JPH05505420A - De-emulsification of oil - Google Patents

Abstract

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

Description

[Detailed description of the invention] 12. The demulsifier or one or more additional constituents containing oxyalkylene groups The invention according to any one of claims 1 to 11, further comprising:

13. The ashless dispersant additive comprises: (i) amines and long-chain hydrocarbon-substituted mono- or dicarboxylic acids or derivatives thereof; reaction product with (ii) a long chain hydrocarbon having one or more polyamine molecules directly attached to it; i) Mannich condensation products containing long-chain hydrocarbon groups (provided that (i), (i The long chain hydrocarbon group in i) and (ii) is a C1 to C1° monoolefin 900) having a number average molecular weight of at least about 900. The invention according to any one of claims 1 to 12, comprising an ashless dispersant.

14. The ashless dispersant additive comprises a polyamine and a hydrocarbyl-substituted succinic acid. or a reaction product thereof with an acid anhydride. The invention described.

15. The invention according to claim 14, wherein the reaction product is borated.

16. said composition or at least one metal-containing detergent additive and/or Claim 2 further comprising at least one zinc dihydrocarbyl dithiophosphate. The invention according to any one of 5 to 5.

17. Any of claims 2 to 16, wherein said composition has a TBN in the range of 9 to 40. The invention described in any of the following.

18. Oil of lubricating viscosity, ashless dispersant additive, demulsifier and fluid in any order. (as previously specified) dicarboxylic acids or their acid anhydrides. A method for preparing a lubricating composition comprising:

19. Concentrates useful as lubricating oil additives, including ashless dispersant additives, crosslinking Demulsifiers containing bound polyoxyalkylene polyols, free (previously identified dicarboxylic acids or their acid anhydrides, overbased metal detergents, ZDDP and Concentrate consisting of base oil.

20. A claim in which the constituent components are those detailed in any of claims A to I5. The concentrate according to claim 19 or claim 20.

Specification De-emulsification of oil This invention relates to improvements in oil compositions, particularly lubricating oil compositions. This invention is a marine engineering It is particularly relevant to, but not limited to, automotive lubricants.

Oils used in marine engines generally come in three main types: cylinder lubricant (MDCL), and trunk piston engine oil (TPEO). ) and system oil. Clan where TPEO is usually used under certain conditions (presence of condensation, possible contamination by water and (use of oil), the water tends to form an emulsion with the oil, which is usually dispersed. This is because it contains a metal-containing cleaning agent and a metal-containing cleaning agent. Emulsion formation is a system However, system oils are usually made with metal-containing cleaners rather than TPEO. The system oil contains less or no metal-containing cleaning agents. is generally less prone to forming emulsions than is the case with TPEO.

Emulsions can interfere with the operation of oil and/or engine parts and/or The close association of oil and water in oil or emulsions results in additives in the oil loss of oil when dissolved or dispersed in water and purified by removal of water The formation of emulsions is undesirable as it can lead to Furthermore, emulsion presence reduces the efficiency of centrifugation used in oil purification resulting in blockage of filters It can also be done.

A number of proposals have been made for incorporating demulsifiers into oil compositions. for example, European Patent No. 333141A describes certain alkylene oxide block combinations. Emulsification of adducts of polymers and specific polyglycidyl ethers into water-in-oil emulsions It is disclosed for use as a clearing agent. On the other hand, U.S. Patent No. 3752657 The No. 1 contains dispersants and long-chain aliphatic hydrocarbon groups bonded to ethylene polyamines. Disclosed are fuels containing demulsifiers and demulsifiers, which may be of a specific formula. Polyalkyleneoxy-modified poly(alkylphenol) formaldehyde It is a combination. Additionally, U.S. Pat. No. 4,398,921 describes certain Manninhi dispersions. and a specific oil-soluble oxyalkylene polyether i and a specific oxyalkyl A two-component demulsifier consisting of phenol-formaldehyde resin is used in fuel. It is disclosed that This fuel also contains hydrogen having 12 to 30 carbon atoms. It also contains a corrosion inhibitor which is dolocarbyl succinic acid or its acid anhydride.

European Patent No. 330522A describes oil-soluble mixtures useful as oil additives. disclosed, which includes certain lubricating oil ashless additives, alkylene oxides and - Demulsifiers consisting of reaction products with adducts of epoxides and polyhydric alcohols Additives and compatible additives that enhance the solubility of the demulsifier in the oil solution used. It consists of Compatible additives include alcohols, such as glycols, and esthetics. total of 24 to 90 carbon atoms per molecule or molecule and less than Consisting of hydroxyamide derivatives of carboxylic acids with sil groups, suitable compatible additions The compound is dimer acid ester, and dimer acid is a C+5-Ctt unsaturated fatty acid. Nclohexanedicarboxylic acid formed from

In many conventional proposals, the starting materials for preparing demulsifiers are dicarboxylic acids or includes its derivatives, and the acid/derivative is one or more added during the preparation of the demulsifier. Reacts with other ingredients.

U.S. Pat. No. 4,440,902 discloses alkenylsuccinic anhydrides of specific formulas. Ethylene oxide/propylene oxide block copolymers of esters and specific formulas The use of coalescence as a demulsifier in oil-water emulsions is disclosed. .

U.S. Pat. No. 4,885,110 discloses oxyalkylation of certain formulas in certain proportions. primary fatty amines, at least trihydrogenated oxyalkylated amines containing specified units; The reaction product of lucanol and dicarboxylic acid/anhydride is added to the crude oil emulsion. It is disclosed for use as a separating demulsifier.

GB 2008146A describes water-in-oil emulsions, particularly water-in-oil emulsions. Demulsifiers are disclosed for use in emulsions, but they are alky(eny)luco Polyester obtained by condensation of uccinic anhydride (alkyl(kenyl)yl in this case) the group has from 9 to I8 carbon atoms), polyalkylenes of specific molecular weight and properties Polyhydric alcohols having three or more hydroxyl groups that can react with glycols and their acid anhydrides The reactants are used in specific proportions.

U.S. Pat. No. 4,705,834 describes water-in-oil emulsions that occur during oil production. Using cross-linked oxyalkylated polyalkylene polyamines to isolate is disclosed. The cross-linking compound cross-links the polyalkylene polyamine. which is completely oxyalkylated at the nitrogen atom. It reacts with the terminal alcohol group of the oxyalkylated polyalkylene polyamine. A crosslinking compound having two or more compatible functional groups is used. crosslinking Examples of compounds include aliphatic and aromatic diisocyanates, dicarboxylic acids, Diesters of rubonic acids and lower alcohols, as well as aliphatic and aromatic polyhydres Bisglycidyl ethers of Roxy compounds are described.

