CN106232783A

CN106232783A - Emulsifier component and using method thereof

Info

Publication number: CN106232783A
Application number: CN201580022317.8A
Authority: CN
Inventors: T·P·奥莱克夏克; D·T·菲利普斯; C·H·怀斯; B·韦斯勒; F·L·克罗托
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2014-03-05
Filing date: 2015-01-28
Publication date: 2016-12-14
Also published as: EP3114195A2; WO2015134129A3; US20170022443A1; KR20160128406A; JP2017510438A; WO2015134129A2; CA2942145A1

Abstract

The present invention relates to comprise and replace the functional group of acylating agent and the additive of the functional group derived from the second alkyl replacement acylating agent derived from the first alkyl, wherein functional group is by the functional groups derived from aklylene glycol.The invention still further relates to the emulsifier component prepared by a kind of method, described method uses described additive and by making it convert it to emulsifier component with neutralizing component reaction.The method that the invention still further relates to prepare described emulsifier component, and the method customizing emulsifier component in the composition by the described additive of use and the described method converting it to described emulsifier component.

Description

Emulsifier component and using method thereof

The present invention relates to comprise and replace the functional group of acylating agent derived from the first alkyl and replace acyl derived from the second alkyl The additive of the functional group of agent, wherein functional group passes through derived from aklylene glycol, in certain embodiments, linear alkylene The functional groups of base glycol.The invention still further relates to the emulsifier component prepared by a kind of method, described method uses described Additive also converts it to emulsifier component by making it and neutralize component reaction.The invention still further relates to prepare described emulsifying The method of agent component, and by using described additive and converting it to the described method of described emulsifier component in compositions The method of middle customization emulsifier component.

Background of invention

The alkyl substituted carboxylic acid acylating agent in substituent group with at least about 30 aliphatic carbon atoms is known in normal liquid combustion As additive in material and lubricant.The example of this kind of acylating agent includes that polyisobutenyl replaces succinic acid and acid anhydride.This kind of carboxylic acid Acylating agent is disclosed in United States Patent (USP) Nos.3,288,714 and 3 as additive purposes in normal liquid fuel and lubricant, In 346,354.

These acylating agents are also used for the additive in normal liquid fuel and lubricant as intermediate for preparation, such as U.S. State's patent Nos.2,892,786；3,087,936；3,163,603；3,172,892；3,189,544；3,215,707；3,219, 666；3,231,587；3,235,503；3,272,746；3,306,907；3,306,908；3,331,776；3,341,542；3, 346,354；3,374,174；3,379,515；3,381,022；3,413,104；3,450,715；3,454,607；3,455, 728；3,476,686；3,513,095；3,523,768；3,630,904；3,632,511；3,697,428；3,755,169；3, 804,763；3,836,470；3,862,981；3,936,480；3,948,909；3,950,341；4,234,435；With 4,471, 091；Described in French Patent (FRP) 2,223,415.

United States Patent (USP) No.3,216,936 describe the nitrogenous dispersant in lubricant, its by alkylene amines with by Hydrocarbon substituent has Hydrocarbyl-substituted succinic acid and the acidic mixed of mono carboxylic acid of aliphatic series composition of at least about 50 aliphatic carbon atoms Thing reacts and obtains.Mono carboxylic acid of aliphatic series is described as including saturated and unsaturated acids, such as acetic acid, dodecylic acid, oleic acid, cycloalkanes Acid, formic acid etc..There are 12 or the acid of more aliphatic carbon atom, particularly stearic acid and oleic acid is described as being particularly useful.

United States Patent (USP) Nos.3,639,242 and 3,708,522 describes by inciting somebody to action list-and polycarboxylate list-or poly-carboxylic Acid acylating agent post processing and the compositions prepared.Report therefore resulting composition as dispersant for lubricant and fuel In.

United States Patent (USP) No.4,642,330 discloses by making without phosphorus carboxylic solubilizers and without sulfonic acid organic acid or mineral acid The dispersant salt composite reacted and prepare.Carboxylic solubilizers is to have at least one hydrocarbon with at least 8-500 carbon atom The polycarboxylic acids acylating agent of base substituent group and the product of at least one poly-(alkylene amines).This reference paper shows that these disperse Agent salt composite has good heat stability with surfactant or hydrophilic organic solvent when mixing, and they can be with Aqueous solution is used for disperseing various filler together, including white carbon black, and by various fluids solubilising.

Nitrogenous without phosphorus carboxylic solubilizers in water base functional fluid is disclosed in United States Patent (USP) Nos.4,329,249；4, 368,133；4,435,297；4,447,348；In 4,448,703.By (I), at least one has at least one in these solubilizing agents (hydroxyl replaces for the carboxylic acid acylating agent of the individual hydrocarbyl substituent with about 12 to about 500 carbon atoms and (II) at least one (a) N- Alkyl) amine, the hydroxyl of (b) described amine (a) replace poly-(oxyl) analog, or the mixture reaction of (a) and (b) and make Standby.These patents show that preferred acylating agent includes replacing succinum acid or anhydride, such as polyisobutenyl substituted succinyl oxide, and Useful amine includes primary, secondary and tertiary alkanolamine, such as diethyl ethylene diamine, and diethyl ethylene diamine and the mixing of ethylene glycol Thing.These solubilizing agents are for being scattered in oil-soluble, water-insoluble functional additive in water base functional fluid.

United States Patent (USP) No.5,047,175 discloses salt composite, and it comprises: (A) at least one salt structure division, described Salt structure division has at least one derived from (A) (I) at least one high-molecular-weight poly carboxylic acid acylating agent, described acylating agent (A) (I) The individual hydrocarbyl substituent with average about 20 to about 500 carbon atoms, and (A) (II) ammonia, at least one amine, at least one alkali or Alkaline-earth metal and/or at least one alkali or alkaline earth metal compound；(B) at least one salt structure division, described salt structure division Derived from (B) (I) at least one low-molecular-weight polycarboxylic acids acylating agent, described acylating agent (B) (I) optionally has at least one and has The hydrocarbyl substituent of average at most about 18 carbon atoms, and (B) (II) ammonia, at least one amine, at least one alkali or alkaline-earth metal And/or at least one alkali or alkaline earth metal compound；Described component (A) and (B) by (C) at least one have (i) two or The more primary amino radical of person, (ii) two or more secondary amino group, (iii) at least one primary amino radical and at least one secondary amino group, (iv) At least two hydroxyl, or the compound of (v) at least one primary or secondary amino and at least one hydroxyl combines.These salt Compositions is used for Water-In-Oil explosivity emulsion, particularly detonator sensitivity explosivity emulsion (cap-sensitive as emulsifying agent Explosive emulsion) in.

United States Patent (USP) No.4,828,633 discloses the emulsion explosive of emulsifying agent based on United States Patent (USP) No.5,047,175.

United States Patent (USP) No.5,422,024 provides the aqueous O/w emulsion official of the salt composite comprising water, oil and emulsifying amount Energy fluid, described salt composite comprises: (A) at least one salt structure division, and described salt structure division is derived from (A) (I) at least A kind of high-molecular-weight poly carboxylic acid acylating agent, described acylating agent (A) (I) has at least one and has average about 20 to about 200 carbon The hydrocarbyl substituent of atom, and (A) (II) ammonia, at least one amine, at least one alkali or alkaline-earth metal and/or at least one alkali or Alkaline earth metal compound；(B) at least salt structure division, described salt structure division gathers derived from (B) (I) at least one low-molecular-weight Carboxylic acid acylating agent, described acylating agent (B) (I) optionally has at least one alkyl with average at most about 18 carbon atoms and replaces Base, and (B) (II) ammonia, at least one amine, at least one alkali or alkaline-earth metal and/or at least one alkali or alkaline-earth metal chemical combination Thing；At least one has (i) two or more primary amino radical by (C) for described component (A) and (B), (ii) two or more Multiple secondary amino groups, (iii) at least one primary amino radical and at least one secondary amino group, (iv) at least two hydroxyl, or (v) at least The compound of individual primary or secondary amino and at least one hydroxyl combines.

These materials above-mentioned prove useful emulsifying agent, it remains desirable, however, that have the emulsifying agent improving performance, Yi Jigeng The easily emulsifier system of customization for concrete application.Need to allow fluid user and/or manufacturer can easily based on The emulsifying agent that the concrete fluid of their process and/or final use adjust and/or use them to use.Therefore, it is still necessary to more preferably Ground performs and/or the most customizable emulsifying agent, and it can be customized by fluid user and/or manufacturer.

Summary of the invention

Described technology provides and comprises (i) functional group derived from the first alkyl replacement acylating agent with (ii) derived from the second hydrocarbon Base replaces the additive of the functional group of acylating agent, and wherein functional group (i) and (ii) are by the most linear sub-derived from aklylene glycol The functional groups of alkyl diol；Wherein the first alkyl replaces acylating agent and comprises the alkyl replacement containing at least 20 carbon atoms Base；And wherein the second alkyl replacement acylating agent comprises containing the hydrocarbyl substituent less than 20 carbon atoms.

