CN1063218C

CN1063218C - Dispersions of waxy pour point depressants

Info

Publication number: CN1063218C
Application number: CN96121729A
Authority: CN
Inventors: J·S·马格亚
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1995-11-29
Filing date: 1996-11-20
Publication date: 2001-03-14
Anticipated expiration: 2016-11-20
Also published as: CA2191036A1; GB2308129B; GB2308129A; AU713217B2; CA2191036C; GB9624768D0; CN1158887A; AU7400496A; NO318427B1; RU2171272C2; NO965075L; NO965075D0

Abstract

A liquid pour point depressant composition comprises a pour point depressant which is a solid at room temperature and which has a number average molecular weight of at least 500, and a liquid medium in which the material of pour point depressant is substantially insoluble at room temperature. The pour point depressant component is dispersed in the liquid medium.

Description

The dispersion of waxy pour point depressants

The present invention relates to the dispersion of wax pour point depressants.

The oils of various types of distillate fuel oils such as diesel oil, various lubricant viscosities, automatic transmission fluid, hydraulic efficiency oil, family's stove oil and crude oil need to use the pour point reducer additive for making it in lesser temps unrestricted flow.These oil contain kerosene usually as wax, particularly the solvent of the wax that exists in the distillate fuel oil.But in recent years, jet fuel was lowered the feasible middle kerosene consumption that distillates fuel oil of the needs of kerosene.So just taking turns to needs to add the scarcity that the wax crystalls modifying agent remedies kerosene.And, be considered to uneconomic because add kerosene, therefore, just more important to the demand of pour point reducer additive in crude oil.

Many pour point reducers itself are exactly the solid shape material of wax in a way owing to there is long alkyl.If these materials are liquid, promptly be dissolved in or be dispersed in some media, just can better be handled at normal temperatures.

The US patent of House on March 6th, 4435309,1984 discloses a kind of method of liquefied material, and this material is at envrionment temperature or waxy solid, or these wax materials and plant the solid or the semisolid mixture of solvent.This wax material forms solution under the temperature that improves in solvent, the solution cooling is produced the semi-solid solid that arrives, and then mixture is sheared.These wax materials are quaternary ammonium compound and polyoxyethylene alkylphenol; Solvent is the mixture of isopropylamine and water, or hexylene glycol.

The US patent 3061544,1962 of Martinek disclosed a kind of method for preparing colloidal dispersion October 30, prepared by reducing temperature, pressure and concentration simultaneously during shearing.Colloid forms by adopting enough thermosols to form solution in the carrying gel phase of minimum.Solution this heat, spissated under high pressure by spraying or nozzle enters low pressure and cold zone, is run into and clashed into the liquid phase plane in this area spray thing or spraying, also can under high pressure inject.

1968 of Lockhart etc., the US patent 3393078 on July 16 discloses a kind of automotive polish, by stir and the heating preparaton till the wax component disperses and is emulsified into trickle fusion (or near fusion) particulate, and the emulsion compositions of gained be cooled to room temperature and make.This emulsion is stirred fast, simultaneously it is cooled to the temperature that is lower than this wax fusing point; Then slowly stir emulsion, make its outlet from (blended) wall of container flow into the container that is used for its sale simultaneously.

Davis etc. disclose the wax emulsion of making emulsifying agent with colloidalmaterial in the US patent 1637475 in August 2 nineteen twenty-seven, colloidalmaterial is the mixture of hard and soft soap.The heating of material and strong mixing are carried out continuously, are broken up into until wax and end.When disperseing, turn cold fast,, continue simultaneously to stir by the sleeve pipe circulation cooling or the refrigerant of container for making material.When temperature of charge reaches about 65 ℃, carry out coarse filtration and make it be cooled to room temperature gradually with coarse cloth.

Martella etc. are in the US patent 5039437 on August 13rd, 1991, and (with the US patent 5082470 on January 21st, 1992, the division of above-mentioned a case) discloses the alkylphenol-formaldehyde condensation products additive that is used to improve the hydrocarbon ils low-temperature fluidity.The number-average molecular weight of this polymeric composition is about 3000 at least, and molecular weight distribution is 1.5 at least; In the alkylating phenol reactant, alkyl is straight chain basically, and carbonatoms is between 6 and 50, and carbon atom mean number is between about 12 and 26; About 10% (mole) moieties carbonatoms that is no more than on alkylating phenol is less than 12, and is no more than about 10% (mole) moieties carbonatoms more than 26 on alkylating phenol.

Dorer, Jr., Deng about US4564460 of 14 days (US4559155 on December 17th, 1985 at 1986 1, the US4565550 on January 21st, 1986, the divisions such as US4613342 in the US4575526 on March 11st, 1986 and on September 23rd, 1986), disclosing is the additive that improves the cold flowability of hydrocarbon fuel composition.This composition comprises pour point reducer, and it can be the phenol that alkyl replaces, and general formula is (R ^*) _a-Ar-(OH) _b, R wherein ^*Be selected from carbonatoms and be the alkyl of the polymkeric substance of 8 to 39 alkyl and carbonatoms at least 30, Ar is the aromatic hydrocarbons part, comprises the polycyclic aromatic hydrocarbons part of connection, general formula be ar-(Lng-ar-)- _w(Q) _Mw, wherein w is 1 to about 20 integer.Each Lng be comprise the alkylidene group bonding type (as wherein having-CH ₂-) bridged bond.

The invention provides a kind of liquid pour point reducer composition of homogenizing, comprising:

(ⅰ) room temperature be solid and number-average molecular weight at least 500 pour point reducer and

(ⅱ) liquid matrix, material wherein (ⅰ) are insoluble in room temperature basically;

Wherein component (ⅰ) is dispersed in the component (ⅱ).

The present invention further provides the method for the following mixture of a kind of homogenizing:

(ⅰ) room temperature be solid-state and the material of its number-average molecular weight at least 500 and

(ⅱ) material (ⅰ) is insoluble to wherein liquid in room temperature basically;

Comprise step:

(a) heating component (ⅰ) and (ⅱ) arrive (ⅰ) and in (ⅱ), can dissolve or the fused temperature;

(b) component with heating mixes; With

(c) mixture with heating is cooled to (ⅰ) undissolved basically temperature.

The present invention is the dispersion of a wax pour point depressants in a kind of material, and this material is insoluble to pour point reducer.This dispersion is homogenizing normally, is homogenizing at macro-scope at least.This wax pour point depressants is such material, and its number-average molecular weight is at least 500, preferably at least 700, more preferably at least 1000, and preferably up to 500000, more preferably up to 50000, most preferably 5000.This material is at 10 ℃, preferably in room temperature, that is to say at least up to about 20 ℃, and preferred up to 30 or 40 ℃ or higher be solid-state (when not adding solvent).This material further is: in the time of in being blended in waxy hydrocarbon liquid, measure by ASTM D-97, play pour point reducer.Suitable material is oligopolymer normally, generally includes the alkyl that at least one per molecule contains at least 12 carbon atoms.

