of reduced size is desirable, because the possibility of its blocking filter is less.From diesel oil mainly is that the wax of N-alkanes chloroflo is with the flap crystallization; Some additive can suppress this situation and make described wax take the needle-like form, and resulting spicule is compared with flap and is more suitable for by strainer, perhaps forms the crystalline porous layer on strainer.Described additive also can have the effect that keeps wax crystalls to be suspended in the fuel, reduces precipitation and also help thus to prevent to block.
Effectively wax crystalls modification (weigh by cold filter clogging temperature (CFPP) and the test of other operability, and simulate its on-the-spot use properties) can realize by the FLOW IMPROVERS based on ethane-acetic acid ethyenyl ester (EVAC) or vinyl propionate ester copolymer.
Britain specification sheets No.1,086,036, EP-A-527,322 and EP-A-518,406 have described and have been suitable for as coating with the terpolymer of network structure, these terpolymers by make ethene and uncle's aliphatic carboxylic acid or season aliphatic carboxylic acid vinyl ester form with other ester monomer copolymerization that can be vinyl-acetic ester.
Britain specification sheets No.1,314,855 have described ethene, vinyl-acetic ester and can be long-chain carboxylic acid's the terpolymers of vinyl ester with saturated carboxylic acid of 8-30 carbon atom.These terpolymers can be used in the lubricating oil as viscosity index improver according to description.
Britain specification sheets No.1,244,512 have described ethene, C 2-C 4Monocarboxylic vinyl ester and have C on a small quantity 10-C 2The terpolymer of the unsaturated ester of 2 alkyl (it preferably has following formula).
Figure S06107447720060216D000021
Wherein X is hydrogen or methyl, and Y be OOCR or-COOR, wherein R C10-C16 straight or branched alkyl preferably.
WO96/07718 discloses the oil-soluble ethylene terpolymer that contains ethylene unit and differing ethylene base ester units, with and as the purposes of the additive of the low temperature flowability that is used to improve fuel oil composition.Polymkeric substance embodiment 1～4th, ethane-acetic acid ethyenyl ester-2 ethyl hexanoic acid vinyl acetate terpolymer, it has the different ratios of described two kinds of unsaturated ester and different number-average molecular weight and branching characteristics.
The polymkeric substance of WO96/07718 is effective cold flow improver and has the advantage that is made by the commercially available vinyl ester monomers that gets.
EP 0 061 895 has described polyoxyalkylene compounds such as polyoxyalkylene esters and the ether that can be used as the FLOW IMPROVERS that distillate fuel uses.These can use with the EVA combination of polymers.
EP 1 007 606 has described the purposes of the FLOW IMPROVERS that ethylene/vinyl base ester copolymer and terpolymer use as distillate fuel.These can be used in combination as those that describe in EP 0,061 895 with polyoxyalkylene compounds.The ethylene vinyl ester copolymers of EP 1 007 606 has the maximum ethylene base ester content of 18mol%, and wherein a part is a vinyl-acetic ester.
Although above-mentioned FLOW IMPROVERS is that effectively the present invention has been found that the validity that has reduction when it is used for some kind of fuel in most of situation.Particularly, the applicant finds for for the application in the fuel with accurate distillation tailings (sharp distillation tails) and low full boiling point, has a high proportion of than the vinyl-acetic ester combination of the ethylene/vinyl base ester polymer of high-grade vinyl ester and the polyoxyalkylene compounds performance that can be improved more.
Thereby according to first aspect, the invention provides a kind of compositions of additives, it comprises at least a polyoxyalkylene compounds and at least a ethene polymers, and wherein said at least a ethene polymers also contains formula (I) unit and non-essential formula (II) unit except the unit that is derived from ethene:
Figure S06107447720060216D000032
Each R wherein 1Group is represented hydrogen or methyl independently; Each R wherein 2Group is represented the alkyl with 5 or more carbon atoms independently; Each R wherein 3Group is represented hydrogen or methyl independently; Each R wherein 4Group is represented the alkyl with 1-4 carbon atom independently; The unitary ratio of wherein said ethene polymers Chinese style (I) is 16-30mol%; And wherein said ethene polymers Chinese style (I) and the unitary overall proportion of formula (II) are 19-30mol%.
Preferably, the unitary ratio of described ethene polymers Chinese style (I) is 18-30mol%, more preferably 20-30mol%, for example 22-28mol%.
Preferably, described ethene polymers Chinese style (I) and the unitary overall proportion of formula (II) are 20-30mol%, more preferably 22-28mol%.For fear of query, should be clear that the present invention includes wherein said ethene polymers does not comprise the unitary embodiment of formula (II).Have been found that ethene polymers Chinese style (I) and (II) unitary ratio be important.When described ethene polymers Chinese style (I) and the unitary overall proportion of formula (II) are all found poor-performing during above and below this preferred range.Cross low formula (I) unit ratio and also have been found that it is disadvantageous.