German Patent No. 3635489A discloses a water-containing demulsifier for crude oils. This demulsifier is compatible with polyglycols and polyglycol ethers. Release of (meth)acrylic acid ester in a copolymer with an unsaturated monomer etherification, esterification, or converting the hydroxyl group of It is formed by neutralizing the acid used as a medium by adding an amine.

European Patent No. 333135A describes (1) alkoxylated primary fatty amines; , (2) Ethylene oxide/propylene block copolymer and glycidyl ether and (3) reaction products of dicarboxylic acids. This anti The reaction product can be used as a demulsifier.

British Patent No. 1,186,659 discloses that at least In a lubricating composition containing a dispersant having a substituent containing 50 aliphatic carbon atoms using demulsifiers, especially polyoxyalkylene polyol block copolymers. It is disclosed that

Despite the above-mentioned proposals, TPEO has very effective demulsifier action, especially TPEO. and for additives with highly effective demulsifier action in system oils. There is still a need to

The present invention provides a method for creating demulsifiers for water-in-oil emulsions containing ashless dispersant additives. free dicarboxylic acid or its acid anhydride (as specified below) This demulsifier is a cross-linked polyoxyalkylene polymer. Consists of Riolu.

The invention also includes an oil of lubricating viscosity, an ashless dispersant additive, a cross-linked polyoxylic acid A demulsifier consisting of a sialkylene polyol, and a free (as specified below) ) A lubricating composition containing a dicarboxylic acid or an acid anhydride thereof is provided.

Further in accordance with the invention, a formulation of an oil of lubricating viscosity, a lubricating oil ashless dispersant additive; Demulsifier consisting of cross-linked polyoxyalkylene polyol and dicarbohydrate A lubricating composition is provided comprising a phosphoric acid or an acid anhydride thereof.

The lubricating composition according to the invention may contain one or more additional additives, in particular one or more excess bases. Overbased metal detergent and/or or may contain zinc dihydrocarbyl dithiophosphate-1-(ZDDP). stomach.

In a preferred aspect of the invention, the lubricating oil is suitable for marine applications, especially TPEO or system oil. suitable for use as a Prescribe using minute proportions. Lubricants suitable for use as TPEO are typically containing at least one overbased metal detergent and at least one ZDDP. The total base number (TBN) can generally range from 9 to 40. system oil The TBN of can typically range from 0 to 6. All TBNs shown in this specification are A It is measured by STM D2896.

According to the invention, there is provided a concentrate useful as an additive for lubricating oils, the ashless dispersant Additive, demulsifier consisting of cross-linked polyoxyalkylene polyol, free Dicarboxylic acids or anhydrides (as specified below), overbased metal cleaners , ZDDP and a base stock. Lubricating oil is TPEO In this case, the concentrate preferably has a TBN in the range of 150-250.

Further in accordance with the invention, an oil of lubricating viscosity, an ashless dispersant additive, Demulsifier and free dicarboxylic acid or anhydride (as specified below) A method of preparing a lubricating composition is provided. The specified concentration When using this method to prepare a condensate, preferably an ashless dispersant additive, adding a demulsifier to a mixture of a dicarboxylic acid and an overbased metal detergent additive; ZDDP is then added to the mixture thus obtained.

By using a demulsifier and a dicarboxylic acid/acid anhydride according to the invention, , obtaining oil compositions, especially lubricating oil compositions and especially TPEO and system oils. It is now possible to use emulsions even when used in the presence of water or steam. There will be little or no tendency to form johns.

The free dicarboxylic acid or its acid anhydride may itself be a minor component of the composition or formulation. (also intended to be an acid or acid anhydride that is first mixed with other ingredients, e.g. The acid or anhydride itself is the container or other container in which the mixture of ingredients is to be prepared. will be introduced in As mentioned above, dicarboxylic acids or their acid anhydrides are It is used in the preparation of anti-inflammatory agents. Ashless dispersant additive used according to this invention Dicarboxylic acid/anhydride with additives and demulsifiers or with either dispersant additives one or both before blending the demulsifier and the acid/anhydride first. chemically into demulsifiers or other ingredients by reaction in the carboxyl groups of The dicarboxylic acid/anhydride derived group to be mixed is not a free dicarboxylic acid/anhydride. stomach.

The dicarboxylic acids used according to the invention (or the anhydrides used according to the invention) The dicarboxylic acid (derived dicarboxylic acid) preferably has the following general formula: HO1C -(R)-Co, H In the formula, R represents a divalent hydrocarbyl group. Hydrocarbyl groups mainly contain hydrogen and and carbon atoms, as desired or as substituents or as members of a chain. may contain other atoms. However, atoms of this type or containing these Due to the presence of groups that This shall not result in a negative reaction. Hydrocarbyl groups are, for example, divalent aromatic groups. but advantageously linear or branched, saturated or unsaturated dihydric fats. It can be an aliphatic group. Advantageously, at most three chain atoms can The boxyl groups shall be spaced apart and, in suitable acids/anhydrides, the carboxyl groups shall be separated by two chain carbon atoms.

Particularly advantageous for use according to the invention are alk(eny)lucuccinic acids and acids. anhydride, the alkyl(kenyl) group preferably having from 9 to 18 carbon atoms; To be. Anhydrides containing alkenyl groups are, for example, monoolefins and malei addition reaction with acid or anhydride at elevated temperature, usually in the presence of a catalyst. This type of acid or anhydride can be prepared by subsequent hydrogenation if desired. to give the corresponding alkyl compound. Linear or branched mono-ol Although branched olefins can be used, in some cases branched olefins are liquid It may be suitable as an anhydride.

Suitable monoolefins for use in the preparation of succinic anhydride are alpha-olefins. For example, it can be obtained from cracking wax. Appropriate α-ole Examples of fins include l-dodecene, 1-tridecene, 1-tetradecene and l-petradecene. There is ntadesen. Other suitable olefins are C2-C, low molecular weight olefins. (i.e., oligomers of C7-C4 olefins), and oligomers of this type Examples of polymers include tetrapropylene, triisobutylene, and tetraisobutylene. be. A suitable alkenylsuccinic anhydride is dodecenylcono\succinic anhydride (DD SA, ), especially its branched form, tetrapropenylsuccinic anhydride (TPSA) It is.

The optimal amount of dicarboxylic acid/anhydride to use for a particular oil depends on the nature of the acid/anhydride and may depend on the properties and proportions of the other constituents of the oil and may not be suitable for routine experiments. Therefore, it can be determined. As a guideline, acids/anhydrides and Demulsifiers are generally used in a weight ratio of about 0.1:1 to 10:1, based on the active ingredients. More specifically, it can be used in a ratio of 0.5:1 to 5:1. One particular system with a TBN of 40 It has been found that ratios in the range from about 1:I to 3:1 are advantageous. 2 or more acids or anhydride, or a mixture of both one acid and less than one anhydride. Of course you can use things.