The present invention includes polytype pour point reducer.In these pour point reducers, comprising (a) and reaction product (b), is solid-state or semi-solid state in room temperature (a), normally " wax " material and be the alkyl substituted phenol that enough carbonatomss are arranged on the hydrocarbyl substituent, be that carbonatoms is 1 to 12 (b), be preferably 1 to 4 aldehyde or its source.

The alkyl substituted phenol is known material, and its preparation method also is known.Term used herein " phenol " is interpreted as this term and usually the aryl of phenol is not defined as benzene (unless so be described in the literary composition, as in an embodiment), but benzene can be preferred aromatic group.Otherwise this term can be interpreted as the aromatic substance that generally includes hydroxyl on wideer meaning, for example, and the phenol of replacement, hydroxyl naphthalene or the like.Like this, the aryl of " phenol " can be monocycle and polycyclic, replacement, can also comprise the aryl of other types.

The aryl of hydroxyaromatic compounds can be a single aromatic proton, as benzene nucleus, pyridine nucleus, thiophene nuclear, 1,2,3,4-naphthane nuclear or the like, or polynuclear aromatic part.This multinuclear part can condense type; In other words, the virtue that wherein constitutes aryl checked 2 shared, as in naphthalene, anthracene, azanaphthalenes or the like, existing.Multinuclear aromatic ring part also can be a connecting-type, and wherein at least two nuclears (monokaryon or multinuclear) are connected to one another by the bridged bond bonding mutually.This bridged bond bonding can be the mixture of the bridged bond bonding of carbon-to-carbon singly-bound, ehter bond, ketonic bond, thioether bond, the polythiaether key that contains 2 to 6 sulphur atoms, thionyl key, sulphonyl key, methylene key, alkylene key, two-(low alkyl group) methylene key, low-grade alkylidene ehter bond, alkylidene group ketonic bond, low-grade alkylidene sulfide linkage, the low-grade alkylidene polythiaether key that contains 2 to 6 carbon atoms, ammonia key, poly-ammonia key and this two valencys between the aromatic ring.In some instances, on the aryl between the virtue nuclear, can there be bridged bond bonding more than one.For example fluorenes nuclear has two benzene nucleus that link to each other with covalent linkage by the methylene key.Can think that this nuclear has 3 nuclears, but wherein have only two to be virtue nuclear.Aryl usually only itself contains carbon atom at virtue nuclear, although also can there be other non-aromatic substituents, as the alkyl substituent of short chain particularly.Like this, for example on aryl, can there be methyl, ethyl, propyl group and the tertiary butyl, although clearly do not express in the listed herein structure of these groups.

The particular example of monocycle aromatic portion is as follows: Or the like, wherein Me is a methyl, and Et suitably is ethyl or ethylidene, and Pr is a n-propyl.

The particular example of condensed ring aromatic portion is as follows:

Or the like.

When aromatic portion was the polynuclear aromatic part of bonding, it can be represented with following general formula

Ar (L-ar-) _wWherein w is 1 to about 20 integer, each ar is that carbonatoms is 4 to about 12 monocycle and condensed ring virtue nuclear, each L be selected from separately carbon-to-carbon singly-bound between the ar nuclear, ehter bond (as-O-), ketonic bond (as-CO-), thioether bond (as-S-), contain the polythioether key of 2 to 6 sulphur atoms (as-S- _2-6), the sulfinyl key (as-S (O)-), the sulphonyl key is (as-S (O) ₂-), rudimentary alkylene base key is (as-CH ₂-,-CH ₂-CH ₂-,-CH ₂-CHR ⁰-), single (low alkyl group)-methene key (CHR ⁰-), two (low alkyl group)-methene keys are (as-CR ⁰ ₂-), the low-grade alkylidene ehter bond is (as-CH ₂O-,-CH ₂O-CH ₂-,-CH ₂-CH ₂O-,-CH ₂CH ₂OCH ₂CH ₂-,-CH ₂CR ⁰HOCH ₂CR ⁰H-,-CH ₂CR ⁰HOCR ⁰HCH ₂-or the like), low-grade alkylidene thioether bond (being replaced by the S atom), low-grade alkylidene polythioether key as the one or more-O-on the low-grade alkylidene ehter bond wherein (as wherein one or more-O-quilt-S _2-6-group replaces), the ammonia key (as-NH-,-NR ⁰-,-CH ₂N-,-CH ₂NCH ₂-,-alk-N-, wherein alk is low-grade alkylidene or the like), poly-ammonia key is (as-N (alkN) _1-10, wherein unsaturated free N key is by H atom or R ⁰Replace), by oxo bridge-or the key of ketone-carboxylic acid derivatives

Each R wherein ₁, R ₂And R ₃Be respectively alkyl, preferably alkyl or alkenyl, be more preferably low alkyl group or H, R ₆Be H or alkyl, X is from 0 to about 8 integer, and the mixture of these bridged bond bondings (each R ⁰All be low alkyl group).

The particular example of connection portion is: Or the like.

All these ar groups all do not have substituting group usually, except those are mentioned especially.For reasons such as cost, obtainable easy degree, performances, aryl moiety is the benzene nucleus or the naphthalene nuclear of benzene nucleus, low-grade alkylidene bridged bond normally.Most preferred aryl moiety is a benzene nucleus.

This first reactant is a hydroxyaromatic compounds, that is, a kind of at least one hydroxyl directly is added to the compound of aromatic ring.The hydroxyl value of each aryl can be from 1 maximum number that fades to this group, so that the aromatic portion that alkyl is replaced is keeping at least one, in the time of preferred at least two positions, with its adaptation, one of them some preferred adjacent with hydroxyl (ortho positions), such group are suitable for further the condensation reaction (described below) with aldehyde.Therefore, most of such reactant molecules just have at least two unsubstituted positions.So, the material that is suitable for comprises pyrocatechol, Resorcinol, the Resorcinol that alkyl replaces, and even pyrogaelol and Phloroglucinol.But modal is on each virtue nuclear a hydroxyl to be arranged, and in the preferred case, when adopting the phenol of alkyl replacement, this material contains a benzene nucleus and a hydroxyl.Certainly, the sub-fraction of aromatic reactant thing molecule hydroxyl substituting group not.For example, the no hydroxylated material of minimum can be used as the impurity existence.But this does not deviate from spirit of the present invention, as long as raw material has functional group, and contains at least one hydroxyl usually get final product on each molecule.

The hydroxyl aromatic reactant is characterised in that similarly it is that alkyl replaces.Term " hydrocarbyl substituent " or " alkyl " are with being meant the meaning that well known to a person skilled in the art common indication herein.Particularly, its group of relating to has the carbon atom that directly is added to the molecule remainder and has dominant hydrocarbon character.The example of alkyl comprises:

(1) hydrocarbon substituent, promptly aliphatic (as alkyl or alkenyl), alicyclic (as cycloalkyl, cycloalkenyl group) substituting group, with the aromatic substituent of aromatics, aliphatic series and alicyclic replacement, and the another part that wherein encircles by molecule becomes ring to constitute the ring substituents of (forming an alicyclic radical together as two substituting groups);

(2) hydrocarbon substituent of Qu Daiing, promptly substituting group contains, and in content of the present invention, does not change the non-hydrocarbyl group of dominant hydrocarbyl substituent (as halogen (particularly chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkane sulfydryl, nitro, nitroso-group and sulfoxide);

(3) assorted substituting group, promptly substituting group is when having dominant hydrocarbon character, in content of the present invention, on ring that is made of carbon atom or chain, also contains non-carbon atom.Heteroatoms comprises sulphur, oxygen, nitrogen and comprises following substituting group, as pyridyl, furyl, thienyl and imidazolyl.The general existence is no more than two on per ten carbon atoms of alkyl, preferably is no more than a non-hydrocarbon substituent; Usually on alkyl, there is not non-hydrocarbon substituent.