Preferably, R 2Representative has the branched-chain alkyl of 7-15 carbon atom.Special preferred source is certainly such as the monomeric unit of 2-ethylhexanoate, vinyl neodecanoate and tripropylene (tripropene) (as different nonyl).
Advantageously, R 1And R 3Be hydrogen.
Described polymkeric substance has at least two kinds of different repeated monomer unit, and promptly it can be derived from least two kinds of different monomers.When comprising formula (II) unit, this polymkeric substance has at least three kinds of different repeated monomer unit.What comprise equally can be to be derived from four kinds or more kinds of polymer of monomers.For example, described polymkeric substance can comprise two or more different formulas (I) or (II) unit, and/or can comprise formula (III) unit:
Figure S06107447720060216D000041
R wherein 5Representative is different from by R 4The alkyl with 5 or more carbon atoms of the group of definition.
As used in this specification sheets, term " alkyl " refers to have the carbon atom that directly links to each other with the rest part of this molecule and has hydrocarbon or mainly be the group of hydrocarbon characteristic.Wherein, can mention aromatics and the aliphatic series of aromatics replacement and the alkyl of alicyclic group that comprises aliphatic series (as alkyl), alicyclic (as cycloalkyl), aromatics, aliphatic series and alicyclic replacement.Aliphatic group is advantageously saturated.These groups can contain non-hydrocarbon substituent, and condition is the main hydrocarbon characteristic that its existence can not change this group.Example comprises ketone, halogen, nitro, cyano group, alkoxyl group and acyl group.If described alkyl replaces, so preferred (list) substituting group.The example of the alkyl that replaces comprises 2-ketone propyl group, ethoxyethyl group and propoxy-propyl group.Described group also can or can be used as selectively and contain the atom that is different from carbon in chain of being made up of carbon atom in addition or ring.Suitable heteroatoms for example comprises nitrogen, sulphur and oxygen preferably.Advantageously, described alkyl contains 30 at the most, preferably 15, more preferably 10 and 8 carbon atoms at the most most preferably at the most at the most.
Described polymkeric substance also can comprise except that above-mentioned general formula unit those, for example formula (IV) unit:
—CH 2CHR 6—(IV)
R wherein 6Representative-OH, perhaps formula V unit
—CCH 3(CH 2R 7)CHR 8—(v)
R wherein 7And R 8Represent hydrogen independently of one another or have the alkyl of 4 carbon atoms at the most, (V) unit advantageously is derived from iso-butylene, 2-methyl but-2-ene or 2-methylpent-2-alkene.
Preferably, described at least a polyvinyl number-average molecular weight (Mn) is 3,000～8,000, more preferably 4,000～8,000, most preferably be 4,000～7,000.Mn refers to the value of relatively measuring by GPC and polystyrene standards in this specification sheets.
Preferably, the described at least a polyvinyl degree of branching for count 2～5, more preferably 2～4 with 100 MU (methylene unit), 2～3.5 methyl for example.The degree of branching of described polymkeric substance is the methyl number in 100 MU (methylene unit), as measuring by NMR and to R 2Methyl in the group and methylene radix carry out gauged.Referring to Fig. 1 of EP 1 007 606 and to the explanation of degree of branching calculated examples.The actual conditions that is used for the NMR measurement of the described ethene polymers degree of branching is well known by persons skilled in the art.For example, the technician knows the NMR spectrum that should avoid differentiating rate variance and selects suitable condition.Usually, the NMR spectrum that preferably obtains by high frequency NMR instrument.Should select suitable NMR solvent to minimize from the signal of solvent and interference between signals from polymkeric substance to guarantee good signal resolving power and to make.The applicant finds that be suitable from the NMR instrument that uses the deuterochloroform solvent to operate in about 40 ℃ of spectrograms that obtain under 400Mhz or bigger frequency.Can use if necessary 1H NMR and 13C NMR experiment.
Provide the composition of the mixture of polymers that comprises two or more first aspect present invention also to belong to scope of the present invention.
Preferably, described at least a polyoxyalkylene compounds comprises polyoxyalkylene esters, polyoxyalkylene ether, blended polyoxyalkylene esters/ether or its mixture.
Particularly preferably be and contain at least a, preferred at least two kinds of C 10-C 30Linear alkyl and molecular weight at the most 5,000, preferred 200-5, the polyoxyalkylene compounds of 000 polyoxyalkylene diols group, the alkylidene group in the wherein said polyoxyalkylene diols contain 1-4 carbon atom.These materials constitute the theme of EP-A-0061895.Other described additives are at US4, are described in 491,455.
Preferred ester, ether or ester/ether are to have those of following general formula
R 31-O-(D)-O-R 32
R wherein 31And R 32Can identical or different and representative
(a) just-alkyl-
(b) just-alkyl-CO-
(c) just-alkyl-O-CO (CH 2) x-or
(d) just-alkyl-O-CO (CH 2) x-CO-
X for example is 1-30, described alkyl be line style and contain 10-30 carbon atom, and D represents wherein that alkylidene group has the poly alkylidene group fragment of this glycol of 1-4 carbon atom, as being poly oxygen methylene radical, poly oxygen ethylidene or the poly oxygen propylidene fragment of line style basically; Can have certain degree of branching (as in polyoxypropylene diols), but preferred described glycol is line style basically with low alkyl group side chain.D also can contain nitrogen.