The amount of demulsifier used in accordance with this invention is small (at least one cross-linked polyoxyalkyl Consisting of Kylene polyol and one or more other components and these, together with cross-linked polyoxyalkylene polyols, are added to the mixture. It provides demulsifying properties.

Polyoxyalkylene polyols are polyoxyalkylene polyols containing a small number (both two oxyalkylene units or and any compound containing at least two hydroxyl groups. "Crosslinking" The term "polyoxyalkylene polyol" refers to one or more polyoxyalkylene polyols. Only compounds created by reacting polyols with cross-linking agents For example, difunctional compounds, such as those suitable for use as cross-linking agents. One of the compounds listed below is treated with one or more alkylene oxides to reduce It also includes compounds that give products containing at least two oxyalkylene chains. It is something.

Demulsifiers suitable for use in accordance with this invention include a crosslinking agent and one or more polyols. Reacts alkylene oxide or oxyalkylene homopolymer or copolymer Produced by reacting with polyoxyalkylene polyol produced by Build. Suitable polyols include, for example, alkylene glycols, alkylene glycols, lyols and alkylene tetrols, such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin and pentaerythritol files are included. Aromatic hydroxy compounds, such as alkylated monovalent and polyvalent Phenol and naphthol can also be used.

The total number of carbon atoms in the alkylene oxide deriving the oxyalkylene group is The value is preferably induced so as not to exceed 1O, preferably from 2 to 4. This kind of alki Examples of lene oxides include ethylene oxide, propylene oxide, xybutane, 2,3-epoxybutane, l,2-epoxybuntas 2,3-ethyl Poxypenkune, l, 2-epoxyhexane, 2,3-epoxyhexane, 3゜ 4-epoxyhexane and 1. There is 2-epoxy-3-methylbutane. Special Suitable alkylene oxides are ethylene oxide and propylene oxide. be. Optionally, the alkylene oxide may contain non-hydrocarbon substituents. However, these may be alkylene oxides or emulsions derived from them. shall not interfere with the use of the deodorant.

polyoxyalkylene polyol derived from one or more alkylene oxides If units are included, these units shall be randomly distributed (two or more (if different alkylene oxides are used) or blocks (if different alkylene oxides are used in the reaction vessel). (when sequentially adding alkylene oxide). When preparing block polymers, Properties of alkylene oxides used to form blocks and repeating units The number of is selected by one skilled in the art as related to the desired properties of the block polymer. It is a choice. For example, oxypropylene blocks are typically relatively hydrophobic The oxyethylene block is relatively hydrophilic.

Suitable polyoxyalkylenes from which the crosslinking compounds used according to the invention can be derived Polyols are dipropylene glycol or triols and propylene oxy It can be obtained by reacting with

Cross-linking of polyoxyalkylene polyols A cross-linked compound having two or more functional groups that can react with a hydroxyl group (usually a terminal hydroxyl group) in the polymer. It can be carried out using a compound. Cross-linked polyol for use according to the invention Preferred crosslinking agents used to prepare xyalkylene polyols include dicarboxylic Diglycidyl ethers of bonic acids and aliphatic and aromatic polyhydroxy compounds It is. An example of a suitable dicarboxylic acid is glutaric acid, preferably adipic acid; On the other hand, an example of a suitable diglycidyl ether is the hydroxy compound diphenylol meta pentaerythritol, trimethylolpropane, ethane-1,2-diol propane-1,2-diol, butane-1,2-diol, butane-2,3 - with diols, glycerin and especially the diglycidyl ether of bisphenol A be.

As indicated above, the demulsifier used according to the invention is a cross-linked polyoxy Along with the alkylene polyol, one or more other components imparting demulsifying properties to the mixture. It can be made up of components. Examples of suitable additional components include one or more alkylene oxides, such as ethylene oxide and/or propylene oxides; A cross-linked polyochine alkylene polyol reacted with a It is an ester of kylated phenol formaldehyde resin.

Oxyamines that can be esterified to provide the demulsifier components used in accordance with this invention. An example of a rkylated phenol formaldehyde resin is a resin of the formula: where A is represents an alkylene group containing from 2 to about 10 carbon atoms, where m is an average of from about 4 to about 200; R represents an alkyl group having from 1 to about 20 carbon atoms, and xL! 1. is a larger integer. The use of this type of resin as a demulsifying property can be used, e.g. As described in the above-mentioned US Pat. No. 4,398,921. represented by R The radical preferably has at least 4 carbon atoms, for example isobutyl, ter It can be a t-butyl or nonyl group.

The demulsifier components used according to the invention are, for example, monocarboxylic acids, preferably is a saturated or unsaturated, straight-chain or branched monocarboxylic acid (this acid is preferred containing about 12 to 20 carbon atoms). It can be prepared by esterifying luminaldehyde resin. easily Due to their availability, mixtures of acids containing fatty acids from C+e to C11I are particularly preferred. suitable.

The optimal amount of demulsifier to use for a particular oil depends on the properties and proportions of the oil's other constituents. can be determined by routine experimentation. as a guideline , the demulsifier 7 dispersant mass ratio in TPEO is calculated on an active component basis. , for example about 0.001:1 to 0.1:1, more specifically 0.002:1 to 0. ．． 07:l range.

The ashless dispersant additive used in accordance with this invention may be an ashless dispersant and/or a viscosity additive. It may consist of a power index improver and a dispersant.

Suitable ashless dispersants for use in accordance with this invention include, for example, amines (amino- alcohol) and hydrocarbyl-substituted mono- or dicarboxylic acids or their derivatives. A length containing one or more polyamine molecules directly attached to the reaction product with the conductor. chain aliphatic hydrocarbons, such as U.S. Pat. Nos. 3,275,554 and 3,565 No. 804 (in this case, the halogen in the halogenated hydrocarbon phenol groups are substituted using alkylene polyamines), and also e.g. There are Mannich condensation products containing long-chain hydrocarbyl groups as substitutes for .