The alkyl preferred alkyl.Alkyl preferably contains at least 12, more preferably at least 20, at least 30 carbon atoms most preferably, if perhaps this alkyl is the mixture of alkyl, this mixture preferably on average contains at least 30 carbon atoms, contains 31 to 400 carbon atoms usually, preferred 31 to 60, more preferably 32 to 50 or 45 carbon atoms are although this not necessarily.In preferred embodiments, the alkyl in composition is the mixture of alkyl, and it can become another from a specific alkyl on the length of chain.When the part of this molecule contained an alkyl that is less than 30 carbon atoms, composition generally had at least 30 substituent features of carbon atom alkyl on the length as a whole.For particular of the present invention, alkyl can be shorter, contains to be less than 30 carbon atoms, as mainly being 24 to 28 carbon atoms or 20-24 carbon atom.Under any circumstance, alkyl not only can but also can have been derived by the branched-chain alkene reactant by straight chain; Although the material that chain length is long is tending towards increasing a chain portion, still preferred sometimes straight chain.Branching is to a certain degree equally seemingly introduced by Mechanism of rearrangement in alkylation process.

In a preferred embodiment, used alkyl comprises that an alkyl length is mainly 30 to 36 carbon atoms, and the number average carbon number is about 34.4, and the alkyl mixture of weight average carbon number about 35.4.The characteristics of this material be have approximately following chain length distribution:

C26 0.3％ C40 3.8

C28 11.9 C42 2.9

C30 16.7 C44 2.3

C32 11.3 C46 1.8

C34 8.6 C48 1.5

C36 6.6 C50 1.4

The number average number that C38 5.0 C52 1.3 so this hydrocarbyl substituent contain is greater than 30 carbon atoms.This substituting group is alkyl preferably, and wherein the carbonatoms mean on alkyl chain is 31-40, is more preferably 32-38.

Alkyl can be derived by corresponding alkene; C for example ₂₆Alkyl is by C ₂₆Alkene, 1-alkene deutero-preferably, a C ₃₄Alkyl is by C ₃₄The alkene deutero-, and blended chain length group is by corresponding alkene mixture deutero-.But, when alkyl has at least 30 carbon atoms, it normally, the alkene or the diolefine that contain 2 to 10 carbon atoms, the aliphatic group (or mixture of this group) that makes as the homopolymer or the interpretation (as multipolymer or trimer) of ethene, propylene, 1-butylene, iso-butylene, divinyl, isoprene, 1-hexene, 1-octene or the like.In order to be suitable for use as pour point reducer, the preferred straight chain of the part of alkyl is catenate in other words basically at least.Should believe, interact preferred this feature with the chain-like structure that becomes the wax hydrocarbon in order to make that chain is more favourable.Can think in many cases, even that when adopting alpha-olefin being added at alkyl chain on the tie point of aromatic ring has methyl branch.Can think that this is within the scope of straight chain or chain-like alkyl.In addition, perhaps owing to the transfer of activity site during the alkylated reaction, in some cases, moieties can contain the low alkyl group side chain on tie point (or alpha-position is put).Used alkene is 1 one alkene normally, as the homopolymer of ethene.These aliphatic hydrocarbyls also can by the halo of this homopolymer or interpretation (as chloro or bromo) the analogue deutero-.But, these groups can be derived by other sources, as high molecular weight olefin monomer (as 1-40 carbenes) and their the chloro analogue and the analogue of hydrochlorinate, the aliphatic series petroleum cuts, the analogue of paraffin and cracked and chlorating analogue and hydrochlorinate thereof particularly, light oil, synthetic alkene is as material (as poly-(ethene) oil) and other sources well known by persons skilled in the art by the preparation of Z-N method.Any degree of unsaturation in alkyl can reduce or eliminate according to hydrogenation known in the art.The raw material that preparation approach or employing do not have chlorine or other halogens substantially carries out preferably based on environment reason sometimes.

In one embodiment, hydrocarbyl portion is derived by polybutene.In another embodiment, hydrocarbyl portion is derived by polypropylene.In preferred embodiments, as mentioned above, alkyl mainly is that the unbranched basically alkene mixture of 30-36 carbon atom is derived by chain length.

Can there be more than one in such alkyl, but is no more than 2 or 3 usually for each aryl virtue nuclear.More generally each aromatic portion has only an alkyl, when particularly the phenol of alkyl replacement is based on a phenyl ring.

Alkyl is connected on the aromatic portion of first reactant of the present invention and can finishes by numerous technology well known by persons skilled in the art.The technology of a particularly suitable is that Fred-Ke comes Ford reaction, and wherein the alkene polymkeric substance of ethylene linkage (as contain) or its halo or the halogenated analogue of hydrogen react with phenol existing under the situation of lewis acid catalyst.The method and the condition of carrying out this reaction are known to those skilled in the art.For example referring to by John Wiley and Company, N.Y. Interscience Publishers publishes, the 3rd edition, the 2nd volume, being entitled as in " Kirk-Othmer Encyclopedia of Chemical Technology " of 65-66 page or leaf discussed in " alkylation of phenol " article.Other with hydrocarbyl group be connected to the equivalence of aromatic portion and easily technology those skilled in the art are obtained easily.

Reaction forms as mentioned above that second component of pour point reducer is that carbonatoms is 1 to 12 aldehyde, or its source thing.The general formula that is suitable for aldehyde is RC (O) H, R preferably hydrogen or alkyl as mentioned above wherein, and but, R can comprise other functional groups that do not influence aldehyde and hydroxyaromatic compounds condensation reaction (describing below).This aldehyde preferably contains 1 to 12 carbon atom, more preferably 1 to 4 carbon atom, most preferably 1 or 2 carbon atom.This aldehyde comprises formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, hexanal, phenyl aldehyde and more senior aldehyde.Preferred single aldehyde.Most preferred aldehyde is formaldehyde, and it can be used as solution, but adopts its poly type usually, as Paraformaldehyde 96.Paraformaldehyde 96 can be considered to reaction equivalent or its source thing of aldehyde.Other reaction equivalents also comprise the hydrate or the cyclic trimer of aldehyde.