The present invention further provides described additive, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturation The product of carboxylic acid；Wherein said long chain hydrocarbon has the number-average molecular weight more than 400.In some embodiments, long chain hydrocarbon Have more than 450, at least 500, at least 750, or the number-average molecular weight of even at least 800.(" single unsaturated carboxylic acid " refers to comprise One olefinic unsaturation, does not the most calculate the carboxylic acid of carbonyl double bond).

The present invention further provides described additive, wherein the first alkyl replaces acylating agent and comprises and have the number more than 400 The polyisobutylene succinic anhydride of average molecular weight.In some embodiments, polyisobutylene succinic anhydride has more than 450, at least 500, at least 750, or the polyisobutylene group of the number-average molecular weight of even at least 800.

The present invention further provides described additive, wherein the second alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturation The product of carboxylic acid；Wherein said long chain hydrocarbon has the number-average molecular weight less than 400 or less than 280 or less than 250.? In some embodiments, long chain hydrocarbon has 100-400, or 200-400, or 200-280, or 200-250, or 300- 400, or even 300-350, or the number-average molecular weight of the most about 322.

The present invention further provides described additive, wherein the second alkyl replaces acylating agent and comprises hexadecenyl succinic acid Acid anhydride.

The present invention further provides described additive, wherein aklylene glycol comprises and has formula Glycol, wherein each R independently be H or has the alkyl of 1-6 carbon atom, and each x independently be the integer of 2-10, and M is the integer of 1-10.That is, some or all of R group can be H and remaining (if any) R group can be described alkyl. In some embodiment described herein, one or more R group can be methyl.In certain embodiments, it is somebody's turn to do whole In file, the carbon atom number in the glycol of said structure is less than 400, or less than 200, or less than 100, or 2- 50, or 2-10, or 2 or 3.

In some embodiments, aklylene glycol is linear alkylene glycol, and in some embodiments, it comprises second Glycol.

The present invention further provides described additive, wherein the first alkyl replaces acylating agent and comprises and have the number more than 750 The polyisobutylene succinic anhydride of average molecular weight；Wherein the second alkyl replaces acylating agent and comprises hexadecenyl succinic anhydride；And its Middle aklylene glycol comprises ethylene glycol.

The present invention further provides the emulsifier component prepared by a kind of method, described method includes step: step (I): make the first alkyl replace acylating agent, the second alkyl replaces acylating agent and the reaction of (the most linear) aklylene glycol；Wherein One alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein the second alkyl replaces acylating agent bag Containing containing the hydrocarbyl substituent less than 20 carbon atoms；Generation comprises (i) and replaces the official of acylating agent derived from described first alkyl Energy group and (ii) replace the additive of the functional group of acylating agent derived from described second alkyl, and wherein functional group (i) and (ii) are logical Cross the functional groups derived from described aklylene glycol；Step (II): provide described additive to be used as emulsifier component precursor； With step (III): by making described additive, with neutralizing component reaction, described additive be changed into emulsifier component.Any Additive described herein can be prepared as the methods described and use.

The present invention further provides mentioned emulsifier component, wherein said neutralization component comprise alkali or alkaline earth metal alkali or Amine.Suitably amine include NaOH, KOH, monoethanolamine, diethanolamine, triethanolamine, methyl diethanolamine, dimethylethanolamine, Butylethanolamine, butyl diethanolamine, octyl diethanolamine, cyclohexyldi, monoisopropanolamine, diisopropanolamine (DIPA), three Isopropanolamine, diglycolamine, 1-amino-2-methyl-1-propanol, 3-amino-4-capryl alcohol, dicyclohexylamine, octylame and any Combination.

The present invention further provides the method preparing emulsifier component, described method includes step: step (I): make first Alkyl replaces acylating agent, the second alkyl replaces acylating agent and the reaction of (the most linear) aklylene glycol；Wherein the first alkyl replaces Acylating agent comprises the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein the second alkyl replacement acylating agent comprises containing being less than The hydrocarbyl substituent of 20 carbon atoms；Generation comprises (i) and replaces functional group and (ii) of acylating agent derived from described first alkyl The intermediate (it is alternatively referred to as additive in whole this document) of the functional group of acylating agent is replaced derived from described second alkyl, Wherein functional group (i) and (ii) are by the functional groups derived from described aklylene glycol；Step (II): described interpolation is provided Agent is used as emulsifier component precursor；And step (III) generally the most thereafter: by making described intermediate (additive) and neutralizing component React and described intermediate (or additive) is changed into emulsifier component.Any additive described herein can be as the methods described Preparation and use.

The present invention further provides described method, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturated carboxylic The product of acid；Wherein said long chain hydrocarbon has the number-average molecular weight more than 400；And wherein the second alkyl replaces acylating agent bag Product containing long chain hydrocarbon with single unsaturated carboxylic acid；Wherein said long chain hydrocarbon has the equal molecule of number less than 400 or less than 280 Amount；Wherein (the most linear) aklylene glycol comprises and has formulaGlycol, respectively Individual R independently be H or has the alkyl of 1-6 carbon atom, and each x independently be the integer of 2-10 and m is the integer of 1-10.

The present invention further provides described method, wherein the first alkyl replaces acylating agent to comprise the number having more than 750 equal The polyisobutylene succinic anhydride of molecular weight；Wherein the second alkyl replaces acylating agent and comprises hexadecenyl succinic anhydride；And wherein Aklylene glycol comprises ethylene glycol.

The present invention further provides the method customizing emulsifier component in the composition, described method includes step: step (I): by making the first alkyl replace acylating agent, the second alkyl replaces acylating agent and (the most linear) aklylene glycol reacts and makes Standby additive；Wherein the first alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein second Alkyl replaces acylating agent and comprises containing the hydrocarbyl substituent less than 20 carbon atoms；Generation comprises (i) derived from described first hydrocarbon The functional group of base replacement acylating agent and (ii) replace the additive of the functional group of acylating agent, Qi Zhongguan derived from described second alkyl Group (i) functional groups derived from described aklylene glycol can be passed through with (ii)；Step (II): described additive is fed and needs Want in the compositions of emulsifier component；And step (III) generally the most thereafter: by make described additive with neutralize component reaction and Described additive in described compositions is changed into emulsifier component；Produce customization emulsifier component.Any described herein add Add agent can prepare as the methods described and use.

The present invention further provides described method, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturated carboxylic The product of acid；Wherein said long chain hydrocarbon has the number-average molecular weight more than 400；And wherein the second alkyl replaces acylating agent bag Product containing long chain hydrocarbon with single unsaturated carboxylic acid；Wherein said long chain hydrocarbon has the equal molecule of number less than 400 or less than 280 Amount；And wherein aklylene glycol comprises and has formulaGlycol, wherein each R is independently For H or the alkyl with 1-6 carbon atom, each x independently be the integer of 2-10, and m is the integer of 1-10.

Detailed Description Of The Invention

Illustrate below by indefiniteness and describe each preferred feature and embodiment.

Find to use described additive by allowing that user makes the hydrophil lipophil balance (HLB) of additive, buffer system With corrosion inhibition system optimization and be supplied to emulsifying agent user advantage, produce and be customized for relevant with user concrete gold Belong to the emulsifying agent in converted products and/or application.This route relates to the purposes itself being never used as the additive of emulsifying agent, then Emulsifying agent user can be the most modified to realize the concrete emulsifying agent performance that they want by it.

Additive

Described technology provides and comprises (i) functional group derived from the first alkyl replacement acylating agent with (ii) derived from the second hydrocarbon Base replaces the additive of the functional group of acylating agent, and wherein functional group (i) and (ii) are by the functional group derived from aklylene glycol In conjunction with, described aklylene glycol can be branched or linear alkylene glycol；Wherein first alkyl replace acylating agent comprise containing The hydrocarbyl substituent of at least 20 carbon atoms；And wherein the second alkyl replacement acylating agent comprises containing the hydrocarbon less than 20 carbon atoms Base substituent group.

Derive functional group (i) and the first alkyl replacement acylating agent of (ii) and the second alkyl replaces acylating agent and also can describe For carboxylic acid acylating agent and can be aliphatic series or aromatics polycarboxylic acids or acid-producing cpd.Unless otherwise expressly noted, such as this paper institute With, term " carboxylic acid acylating agent " is intended to include carboxylic acid and produce acid derivative, such as acid anhydride, ester, acyl halide and mixture thereof.