Suitable ashless dispersant additives for use in accordance with this invention include, for example (1)(i) Oil-soluble salts of long-chain hydrocarbon-substituted mono- and dicarboxylic acids or their derivatives; (i) directly attached long chain aliphatic hydrocarbons with polyamines, and (iii) long chain hydrocarbon substitutions. Condensing phenol with formaldehyde and polyalkylene polyamine Ashless dispersants ((1), (1) containing Mannich condensation products formed by The long-chain hydrocarbon group in 1) or (ii) is advantageously 02-Coo, such as For example, it is a polymer of C2-C, monoolefin, and the said polymer is small (both about 9 00), and (2) a polymerizable viscosity index improver dispersant. At least one member selected from the group consisting of:

Preferred dispersants for use according to the invention include hydrocarbyl-substituted carboxylic acids or The acid derivatives consist of hydrocarbon chains, generally polyolefin chains, whereas at least one ethylene bond and at least one carboxylic acid or anhydride thereof a hydrate group, or a polar group that can be converted to a carboxyl group by oxidation or hydrolysis Grafting a material containing groups. Preferably two such carboxylic acid groups (or or its derivatives), α- or β-unsaturated C4-Cu dicarboxylic acids or Particular preference is given to derivatives thereof. Examples of suitable acids and anhydrides include itaconic acid, Leic acid, maleic anhydride, chloromaleic acid, dimethyl fumaric acid, co/X Acid anhydride, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid and and cinnamic acid. Preferably the dispersant product is the polyolefin starting material used. per mole of material, 0.5 to 2, preferably 0.8 to 1.7, more preferably 1. It contains 0 to 1.5, such as 1.05 to 1.2, acid groups, such as succinic acid groups.

Refine polymers suitable for reaction with unsaturated carboxylic acids or their derivatives are mainly as derived from molar amounts of C7-C2°, e.g. 02-C5 monoolefins. It is a polymer. This type of resin includes, for example, ethylene, propylene, Includes butylene, isobutylene, pentene, octene-1 and styrene .

The polymer may be a homopolymer, such as polyisobutylene or a polymer of this type. The above copolymers can be used. These include ethylene, propylene, and butylene. Copolymers of propylene and isobutylene, and propylene and isobutylene are included.

Other copolymers may contain small molar amounts of copolymer monomers, such as 1-10 mole parts. 04 to CI8 diolefins, such as copolymerization of isobutylene and butadiene. body or ethylene, propylene and 1. Make it a copolymer of 4-hexadiene things are included.

In some cases, the olefin polymer can be fully saturated, such as For example, in Ziegler-Natsuta type synthesis using hydrogen as a regulator to control molecular weight. There is an ethylene-propylene copolymer made from

A particularly suitable starting material for the dispersant additive is polyisobutylene.

The olefin polymer usually has a number average of greater than about 700, preferably greater than about 900. may have an average molecular weight I, including a number average molecular weight within the range of 500 to 5.000 It has about one double bond per polymer chain. Number of polymers of this type Average molecular weight can be determined by any suitable technique. for this kind of decision A convenient method is by gel permeation chromatography (GPC), which Additional information on molecular weight distribution is provided (W, W, Nia, Jie). I. Noei Kirkland and D. D. Bry, “Latest Dimensional Exclusion Liquid Curtains” "Romatography", Butane Riley & Song, New York, 19 79).

In order to react an olefin polymer with an unsaturated carboxylic acid or its derivative, Any suitable method can be used, many of which are known in the art. There is. For example, simply adding an olefin polymer and a carboxylic acid or acid derivative together U.S. Pat. Nos. 3,361,673 and 340,111 As disclosed in No. 8, those that cause the occurrence of the thermal "ene J reaction" It is. For example, about 1 to 8, preferably 3 to 7, based on the weight of the polymer. First halogenation of olefin polymers for weight percent chlorine or bromine , for example chlorinated or brominated, from 100° to 250°C, e.g. polyolefin for about 0.5 to IO1 preferably 1 to 7 hours at a temperature of 120° to 160°C. by passing chlorine or bromine through the fin. Then halogenated The obtained polymer is heated at 100° to 250°C, for example 180' to 220°C, at a temperature of 0.5 to 10 can be reacted with a fully unsaturated acid or acid derivative, for example for 3 to 8 hours. Ru.

Methods of this general type are described, for example, in U.S. Pat. No. 92 and No. 3,272,746. In a further method, olefins While mixing and heating the polymer and unsaturated acid material, chlorine is added to the hot material. child Methods of this type are described in U.S. Pat. 4, 4], 10349 and 4234435 and British Patent No. 144 No. 0219.

When using halogens, 65 to 95 weight percent of the polyolefin usually reacted with phosphoric acid or its derivatives. Thermal reaction (i.e. halogen or catalytic 50 to 75 weight percent of the reacted Usually only polyolefins occur. Therefore, chlorination contributes to increased reactivity. It is clear that

Amine compounds useful in reactions with hydrocarbyl-substituted carboxylic acids or their derivatives has 2 to 60, e.g. 3 to 20 carbon atoms and 1 to 12, e.g. Included are mono- and polyamines having from 2 to 8 nitrogen atoms. These a amine can be a hydrocarbyl amine, which contains other groups such as hydroxyl groups, alkokene groups, amido groups, nitrile groups and imidacilline groups.

Particularly preferred are hydroxyamines having 1 to 6 hydroxyl groups, preferably 1 to 3 hydroxyl groups. It is for use. Preferred amines are aliphatic saturated amines, including those of the following general formula: It will be done.

In the formula, R, R' and R# are hydrogen, C1-Cts alkyl group, 01-CI! a Rukoxy group, C7-C6 alkylene group, C2-Crt alkylamino group and 0 independently selected from the group consisting of 2-C6 alkylene groups, S and S' are the same or may be different, each being a number from 2 to 6, preferably from 2 to 4, and t is from 0 to I O1 is preferably a number from 2 to 7. At least one of R, R' or R' is hydrogen Must be atomic. Non-limiting examples of suitable amine compounds include 1.2 -7-aminoethane, 1,3-diaminopropane, 1,4-diaminobutane, l, 6-diamithexane, poly(ethylene amine), e.g. diethylene tria triethylenetetramine and tetraethylenepentamine, poly(propylene) renamine), for example 1. 2-propylene diamine, di(1,2-propylene ren) triamine and di(■, 3-propylene) triamine, N, N-di Methyl-1,3-diaminopropane, N, N-di(2-aminoethyl)ethyl Diamine, N, N-di(2-hydroxyethyl)-1,3-propylene diamine, 3-dodecyloxypropylamine, N-dodecyl-1,3-propylamine diamine, trishydroquine methylaminomethane (THAM), diisopropylene Paturamine, jetanolamine, triethanolamine and aminomol Holins such as N-(3-aminopropyl)morpholine are included.

Other useful amine compounds include cycloaliphatic diamines such as 1. 4-G (Ami) cyclohexane and heterocyclic nitrogen compounds, such as imidacillin and N-aminoalkylpiperazine, represented by the following general formula.