Alkyl phenol and aldehyde with the scope of relative quantity from waiting mole to react approximately to excessive about 30% (mole) of aldehyde (based on the calculating of aldehyde monomer).The amount of preferred aldehydes Duos 5 to 20 than alkyl phenol, more preferably 8 to 15% (in moles).This component is to react under the condition that causes the reaction of oligopolymer or polymer formation.The molecular wt of product is decided according to the temperature and time of the equivalence ratio that comprises reactant, reaction and the features such as impurity that exist.This product can contain 2 to 50 multiple fragrance unit, preferred 3 to 30 such unit, more preferably 4 to 14 unit on its chain.When alkyl phenol particularly has the alkylphenol of 24-28 carbon atom on alkyl chain, and when aldehyde was formaldehyde, the number-average molecular weight of preferred substance was 1000 to 24000, more preferably 2000 to 18000, most preferably 300 to 6000.The molecular weight of material that based on chain length is the hydrocarbyl substituent of about 34 carbon atoms accordingly can be higher.

This alkyl phenol and aldehyde be by with alkylphenol and aldehyde at an amount of thinning oil or other solvents of optionally existing, for example in aromatic solvent such as the dimethylbenzene, exist acid as sulfuric acid, sulfonic acid such as alkyl phenyl sulfonic acid, tosic acid or methylsulfonic acid, organic acid such as Glyoxylic acid hydrate, or Amberlyst ^TMCatalyzer, hybrid reaction under the situation of promptly a kind of solid, sulfonated polystyrene-divinylbenzene resin catalyst macropore, lightly crosslinked from Rohm and Haas.With mixture heating up, normally 90 to 160 ℃, preferably 100 to 150 or to 120 ℃, as 30 minutes to 6 hours, preferred 1 to 4 hour, remove the water of condensation reaction through reasonable time.Time will conform to temperature, and therefore just reacting at low temperatures needs long time or the like.Determine that accurate condition is that those skilled in the art can accomplish.If desired, reaction mixture can be heated to higher temperature, as 140-180 ℃, and preferred 145-155 ℃, further remove volatile matter, reaction is carried out fully.As required, this product can be handled with alkali such as NaOH, in coming and strong acid catalyst, and prepares the sodium salt of this product, as required, after this also can separate by suitable routine techniques such as filtration.

The product of this reaction can be thought usually and comprises polymkeric substance or the oligopolymer with following repeating structure:

And positional isomers.But the preferred aldehyde that uses it is believed that partly remaining combined entering is substituting group and the molecular structure that is connected basic form, illustrates as following illustrated type, comprises ehter bond and methylol:

The wax pour point depressants of other types also is applicable to content of the present invention.The kind of a demonstration is the alhpa olefin/acylating agent multipolymer with the Fatty Alcohol(C12-C14 and C12-C18) esterification.This is that the alkene of comonomer is the alpha-olefin of one or more c-alkene (being meant list-1-alkene sometimes) or isomery in multipolymer.The example of alpha-olefin generally includes ethene, propylene, butylene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene, 1-heneicosene, 1-two dodecylenes, 1-tetracosene or the like.Commercially available suitable-alkene partly comprises C _15-18Alpha-olefin, C _12-16Alpha-olefin, C _14-16Alpha-olefin, C _14-18Alpha-olefin, C _16-18Alpha-olefin, C _6-20Alpha-olefin, C _22-28Alpha-olefin or the like.In one embodiment, alkene is C ₁₆And C _16-18Alpha-olefin.In addition, can adopt the C of trade mark Gulftene ₃₀+ alpha-olefin part, Gulf Oil Company is on sale.In preferred embodiments, alhpa olefin is at C ₁₆To C ₃₀In the higher scope.

The method that is used to prepare alkene is known to those skilled in the art, and in the literary composition that is entitled as " alkene ", done detailed description, this digest is from Encyclopedia of Chemical Technology, second edition, Kirk and Othmer increase version, the 632nd, 657 page, the Interscience Publishers of Jonh Wiley and Son publishes, and 1971.

But other components of this multipolymer are acylating agents of copolymerization.A kind of acylating agent is a kind of raw material that can generate ester with the alcohol reaction; Normally a kind of acid, a kind of ester or preferably reactive stronger equivalent are as acyl halide or acid anhydride.The acylating agent that comprises mono carboxylic and many carboxyls.Particularly preferably be the dicarboxyl acylating agent, as succinic acid acylating agent.They also comprise Succinic Acid, halogenide, ester and acid anhydrides, preferred acid, ester or acid anhydrides, more preferably acid anhydrides.

This multipolymer is with one or more Fatty Alcohol(C12-C14 and C12-C18) esterifications.Fatty Alcohol(C12-C14 and C12-C18) is exactly the alkyl hydroxy compound of alkyl hydroxy compound, particularly straight chain, and more especially contains at least 6, preferred at least 12 or 18 carbon atoms.Preferred Fatty Alcohol(C12-C14 and C12-C18) contains 16 to 30 carbon atoms.The example of Fatty Alcohol(C12-C14 and C12-C18) comprises capryloyl alcohol, nonanoyl alcohol, lauryl alcohol, tetradecanoyl alcohol, hexadecanoyl alcohol, heptadecane acyl group alcohol, octadecanoyl alcohol, eicosanol, behenyl alcohol, hexacosyl alcohol, and is commercially available and as contain the pure mixture of 8-12 carbon atom, 16-20 carbon atom or the like.

A representational pour point reducer of the above-mentioned type is C _20-24The behenyl alcohol diester of the multipolymer of alpha-olefin and maleic anhydride (mol ratio 1: 1).

Be applicable to that other types wax pour point depressants of the present invention comprises polymkeric substance and the oligopolymer that contains ester, comprise ethylidene/vinyl acetate copolymer, particularly those melt indexs are less than 100 (ASTM1238 condition E) and also comprise the polymkeric substance that contains acrylate or methacrylate monomer; By the ester polymer of the Fatty Alcohol(C12-C14 and C12-C18) of Fatty Alcohol(C12-C14 and C12-C18) preparation, as the multipolymer of vinyl carboxylate/dialkyl group fumarate, especially vinylacrylic acid ester/C _16-30The alkyl fumarate; Poly-(methyl acrylate) or poly-(methyl methacrylate) carries out transesterification reaction with the Fatty Alcohol(C12-C14 and C12-C18) that contains 16 to 30 carbon atoms and forms long-chain ester; By using C _16-30Alcohol esterification vinylformic acid and then carry out polymerization and the similar polymkeric substance that makes; And vinylbenzene/maleic anhydride copolymers, by C _16-30The Fatty Alcohol(C12-C14 and C12-C18) esterification.Some specific polyalphaolefins also can be used as pour point reducer.Also comprise alkylated naphthalene, comprise those materials by clorafin and alhpa olefin and naphthalene reaction generation.The wax pour point depressants of these or other types is known to those skilled in the art, and commodity normally.