Acylating agent can comprise polar substituent, and condition is that polar substituent is not be enough to substantially change the hydrocarbon character of acylating agent Vast scale exist.Typical suitable polarity substituent group includes halogen, such as chlorine and bromine, oxo, epoxide, formoxyl, sub-oxygen sulfur Base, sulfinyl, sulfur generation, nitro etc..If it exists, this kind of polar substituent is preferably more than the hydrocarbon part of acylating agent About 10 weight % of the gross weight of (not including carboxyl).

Low-molecular-weight polycarboxylic acids (i.e. comprises the second alkyl containing the hydrocarbyl substituent less than 20 carbon atoms and replaces acylated Agent) include dicarboxylic acids and derivant, such as maleic acid, maleic anhydride, chloromaleic acid acid anhydride, malonic acid, succinic acid, succinic acid Acid anhydride, 1,3-propanedicarboxylic acid, glutaric anhydride, adipic acid, 1,5-pentanedicarboxylic acid., Azelaic Acid, decanedioic acid, glutaconate, citraconic acid, itaconic acid, pi-allyl Succinic acid, cetyl malonic acid, four propylidene substituted succinyl oxides etc..It is used as the lower level Arrcostab of these acid.

In some embodiments, the first alkyl replaces acylating agent and the second alkyl replacement acylating agent is Hydrocarbyl-substituted succinic Acid and acid anhydride.

Hydrocarbyl succinic acid acylating agent can comprise polar substituent, and condition is that polar substituent is not acylated be enough to substantially to change The vast scale of the hydrocarbon character of agent exists.Typical suitable polarity substituent group includes halogen, such as chlorine and bromine, oxo, epoxide, formyl Base, sulfenyl, sulfinyl, sulfur generation, nitro etc..If it exists, this kind of polar substituent is preferably more than acylating agent About 10 weight % of gross weight of hydrocarbon part (not including carboxyl).

(the first alkyl i.e. comprising the hydrocarbyl substituent containing at least 20 carbon atoms takes high-molecular-weight poly carboxylic acid acylating agent For acylating agent) it is well known in the art and is described in detail in such as United States Patent (USP) Nos.3,215,707；3,231,587；3, 288,714；3,346,354；3,912,764；4110,349；With 4,234,435；With in British patent 1,492,337.By drawing It is incorporated herein in by these patents.

The alkyl that first and second alkyl replace acylating agent is the most limited, and condition is that they meet requirement described herein. It is especially useful that 1-monoolefine such as ethylene, propylene, 1-butylene, isobutene., 1-hexene, 1-octene, 2-methyl isophthalic acid-heptene, 3- Cyclohexyl-1-butylene and 2-methyl-5-propyl group-1-hexene containing hydrocarbyl polymers.Internal olefin (medial olefin), i.e. its The polymer of the middle ethylene linkage not alkene on terminal position is also useful.These are illustrated by 2-butylene, 3-amylene and 4-octene. As mentioned above 1-monoolefine to each other and with other copolymerizable olefinic material such as atomatic olefins, cycloolefin and polyolefinic copolymerization Thing is also useful.This analog copolymer includes such as by isobutene. and styrene, isobutene. and butadiene, propylene and isoamyl two Alkene, propylene and isobutene., ethylene and piperylene, isobutene. and chlorobutadiene, isobutene. with to methyl-styrene, 1-hexene With 1,3-hexadiene, 1-octene and 1-hexene, 1-heptene and 1-amylene, 3-methyl-1-butene and 1-octene, 3,3-dimethyl 1- Amylene be polymerized with styrene and piperylene etc. with 1-hexene, isobutene. and prepare those.

Reason due to hydrocarbon dissolubility, it is contemplated that be preferably basic aliphatic series and base for preparing the copolymer of acylating agent of the present invention This is saturated, and i.e. they should comprise based on weight at least about 80%, the unit derived from aliphatic monoolefine of preferably from about 95%. Preferably, they comprise sum no more than about 5% ethylene linkage based on the carbon-to-carbon covalent bond existed.

In one embodiment of the invention, polymer is by having the butene content peace treaty of about 35% to about 75 weight % The C4 refinery stream of the isobutene content of 30% to about 60 weight % is polymerized and is obtained.These polyisobutylene are preferably mainly (the biggest In total repetitive about 80%) comprise structure C H₂C(CH₃)₂-isobutylene repeat units.For preparing higher molecular weight amber The hydrocarbon of amber acid acylating agent and ethylenically unsaturated hydrocarbons per molecule can have at most about 200 carbon atoms.Some acylating agents are for comprising about 20 to about 150, or 30 to about 120, or those of the alkyl of about 50 to about 80 carbon atoms.Hydrocarbyl-substituted succinic acid and acid anhydride Can be reacted with high molecular weight olefin by maleic anhydride and prepare.Hydrocarbyl-substituted succinic anhydride can be by with water or steam process It is hydrolyzed into respective acids, and acid anhydride or acid can be changed into respective acids or ester.

First alkyl replaces the alkyl of acylating agent, and to can include about 20 to about 200 carbon atoms, about 30 to about 150 carbon former Son, about 50 to about 200 carbon atoms, or the most about 70 to about 80 carbon atoms.

Alternatively referred to as the second alkyl of low-molecular-weight succinic acylating agent replace acylating agent can with high molecular weight material Prepared by substantially similar way.In some embodiments, its alkyl be the carbon-carbon bond of less than about 10% be undersaturated fat Race or alicyclic alkyl.Its alkyl can be derived from the alkene of 2 to about 18 carbon atoms, and wherein alpha-olefin is useful especially. The example of this kind of alkene include ethylene, propylene, 1-butylene, isobutene., 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, 1-tridecylene, 1- Tetradecene, 1-15 carbene, cetene, 1-heptadecene, 1-vaccenic acid.

Commercially available alhpa olefin part, such as C_12-18Alpha-olefin, C_12-16Alpha-olefin, C_14-16Alpha-olefin, C_14-18Alpha-olefin and C_16-18Alpha-olefin is useful especially.These business alpha-olefin parts also generally comprise the α-alkene outside given range of minor amount Hydrocarbon.Such as the situation about high molecular weight material, make unsaturated material or optional chlorination analog and maleic acid or maleic anhydride Reaction.The preparation of this kind of replacement succinic acid and derivant thereof is well known to those skilled in the art, and is being not required here in detail Thin discussion.

In some embodiments, the first alkyl replaces acylating agent and comprises the reaction product of long chain hydrocarbon and single unsaturated carboxylic acid Thing；Wherein said long chain hydrocarbon has the number-average molecular weight more than 400.In some embodiments, long chain hydrocarbon have more than 450, At least 500, at least 750, or the number-average molecular weight of even at least 800.In some embodiments, the first alkyl replaces acylated Agent comprises the polyisobutylene succinic anhydride with the number-average molecular weight more than 400.In some embodiments, polyisobutene succinic Anhydride has more than 450, at least 500, at least 750, or the number-average molecular weight of even at least 800.

In some embodiments, the second alkyl replaces acylating agent and comprises the reaction product of long chain hydrocarbon and single unsaturated carboxylic acid Thing；Wherein said long chain hydrocarbon has the number-average molecular weight less than 400 or less than 280.In some embodiments, long chain hydrocarbon has 100-400, or 200-400, or 300-400, or even 300-350, or the most about 322, or 100 to being less than The number-average molecular weight of 280.In some embodiments, the second alkyl replaces acylating agent and comprises hexadecenyl succinic anhydride.

Above-mentioned functional group (i) and (ii) are by the functional groups derived from aklylene glycol.This trifunctional serves as Derived from the bridge between the low of above-mentioned acylating agent and high molecular functional group.Low and high-molecular weight agents can mix and React with bridging molecules.Reaction makes the dominant species in reactant mixture serve as the first alkyl replacement for wherein aklylene glycol Acylating agent and the second alkyl replace the product of the bridge between acylating agent.But, some two of which low-molecular-weight succinums can be there are The formation of the molecule that acid reagent connects, and the formation of the species of two of which high molecular succinic acid reagent connection.At some In embodiment, low and high-molecular weight agents can sequentially react with aklylene glycol.In this case, comprise by alkylidene The first alkyl that glycol connects replaces acylating agent and the second alkyl and replaces the species of acylating agent molecule compared with other species very Preponderate.

It is said that in general, any there is (i) two or more primary amino radical, (ii) two or more secondary amino group, (iii) at least one primary amino radical and at least one secondary amino group, (iv) at least two hydroxyl, or (v) at least one primary or secondary ammonia The compound of base and at least one hydroxyl can be used as linking group.But, in the present invention, it was discovered that use aklylene glycol, example As in some embodiments, linear alkylene glycol provides best result, the most customizable additive.

Aklylene glycol in the present invention also can be generally known as polyhydric alcohol, and includes general formula R¹(OH)_mThose Compound, wherein R¹For the bivalence being connected with OH group by carbon-oxygen bond (i.e. COH, wherein carbon is not a part for carbonyl) Organic group, and m is 2.These alcohol are aliphatic series, and in some embodiments, comprise no more than about 40, or be not more than About 20 carbon atoms.