In the formula, pl and pt may be the same or different, and each is an integer of 1 to 4. n+, nt and n may be the same or different, and each is an integer of 1 to 3. It is a number. Non-limiting examples of amines of this type include 2-pentadecyl imidasilicate. and N-(2-aminoethyl)piperazine.

Commercially available mixtures of amine mixtures can also be used advantageously. For example, Archile One method of preparing amines includes alkylene civalides (e.g., ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines. At that time, the pair of nitrogen atoms becomes a linked by a lekylene group, diethylenetriamine, triethylenetetramine, Form compounds like tetraethylenepentamine and the corresponding piperazine .

Low-cost poly(ethyleneamine) compounds with an average of 5 to 7 nitrogen atoms per molecule are , such as "Polyamine H", "Polyamine 400" and "Dow Polyamine It is commercially available under trade names such as E-100J. A mixture of alkylene amines is , e.g. Encyclopedia of Chemical Technology (Kirk Othmer), Interscience Pub Richards, New York (1950), vol. 5, pp. 898-905. It is listed under the title tyrenamine J.

Useful amines also include polyoxyalkylene polyamines, such as: the formula of %formula%) (wherein m has a value of 3 to 70, preferably IO to 35) and (ii) R -(alkylene-(○-alkylene), -NH,) 5-a (wherein, n is approximately 1 ~40, provided that the sum of all n's is from 3 to 70, preferably from 6 to 35 and R is a saturated hydrocarbon group of carbon atoms up to IO, in which case the substitution on the R group The number of groups is 3 to 6). Alkylene of formula (i) and formula (ii) The group may be straight-chain or branched containing 2 to 7, preferably about 2 to 4 carbon atoms. can be done.

Preferably polyoxyalkylene diamines and polyoxyalkylene triamines The polyoxyalkylene polyamine used as the The average molecular weight can range from 100 to 2.000. Suitable polyoxia Lukylene polyamines include polyoxyethylene and polyoxypropylene diamines. polyoxypropylene with an average molecular weight ranging from 200 to 2.000. and triamines. Polyoxyalkylene polyamines are commercially available. , for example/from Efferson Chemical Company, Inc. , Product name “Chefamine D-230, D-400, D-1000, D-2000 , T-403J, etc.

The amine can be prepared by any suitable method such as a carboxylic acid or its derivative, e.g. It can be reacted with rukenylsuccinic anhydride. For example, 5 to 95 weight The oil solution containing the carboxylic acid material of 125-175°C for generally 1-10, e.g. 2-6 hours until the desired amount of water is removed. It may be heated until This heating is more effective for imides than for amides and salts. or mixtures of imides and amides.

The reaction ratio depends on, for example, the amount of reactants, excess amine and the type of bond formed. can vary quite significantly. Generally 0.3-2, preferably 0.3-1.0 , for example 0.4 to 0.8 moles of an amine, such as a diprimary amine, to a carboxylic acid. Partial content is used, for example per mole of grafted maleic anhydride content. Ta For example, to add 1.10 moles of maleic anhydride groups per mole of olefin, One mole of olefin is mixed with amide and imide and reacted with sufficient maleic anhydride. When converted to a compound, about 0.55 mole of amine having two primary groups is preferably used. may be used, i.e. 0.50 per mole of carboxylic acid moiety. mole of amine.

Nitrogen-containing dispersants are generally described in U.S. Pat. Nos. 3,087,936 and 3,254,025. As taught in (the entire disclosure of which is incorporated herein by reference), the desired Depending on the conditions, further treatment can be carried out by boration.

Reacting tris(hydroxymethyl)aminomethane (THAM) with the acid material described above. to form amide, imide or ester type additives (UK patent No. 984,409), or oxazoline compounds and Oxylated oxazoline compounds can be formed (e.g., U.S. Pat. No. 410 2798, 4116876 and 4113639) .

The dispersant can be, for example, one or more amino-alkylene or amino-arylene or is an amino-alkylene- and amino-arylene group having an amino-aryleneoxy-arylene group. Also derived from amino-alcohols, including amino-arylene substituted alcohols. be able to. These are N, N, N', N'-tetrahydroxy-tri - methylene diamine. Hydrocarbon-substituted carboxylic acids Other hydroxyamines that can react with acid derivatives to form dispersants include 2-alpha Mino-1-butanol, 2-amino-2-methyl-■-propatol, p-(β -hydroxy-ethyl)-aniline, 2-amino-1-propanol, 3-amino No-I-propatol, 2-amino-2-methyl-1,3-propanediol, 2-Amino-2-ethyl-1,3-propantool, N-(β-hydroxypropane) ropyru)-N’-(β-amino-ethyl)-piperidine, tris(hydroxy methyl) aminomethane (also known as trismethylolaminomethane) , ethanolamine and β-(β-hydroxyethoxy)-ethylamine are included. Included.

Mixtures of these and similar amines can also be used.

For example, as described in U.S. Pat. No. 3,649,229 and 3,798,165 Certain nitrogen-containing manni, such as Dispersants of the base type can also be used. This kind of Mannich base dispersant is , such as high molecular weight hydrocarbyl-substituted mono- or polyhydroxybenzene For example, amines (having a number average molecular weight of 1.000 or more) and amines (for example, polyalcohols) Kill polyamines, polyalkenyl polyamines, aromatic amines, or carboxylic acids Substituted polyamine or any of these and olefinic conohydric acid or its acid succinimide formed from anhydrides) and carbonyl compounds (e.g. formaldehyde or formaldehyde) be able to.

A very suitable dispersant for use in lubricating oil compositions is anhydrous colloid substituted with acid groups. derived from converted polyisobutylene, polyethylene amines such as tetra Ethylenepentamine, pentaethylenehexamine, polyoxyethylene or polymer polyoxypropylene amines, such as polyoxypropylene cyamine, trismet Reacts with tyrolaminomethane or pentaerythritol, and combinations thereof. This is what I adapted. One suitable dispersant combination includes (A) cotz9 acid anhydride; Polyisobutylene substituted by groups ((B) hydroxy compounds, e.g. pen taerythritol, (C) polyoxyalkylene polyamines, e.g. cypropylenecyamine, and (D) polyalkylene polyamines, such as poly (reacted with ethylenediamine and tetraethylenepentamine). including moles of (A) as described in U.S. Pat. No. 3,804,763. 0.3 to 2 mol of each of (B) and (D) and 0.3 to 2 mol of ( C) is used.