Pour point reducer of the present invention is to provide as dispersion agent in liquid medium, and it generally is insoluble in 10 ℃ in liquid, preferably in room temperature, and promptly about 20 ℃, even 30 ℃ or 40 ℃ be insoluble equally.In other words, at first this medium is liquid in room temperature (about 20 ℃), and preferred zero pour is 10 ℃ or lower.The zero pour of some preferable medium, especially mixture is low to moderate 0 ℃ ,-20 ℃ ,-30 ℃ ,-40 ℃ or lower.And this medium can not dissolve this pour point reducer under the preferred room temperature in a large number under these temperature.In particular, medium can dissolve and is lower than 4% preferably under room temperature or appropriateness heat up, and preferably is lower than 2% or even the pour point reducer of 1% (weight).Therefore (part that solvability is low may comprise impurity and unreacted matters in some cases, and in fact pour point reducer dissolved amount is proportional reduces, as less than 0.5% weight.) preferred medium is until 30 ℃ or preferred 40 ℃ or 50 ℃ or highlyer still keep insoluble.

In order to make wax pour point depressants be insoluble to liquid medium, medium should have polarity to a certain degree usually.Polarity can be measured and expression by diverse ways.Therefore in one embodiment, in the molecule of solvent, preferably have 10 to 80% weight, more preferably 20 to 70% weight, the further heteroatoms of preferred 25 to 60% weight is as oxygen or nitrogen.Alternatively the specific inductivity of medium is at least 3, preferably at least 10.Above-mentioned parameter typically refers to medium parameter as a whole, if mixture comprises all components of blended.

Suitable liquid medium comprises that acetic ester (as acetate 2-ethoxy ethyl ester, also is called Cellosolve ^TMAcetic ester), ketone (as acetone, butanone, pentanone, hexanone), perhaps moisture 1 mixture (as the mixture of ethylene glycol and water).Can be separately in these raw materials or what be used in combination with water is ethylene glycol and derivative thereof, as monomethyl ether (Methyl Cellosolve ^TM), monoethyl ether (Cellosolve ^TM), a propyl ether, a monobutyl ether and a hexyl ether; Diethylene Glycol and derivative thereof are as monomethyl ether (Methyl Carbitol ^TM), monoethyl ether (Carbitol ^TM), a propyl ether, a monobutyl ether and a hexyl ether; Propylene glycol and derivative thereof comprise monomethyl ether (Methyl Propasol ^TM), a propyl ether and monobutyl ether; With dipropylene glycol and derivative thereof, as monomethyl ether (Methyl Dipropasol ^TM), a propyl ether and monobutyl ether.

The raw material of other application types is lactone, as butyrolactone, and alcohols, as butanols, diacetone alcohol (4-hydroxy-4-methyl-2 pentanone), 2,6-2,6-dimethyl-4-heptanol (Diisobutyl Carbinol ^TM) hexanol, Virahol, 2-Ethylhexyl Alcohol and 1-amylalcohol.

Liquid raw material can be the mixture of any aforementioned base materials, comprises the mixture with water, although wax pour point depressants is approximate insoluble in these mixtures.If these liquid raw materials are mixtures of binary alcohol and water, the relative consumption of raw material is exactly: the water component does not solidify as 0--40 ℃ at low temperature.Concerning these aqueous mixtures, preferably about 1: 1 of weight ratio, normally 1: 2 to 2: 1, preferred 1: 1.5 to 1.5: 1st, gratifying.

Many wax pour point depressants adopt spissated form usually, comprise the aromatic solvent of various ratios, are about 179 ℃ commercially available mixed aromatic solvent as dimethylbenzene or boiling point.Exist these an amount of solvents (coming as the weight in pour point reducer/solvent mixture, is 10-50%, as 25%) to be proved to be and help sometimes pour point reducer is dispersed in the medium, although its existence does not require.If there are these aromatic solvents, can be used as it is a component of liquid medium, and constitutes the total amount part of medium, helps the formation of the character (polarity) of solvent in the medium simultaneously.

Dispersive composition also preferably includes a kind of dispersion agent that helps to form and keep dispersion.Dispersion agent is called tensio-active agent again, can be divided into anionic, cationic, zwitterionic or non-ionic.Anion surfactant comprises the material that contains at the oleophylic long-tail chain of the other end bonding water-soluble (wetting ability) group, and wherein hydrophilic group contains anionicsite, as carboxylic acid, sulfonic acid or by positively charged ion, as basic metal or ammonium neutral phenolic group group.This oleophylic tail chain is alkyl preferably, and common is the alkyl that contains 8 to 21 carbon atoms.

Common anion surfactant comprises carboxylate salt, as has general formula R ₁COOR ₂Soap, R wherein ₁Be straight chain, saturated or undersaturated, the alkyl that contains about 8 to 21 carbon atoms, R ₂Be that alkali forms base, as Li, Na, K or NH ₄Group, it can make the tensio-active agent of washing composition class can be water-soluble or improve the affinity of this tensio-active agent to water.Optionally be R ₂Can be divalence or polyvalent metal, wherein, the acidic group that has proper amt usually be for neutral salt is provided.Polyvalent metal ion comprises Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb or the like.Common soap comprises sodium stearate, sodium palmitate, ammonium oleate, Palmiticacid triethanolamine salt.The carboxylate salt that can be used as anion surfactant in addition comprises the salt of coco-nut oil fatty acid and tall oil acid; particularly sodium and sylvite; and other carboxylate compounds; comprise amine salt; as the salt of triethanolamine salt, acyl polypeptide and N-lauryl sarkosine, as N-lauroyl-sarcosine sodium salt.

Other anion surfactant comprises aryl and alkylaryl sulphonate; as alkylbenzene sulfonate, chain-like alkyl benzene sulfonate, four propylidene benzene sulfonic acid sodium salts, Sodium dodecylbenzene sulfonate, benzene-, toluene-, dimethylbenzene and cumene sulfonate, Sulfite lignin, sulfonated petro-leum, paraffin sulfonate, secondary normal chain alkyl sulfonate, sulfonated, sulfonated alkyl naphathalene, positive structure acyl group normal chain alkyl taurate, sulfosuccinate, different thiosulphate, alkyl-sulphate, general formula is R ₁OSO ₃R ₂, R wherein ₁And R ₂Be defined as above, as lithium dodecyl sulfate, sodium lauryl sulphate, dodecyl sulphate potassium, Trombovar, alkylsulfonate, its general formula is R ₁SO ₃R ₂, R wherein ₁And R ₂Be defined as above, as sodium laurylsulfonate, Sulfated and sulfonated acid amides and amine, Sulfated and sulfonated ester such as lauric acid monoglyceride sodium sulfate, sulfoethyl sodium oleate, lauryl sulfoacetate sodium, sulfuric acid such as sulfation chain primary alconol, sulfation polyoxyethylene straight chain alcohol and sulfation triglyceride oil, phosphoric acid and poly phosphate, perfluorinated carboxylic acid, polymeric anion surfactant such as alginic acid.

Also comprise the polymeric anion surfactant, as the salt of the polymkeric substance of alkyl acrylate and/or alkyl methacrylate and vinylformic acid and/or methacrylic acid, and the salt of the partial ester of maleic anhydride-styrol copolymer.