The example of suitable diol is that molecular weight is 100-5,000, preferred 200-2, and the polyoxyethylene glycol (PEG) of 000 line style basically and polypropylene glycol (PPG).Ester is preferred, the lipid acid that contains 10-30 carbon atom can be used for described diol reaction to form described ester additive, preferably use C18-C24 lipid acid, especially docosoic.Described ester also can make by esterification polyethoxylated lipid acid or polyethoxylated alcohols.
Polyoxyalkylene diester, diether, ether/ester and composition thereof are suitable for as additive, and preferred diester is used for the narrow boiling range overhead product, also may have more a spot of monoether and monoesters (it forms usually in process of production) therebetween.The preferred described dialkyl compound that has main amount.Especially, the stearic acid diester Huo docosoic diester of preferred polyoxyethylene glycol, polypropylene glycol or polyethylene/polypropylene glycol mixture.
Other examples of polyoxyalkylene compounds are those that describe in Japanese patent application No.2-51477 and 3-34790, and at EP-A-117, the alkoxylated amines of the esterification that is described in 108 and EP-A-326,356.
Preferably, the ratio of polyoxyalkylene compounds consumption and ethene polymers consumption is 1:99-99:1 in the described compositions of additives, more preferably 1:10-10:1, for example 1:2 or 1:1.
In a preferred implementation, described compositions of additives further comprises comb-shaped polymer.This can cause further being improved by the low temperature flowability that CFPP weighs.
Comb-shaped polymer is that the side chain that wherein contains alkyl is suspended on the polymkeric substance on the polymer backbone, and in " Comb-Like Polymers.Structure and Properties ", done argumentation, N.A.Plate and V.P.Shibaev, J.Poly.Sci.Macromolecular Revs., 8, the 117～253 pages (1974).
Usually, comb-shaped polymer has one or more long chain hydrocarbon groups side chain such as oxidation alkyl side chains that are suspended on the polymer backbone, and it generally has 10～30 carbon atoms, and described side chain is connected on this skeleton directly or indirectly.The example that connects comprises that atom or group by inserting connect indirectly, and this connection can comprise that covalency and/or electricity price connect for example salify.
Advantageously, described comb-shaped polymer be have at least 25 and preferred at least 40, more preferably the side chain of at least 50 moles of % contains the unitary multipolymer or the homopolymer of at least 6 and preferred at least 10 atoms.
As for the example of preferred comb-shaped polymer, can mention those with following general formula
Figure S06107447720060216D000071
D=R wherein 11, COOR 11, OCOR 11, R 12COOR 11Or OR 11,
E=H, CH 3, D or R 12,
G=H or D,
J=H, R 12, R 12COOR 11, aryl or heterocyclic radical,
K=H, COOR 12, OCOR 12, OR 12Or COOH,
L=H, R 12, COOR 12, OCOR 12, COOH or aryl,
R 11〉=C 10Alkyl
R 12〉=C 1Alkyl or alkylene,
And m and n represent molar fraction, and m is limited and is preferably 1.0～0.4 that n is less than 1 and preferred 0～0.6.R 11Advantageously representative has the alkyl of 10～30 carbon atoms, and R 12Advantageously representative has the alkyl or the alkylene of 1～30 carbon atom.
If desired or the described comb-shaped polymer of words that requires can comprise and be derived from other monomeric unit.
These comb-shaped polymers can be the multipolymers of maleic anhydride or fumaric acid or methylene-succinic acid and other ethylenically unsaturated monomers alpha-olefin or the unsaturated ester such as the vinyl-acetic ester of vinylbenzene (as comprise), or the homopolymer of fumaric acid or methylene-succinic acid.Preferred but the non-essential described comonomer that is to use equivalent, but the molar ratio in 2:1 and the 1:2 scope is suitable.Can comprise 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene and 1-octadecylene with for example example of the alkene of maleic anhydride copolymerization.
The acid of described comb-shaped polymer or anhydride group can be by any suitable technique esterifications, but preferred but non-essential be at least 50% esterified of described maleic anhydride or fumaric acid.The example of available alcohol just comprising-last of the ten Heavenly stems-1-alcohol, just-dodecane-1-alcohol, the just-tetradecane-1-alcohol, just-n-Hexadecane-1-is just pure and mild-octadecane-1-alcohol.Described alcohol can also comprise 1 methyl branch at the most in every chain, for example 1-methyl pentadecane-1-alcohol or 2-methyl tridecane-1-alcohol.Described alcohol can be the mixture of the alcohol of n-alkanol and monomethyl branching.Preferred pure alcohols rather than the commercially available alcohol mixture that gets of using is if but use mixture, R so 12The mean number that relates to carbon atom in the described alkyl; On 1 or 2, have ramose alcohol, R so if use 12Relate to this pure straight chain skeleton part.