Other suitable dispersant combinations include (A) polyisobutenylconoyl anhydride and (B ) polyalkylene polyamines such as tetraethylenepentamine and (C) Polyhydric alcohols or polyhydroxy-substituted aliphatic primary amines, such as pentae Includes combinations with lythritol or trismethylolaminomethane, US This is as described in Japanese Patent No. 3632511.

Viscosity index improvers (or viscosity modifiers) improve high and low temperature operability for lubricating oils. which maintains shear stability at elevated temperatures and an acceptable viscosity or viscosity at low temperatures. indicates liquidity. Viscosity index improver Dispersant not only works as a dispersant but also improves the viscosity index. It also functions as an agent. Examples of viscosity index improver dispersants of this type include those described in detail above. Compounds primarily similar to dispersants (i.e., amines and hydrocarbyl-substituted mono- or dicarboxylic acids or their derivatives), in which case hydrocarboxylic acids Le substituents are derived from chains of sufficient length to impart viscosity index-improving properties to the compound. It is what it is. Compounds of this type include those described above in connection with the corresponding dispersants. can be prepared in a manner generally similar to that of

The optimal amount of dispersant may depend on the intended use of the oil, but this may depend on other constituents in the oil. may depend on the exact nature and proportions of the In TPEO, dispersant The proportion of is typically 0.1-10% by weight, calculated on the basis of the active component. , in particular in the range from 0.2 to 5% by weight. Those skilled in the art will be able to determine this by routine experimentation. One will be able to determine the most appropriate proportion of dispersant for a particular use. TPEO For one particular oil suitable for use as a dispersant, the most appropriate amount of dispersant is It was found to be 0.25 to 2% by mass calculated on a per minute basis.

As indicated above, lubricating oils for marine applications advantageously have a low (at least one) metal content. A detergent additive and at least one ZDDP.

Overbased metal-containing detergent additives used in accordance with this invention include, for example, alkaline Overbased phenates of metals, alkaline earth metals and magnesium, sulfide phenates sulfonates, salicylates and naphthinates. CH～C Overbased calcium sulfate of soalkyl-substituted benzene or toluene sulfonic acid honates, and overbased calcium sulfide phenates (200-500, typical (with a TBN of 300 to 400) are preferred.

For example, heating a mixture consisting of an oil-soluble alkaryl sulfonic acid or sulfonate Although highly basic metal sulfonates can be produced by Excess alkali gold beyond that required for complete neutralization of any sulfonic acids present. using metal or alkaline earth metal compounds or magnesium, excess metal and diacid to form a dispersed carbonate complex by reacting with gives a base excess of Sulfonic acids are alkyl-substituted aromatic hydrocarbons, e.g. alkyl of aromatic hydrocarbons or by fractionation of petroleum by distillation and/or extraction; Those obtained by chemical reaction, such as benzene, toluene, xylene, naphthalene, phenyl and its halogen derivatives, such as chlorobenzene, chlorotoluene sulfones obtained by alkylating chlorine and chloronaphthalene. It is typically obtained by Alkylation is carried out in the presence of a catalyst over about 3 to 30 It can be carried out using an alkylating agent having carbon atoms of For example, No.1 0 paraffins, olefins obtained by dehydrogenation of paraffins, and ethylene and/or polyolefin polymers made from propylene are all suitable. Ru.

The alkaryl sulfonate usually contains 9 to 70 or more per alkyl-substituted aromatic moiety. of carbon atoms, preferably 16 to 50 carbon atoms.

These alkaryl sulfonic acids can be used to neutralize to give sulfonates. Compounds include sodium, magnesium, calcium, strontium and Barium oxide and hydroxide, alkoxide, carbonate, carbo xylate, sulfide, hydrosulfide, nitrate, borate and ether Tel is included. Examples of suitable compounds include calcium oxide, calcium hydroxide , magnesium oxide, magnesium acetate and magnesium borate. description As mentioned above, the metal compound is necessary for complete neutralization of alkaryl sulfonic acid. Use in excess. Generally, the amount ranges from 100 to 220 percent but at least 125/<-cent of the stoichiometric amount of metal required for complete neutralization. It is preferred to use

Various other preparations of basic alkaline earth metal alkaryl sulfonates are available, such as is known from US Pat. Nos. 3,150,088 and 3,150,089; In the case of alkoxides using alkaryl sulfonates in hydrocarbon solvent diluent oil Excess base is achieved by hydrolyzing the carbonate complex.

Sulfurized metal phenates can be condensed to form metal salts of phenol sulfides. For example, metal salts of compounds of the following general formula, whether neutral or basic.

(wherein x=1 or 2, n=0, l or 2) or a compound of this type In the formula, R represents an alkyl group, and n and X are each 1 to an integer of 4 and the average number of carbon atoms in all R groups is at least about 9 in the oil. The aim is to ensure adequate solubility of the Each individual R group has 5 to 40 , but preferably contains 9 to 12 carbon atoms, as indicated above.

Regardless of the manner in which they are prepared, useful sulfurized alkylphenols include sulfurized 2 to 14% by weight, preferably 4 to 1% by weight, based on the weight of the alkylphenol It generally contains 2% by weight of sulfur.

Sulfurized alkylphenols can be used to neutralize phenols and optionally Metal-containing materials, e.g. can be converted into salts by reactions with metal oxides, hydroxides or complexes. Wear. Preferred methods include neutralization using a solution of the metal in glycol ether. Included.

Neutral or regular sulfurized metal phenates have a substantially reduced ratio of metal to phenolic nuclei. This is stoichiometric theory. "Overbased" or "basic" sulfurized metal phenates are A sulfurized metal phenate, in which the metal to phenol ratio is stoichiometric. larger than required, e.g. basic sulfide metal dodecyl phenate corresponds to Up to and exceeding 100% excess of metal present in normal sulfided metal phenates with a metal content of (due to reaction with Ot).

These overbased materials can be used as additives in all metal cleaners or in their neutral form. Can be used in combination with the same additives.

ZDDP, which is used as an anti-wear agent and also provides antioxidant activity, is commonly is first prepared by reacting alcohol or phenol with P2S5. Formation of oleic acid and subsequent neutralization of dithiophosphoric acid using a suitable zinc compound It can be prepared by a known technique.

Mixtures of alcohols can be used, but mixtures of primary and secondary alcohols are preferred. The second alcohol generally provides improved anti-wear properties and the first Alcohol provides improved thermal stability properties. Particularly useful are mixtures of the two.

In general, any basic or neutral zinc compound may be used, but oxides, hydroxides carbonates and carbonates are most commonly used. Excess basic zincation due to neutralization reaction Because compounds are used, commercially available additives often contain excess zinc.