Other materials that can be incorporated into anion surfactant are overbasic or the material of ultrahigh basicity.They are the alkaline metal salt of acidic organic compound (carboxylic acid, sulfonic acid, phosphonic acids, phenol or the like), preferably basic metal or alkaline earth salt.The high alkalinity material is a phase normally, neutralizes and the metal content that exists is the homogeneous phase newton system of feature to exceed for the stoichiometry according to the acidic organic compound of metal and specific and metal reaction.This high alkalinity material is that (that common is mineral acid or low-grade carboxylic acid by acidic substance, preferably carbon dioxide) make with the mixture reaction that contains acidic organic compound, reaction medium comprises that at least a is organic solvent inert (mineral oil, petroleum naphtha, toluene, dimethylbenzene or the like), stoichiometry excessive metal base and a kind of promotor such as phenol or alcohol to said acid organic substance.This acid organic substance contains enough carbonatomss usually, can be to a certain degree being dissolved in the oil, and make product have surfactant activity.The amount of excess metal is represented with metal ratio usually.Term " metal ratio " is the equivalence ratio of the total yield and the acidic organic compound of metal: the metal ratio of neutral metal salt is 1; A kind of excessive 3.5 equivalents of 4.5 times salt metal, or metal ratio 4.5 with metal amount in the neutral salt.

Usually as slip additive, this is a technology well known in the art to the high alkalinity material.They also have other purposes, and the scope of its use is different from other tensio-active agent.In other words, they can be observed the precipitation that is considered to lime carbonate once in a while and occur after electric field exposes.But, under this situation can not bothersome condition, it was feasible to use above-mentioned substance to be still, and still thinks within the scope of the present invention.The patent of technology of basic salt of having described the mixture of preparation sulfonic acid, carboxylic acid and any two or more these materials comprises US2501731; 2616905; 2616911; 2616925; 2777874; 3256186; 3384585; 3365396; 3320162; 3318809; 3488284; With 3629109.

Cats product and anion surfactant are similar, and different is the surfactivity part positively charged of molecule.The example of cats product is long-chain amine and salt thereof, as by animal and plant lipid acid and Yatall MA deutero-primary amine and synthetic C _12-18Primary amine, secondary amine or tertiary amine; Diamines and salt thereof, quaternary ammonium salt comprise tetraalkylammonium salt and the imidazoline salt that comes by deriving as fat or hydrogenated fat, the perhaps halogenide of N-benzyl-N-alkyl dimethyl ammonium; The long-chain amine of polyoxyethyleneization; The long-chain amine of quaternised polyoxyethyleneization; With amine oxide such as N-alkyl dimethyl amine oxide (being actually zwitter-ion) as hexadecyldimethyl benzyl ammonium amine oxide or stearyl-dimethyl amine oxide compound.

Zwitterionics comprises amino acid, as β-N-alkyl aminopropionic acid, and N-alkyl-β-imino-diacetic propionic acid, tetrahydroglyoxaline carboxylate, N-alkyltrimethylammonium second lactone, sulphobetaine and sultaines.

Nonionogenic tenside preferred for this invention is such similar substance, wherein its polar functional group is not provided by negatively charged ion or cation group, but is provided by neutral group, and is common as alcohol, amine, ether, ester, ketone or amide functional group.Common ionic surfactant pack is drawn together the polyoxyethylene alkylphenol, as polyoxyethyleneization to nonyl phenol, to octyl phenol or to 4-dodecylphenol, by Oleum Cocois, tallow comprises the synthetic deutero-polyoxyethylene straight chain alcohol of oil base derivative; Polyoxyethylene polyoxy propylene glycol (segmented copolymer of oxyethane and propylene oxide), common molecular weight is 1000 to 30000; Polyoxyethylene glycol; Polyoxyethylene mercaptan; Long-chain carboxylic acid's ester comprises the glyceryl ester and the polyglycerol ester of natural acid, propylene glycol ester, sorbitol ester, the sorbitol ester of polyoxyethyleneization, polyoxyethylene glycol ester and polyoxyethylene lipid acid; Alkanolamine " condenses " as the methyl esters by lipid acid or triglyceride with etc. mole or the condenses of the alkanolamine prepared in reaction of twice molar weight; Uncle's alkynes dibasic alcohol; The polyoxyethylene siloxanes makes by the siloxanes intermediate that can react and end capped allyl group polyalkylene oxides such as propylene oxide or mixed ethylene oxide/propylene oxide copolymer reaction; N-alkyl pyrrolidone, and alkylpolyglycosides (the long-chain acetal of glycan)." the Surfactants and Interfacial Phenomena " that most and other ionic in these or non-ionic tensio-active agent are disclosed in Rosen, John Wiley and Sons publish, pp.7-31,1989.

Some are usually being that the material of feature is similar to some above-mentioned liquid medium as nonionogenic tenside.Need explain the difference between these materials, preferred even be solid-state at 30 ℃ or 40 ℃ if this material has the character of nonionogenic tenside and in room temperature, it just can be classified as the said nonionogenic tenside of the present invention.At said temperature, particularly room temperature or lower temperature are that liquid material it would be better to and can return the component of making liquid medium.

Other nonionogenic tenside comprises the ethoxylation cocoamide in particular, oleic acid, uncle's lauryl mercaptan, the polyester dispersants of modification, ester, acid amides, or based on the blended ester-acid amide dispersion agent of isobutenyl succinic anhydride, dispersion agent based on poly-isobutyl-phenol, ABA type block copolymerization nonionogenic tenside, acrylic acid graft copolymer, octylphenoxy polyethoxy ethanol, the Nonylphenoxy polyethoxyethanols, alkyl aryl ether, alkyl aryl polyether, amine polyglycol condenses, the polyethoxye adducts of modification, the end-blocking alkyl aryl ether of modification, the polyethoxylated straight chain alcohol of modification, the chain primary alconol of end-blocking ethoxylation, high-molecular weight tertiary amine such as 1-hydroxyethyl-2-alkyl imidazoline, oxazoline, the perfluoro alkyl sulfonic acid ester, fatty acid esters of sorbitan, macrogol ester, fat base or aryl phosphate ester.Also comprise the amber acylation agent of alkyl replacement and the reaction product of amine.These reaction product and their preparation method are at US4234435; 4952328; 4938881; With 4957649 done record.

Other ionic surfactant pack is drawn together functionalized polysiloxane.These materials contain functional group as amino, amide group, imino-, alkylsulfonyl, sulfoxide group (sulfoxyl), cyano group, hydroxyl oxygen base,-oxyl, sulfydryl, carbonyl (comprising aldehyde and ketone), carboxyl, epoxy, acetoxyl group, phosphoric acid ester, phosphono and haloalkyl.These polysiloxane can be catenate or side chain, and its molecular weight is normally more than 800, promptly up to 10000 or 20000.This functional group also can be distributed in polyester chain randomly or be present among the block.This functional group can be alkyl or alkaryl, and group is as-(C ₂H ₄O) _a-(C ₃H ₆O) _b-R, wherein a and b are respectively 0 to about 100 numbers, and at least one is at least 1 among a or the b, R is hydrogen, acetoxyl or alkyl.Other groups that are suitable for comprise C ₃H ₆X, wherein X is OH, SH or NH ₂The example of this material comprises the Silwet from Union Carbide ^TMTensio-active agent and from Goldschmidt ChemicalCorp., Hopewell, the Tegopren of VA ^TMSilicone surfactant.