These comb-shaped polymers especially can be fumarate or itaconic ester polymkeric substance and multipolymer as at described in EP-A-153176, EP-A-153177, EP-A-225688 and the WO91/16407 those.
Particularly preferred fumarate comb-shaped polymer be for example by solution copolymerization fumarate and vinyl-acetic ester etc. the fumaric acid alkyl ester made of molar mixture and the multipolymer of vinyl-acetic ester, wherein said alkyl has 10～20 carbon atoms, and more particularly wherein said alkyl has 12 carbon atoms or wherein said alkyl is C 12/ C 14The polymkeric substance of alkyl mixture.When using mixture, advantageously positive structure C 12And C 14The 1:1 weight ratio mixture of alcohol.In addition, described C 12Ester and blended C 12/ C 14The mixture of ester also can advantageously use.In the said mixture, C 12With C 12/ C 14Ratio advantageously be 1:1～4:1 weight ratio, be preferably 2:1～7:2 weight ratio, and most preferably be about 3:1 weight ratio.Particularly preferred comb-shaped polymer is that the number-average molecular weight of measuring by the gas-phase permeation platen press is 1,000～100,000, more particularly 1,000～30, those of 000.
The esterified copolymer of polymkeric substance that other suitable comb-shaped polymers are alpha-olefins and multipolymer and vinylbenzene and maleic anhydride and the esterified copolymer of vinylbenzene and fumaric acid; Can use the mixture of two or more comb-shaped polymers according to the present invention, and as mentioned above, this use may be favourable.Other examples of comb-shaped polymer are hydrocarbon polymers, and as the multipolymer of ethene and at least a alpha-olefin, this alpha-olefin preferably has 20 carbon atoms at the most, example be just-decylene-1 and just-laurylene-1.Preferably, the number-average molecular weight of described multipolymer is measured as at least 30,000 by GPC.Described hydrocarbon copolymer can for example adopt Ziegler type catalyzer by the known method preparation in affiliated field.
Preferably, the ratio of comb-shaped polymer consumption and ethene polymers consumption is 1:99～99:1 in the described compositions of additives, more preferably 1:10～10:1, for example 1:1.
Preferably, the ratio of comb-shaped polymer consumption and polyoxyalkylene compounds consumption is 1:99～99:1 in the described compositions of additives, more preferably 1:10～10:1, for example 1:1.
According to second aspect, the invention provides the additive concentrate compositions of a kind of compositions of additives that comprises first aspect and the solvent compatible with each other with it.
According to the third aspect, the invention provides a kind of oil compositions that comprises first or second aspect composition of oil and minor amount.
According to fourth aspect, the invention provides first or the second aspect composition be used to improve the purposes of the low-temperature performance of oil.
According to the 5th aspect, the invention provides a kind of method of low-temperature performance of improving oil, this method comprise with first or the second aspect composition join in the described oil.
Another favorable characteristics of compositions of additives of the present invention be its to the influence of the pour point of oil fuel.Even if influential to the pour point of oil fuel usually when described polyoxyalkylene compounds uses separately also is very little.The ethene polymers of first aspect present invention definition can significantly reduce the pour point of oil fuel when using separately, yet the combination of having observed described two kinds of materials can cause good especially pour point to descend.Thereby the composition of first aspect present invention definition is effective for reducing measured CFPP and pour point simultaneously.The adding of comb-shaped polymer can provide the raising of CFPP performance as mentioned above, the advantage that keeps good pour point to descend simultaneously.
Preferably, described oil is oil fuel, for example based on oil fuel, the especially intermediate distillate fuel oil of oil.Above-mentioned distillate fuel oil usually 110 ℃-500 ℃, seethe with excitement in as 150 ℃ of-400 ℃ of scopes.Described oil fuel can comprise normal pressure cut or vacuum cut, cracked gasoil, or with the straight run of any ratio and the mixture of heat and/or catalytic cracking cut.Modal petroleum fractions fuel is kerosene, rocket engine fuel, diesel oil, heater oil and heavy fuel oil (HFO).Heater oil can be a straight run normal pressure cut, or its can comprise vacuum gas oil a small amount of as 35wt% at the most or cracked gasoil or both.Above-mentioned low temperature flow problem runs in diesel oil and heater oil the most commonly.The present invention also is applicable to the oil fuel based on plant, rapeseed oil methyl ester (RME) for example, and it mixes use individually or with fraction oil of petroleum.