Zinc dihydrocarbyl dithiophosphates suitable for use in this invention include: Dialkyl dithiophosphoric acid represented by the formula [RO(R'0)PS2]zZn is an oil-soluble salt of an ester, in which R and R' are the same or different alkyl salts. groups, preferably containing 3 to 10, more preferably 3 to 8 carbon atoms. n-propyl, i-propyl, n-butyl, ■-butyl, 5e C-butyl, amyl, n-hexyl, l-hexyl, n-octyl, 2-ethyl Included are hexyl, cyclohexyl and methylcyclopentyl groups.

Other additives that may be used in formulating TPEO include, for example, antioxidants, and e.g. alkylated diphenylamines, and rust inhibitors e.g. alkylthiodiazo There is a rule.

A wide variety of lubricant bases can be used in accordance with the present invention, such as used in the preparation of lubricating compositions or concentrates. Thus, for example, on a suitable base includes natural base oils and synthetic base oils, such as alkyl esters of dicarboxylic acids. esters, polyglycols and alcohols, polyalpha-olefins, polybutenes, There are alkyl hensens, organic esters of phosphoric acid and polysilicon oils.

Natural base oils include mineral lubricating oils, which vary widely depending on their crude source. may be paraffinic, naphthenic, or a mixture. or paraffin-naphthenic, and the details of its production, e.g. range, straight-run operation or crab king, hydro-refining treatment, solvent extraction, etc.

More specifically, the natural lubricant base stock that may be used in accordance with this invention is lubricating oil or paraffinic, naphthenic, bituminous or mixed base coarse It can be a distillate derived from oil refinery. Also, various combinations can be made as desired. The oil can be used in the same way as residual oil, especially after the asphalt components have been removed. Wear. Oils can be purified by any suitable method, e.g. acid, alkali and/or clay or other agents such as aluminum chloride. but also these include solvents such as phenol, sulfur dioxide, Furfural, chlorodiethyl ether, nitrohensen or crotonal The extracted oil may be produced by solvent extraction using dehyde.

Suitable lubricant bases for preparing TPEO typically have a viscosity of about 3 to about 1 at 100°C. The viscosity is 5 cSt (approx. 3 x 10-' to approx. 15 Bases of other viscosities can also be used, although they have advantages. for example , typically has a viscosity of about 30 cSt (about 30xlO-'m2/s) at 100°C. Brightstocks with 100% polyester can also be used in some applications.

The additives used in accordance with this invention are oil-soluble and can be dissolved in oil by using a suitable solvent. It is a material that can be dissolved or stably dispersed. This is what we use here. The terms oil-soluble, soluble or stably dispersible mean that the material is does not necessarily indicate that it is soluble, soluble, compatible, or suspendable in oil. It's not a thing. However, this does not actually mean that additives are be sufficiently soluble or stably dispersible in the oil to exert its intended effect. It means to do something. Furthermore, if desired, by additional incorporation of other additives, Higher levels of incorporation of certain additives may also be possible.

The additives used in accordance with this invention may be incorporated into the lubricating oil by any convenient method. be able to. These can therefore be added by dispersion or at a desired level of concentration. can be added directly to the oil by dissolving it in the oil. Such a combination is , can be carried out at room temperature or at elevated temperatures.

The additives used according to the invention can be used in lubricating oil compositions, which It consists of a lubricating oil (typically a major amount) and an additive (typically a minor amount). Ru. Additional additives, such as those described above, may be incorporated into the composition to enhance its properties. It may be possible to meet certain requirements.

As indicated above, the present invention is particularly relevant to TPEO. This issue Typical proportions of additional additives in TPEO according to Akira are as follows: Additive quality Amount % active constituents Cleaning agent 1-10 ZDDP 0.1 - 1.5 Antioxidant 0.2 ~ 2 Rust preventive agent o, oos ~ 0.05 Also, as mentioned above, although not essential, additive concentrates consisting of additives (concentrates are In some cases, it may also be desirable to prepare an additive package (herein referred to as an additive package); Several additives can be added simultaneously to the base oil to form a lubricating oil composition. Wear. Additive concentrates can be dissolved in lubricating oils by solvents and by mixing with heating. It can be facilitated, but this is not required. Concentrate or additive package The additive package is typically formulated to contain the appropriate amount of additive. which when combined with a metered amount of base lubricant will give the desired concentration in the final formulation. It is possible. Thus one or more additives may be added along with other desired additives to a small amount of base oil or other additives. compatible solvent, for example, from about 20 to about 70% by weight, preferably from about 40 to about It is possible to form an additive package containing the active component in an amount of 65% by weight. Additives are added in appropriate proportions and the remainder is used as base oil. The final formulation combines the remainder with base oil. Typically about 4-20% by weight of the additive package may be used.

The invention is illustrated by the following examples.

Example 1 and comparative example Cl-C5 Made from the boration reaction product of polyisobutenyl succinic anhydride using polyamines. The ashless dispersant of (TPSA) (if used) and an overbased calcium sulfonate detergent. I entered. The contents of the container were mixed for 1 hour at 80°C and then cooled to 60°C, followed by A demulsifier (shown in Table 1), an antioxidant, a rust inhibitor, and a base oil were then added. Mixed The mixture was stirred for 1 h at 60°C and the zinc hydrocarbyl dithiophosphate was then added to Added. Table 1 shows the proportions of the components. Dispersants, cleaning agents, antioxidants, rust inhibitors The respective proportions of demulsifier and demulsifier were the same in each example.

The demulsifier used in these examples was diglycidyl ether of bisphenol A. Propoxylated dipropylene glycol cross-linked with propylene oxide or ethylene oxide and propylene oxide, propoxylated di Propylene glycol (cross-linked with diglycidyl ether of bisphenol A) A blend of two different components prepared by reacting with (92% active components by weight in diluent oil).

The mixture obtained as described above had a TBN of 220 and was added to the base oil. For use as a concentrate to form lubricant compositions suitable for use as TPEO It was appropriate to The ability of petroleum or synthetic fluids to separate from water (oil or other A test method for measuring the ability of a fluid to "push through" water A composition suitable for use in TMD1401 includes about 18 parts by weight of concentrate and about 82 parts by weight of concentrate. It was prepared by mixing parts by mass of base oil. The final composition has a TBN of 40 had. According to test method D1401, 40 ml of the composition to be tested and The emulsion thus prepared by mixing 40 ml of water in a graduated cylinder Separation into oil and water (if present) was observed. Table 2 shows the times specified in that table. The volume percentages of oil, water and emulsion obtained afterwards are shown.