Alcohol in the present invention includes aklylene glycol, and wherein alkylidene contains about 2-10 or 2-8 carbon atom.They May also include polyoxyalkylene diols, i.e. byThe material represented, wherein each R is independently For H or the alkyl with 1-6 carbon atom, each x independently be the integer of 2 to about 10, and m is more than 1, i.e. 2-10's is whole Number.They are such as illustrated as ethylene glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., tetraethylene glycol (TEG), dipropylene glycol, tripropylene glycol, dibutylene glycol, three fourths Glycol, and wherein alkylidene contains other aklylene glycol and the polyoxyalkylene diols of 2 to about 8 carbon atoms.It is used as For the polyoxyalkylene diols of the copolymer of different oxyalkylene units, such as ethylene glycol and propylene glycol such as 1,2-or 1,3-PD Copolymer.As the alternative thing of name " poly alkylene glycol ", they can be described as two kinds of this kind of materials of aklylene glycol and all may be used Use.This kind of material is alternatively referred to as oligomer, because the number of repetitive is typically not greater than 10.In one embodiment, Linear alkylene glycol comprises PEG, poly-(1,3-propylene glycol) or ethylene glycol and the copolymer of 1,3-propylene glycol.

In some embodiments, one or more connect compound and linear alkylene diol combination described herein.Should Other bridging agent can include having (i) two or more primary amino radical, (ii) two or more secondary amino group, (iii) extremely A few primary amino radical and at least one secondary amino group, (iv) at least two hydroxyl is, or (v) at least one primary or secondary amino and at least Any compound that can be used as linking group of one hydroxyl.In other embodiments, connect compound and comprise described herein Aklylene glycol, and be substantially free of, or even it is entirely free of other connection compound any.

In some embodiments, described additive, wherein aklylene glycol comprises and has formula HO (CH₂)_xThe two of OH Alcohol, wherein x is the integer of 2-10.In some embodiments, aklylene glycol comprises ethylene glycol.

In some embodiments, the first alkyl replaces acylating agent and comprises the reaction product of long chain hydrocarbon and single unsaturated carboxylic acid Thing；Wherein said long chain hydrocarbon has the number-average molecular weight more than 400；And second alkyl replace acylating agent comprise long chain hydrocarbon with single the most not The product of saturated carboxylic acid；Wherein said long chain hydrocarbon has the number-average molecular weight less than 400 or less than 280；And alkylidene two Alcohol comprises and has formulaGlycol, wherein each R independently be H or has 1-6 The alkyl of carbon atom, each x independently be the integer of 2 to about 10, and the integer that m is 1 to about 10.

In some embodiments, the first alkyl replaces acylating agent and comprises and have the poly-different of the number-average molecular weight more than 750 Butylene succinic anhydrides；Second alkyl replaces acylating agent and comprises hexadecenyl succinic anhydride；And aklylene glycol comprises ethylene glycol.

Emulsifier component

The present invention further provides the emulsifier component prepared by the method allowing customization emulsifying agent.Emulsifier component leads to Cross following steps to prepare: step (I): make the first alkyl replace acylating agent, the second alkyl replaces acylating agent and (the most linear) is sub- Alkyl diol reacts；Wherein the first alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein Second alkyl replaces acylating agent and comprises containing the hydrocarbyl substituent less than 20 carbon atoms；Generation comprises (i) derived from described The functional group of one alkyl replacement acylating agent and (ii) replace the additive of the functional group of acylating agent derived from described second alkyl, its Middle functional group (i) and (ii) are by the functional groups derived from described aklylene glycol；Then step (II): add described in offer Add agent and be used as emulsifier component precursor；(the most thereafter) step (III): by make described additive with neutralize component reaction and Described additive is changed into emulsifier component.Emulsifier component described herein can use any additive described herein to prepare, Wherein additive is emulsifier component precursor, then converts it into emulsifier component.

In step (II), it is provided that described additive is used as emulsifier component precursor and means emulsifier component precursor (its Alternatively referred to as additive) process as processed conventional emulsifier component.But, in the case of emulsifier component precursor, Converting it to downstream client the most final fluid mixer and/or the concrete emulsifier component of user selection, it follows step Suddenly (III) and by make described additive with neutralize component reaction and additive is changed into emulsifier component.

In some embodiments, it is provided that described additive is included in as emulsifier component precursor and is changed into by additive Use before emulsifier component, store, transport, sell, mix and/or treatment additive.In some embodiments, emulsifying agent Component precursor is after forming additive, but transports and/or stored before additive changes into emulsifier component.

The most limited for forming the neutralization component of mentioned emulsifier component.Generally, gained emulsifier component is salt Form.The mixture that emulsifier component can be neutralized component by one or more is formed.In some embodiments, single kind is used The neutralization component of class.In other embodiments, two or more are used to neutralize the mixture of component.

Alkali and the alkaline-earth metal that can find in metal base is included as the metal neutralizing component.It is used for as neutralizing component The amine preparing salt composite of the present invention includes ammonia and primary amine, secondary amine and/or azanol.In addition to ammonia, primary amine, secondary amine and azanol, The amine being used as to neutralize component also includes primary and secondary monoamine and tertiary monoamines and polyamines.Useful primary and secondary monoamine includes aliphatic series, fat Ring race and aromatic monoamine.Tertiary amines is similar to primary amine, secondary amine and azanol, except for the difference that they can be monoamine or polyamines and H-N < Or-NH₂Hydrogen atom in group is substituted by alkyl.

The feature of useful polyamines is to there are at least 2-NH in its structure₂Group, at least two > NH group or extremely A few-NH₂Group and at least one > NH group.These polyamines can be aliphatic, alicyclic, aromatics or heterocycle, including fat The substituted aromatics of race, aliphatic series substituted substituted heterocycle alicyclic, aliphatic, alicyclic substituted aliphatic series, alicyclic substituted virtue Substituted alicyclic, the substituted heterocycle of aromatics of race, alicyclic substituted heterocycle, the substituted aliphatic series of aromatics, aromatics, heterocyclic replacement Aliphatic series, heterocyclic substituted alicyclic and heterocyclic substituted aromatic amine.These amine can be saturated or undersaturated.If Being undersaturated, amine is preferably unsaturated without acetylene.These amine also can comprise substituents or group, and condition is these groups Do not interfere significantly with reaction.This kind of substituents or group include lower level alkoxyl, lower level alkyl, sulfydryl, nitro, and Spacer groups, such as-O-or-S-.Polyamines includes being similar to aliphatic series hereinafter described, alicyclic and the aliphatic series of aromatic monoamine, fat Ring race and aromatic polyamine, except for the difference that its structure exists at least one other > NH or-NH₂Group.

Aliphatic monoamine includes monoester race and two aliphatic substituted amine, wherein aliphatic group can be saturated or undersaturated and For straight or branched.Therefore, they are primary or secondary aliphatic amine.This kind of amine include the most single-and di-alkyl replace amine, list-and Two-alkenyl substituted amine, and there is a N-alkenyl group and the amine etc. of a N-alkyl substituent.In these aliphatic monoamines The total number of carbon atoms preferably more than about 40, usually no more than about 20 carbon atoms.The instantiation of this kind of monoamine include ethamine, Diethylamine, n-butylamine, two-n-butylamine, allylamine, isobutyl amine, coco amine, stearylamine, lauryl amine, methyl lauryl amine, oleyl amine, N- Methyl-octylame, lauryl amine, 18-amine. etc..Alicyclic substituted aliphatic amine, the substituted aliphatic amine of aromatics and heterocyclic substituted fat The example of race's amine includes 2-(cyclohexyl)-ethamine, benzylamine, phenylethylamine and 3-(furyl propyl group) amine.

Alicyclic monoamine is those monoamines, wherein has one and is directly connected with amine nitrogen by the carbon atom in cyclic rings structure The cycloaliphatic substituents connect.The example of alicyclic monoamine include cyclohexylamine, Aminocyclopentane, hexamethylene enamine, cyclopentamine, N-ethyl- Cyclohexylamine, hexanamine etc..Aliphatic series replaces, aromatics replaces and the example of heterocyclic substituted alicyclic monoamine includes that propyl group replaces Cyclohexylamine, the substituted Aminocyclopentane of phenyl and the substituted cyclohexylamine of pyranose.

Aromatic monoamine includes those monoamines, and wherein the carbon atom of aromatic ring structure is directly connected to amino nitrogen.Aromatic ring is usually Monokaryon aromatic ring (i.e. derived from the one of benzene), but can include fused aromatic rings, especially derived from those of naphthalene.The reality of aromatic monoamine Example includes aniline, two (p-aminomethyl phenyl) amine, naphthylamines, N-(normal-butyl) aniline etc..Aliphatic series replacement, alicyclic replacement and heterocycle The example of the substituted aromatic monoamine of race includes p-phenetidine, replaces lauryl amine, the substituted naphthylamines of cyclohexyl and thienyl Aniline.