Other examples of oil fuel comprise fischer-tropsch fuel.The fischer-tropsch fuel FT fuel that is otherwise known as, it comprises that being described as GTL (gas-to-liquid) fuel and coal transforms those of fuel.For preparing described fuel, at first generate synthetic gas (CO+H 2) and convert it into normal paraffin by Fischer-Tropsch process then.These normal paraffins can be then the method modification by for example catalytic cracking/reformation or isomerization, hydrocracking and hydroisomerization whole or in part to obtain multiple hydrocarbon for example isoparaffin, naphthenic hydrocarbon and aromatic substance.Resulting FT fuel can so use or with other fuel compositions and fuel type such as this specification sheets in mention those be used in combination.
Preferably, described oil fuel has at the most 0.2 weight %, the particularly sulphur content of 0.05 weight % at the most.Have in addition more the fuel of low levels sulphur also be suitable for, for example have less than 50ppm weight sulphur, preferably less than the 20ppm for example 10 or fuel of ppm weight still less.
Additive of the present invention is particularly suitable for being used in the fuel with tangible distillation tailings and low full boiling point (FBP).The feature of described fuel can be have the FBP-90% distillation of 30 ℃ or littler, for example 25-20 ℃ and 370 ℃ or littler, for example less than 360 ℃ FBP.FBP-90% distillation refers to the difference between the temperature of 90% of FBP and volume of fuel when being distilled.The example of these kind of fuel is narrow fraction, ultra-low-sulphur diesels of Northern Europe heater oil and Japan.
As selection, described oil can be lubricating oil, and it can be animal, plant or mineral oil, as the petroleum fractions from petroleum naphtha or spindle oil to SAE30,40 or 50 lubricating oil rate ranges, the mineral oil of Viscotrol C, fish oil or oxidation.Described oil can comprise additive according to its intended purpose; Example is viscosity index improver such as ethylene-propylene copolymer, the dispersion agent based on succsinic acid, metallic dispersing additive and zinc dialkyl dithiophosphate wear preventive additive.
Described compositions of additives also can comprise other cold flow improvers.
Other additives that are used to improve low-temperature performance comprise polar nitrogen compounds.Described compound is to have one or more, preferred two or more formulas〉NR 13Substituent oil soluble polar nitrogen compounds, wherein R 13Representative contains the alkyl of 8～40 atoms, and one or more in this substituting group or these substituting groups can be by its deutero-cationic form.Described oil soluble polar nitrogen compounds normally can be used as the compound of wax crystalls growth inhibitor in fuel.It comprises for example one or more following compounds:
Replace the alkyl acid with 1～4 hydroxy-acid group of amine and certain mol proportion example or amine salt and/or the acid amides that its anhydride reaction forms, formula by the alkyl that makes at least 1 molar ratio〉NR 13Substituting group is formula-NR 13R 14, R wherein 13As mentioned the definition and R 14Represent hydrogen or R 14, condition is R 13And R 14Can be identical or different, described substituting group constitutes the part of the amine salt and/or the amide group of this compound.
Can use the ester/acid amides that comprises total 30～300, preferred 50～150 carbon atoms.These nitrogen compounds are at US4, are described in 211,534.Suitable amine mainly is C 12-C 40The primary, the second month in a season, uncle or quaternary amine or its mixture still can use the amine than short chain, and condition is that the nitrogen compound that obtains is oil-soluble, and it comprises about 30～300 carbon atoms of total usually.Described nitrogen compound preferably comprises at least one straight chain C 8-C 40, preferred C 14-C 24The alkyl fragment.
Suitable amine comprises primary amine, secondary amine, tertiary amine or quaternary amine, but preferred secondary amine.Tertiary amine and quaternary amine only form amine salt.The example of amine comprises four decyl amine, coco amine and hydrogenated tallow amine.The example of secondary amine comprises dioctadecylamine and methyl docosyl amine.Amine mixt also is fit to, as is derived from crude substance those.A kind of preferred amine is the para-hydrogenation tallow amine, and its alkyl is derived from by about 4%C 14, 31%C 16And 59%C 18The h-tallow fat of forming.
The example that is suitable for preparing the carboxylic acid of described nitrogen compound and acid anhydrides thereof comprises ethylenediamine tetraacetic acid (EDTA) and based on the carboxylic acid such as the hexanaphthene-1 of cyclic skeleton, 2-dicarboxylic acid, tetrahydrobenzene-1,2-dicarboxylic acid, pentamethylene-1,2-dicarboxylic acid and naphthalene dicarboxylic acids and comprise 1 of dialkyl group spirodilactone, the 4-dicarboxylic acid.Usually, these acid have about 5-13 carbon atom in circular part.Being preferred for acid of the present invention is benzene dicarboxylic acid class such as phthalic acid, m-phthalic acid and terephthalic acid.Preferred especially phthalic acid and acid anhydrides thereof.Particularly preferred compound is acid amides-amine salt that the dihydro tallow amine reaction by Tetra hydro Phthalic anhydride that makes 1 molar ratio and 2 molar ratios forms.Another preferred compound is by making the diamide that this acid amides-the amine salt dehydration forms.
Other examples are dicarboxylic acid derivatives of replacing of chain alkyl or alkylidene group as the amine salt of the monoamide that replaces succsinic acid, and the example is known and at for example US4 in the affiliated field, are described in 147,520.Suitable amine can be mentioned above those.