Ionic surfactant pack is drawn together polyoxy alkylidene alkyl alcohol or phenol, as the alkanoates (preference chain alkanoic acid partial ester) of ethoxylized nonylphenol, polyvalent alcohol, as monooleate glyceryl ester, Tegin L 90, monooleate Isosorbide Dinitrate, sesqui oleic acid Isosorbide Dinitrate, a lauric acid Isosorbide Dinitrate and sesqui lauric acid Isosorbide Dinitrate, and 4,4-dihydroxyl methyl-2-heptadecyl-2-oxazoline.Preferred material comprises by diethanolamine neutral ready denier oil acid, Triton ^TMTensio-active agent (from Rohm and Haas), include the octyl phenol series of 1 to 70 ethylene oxide unit and the nonyl phenol series of 4 to 40 ethylene oxide units is arranged, by the Neodol of 2～13 ethylene oxide units ^TMTensio-active agent ethoxylate (from Shell Chemical Co.), contain the Igepal of 7 to 50 ethylene oxide units ^TMTensio-active agent (from Rhone-Poulenc), contain the Tergtitol of 4 to 41 ethylene oxide units ^TMTensio-active agent (from Union Carbide).These aforesaid commercially available materials are the ethoxylate of chain primary alconol or the alkylphenol ethoxylate of (under the situation that is the Triton material) side chain normally.

The relative quantity of pour point reducer, liquid medium and the selectable tensio-active agent of fat changes very widely, but preferably in weight part at (20-60): (40-80): (0-10) in the scope, preferably at (30-50): (50-70): (1-7) in the scope, more preferably (35-45): (55-65): (2-6) in the scope, especially about 38: 58: 4.

Dispersive composition of the present invention prepares in the following manner, at first component is heated to that this waxy substance can be distributed to liquid medium by rights and the tensio-active agent that optionally exists in temperature.If under the temperature that suitably improves, this wax material may be dissolved in the work in the liquid medium, this condition can be met.Common this solvability is not only the solvability by the institute of wax material inherent solvability own and medium, and by the decision of the boiling point of liquid medium.The combination of preferred liquid medium and wax material is as follows: in this embodiment, can or be lower than an amount of dissolving of acquisition under the medium normal boiling point situation at the normal boiling point of medium, as per 100 gram medium dissolves, 80 grams, but, if desired also can by for the fusing point that improves medium with component under high pressure the bonded mode improve solubleness.As selection, can be by mixture heating up is improved the dispersiveness of wax material to the temperature that is higher than the wax boiling point substance, even the wax material is insoluble to medium.In general, mixture heating up is become liquid state until composition.At last as long as dispersion is carried out suitable mechanical treatment, what just can obtain to have suitable dispersiveness in some cases neither dissolves infusible again material under heating up.Heated composition if particularly they are liquid (fusings or dissolved), will mix and makes required dispersion.This mixing can be carried out under high-shear or cavitation conditions." high-shear " typically refers to shearing condition is per second 10 at least ³, preferably be per second 10 at least ⁵, and more preferably be per second 10 at least ⁶Cavitation conditions also can be thought shear conditions; Cavitation is usually included in the trickle bubble of formation in the liquid, and these bubbles expand under the influence of ultrasonic energy, and is then poly-cruelly under violent shearing action.The equipment that can produce enough high-shears and cavitation conditions comprises Sonicator ^TM, the high-strength ultrasonic treater, wherein high-frequency voltage (as 20kHz) is converted into mechanical vibrational energy, directly acts on liquid sample by probe.Comprise that also the high-shear dispersion mixer is (as Dispersator ^TM), wherein high speed rotor is with the assembling of close clearance and fixed stator, when liquid flows into rotor, and by when promoting by stator at a high speed, because the mechanical strength with water produces quite high shear environment, perhaps uses Microfluidizer ^TM(from Microfluidics Intl.Inc), wherein interacting at a high speed, so shearing, bump, cavitation force produce ultrafine particle usually in the microchannel of setting for two high-pressure sprays.Composition wants heated temperature to depend on the volatility of fusing point, solubleness and used material; Usually be heated to 40 to 100 ℃, preferably be heated to 50 to 90 ℃, more preferably 70 to 83 ℃.Being cooled to heated mixture wherein, in fact the wax material does not dissolve and usually with temperature solid-state or that semi-solid state exists, keeps mixing condition simultaneously.The mixture of gained is stable dispersion.

In one embodiment,, in this molten mass, add an amount of tensio-active agent, stir simultaneously the pour point reducer fusion.Add an amount of same liquid medium (as water/1), and component is mixed through heating.Mixture in heat and in process of cooling, perhaps optionally after mixture cooling, is carried out high shear mixing or sonication.

Material by any preceding method preparation can also be described as equal phase materials.They are such materials in other words, and promptly because aforesaid treatment process, the granulometric facies of suspended material are right reduces and preferred homogeneous relatively, and particles suspended is evenly distributed in the medium relatively, and keep dispersion state in the industrial rational time.

Dispersion of the present invention can be used as the content of wax (paraffin) hydrocarbon materials such as crude oil or crude oil fractions such as Residual oil, vacuum gas oil or vacuum resid (Bunker C crude oil) by conc forms, that is to say natural or part purified oil, comprise that the oil of part processing derives from the pour point reducer of oil.Be used in the amount that contains the pour point reducer in the vasoliniment for being fit to depression of pour point to measuring promptly at least 0.6 ℃ of numerical value (1) preferably at least 2 ℃ (3 or 4), more preferably 3 ℃ (5), even the amount of more preferably 6 ℃ (10).The attenuating of this pour point can be measured by the method that adopts ASTM D-97 by this area professional easily.The typical amounts of pour point reducer, except that it was scattered in wherein liquid medium, the fluid weight based on adding wherein accounted for 50/1000000ths to 10000 parts (ppm), and preferred 100 to 5000ppm, more preferably 200 to 2000ppm.The total amount of enriched material can raise in proportion based on pour point reducer concentration therein.

Embodiment 1

Ethylene glycol 571.5g and distilled water 571.5g be by mixing, and be heated to about 50 ℃ (120 °F).The condenses that adds 1143.0g formaldehyde and alkylphenol respectively, the chain length of alkyl substituent is mainly C _30-36Individual carbon atom, (in 50% dilution mineral oil, contain 50% activeconstituents) as mentioned above, add 114.3g again and contain the disperser composition of 75.6% weight ready denier oil acid and 24.4% weight diethanolamine, heating, until (about 82 ℃ of fusions take place, 180 °F) till, and mix approximately more than 10 minutes with the form of abundant shearing, make homogeneous mixture.The glycol/water mixtures of heating is added in other mixtures, fully shear more than 20 minutes.

With the mixture cooling of making, pass through Micronizer twice again ^TM, it is equipped with " 3669 " interaction chamber (producing 75 microns particle) and 3839 back pressure modulus (200 microns), and pressure is set at 170MPa (25000psi).The material that collection is handled fully.