Component ratio (mass%) Example CI C2C3 Example 1 TPSA 0 1 Q l Base part 3.3 2.3 2.77 1.77 Performance in test D1401 Example CI C2C3 Example 1 Oil (volume%) 0 0 40 40 Water (volume I%) 0 0 30 40 Emulsion (volume%) 80 80 10. 0 hours (minutes) 60 60 6 0 20 As can be seen from the table above, in Comparative Example CI, separation of oil and water did not occur after 60 minutes. However, in this case the composition did not contain TPSA or demulsifier; In Comparative Example C2, the composition contained TPSA but did not contain a demulsifier. stomach. Furthermore, in Comparative Example C3 (in which case the composition tested contained a demulsifier) (but no TPSA), an emulsion of 10% by volume remained after 60 minutes. It existed. In contrast, this formulation containing both demulsifier and TPSA The composition according to Ming (Example 1) has excellent performance, initial emitter formation in only 20 minutes. showed complete separation of the fusions. Therefore, there is a synergistic relationship between the demulsifier and TPSA. It turns out that there is some effect.

Example 2 and comparative example 4 Overbased Calcium Phenate Detergent, Detergent Used in Example I, Polyisobutylene Ashless dispersion obtained by reacting tenyl succinic anhydride and polyamine By mixing the agent, ZDDP, demulsifier and base part, as TPEO. A suitable lubricating oil was prepared for use.

The demulsifier used in Comparative Example 4 contained 15.7% active component and contained adipine. Mixture of propoxylated triols, CI6-C]8 fatty acids cross-linked by acid ethoxylated phenol formaldehyde resin esterified with The demulsifier used in Example 2 consisted of a base solvent, but the demulsifier used in Example 2 did not contain a solvent mixture. Approximately 75% of the product is calculated based on the demulsifying active component by replacing TPSA. A demulsifier/TPSA mixture containing % TPSA by weight was to be provided.

The total proportion of demulsifier or demulsifier and TPSA in the final song is 0.02 % by mass and the TBN of the final song was 40 in each case.

Results of testing the compositions of Comparative Example C4 and Example 2 with ASTM Test Method D1401 The results are shown in Table 3: Performance in test D1401 Example C4 Example 2 Oil (volume%) 40 40 Water (volume%) 38 40 Emulsion (volume%) 2 0 Time (minutes) 60 45 The use of TPSA and demulsifiers in accordance with this invention results in more complete oils. It can be seen that separation of water and water and a shorter separation time are given.

Summary book Cross-linked polyoxy to water-in-oil emulsions containing ashless dispersant additives The action of the alkylene polyol demulsifier is controlled by free dicarboxylic acid or its acid. Strengthen by using anhydride. This invention is suitable for marine applications, especially trunk piers. Particularly relevant to lubricating oils for engine oils and system oils .

Tano 1 Inquiry Cow

Claims (20)

[Claims] 1. Increases the action of demulsifiers in water-in-oil emulsions containing ashless fractionator additives. With the use of free (as previously specified) dicarboxylic acids or their acid anhydrides to strengthen The demulsifier contains a cross-linked polyoxyalkylene polyol. use. 2. Oil of lubricating viscosity, ashless dispersant additive, cross-linked polyoxyalkylene polio Demulsifiers containing demulsifiers, and free (as previously identified) dicarboxylic acids or is a lubricating composition containing the acid anhydride. 3. Oil formulations of lubricating viscosity, lubricating oil ashless dispersant additives, cross-linked polyoxia Demulsifiers containing lekylene polyols and dicarboxylic acids or their acid anhydrides A lubricating composition containing. 4. The dicarboxylic acid deriving the dicarboxylic acid or its acid anhydride has the following general formula: :HO2C-(R)-CO2H (wherein R represents a divalent hydrocarbyl group) The invention described in Crab. 5. In the formula according to claim 4, R is linear or branched, saturated or The invention according to claim 4, which represents an unsaturated divalent aliphatic group. 6. The dicarboxylic acid or its acid anhydride is an alkyl(kenyl)succinic acid or its acid anhydride. The invention according to any one of claims 1 to 3, which is an acid anhydride of. 7. Claim 1: It is dicarboxylic anhydride or tetrapropenylsuccinic anhydride. The invention according to any one of item 3. 8. The cross-linked polyoxyalkylene polyol is composed of a polyol and an alkylene polyol. a compound containing a group derived from an alkylene oxide or an alkylene oxide; Any one of claims 1 to 7 prepared by crosslinking reaction products. The invention described in . 9. The cross-linked polyoxyalkylene polyol may be an alkylene glycol or or alkylene triol and alkylene oxide or alkylene oxide. By crosslinking the reaction product of a compound containing a group derived from The invention according to claim 8, which is prepared. 10. The alkylene oxide is ethylene oxide and/or propylene oxide. The invention according to claim 8 or 9, which is an oxide. 11. dicarboxylic acids or aliphatic or aromatic hydroxy compounds 11. The compound according to claim 8, wherein the crosslinking is carried out using a ether. Akira. 12. The demulsifier may contain one or more additional constituents containing oxyalkylene groups. The invention according to any one of claims 1 to 11, further comprising: 13. The ashless dispersant additive is (i) amines and long-chain hydrocarbon-substituted mono- or dicarboxylic acids or derivatives thereof; reaction product with (ii) a long chain hydrocarbon having one or more polyamine molecules directly attached; i) Mannich condensation products containing long-chain hydrocarbon groups (provided that (i), (ii) ) and (iii) in which the long-chain hydrocarbon groups are C2-C10 monoolefin heavy and having a number average molecular weight of at least about 900) The invention according to any one of claims 1 to 12, containing a dispersing agent. 14. The ashless dispersant additive comprises a polyamine and a hydrocarbyl substituted succinic acid. or a reaction product thereof with an acid anhydride. The invention described. 15. 15. The invention according to claim 14, wherein said reaction product is borated. 16. The composition may contain at least one metal-containing detergent additive and/or Claim 2 further comprising at least one zinc dihydrocarbyl dithiophosphate. The invention according to any one of 5 to 5. 17. Any of claims 2 to 16, wherein the composition has a TBN in the range of 9 to 40. The invention described in any of the following. 18. Oil of lubricating viscosity, ashless dispersant additive, demulsifier and fluid in any order. (as previously specified) dicarboxylic acids or their acid anhydrides. A method for preparing a lubricating composition comprising: 19. Concentrates useful as lubricating oil additives, including ashless dispersant additives, cross-linking Demulsifiers containing bound polyoxyalkylene polyols, free (previously identified dicarboxylic acids or their acid anhydrides, overbased metal detergents, ZDDP and Concentrate consisting of base oil. 20. A claim in which the constituent component is as detailed in any one of claims 4 to 15. The concentrate according to claim 19 or claim 20.