Other examples are condensess, for example those that describe in EP-A-327423.
Other additives that are used to improve low-temperature performance are to have at least two substituent compounds that contain member ring systems of following general formula on described member ring systems
-A-NR 15R 16
Wherein A is randomly by one or more heteroatomss linear chain or side chain aliphatic series alkylene at interval, R 15And R 16Identical or different and be randomly by the one or more heteroatomss alkyl that contains 9～40 atoms at interval independently of one another, identical or different and this compound of described substituting group is randomly with the form of its salt.Advantageously, A has 1～20 carbon atom and preferably methylene radical or poly methylene radical.Above-claimed cpd is described in WO93/04148.
Suitable in addition is hydrocarbon polymer.Example is to have those of following general formula:
Wherein T=H or R 21, wherein
R 21=C 1-C 40Alkyl and
U=H, T or aryl,
And v and w represent molar fraction, and v is 1.0～0.0, and w is 0.0～1.0.
Described hydrocarbon polymer can directly be made by single ethylenically unsaturated monomers or the polymkeric substance that is derived from many unsaturated monomers such as isoprene and divinyl by hydrogenation is indirectly made.
The example of hydrocarbon polymer has been done open in WO91/11488.
Preferred multipolymer is the ethylene of number-average molecular weight at least 30,000.Preferably this alpha-olefin has 28 carbon atoms at the most.The example of above-mentioned alkene be propylene, butylene, iso-butylene, just-octene-1, isooctene-1, just-decylene-1 and just-laurylene-1.Described multipolymer also can comprise a small amount of as other copolymerisable monomers of 10 weight % at the most, as is different from the alkene and the non-conjugated diene of alpha-olefin.Preferred multipolymer is an ethylene-propylene copolymer.
The number-average molecular weight of described ethylene as mentioned above preferably at least 30,000, as measuring with respect to polystyrene standards by gel permeation chromatography (GPC), advantageously at least 60,000 and preferably at least 80,000.Do not have the upper limit with regard to its function, but can cause greater than the viscosity that increased in about 150,000 o'clock at molecular weight and to mix difficulty, preferred molecular weight is from 60,000 and 80,000 to 120,000.
Advantageously, described multipolymer has the ethylene content of 50-85 mole %.More advantageously, described ethylene content is 57-80%, preferred 58-73%, more preferably 62-71% and most preferably 65-70%.
Preferred ethylene is that molar ethylene content is that 62-71% and number-average molecular weight are 60,000-120,000 ethylene-propylene copolymer; Particularly preferred multipolymer is that ethylene content is that 62-71% and number-average molecular weight are 80,000-100,000 ethylene-propylene copolymer.
Described multipolymer can for example adopt Ziegler type catalyzer by known any method preparation in the affiliated field.Described polymkeric substance should be unbodied basically, because the highly crystalline polymkeric substance is in being insoluble relatively in oil fuel under the low temperature.
Other suitable hydrocarbon polymers comprise low-molecular-weight ethylenic-alpha-olefin copolymer, preferably have at the most 7,500, more preferably 1,000-6, and 000, for example 2,000-5,000 number-average molecular weight is as measuring by the gas-phase permeation platen press.Suitable alpha-olefin provides as mentioned, or vinylbenzene, preferred propylene.Advantageously ethylene content is 60-77mol%, but advantageously can adopt the nearly ethene of 86 moles of % weight for ethylene-propylene copolymer.
Described hydrocarbon polymer can most preferably be an oil soluble hydrogenated diblock diene polymer, its comprise at least a crystallizable block that can obtain by the polymerization end to end of line style diene and at least a can not crystalline blocks, this can not crystalline blocks can be by 1 of line style diene, the polymerization of 2-configuration, mix by the polymerization of branching diene or by above-mentioned polymeric and to obtain.
Advantageously, described segmented copolymer comprises the unit that only is derived from divinyl before hydrogenation, or is derived from the unit of divinyl and at least a following formula comonomer
CH 2＝CR 22—CR 23＝CH 2
R wherein 22Represent C 1-C 8Alkyl and R 23Represent hydrogen or C 1-C 8Alkyl.Advantageously the total number of carbon atoms in this comonomer is 5-8, and this comonomer isoprene advantageously.Advantageously, described multipolymer comprises the unit that is derived from divinyl of at least 10 weight %.
Usually, described crystallizable block is mainly by 1 of divinyl, the 4-or the unitary hydrogenated products of polymerization gained end to end, and described can not crystalline blocks be by 1 of divinyl, 2-polymerization or alkyl replace 1 of divinyl, the unitary hydrogenated products of 4-polymerization gained.
Multifunctional additive for lubricating oils(a second aspect of the present invention)
Multifunctional additive for lubricating oils of the present invention advantageously oil or with the mixable solvent of oil in comprise the described compositions of additives of 3-75%, preferred 10-65%.