It is used as heterocyclic polyamines.As used herein, term " heterocyclic polyamines " is intended in description heterocycle comprise at least 2 primary Amino, at least 2 secondary amino groups or every kind at least one and at least one nitrogen is as those heterocyclic amines heteroatomic.If it is miscellaneous Ring polyamines exists at least 2 primary amine groups, at least 2 secondary amino groups or every kind at least one, the miscellaneous atom N in ring can be uncle Amino nitrogen；That is, not there is the one of the hydrogen being directly connected to ring nitrogen.Miscellaneous atom N can be one in secondary amino group；I.e. it is permissible For having the ring nitrogen of the hydrogen being directly connected to it.Heterocyclic amine can be saturated or undersaturated, and can comprise various substituent group, Such as nitro, alkoxyl, alkyl thiol, alkyl, thiazolinyl, aryl, alkaryl or aralkyl substituents.It is said that in general, substituent group The sum of middle carbon atom is no more than about 20.Heterocyclic amine can comprise the hetero atom being different from nitrogen, especially oxygen and sulfur.Obviously, they More than one nitrogen heteroatom can be comprised.Preferably 5-and 6-element heterocycle.

Wherein suitably heterocyclic polyamines be aziridine, azetidine, oxazolidine (azolidine), four-and two-pyridinium hydroxide, Pyrroles, indole, piperidines, imidazoles, two-and imidazolidine, piperazine, iso-indoles, purine, morpholine, thiomorpholine, N-aminoalkyl Quinoline, N-aminoalkyl thiomorpholine, N-aminoalkyl piperazine, N, N'-Diaminoalkyl piperazine, azepines, azocine, azo Rather, azecine and above respective four-, two-and perhydro derivant and these heterocyclic amines in two or more mixing Thing.Useful heterocyclic polyamines is saturated 5-and the 6 element heterocycle polyamines only comprising nitrogen, oxygen and/or sulfur in heterocycle, especially piperidines, Piperazine, thiomorpholine, morpholine, pyrrolidine etc..Generally, aminoalkyl substituent group takes on the nitrogen-atoms of a part forming heterocycle Generation.The instantiation of this kind of heterocyclic amine includes N-aminoethyl piperazine and N, N'-diamino ethyl piperazine.

It is used as hydrazine and replaces hydrazine.May be present in the substituent group on hydrazine and include alkyl, thiazolinyl, aryl, aralkyl, alkane virtue Base etc..Generally, substituent group is alkyl, especially lower level alkyl, phenyl and substituted-phenyl, and such as lower level alkoxyl is substituted Phenyl or the substituted phenyl of lower level alkyl.The instantiation replacing hydrazine is methyl hydrazine, N, N-dimethylhydrazine, N, N'-dimethyl Hydrazine, phenyl hydrazine, N-phenyl-N'-ethyl hydrazine, N-(p-tolyl)-N'-(normal-butyl)-hydrazine, N-(p-nitrobenzophenone)-hydrazine, N- (p-nitrobenzophenone)-N-methyl hydrazine, N, N'-bis--(p-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexyl hydrazine etc..

Another histamine be applicable to the present invention is branched polyalkylene polyamine.Branched polyalkylene polyamine is that polyalkylene is many Amine, wherein branched group is to comprise at least one nitrogen average to combine the side of every 9 amino unit being present on main chain of amino alkylidenyl Chain；Such as unit on 1-4 every 9 main chains of this kind of side chain, but preferably 1 every 9 backbone units of side chain.Therefore, these polyamines bags Containing at least 3 primary amino radicals and at least 1 tertiary amino.These amine can be by formula Representing, wherein R is alkylidene, such as ethylidene, propylidene, butylidene and other homologue (straight chain and branched) etc., but preferably Ethylidene；And x, y and z are integer；X is about 4 to about 24 or more, the integer of preferably from about 6 to about 18；Y is 1 to about 6 or more, preferably The integer of 1 to about 3；And z is 0 to about 6, the integer of preferably 0 to about 1.X and y unit can be order, or orderly or random Distribution.Useful this polyamines of one class includes formula Those, wherein n is 1 to about 20 or more, the integer of preferably 1 to about 3, and R is preferably ethylidene, but can be propylidene, Butylidene etc. (straight chain or branched).By quoting United States Patent (USP) Nos.3,200,106 and 3,259,578 about described polyamines Disclosure be incorporated herein in.

Suitably polyamines also includes polyoxyalkylene, such as polyoxyalkylene diamines and polyoxyalkylene triamine, and it has about 200 to about 4000, the mean molecule quantity of preferably from about 400-2000.The example of these polyoxyalkylene includes by formula NH₂-alkylene Base-(O-alkylidene)_m-NH₂Those amine represented, wherein m has about 3 to about 70, the value of preferably from about 10 to about 35.R-[-alkylene Base-(O-alkylidene)_n-NH₂]_3-6, wherein n is the number of 1 to about 40, and condition is all n' and about 3 to about 70, normally about 6 to About 35, and R is to have at most about 10 carbon atoms and have the multivalence saturated hydrocarbyl of quantivalence of about 3 to about 6.Alkylidene is permissible For straight or branched, and comprise 1 to about 7 carbon atom, usual 1 to about 4 carbon atom.Each alkylene being present in above formula Base can be identical or different.

Useful polyoxyalkylene includes polyethylene glycol oxide and polyoxypropylene diamine and has about 200 to about 2000 The polypropylene oxide triamine of mean molecule quantity.Polyoxyalkylene is commercially available with trade name " Jeffamine " by Texaco.By drawing It is attached to herein about the disclosure of this kind of polyoxyalkylene with by United States Patent (USP) Nos.3,804,763 and 3,948,800 In.

Useful polyamines is alkylene polyamine, including polyalkylene polyamine as described in greater detail below.Alkylidene is many Amine includes meeting formula (R) (R) N-(alkylidene-N (R))_nThose of-R', wherein n is 1 to about 10, preferably 1 to about 7；Each R and R' independently be hydrogen atom, has at most about 700 carbon atoms, preferably up to about 100 carbon atoms, more preferably up to about 50 The alkyl of carbon atom, more preferably up to about 30 carbon atoms or hydroxyl substituted hydrocarbon radical, condition is at least one R and at least one R' For hydrogen；And " alkylidene " has about 1 to about 18 carbon atom, preferably 1 to about 4 carbon atom, preferred alkylidene is ethylidene Or propylidene.Useful alkylene polyamine is that wherein each R and each R' are those of hydrogen, ethylene and ethylene Mixture be particularly preferred.This kind of alkylene polyamine includes methylene polyamines, ethylene, butylidene polyamines, Asia third Quito amine, pentylidene polyamines, hexylidene polyamines, heptamethylene polyamines etc..Also include the relatively higher homologue of this kind of amine and relevant ammonia The substituted piperazine of base alkyl.

Useful alkylene polyamine include ethylenediamine, diethylenetriamines, trien, tetren, five Ethylidene hexamine, propane diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, eight methylene diamine, two (seven Asias Methyl) triamine, tri propylidene tetramine, tetren, trimethylene diamine, penten, two (trimethylenes) three Double (2-amino-ethyl) piperazines of amine, N-(2-amino-ethyl) piperazine, 1,4-etc..Two or more by above-mentioned alkylene amines The relatively higher homologue planting condensation and obtain is used as the amine in the present invention, such as any two or more kinds of mixing in above-mentioned polyamines Thing.

Ethylene, such as those described above be described in detail in title " Diamines and Higher Amines, Aliphatic ", The Encyclopedia of Chemical Technology, the 3rd edition, Kirk-Othmer, volume 7, the 580-602 page, Wiley-Interscience Publication, John Wiley and Sons, in 1979, by quoting These pages are incorporated herein in.This compounds is most conveniently reacted with ammonia by alkylidene chlorine or passes through ethylene imine and open Cyclization reagent such as ammonia etc. react and prepare.These reactions result in somewhat complicated alkylene polyamine mixture, including ring-type contracting Close product such as piperazine.

Alkoxylate alkylene polyamine (such as N, N-1 (diethanol)-ethylenediamine) can be used.This kind of polyamines can be by making Asia Alkylamine (such as ethylenediamine) has the oxyalkylene of 2 to about 20 carbon (such as ethylene oxide, oxidation 18 carbon with one or more Alkene) react and prepare.It is used as the oxyalkylene-alkanolamine product being similar to, such as by making above-mentioned primary, secondary or uncle Alkanolamine is prepared with 1:1 or 1:2 molar ratio reaction with ethylene, propylene or more senior epoxide.This kind of for carrying out The reactant of reaction is well known by persons skilled in the art than with temperature.