Embodiment 2

(mol ratio is 1: 1 with the vinylbenzene/maleic anhydride copolymers of 2.2 moles behenyl alcohol esterification to add (a) 70.57g in the little stainless steel cup, reduced viscosity about 0.42) pour point reducer and (b) the 2-ethoxyethyl acetic ester (Cellosolve of 105.86g ^TMAcetic ester).The experiment Dispersator of homogenizer is housed with the top ^TMMix these chemical substances.Continue simultaneously to shear, with mixture heating up to 77 ℃ (170 °F), under this temperature, it is transparent that mixture becomes.Continue to be heated to 82 ℃ (180 °F).Stop heating, continue shearing mixture is cooled to room temperature.

Embodiment 3

Do not improve pour point for adding the pour point reducer composition of the embodiment 2 of 0.05g in the crude oil sample of-18 ℃ (0) toward 50 milliliters.The pour point of the mixture that makes is-46 ℃ (50 °F).

Embodiment 4

Toward the Pyrex on hot-plate ^TMAdd in the beaker 28.0 weight parts the pour point reducer (a) of embodiment 2 preparations and (b) the glycol tertiary butyl ether of 65.0 weight parts (from the Arcosolve of Arco ^TMPTB).With the heating of these chemical substances, and mix with laboratory stirrer, simultaneously with mixture heating up till pour point reducer dissolves fully.Stop heating, continue stirring mixture is cooled to room temperature.

By mixture being put in the grease milling train (comprise steel pipe and wherein the cylindrical bar of packing into, and mixture), and with mixture kneading 1 hour, the granularity of pour point reducer that will be in mixture further reduces.

Embodiment 5

Repeat embodiment 4, the pour point reducer (a) of different the is embodiment 1 that mixture contains 120g and (b) contain the propylene glycol monobutyl ether of 60g, the Cellosolve of 60g ^TMThe medium of acetic ester and 60g propylene glycol.Begin heating till the pour point reducer fusing.

Embodiment 6

Toward Pvrex ^TMAdd the pour point reducer that contains formaldehyde and alkylphenol condensation of (a) 15 weight parts in the beaker, wherein the alkyl substituent chain length is mainly C _30-36Individual carbon atom (contains 50% activeconstituents) and (b) disperser composition that contains 75.6% weight ready denier oil acid and 24.4% weight diethanolamine of 1.5 weight parts as mentioned above in 50% dilution mineral oil.With mixture heating up to 82 ℃ (180 °F), stir, place on the hot-plate, and be preheating to (c) the 7.5 weight part ethylene glycol of 50-70 ℃ (120-160) and the mixture of 7.5 weight parts waters to the slow adding of mixture.After having added, mixture is passed through Microfluidizer ^TMAnd it is cooled to room temperature.Embodiment 7

Repeat embodiment 6, different is replaces alkylphenol condensation with the pour point reducer of the embodiment 1 of component (a) 15 weight parts.

Embodiment 8

Toward Pvrex ^TMWhat add (a) 15 weight parts in the beaker contains ethylene vinyl acetate copolymer (from the Elvax of Du Pont ^TM150, contain 33% vinyl-acetic ester, melt index 43 (ASTM D1238-E)) the pour point reducer and (b) dispersion agent that contains 75.6% weight ready denier oil acid and 24.4% weight diethanolamine of 1.5 parts of weight.With mixture heating up to 82 ℃ (180 °F), stir, place on the hot-plate, and in this mixture ethylene glycol (being heated to 82 ℃) of adding 7.5 weight parts, then add the water (being heated to 71 ℃) of 7.5 weight parts.After having added, mixture is passed through Microfluidizer ^TMAnd it is cooled to room temperature.

Embodiment 9

Repeat embodiment 2, the C that different is with 2.2 moles of behenyl alcohol esterifications ₁₈Alhpa olefin/maleic anhydride copolymers (mol ratio is 1: 1) replaces vinylbenzene-maleic anhydride polymkeric substance.

Each above-mentioned file all can supply in conjunction with reference.Except in an embodiment, unless other clearly indication is perhaps arranged, all can be regarded as in these all numerical quantities of concrete amount, reaction conditions, molecular weight, carbonatoms or the like of describing material is " approximately ".Unless other explanations are arranged, and each chemical substance of indication or composition all are meant the material of commercially available grade herein, promptly they can contain isomer, by product derivative and other it has been generally acknowledged that the material that exists in the commercially available prod.But the amount of each chemical composition of appearance does not comprise any solvent or thinning oil that exists usually in the commercially available prod, unless special indication is arranged." mainly containing " expression mode that adopt in this place is to allow to comprise not influence the basic material with new character of said composition in fact.

Claims

1. the liquid pour point reducer composition of a homogenizing, comprising:

Be that 100 weight parts be benchmark 20～60 weight parts at 10 ℃ are solid-state and its number-average molecular weight is at least 500 the pour point reducer that is selected from following material: phenol and C that alkyl replaces (ⅰ) in the said composition gross weight _1-12The reaction product that aldehyde or its source form, the ester/acylating agent multipolymer and the ethylene of alpha-olefin; With

(ⅱ) material (ⅰ) is selected from the liquid medium of following material basically at 10 ℃ of 40～80 weight parts that are insoluble to wherein: water, alkanediol, acetate alkoxyalkyl methacrylate, alkanediol alkyl oxide and composition thereof;

Wherein component (ⅰ) is dispersed in the component (ⅱ).

2. the composition of claim 1, wherein pour point reducer comprises (a) alkyl substituted phenol and (b) C _1-12The reaction product in aldehyde or its source.

3. the composition of claim 2, wherein aldehyde is formaldehyde or its source.

4. the composition of claim 1, wherein pour point reducer comprises a kind of by the alhpa olefin of Fatty Alcohol(C12-C14 and C12-C18) esterification/acylating agent multipolymer, the polymkeric substance that contains ester or oligopolymer, vinyl carboxylates/dialkyl group fumarate multipolymer, alkylated naphthalene or polyalphaolefin.

5. the composition of claim 1, wherein the zero pour of liquid medium is equal to or less than 10 ℃.

6. the composition of claim 1, wherein liquid medium contains 10～80% weight heteroatomss.

7. the composition of claim 1, wherein the specific inductivity of liquid medium is at least 3.

8. the composition of claim 1, wherein liquid medium is selected from acetic ester, ketone, alcohol and moisture diol mixture.

9. the composition of claim 1 wherein also comprises (ⅲ) dispersion agent, and its amount should help to form and keep the dispersion of component (ⅰ) in component (ⅱ).

10. the liquid pour point reducer preparation of compositions of each homogenizing method in the claim 1～10, comprising the following step:

(b) component with heating mixes; With

(c) mixture with heating is cooled to (ⅰ) undissolved basically temperature in the liquid of (ⅱ).

11. the method for claim 10, wherein component (ⅰ) and (ⅱ) be heated to 40～100 ℃.

12. the method for claim 10, wherein heated component mixes under high-shear or cavitation conditions.

13. the method for claim 10, wherein cooling step (c) carries out under mixing condition.

14. the liquid pour point reducer composition of each homogenizing contains the purposes aspect the pour point of vasoliniment in the claim 1～10 in reduction.