Comprise enriched material with the described additive of suitable solvent blended and be suitable as this additive is introduced for example means in the oil fuel of bulk oil, this introducing can be finished by the known method in affiliated field.Described enriched material also can contain other additives as required, and preferably contains 3～75wt%, more preferably 3～60wt%, the described additive of 10～50wt% most preferably, in its preferred oil-soluble.The example of solvent is the organic solvent that comprises hydrocarbon solvent, for example petroleum fractions such as petroleum naphtha, kerosene, diesel oil and heater oil; Aromatic hydrocarbon such as aromatic fractions, for example those that sell with " SOLVESSO " trade(brand)name; Alcohol and/or ester; And alkane such as hexane and pentane and isoparaffin.Described solvent certainly must be considered itself and described additive and select with the consistency of described oil.
Oil compositions(a third aspect of the present invention)
Oil compositions of the present invention advantageously comprises 0.0005%-1% based on weight of oil, the compositions of additives of the present invention of 0.001-0.1% and preferred 0.01-0.06 weight % advantageously.
Now the present invention is described as demonstration.
The CFPP performance
Only use 200ppm polyoxyalkylene compounds (polyoxyethylene glycol Er docosoic ester, about 600 (PEG600) of molecular weight) to handle to have the sample of the FBP-90% distillatory heater oil of 355 ℃ full boiling point and 14 ℃.This processing makes the CFPP of described fuel be reduced to-7.5 ℃ (comparing with-2.5 ℃ of basic fuel).Use described polyoxyalkylene compounds can not obtain further improvement separately.
The same oil of only using 400ppm to contain the unitary ethene polymers processing of 18.6mol% formula (I) obtains-7.0 ℃ CFPP, and this unit contains the 2 ethyl hexanoic acid vinyl acetate.The combination of this ethene polymers and above-mentioned polyoxyalkylene compounds causes the CFPP performance degradation to-6.0 ℃.
The same oil of only using 400ppm to contain the unitary ethene polymers processing of 27.4mol% formula (I) obtains-3.0 ℃ CFPP, and this unit contains the 2 ethyl hexanoic acid vinyl acetate.Yet in this case, the adding of above-mentioned polyoxyalkylene compounds causes CFPP significantly further to be reduced to-10.5 ℃.The validity of present embodiment explanation compositions of additives of the present invention (be polyoxyalkylene compounds with have a high proportion of) than the more polyvinyl combination of high-grade vinyl ester of vinyl-acetic ester.
Other the results are shown in the following table 1.
Table 1
Composition Formula (I) unit/mol% Formula (II) unit/mol% (I)+(II) total amount/mol% CFPP/℃ CFPP/ ℃+comb-shaped polymer
A 19.79 5.91 25.70 -11.00 -13.50
B 27.40 0.00 27.40 -10.50 -11.50
C 22.60 6.10 28.70 -10.00 -14.00
D 18.30 9.25 27.55 -9.75 -13.40
E 18.20 5.80 24.00 -9.00 -13.00
F 18.80 4.90 23.70 -9.00 -12.50
G 18.61 2.73 21.34 -9.00 -14.50
H 18.91 6.21 25.11 -8.75 -12.30
I 16.16 3.98 20.15 -8.00 -13.00
J 17.98 2.55 20.53 -7.75 -14.00
K 20.79 0.00 20.79 -7.50 -13.80
Comparative example 1 24.36 6.91 31.27 -5.50 -8.50
Comparative example 2 14.44 5.38 19.82 -4.00 -9.30
Composition A-K comprises 200ppm polyoxyethylene glycol Er docosoic ester (about 600 (PEG600) of molecular weight) and 400ppm and has the formula (I) of listed ratio in the table 1 and (II) unitary ethene polymers.Last row of table 1 have shown adding 200ppm comb-shaped polymer (C 12/ C 14Blended fumaric acid alkyl ester/vinyl acetate copolymer) result of composition A-K.In these three components compositions, use each material of 200ppm.These results show good CFPP performance, prove the further raising by described comb-shaped polymer.
Observe the poor-performing of two comparative examples.Comparative example 1 has high formula (I) and (II) unitary total amount and comparative example 2 has the unitary ratio of the formula lower than the present invention requirement (I).These data presentation formulas (I) and (II) importance of unitary relative quantity and total amount.
Compositions of additives is to the influence of pour point
Following table 2 has been listed measurement fuel pour point result of experiment in detail.Fuel used and the above-mentioned CFPP of being used for test identical and do not containing under any additives pour point with-3 ℃.
Table 2
Comb-shaped polymer/ppm PEG600/ppm Ethene polymers/ppm Pour point/℃
200 -3
300 -3
400 -3
150 -12
150 -3
150 -45
150 150 -15
150 150 -60
150 150 150 -51
300 150 -15
150 300 -63
200 200 200 -57
200 400 -60
Be clear that from the result of table 2 using PEG600 separately is not effective for the reduction of fuel pour point.Adding (being used for table 1 composition H's) ethene polymers separately makes depression of pour point to-45 ℃.This is by PEG600 and described polyvinyl combination and further be improved.The combination of all three kinds of components also obtains good pour point and descends.By comparison, independent comb-shaped polymer (C 12/ C 14Blended fumaric acid alkyl ester/vinyl acetate copolymer) and the validity of the combination of this comb-shaped polymer and PEG600 lower.