The instantiation of alkoxylate alkylene polyamine include N-(2-ethoxy) ethylenediamine, N, N-double (2-ethoxy)- Ethylenediamine, 1-(2-ethoxy) piperazine, list (hydroxypropyl) substituted diethylenetriamines, two (hydroxypropyl) substituted four ethylidene Five amine, N-(3-hydroxyl butyl) tetra-methylenedimine etc..Above-mentioned hydroxy alkylidene polyamines is made to be condensed by amino or by hydroxyl And the relatively higher homologue obtained also is useful.Produce relatively higher amines by amino condensation with the removing of ammonia, and pass through Hydroxyl condensation produces the product containing ehter bond with the removing of water.In above-mentioned polyamines, any two or more kinds of mixture are also It is useful.

Useful azanol can be primary or secondary amine.They can also be tertiary amine, and condition is that described tertiary amine also comprises at least two Individual hydroxyl.These azanols comprise at least 2 > NH group, at least 2-NH₂Group, at least one-OH group and at least one > NH or-NH₂Group, or at least 2-OH groups.Term " azanol " and " amino alcohol " describe similar compound, therefore may be used It is used interchangeably.

Azanol can be uncle or sec alkanol amine or its mixture.This kind of amine can be represented by formula (H) (R) N-R'-OH, its Middle R is to have the alkyl of 1 to about 8 carbon atom or have the hydroxyl substituted hydrocarbon radical of 2 to about 8 carbon atoms, and R' is for having The bivalent hydrocarbon radical of about 2 to about 18 carbon atoms.Group-R'-OH in this formula represents hydroxyl substituted hydrocarbon radical.R' can be aliphatic series, Alicyclic or aromatic group.Generally, R' is aliphatic straight chain or sub-branched alkyl, such as ethylidene, propylene, 1,2-Aden Base, 1,2-alkylene octadecyl etc..Generally, R is the lower level alkyl with at most 7 carbon atoms.Primary or secondary alkanolamine can wrap Containing slightly greater R and R' group, and may comprise up to about 40 carbon atoms.

Azanol can also be ether N-(hydroxyl substituted hydrocarbon radical) amine.These are that the hydroxyl of above-mentioned primary and secondary alkanolamine replaces poly- (oxyl) analog (these analog also include hydroxyl substituted oxyalkylene analog).This kind of N-(hydroxyl substituted hydrocarbon radical) amine Can prepare conveniently by epoxide reacts with above-mentioned amine, and can be by formula H₂N-R'-OH and (H) (R) N-R'-OH table Showing, wherein x is about the number of 2 to about 15, and R and R' is as described above.

It is used as the polyamine analogs of these azanols, particularly alkoxylate alkylene polyamine (such as N, N-(diethyl Alcohol)-ethylenediamine).This kind of polyamines can pass through alkylene amines (such as ethylenediamine) and have the oxygen of 2 to about 20 carbon with one or more Change alkene (such as ethylene oxide, oxidation vaccenic acid) reaction and prepare.Oxyalkylene-alkanolamine the reaction being used as being similar to is produced Thing, such as, pass through above-mentioned uncle or sec alkanol amine with ethylene oxide, propylene oxide or more senior epoxide with 1:1 or 1:2 Molar ratio reaction and the product prepared.It is known to those skilled in the art for carrying out reactant ratio and the temperature of this kind of reaction 's.

The instantiation of alkoxylate alkylene polyamine includes double (2-ethoxy) second of N-(2-ethoxy) ethylenediamine, N, N- Diamidogen, 1-(2-ethoxy) piperazine, list (hydroxypropyl) substituted diethylenetriamines, substituted four ethylidene five of two (hydroxypropyls) Amine, N-(3-hydroxyl butyl)-tetra-methylenedimine etc..By amino or by hydroxyl make above-mentioned hydroxy alkylidene polyamines be condensed and The relatively higher homologue obtained also is useful.Produce relatively higher amines by amino condensation with the removing of ammonia, and pass through hydroxyl Base condensation produces the product containing ehter bond with the removing of water.Any two or more kinds of mixing in above-mentioned monoamine or polyamines Compound is also useful.

The example of N-(hydroxyl substituted hydrocarbon radical) amine includes single-, two-and triethanolamine, diethyl ethylene diamine, two-(3-hydroxypropyl Base) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine, N, N-bis--(2-hydroxypropyl) amine, N-(2-ethoxy) morpholine and Thip-analogues, N-(2-ethoxy) cyclohexylamine, N-3-hydroxycyclopent amine, o-, m-and para-aminophenol, N-(ethoxy) Piperazine, N, N'-bis-(ethoxy) piperazine etc..

It addition, azanol is United States Patent (USP) No.3, by general formula R in 576,743^a-NH₂The hydroxyl described replaces primary amine, wherein R^a For comprising the monovalent organic groups of at least one alcohols hydroxyl.R^aIn the total number of carbon atoms preferably more than about 20.Comprise total It is useful that the hydroxyl of at most about 10 carbon atoms replaces aliphatic primary amine.Wherein only exist an amino (i.e. primary amino radical) and have One replaces alkanol primary amine containing the alkyl substituent of at most about 10 carbon atoms and the polyhydroxy of at most about 6 hydroxyls is to have ?.These alkanol primary amine correspond to R^a-NH₂, wherein R^aAlkyl is replaced for list-or polyhydroxy.Hydroxyl replaces the concrete of primary amine Example include 2-amino-n-butyl alcohol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propylene glycol, 2-amino-2-ethyl-1,3-propylene glycol, N-(β-hydroxypropyl)- N'-(beta-aminoethyl)-piperazine, three-(methylol) aminomethanes (also referred to as trishydroxymethylaminomethane), 2-amino-1-fourth Alcohol, ethanolamine, β-(beta-hydroxy ethyoxyl)-ethamine, glycosamine, glusoamine, 4-amino-3-hydroxy-3-methyl-1-butylene (it can be reacted by oxidizing isoprene and ammonia according to program as known in the art and prepare), N-3-(aminopropyl)-4- (2-ethoxy) piperidines, 2-amino-6-methyl-6-enanthol, 5-amino-1-amylalcohol, N-(beta-hydroxyethyl) 1,3-diaminopropanes, 1,3-diaminourea-2-hydroxy propane, N-(beta-hydroxy ethoxyethyl group) ethylenediamine, trishydroxymethylaminomethane etc..By quoting United States Patent (USP) No.3,576,743 is incorporated herein in.

The hydroxyalkyl alkylene polyamine on nitrogen-atoms with one or more hydroxyalkyl substituted groups is also useful.Useful The substituted alkylene polyamine of hydroxyalkyl includes that wherein hydroxyalkyl is lower level hydroxyalkyl, i.e. has the hydroxyl alkane less than 8 carbon atoms Those of base.The example of this kind of hydroxyalkyl substituted polyamines includes double (2-ethoxy) second two of N-(2-ethoxy) ethylenediamine, N, N- Amine, 1-(2-ethoxy)-piperazine, the single substituted diethylenetriamines of hydroxypropyl, the substituted tetren of dihydroxypropyl, N- (3-hydroxyl butyl) tetra-methylenedimine etc..The condensation of above-mentioned hydroxy alkylidene polyamines is made to obtain by amino or by hydroxyl Also it is useful compared with higher homologue.Produce relatively higher amines by amino condensation with the removing of ammonia, accompanied by hydroxyl condensation The product containing ehter bond is produced with the removing of water.

Useful tertiary amine includes aliphatic series, alicyclic, aromatics or heterocycle, including aliphatic substituted aromatics, aliphatic series substituted Substituted heterocycle alicyclic, aliphatic, alicyclic substituted aliphatic series, alicyclic substituted aromatics, alicyclic substituted heterocycle, aromatics Substituted aliphatic series, aromatics substituted alicyclic, the substituted heterocycle of aromatics, heterocyclic substituted aliphatic series, heterocyclic substituted alicyclic ring Race and heterocyclic substituted aromatic amine.These tertiary amines can be saturated or undersaturated.If undersaturated, then amine is the most not Unsaturated containing acetylene.Tertiary amine also can comprise substituents or group, and condition is that these groups are inconspicuous interferes reaction.This kind of Substituents or group include lower level alkoxyl, lower level alkyl, sulfydryl, nitro and spacer groups, such as-O-and- S-is (such as, as in this kind of group, such as-CH₂CH₂-X-CH₂CH₂-, wherein X is-O-or-S-).

Monoamine can be by formula N (R¹)(R²)(R³) represent, wherein R¹、R²And R³For identical or different alkyl.Preferably, R¹、R²With R³Independently be the alkyl with 1 to about 20 carbon atom.

The example of useful tertiary amine includes trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, monomethyl diethylamine, single ethyl diformazan Amine, dimethyl propylamine, dimethyl butylamine, dimethylamylamine, dimethylhexylamine, dimethyl heptyl amice, dimethyl octylame, dimethyl nonyl Amine, dimethyldodecyl amide, dimethylaniline, N, N-dioctyl-1-octylame, N, N-bis--dodecyl-1-lauryl amine, three coco amine, The methyl dihydrogenated tallow amine of three hydrogenated tallow amines, N-, N, N-dimethyl-1-lauryl amine, N, N-dimethyl-1-tetradecy lamine, N, N- Dimethyl-1-cetylamine, N, N-dimethyl-1-18-amine., N, N-dimethylcocoamine, N, N-dimethyl Semen sojae atricolor amine, N, N-bis- Hydrogenated tallow dimethyl amine etc..

Useful tertiary alkanolamine is represented by formula (R) (R) N R'OH, and wherein each R independently be and has 1 to about 8 carbon The alkyl of atom or there is the hydroxyl substituted hydrocarbon radical of 2 to about 8 carbon atoms, and R' is to have about 2 to about 18 carbon atoms Bivalent hydrocarbon radical.Group R'OH in this formula represents hydroxyl substituted hydrocarbon radical.R' can be aliphatic, alicyclic or aromatic group.Logical Often, R' is aliphatic straight chain or sub-branched alkyl, such as ethylidene, propylene, 1,2-butylidene, 1,2-alkylene octadecyl Deng.If two R group are present in identical molecule, then they can pass through carbon-to-carbon direct bond or pass through hetero atom (such as Oxygen, nitrogen or sulfur) connect to form 5-, 6-, 7-or 8 Yuans ring structures.The example of this kind of heterocyclic amine includes N-(hydroxyl lower level alkane Base)-morpholine ,-thiomorpholine ,-piperidines ,-Oxazolidine ,-Thiazolidine etc..But, generally, each R is former for having at most 7 carbon The lower level alkyl of son.Azanol can also be ether N-(hydroxyl substituted hydrocarbon radical) amine.These be above-mentioned azanol hydroxyl replace many- (oxyl) analog (these analog also include that hydroxyl replaces oxyalkylene analog).Amine can for this kind of N-(hydroxyl substituted hydrocarbon radical) Prepare conveniently by epoxide reacts with above-mentioned amine, and can be by formula (R) (R) N-(R'-O)_xH represents, wherein x is about The number of 2 to about 15, and R and R' is as described above.

Useful polyamines includes above-mentioned alkylene polyamine and has one or do not have the hydrogen that is connected with nitrogen-atoms Alkylene polyamine.Therefore, the alkylene polyamine being used as to neutralize component includes meeting formula (R) (R) N-(R'-O)_xThose of-H, its Middle x is 1 to about 10,1 to about 7；Each R independently be hydrogen atom, has at most about 700 carbon atoms, preferably up to about 100 Carbon atom, more preferably up to about 50 carbon atoms, the alkyl of more preferably up to about 30 carbon atoms or hydroxyl substituted hydrocarbon radical；And " alkylidene " has about 1 to about 18 carbon atom, preferably 1 to about 4 carbon atom, and preferred alkylidene is ethylidene or sub-third Base.

It is used as to neutralize the alkali of component and alkaline-earth metal can be any alkali or alkaline-earth metal.Preferred as alkali.Particularly preferably Sodium and potassium.Useful alkali and alkaline earth metal compound include such as oxide, hydroxide and carbonate.Particularly preferably hydroxide Sodium and potassium hydroxide.

The present invention further provides the method preparing described emulsifier component.Described method includes step: step (I): make First alkyl replaces acylating agent, the second alkyl replaces acylating agent and the reaction of (the most linear) aklylene glycol；Wherein the first alkyl Replace acylating agent and comprise the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein second alkyl replace acylating agent comprise containing Hydrocarbyl substituent less than 20 carbon atoms；Generation comprise (i) derived from described first alkyl replace acylating agent functional group and (ii) replace the additive of the functional group of acylating agent derived from described second alkyl, wherein functional group (i) and (ii) are by derivative Functional groups from described aklylene glycol；Step (II): provide described additive to be used as emulsifier component precursor；Step (III): by making described additive, with neutralizing component reaction, described additive be changed into emulsifier component.Any of the above described breast Agent component can be prepared by the method.

In some embodiments, the method can be described as first making the first alkyl replace acylating agent and the second alkyl replaces Acylating agent aklylene glycol is reacted to form additive, provides thereafter above-mentioned additive to final use, and it then can be by making Described intermediate uses additive to form the emulsifier component that he/her selects with neutralizing component reaction to form required salt.

Can become through wide scope for preparing the ratio of the reactant of additive (and/or emulsifier component precursor) emulsifier component Change.Generally, for each acylating agent of every equivalent, use at least about 1 equivalent aklylene glycol.Every equivalent component is acylated Agent, uses about 0.1 to about 2 equivalent or more neutralization component respectively.The upper limit of aklylene glycol is for every equivalent acylating agent, About 2 equivalent aklylene glycols.It is said that in general, the equivalent proportion of acylating agent is about 0.5 to about 2, preferably from about 1:1.Preferably reactant Amount respectively neutralize component for acylating agent about 2 equivalent aklylene glycol each for every equivalent and about 0.1 to about 2 equivalent.

The equivalents of acylating agent depend on each present in carboxylic-acid functional sum.At the equivalents measuring each acylating agent In, not including can not be as those carboxyl-functional of carboxylic acid acylating agent's reaction.It is however generally that, for each carboxyl, this There is monovalent acylating agent in a little acylating agents.Such as, the acid anhydride reacted derived from 1 olefin polymer and 1 mol maleic anhydride Middle existence 2 equivalent.Routine techniques is readily used for measuring the number (such as acid number, saponification number) of carboxyl-functional, therefore, each acylating agent Equivalents can easily be measured by those skilled in the art.

The equivalent of polyamines is the molecular weight sum divided by the nitrogen being present in molecule of polyamines, wherein calculates tertiary amino.Cause This, ethylenediamine has the equivalent of the half equal to its molecular weight；Diethylenetriamines has 1/3rd equal to its molecular weight Equivalent.The equivalent of the commercial mixture of polyalkylene polyamine can be by the atomic weight (14) of nitrogen divided by %N contained in polyamines And measure；Therefore, the polyamine mixture of the %N with 34 has the equivalent of 41.2.The equivalent of ammonia or monoamine is its molecular weight.

The equivalent of polyhydric alcohol is its molecular weight sum divided by the hydroxyl being present in molecule.Therefore, the equivalent of ethylene glycol Half for its molecular weight.

The equivalent of hydroxyl is its molecular weight sum divided by the nitrogen groups being present in molecule.Therefore, dimethylethanolamine There is the equivalent equal to its molecular weight；Ethanolamine also has the equivalent equal to its molecular weight.

The equivalent of alkali or alkaline-earth metal is its molecular weight.The equivalent of alkali or alkaline earth metal compound is that its molecular weight is divided by depositing The alkali being in molecule or the number of alkaline earth metal atom.

Acylating agent can form technology according to conventional ester and/or amide and react with aklylene glycol.This is usually directed to acylated Agent is optionally heated with aklylene glycol in the presence of liquids in general, substantially inert organic liquid solvent/diluent.

Additive and the reaction neutralized between component use routine techniques to carry out under salt-forming condition.Generally, by each component Mix and optionally at liquids in general, be heated to about 20 DEG C in the presence of substantially inert organic liquid solvent/diluent extremely There is the temperature of the reactive component of this temperature minimum and/or the decomposition temperature of product until forming required product.

The present invention further provides an above-mentioned additive part as the method customizing emulsifier component in the composition Method and/or purposes.The method and/or purposes include step: step (I): by make the first alkyl replace acylating agent, second Alkyl replaces acylating agent and the reaction of (the most linear) aklylene glycol and prepares additive；Wherein the first alkyl replaces acylating agent bag Containing the hydrocarbyl substituent containing at least 20 carbon atoms；And wherein the second alkyl replacement acylating agent comprises containing former less than 20 carbon The hydrocarbyl substituent of son；Generation comprises (i) and replaces the functional group of acylating agent with (ii) derived from institute derived from described first alkyl Stating the additive that the second alkyl replaces the functional group of acylating agent, wherein functional group (i) and (ii) are by derived from described alkylidene The functional groups of glycol；Step (II): described additive is fed in the compositions needing emulsifier component；Step (III): By making described additive, with neutralizing component reaction, the described additive in described compositions be changed into emulsifier component；Produce Raw customization emulsifier component.