Claims (33)

1. compositions of additives, it comprises at least a polyoxyalkylene compounds and at least a ethene polymers, and wherein said at least a ethene polymers also contains formula (I) unit and non-essential formula (II) unit except the unit that is derived from ethene:
Each R wherein 1Group is represented hydrogen or methyl independently; Each R wherein 2Group is represented the alkyl with 5 or more carbon atoms independently; Each R wherein 3Group is represented hydrogen or methyl independently; Each R wherein 4Group is represented the alkyl with 1-4 carbon atom independently; The unitary ratio of wherein said ethene polymers Chinese style (I) is 16-30mol%; And wherein said ethene polymers Chinese style (I) and the unitary overall proportion of formula (II) are 19-30mol%.
2. the described compositions of additives of claim 1, wherein R 2Representative has the branched-chain alkyl of 7-15 carbon atom.
3. the described compositions of additives of claim 1, wherein R 4Represent ethyl or methyl.
4. the described compositions of additives of claim 2, wherein R 4Represent ethyl or methyl.
5. the described compositions of additives of claim 1, wherein said polyoxyalkylene compounds comprises polyoxyalkylene esters, polyoxyalkylene ether, blended polyoxyalkylene esters/ether or its mixture.
6. the described compositions of additives of claim 2, wherein said polyoxyalkylene compounds comprises polyoxyalkylene esters, polyoxyalkylene ether, blended polyoxyalkylene esters/ether or its mixture.
7. the described compositions of additives of claim 3, wherein said polyoxyalkylene compounds comprises polyoxyalkylene esters, polyoxyalkylene ether, blended polyoxyalkylene esters/ether or its mixture.
8. the described compositions of additives of claim 4, wherein said polyoxyalkylene compounds comprises polyoxyalkylene esters, polyoxyalkylene ether, blended polyoxyalkylene esters/ether or its mixture.
9. the described compositions of additives of claim 5, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
10. the described compositions of additives of claim 6, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
11. the described compositions of additives of claim 7, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
12. the described compositions of additives of claim 8, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
13. the described compositions of additives of claim 5, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
14. the described compositions of additives of claim 6, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
15. the described compositions of additives of claim 7, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
16. the described compositions of additives of claim 8, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight be 5,000 polyoxyalkylene diols group at the most, and the alkyl in the described polyoxyalkylene glycols contains 1-4 carbon atom.
17. the described compositions of additives of claim 5, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
18. the described compositions of additives of claim 6, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
19. the described compositions of additives of claim 7, wherein said polyoxyalkylene compounds contains C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
20. the described compositions of additives of claim 8, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
21. the described compositions of additives of claim 5, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
22. the described compositions of additives of claim 6, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
23. the described compositions of additives of claim 7, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
24. the described compositions of additives of claim 8, wherein said polyoxyalkylene compounds contains at least two kinds of C 10-C 30Linear alkyl and molecular weight 200-5,000 polyoxyalkylene diols group, the alkyl in the described polyoxyalkylene glycols contain 1-4 carbon atom.
25. the described compositions of additives of aforementioned each claim, it further comprises comb-shaped polymer.
26. comprising wherein said alkyl, the described compositions of additives of claim 25, wherein said comb-shaped polymer have the fumaric acid alkyl ester of 10-20 carbon atom and the multipolymer of vinyl-acetic ester.
27. the described compositions of additives of claim 26, wherein said alkyl have 12 carbon atoms or wherein said alkyl comprises C 12/ C 14The mixture of alkyl.
28. an additive concentrate compositions, it comprises described compositions of additives of aforementioned each claim and the solvent compatible with each other with it.
29. an oil compositions, it comprises each the described compositions of additives of claim 1-27 or the described multifunctional additive for lubricating oils of claim 28 of oil and minor amount.
30. the purposes of each described compositions of additives of claim 1-27 or the described multifunctional additive for lubricating oils of claim 28 wherein is used to improve oily low-temperature performance.
31. the described purposes of claim 30, wherein said oil comprise the oil fuel with 30 ℃ or littler FBP-90% distillation and 370 ℃ or littler FBP.
32. a method of improving the low-temperature performance of oil, this method comprise each described compositions of additives of claim 1-27 or the described multifunctional additive for lubricating oils of claim 28 are joined in the described oil.
33. the described method of claim 32, wherein said oil comprise the oil fuel with 30 ℃ or littler FBP-90% distillation and 370 ℃ or littler FBP.
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DE19758887A1 (en) * 1997-07-08 2006-10-19 Clariant Gmbh Flow improver for mineral oils
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