Functional fluid composition

Emulsion components described herein can be used for preparation official energy compositions, such as, comprise continuous aqueous phase, discontinuous organic facies, breast Change compositions and relate to the O/w emulsion of additive of the function performed by functional fluid.Discontinuous organic facies is preferably with base Gross weight in emulsion is at least about 1 weight %, more preferably from about 1% to about 50 weight %, more preferably from about 1% to about 20 weight % Content exist.Continuously aqueous phase is preferably about the content of 99 weight % with the gross weight based on described emulsion, and more preferably from about 50% To about 99 weight %, the content of more preferably from about 80% to about 99 weight % exists.Salt composite of the present invention is preferably with based on organic The gross weight of phase is about 1% to about 100 weight %, and the content of more preferably from about 20% to about 80 weight % exists.When emulsifying agent is During 100% organic facies, emulsifying agent is for forming its emulsion in aqueous phase, and organic facies is emulsifying agent.

Oil can include most liquid hydrocarbon, such as alkane, alkene, cycloalkane, aromatics, saturated or unsaturated hydrocarbons.General and Speech, oil be at room temperature be liquid the emulsifiable hydrocarbon of water-insoluble.The oil from multiple source can be used, including natural and synthesis Oil and mixture thereof.

Natural oil includes animal oil and vegetable oil (such as Oleum Ricini, Adeps Sus domestica), and alkane, cycloalkane or combination chain The solvent refined of alkane-naphthenic type or acid refined mineral oil.Oil derived from coal or shale is also useful.Artificial oil includes Hydrocarbon ils and the hydrocarbon ils of halogen substiuted, such as polymerization and copolyalkenamer, such as polybutene, polypropylene, propylene-isobutylene copolymers, Chlorinated polybutylenes；Alkylbenzene, such as detergent alkylate, Tetradecylbenzene, dinonyl benzene, two-(2-ethylhexyl) benzene etc..

Spendable another kind of suitable artificial oil includes dicarboxylic acids (such as phthalic acid, succinic acid, alkyl Acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, Alkenyl malonic etc.) with multiple alcohol (such as butanol, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, hexanediol, monoalkyl ethers of diethylene glycol, the third two Alcohol, tetramethylolmethane etc.) ester.The instantiation of these esters includes dibutyl adipate, decanedioic acid two (2-ethylhexyl) ester, richness Horse acid di-n-hexyl ester, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, neighbour Phthalic acid didecyl, decanedioic acid two-eicosyl ester, the 2-ethylhexyl diester of linoleic acid dimer, by 1 mole of last of the ten Heavenly stems two The complex ester etc. that acid is reacted with 2 moles of tetraethylene glycol (TEG) and 2 moles of 2 ethyl hexanoic acids and formed.

Ester as artificial oil also includes by C₅-C₁₂Monocarboxylic acid and polyhydric alcohol and polyol ethers such as neopentyl glycol, three hydroxyl first Those of the preparation such as base propane, tetramethylolmethane, dipentaerythritol, tripentaerythritol.

Silicon-based oil, the most poly-alkyl-, poly-aryl-, poly-alkoxyl or poly-aryloxy group-silicone oil and silicic acid ester oil constitutes Another kind of useful oil.These include tetraethyl orthosilicate, silicic acid four isopropyl ester, silicic acid four-(2-ethylhexyl) ester, silicic acid four- (4-methylhexyl) ester, silicic acid four (p-tert-butyl-phenyl) ester, hexyl-(4-methyl-2-amoxy)-two-siloxanes, poly-(first Base)-siloxanes, poly-(aminomethyl phenyl)-siloxanes etc..Other useful artificial oil includes liquid ester (the such as phosphoric acid of phosphoric acid Front three phenyl ester, trioctyl phosphate, the diethyl ester etc. of decane phosphonic acids), PolyTHF etc..

The non-refine of above-disclosed type, refine and refined oil (with each mixture the most each other) again can be used.Not essence Refine oil as those that by naturally occurring or synthetic source obtain direct without further purification processes.Such as, directly by retorting operation The shale oil that obtains, the oil directly obtained by distillation or the ester oil directly obtained by esterification process and without further Reason and use for non-refined oil.Refined oil is similar to non-refined oil, except for the difference that by them in one or more purification step In process to improve one or more performances further.Many this kind of purification techniques are well known by persons skilled in the art, such as Solvent extraction, distillation, acid or alkali extraction, filtration, diafiltration etc..Refined oil is by will be similar to that the method obtaining refined oil is applied again Obtain in the refined oil having been used to service.This kind of refined oil more also referred to as regeneration or reprocessed oils, and typically also through It is intended to remove the technology processing of useless additive and oil decomposition product.

The example of useful oil includes the white that can be obtained with trade name KAYDOL by Witco Chemical Company Mineral oil；The slab oil that can be obtained with trade name ONDINA by Shell；With can be by Pennzoil with trade name N-750-HT The mineral oil obtained.

Optionally other material can be attached in the present composition.Typical final composition can comprise lubricant, resist Grinding agent, dispersant, corrosion inhibitor, other surfactant etc..Emulsion of the present invention is that storage is stable, and this means that they show Go out at least 6 months, the bin stability of usual 1 year or more long.

The method for optimizing preparing emulsion of the present invention includes step: emulsifying agent is mixed by (1) with oil phase, (2) by additive with Oil phase mixes, and (3) stirring oil phase and aqueous phase are to form O/w emulsion.Oil and the mixing of appropriate addn can any suitably Mixing apparatus is carried out.Can be used for mixing to prepare these water oil and aqueous phase by low or high shear mixing any sort equipment Bag fat liquor.

Unless otherwise noted, the amount of each chemical constituent described is expressed as eliminating and generally may be present in commercial materials Any solvent or flux oil, i.e. based on active chemistry.But, unless otherwise noted, each chemical substance mentioned above Or compositions should be understood to contain isomer, by-product, derivant and being generally understood that be present in commerical grade other this The commercial grade material of class material.

As used herein, term " hydrocarbyl substituent " or " alkyl " make with its conventional meaning well known to those skilled in the art With.Specifically, it refers to have the carbon atom being connected directly between on molecule remainder and mainly have the group of hydrocarbon character.Hydrocarbon The example of base includes:

-hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituent group, and virtue Race-, aliphatic series-and alicyclic substituted aromatic substituent, and its medium ring completes (such as two by another part of this molecule Substituent group forms ring together) cyclic substituents；

-substituted hydrocarbon substituent, i.e. contains the nonhydrocarbon of the main hydrocarbon character the most not changing substituent group Group (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl (sulfoxy) substituent group)；

-miscellaneous substituent group, the most in the context of the present invention, at the ring being made up of carbon atom while having main hydrocarbon character Or chain contains the substituent group being different from carbon, and include substituent group such as pyridine radicals, furyl, thienyl and imidazole radicals.Hetero atom Including sulfur, oxygen and nitrogen.Generally, for every 10 carbon atoms, no more than 2 in alkyl, or not more than 1 nonhydrocarbon Substituent group；As selection, alkyl can not exist substituents.

More known above-mentioned materials may interact in final preparaton so that the component of final preparaton may be with Originally those added are different.Such as, to can migrate to other of other molecule acid or cloudy for metal ion (such as detersive) Ion position.The product being consequently formed, may not allow including the product through being formed with its intended use use present composition Easily describe.But, all such is improved and product is included within the scope of the present invention；The present invention includes by by above-mentioned The compositions that component mixes and prepares.

Refer to following nonlimiting examples and be more fully understood that the present invention.

Embodiment

Prepare several embodiment to prove the present invention.

Comparative example 1

Preformed emulsifying salt agent component is highly reactive poly-different by adding the 1000Mn of 33.33pbw in reaction vessel Butylene succinic anhydrides, 28.41pbw hexadecenyl succinic anhydride and 23.15pbw ISO 22 mineral oil and prepare.By mixture It is heated to 99 DEG C under nitrogen cleans.Then 3.87pbw ethylene glycol is slowly added in reaction vessel and by gained mixture Keep 4 hours at about 99 DEG C.Before adding 11.24pbw dimethylethanolamine, reactant mixture is cooled to 68 DEG C.Below Reaction is maintained at less than 93 DEG C.Then amine salt product is cooled to ambient temperature.

The embodiment of the present invention 2

Non-salinization ester acids emulsifiers component is prepared in the lab.In reaction vessel, by 40.45 weight portions (pbw) 1000 number-average molecular weights (Mn) highly reactive polyisobutylene succinic anhydride, 34.83pbw hexadecenyl succinic anhydride and 20.00pbw ISO 22 mineral oil is also heated to 135 DEG C under nitrogen cleans.Then by 4.72pbw ethylene glycol lentamente Add in reaction vessel and gained mixture is kept 4 hours at about 135 DEG C.Then non-for gained salinization product is cooled to ring Border temperature is also collected.

Use comparative example 1 and the additive of the embodiment of the present invention 2, prepare one group of additive bag (embodiment A-1 to G-1), It is subsequently used for preparing emulsion sample (embodiment A-2 to G-2) to assess the emulsion property of additive.Joining of the additive bag of test Side is summarized in following table, and the most unless otherwise indicated, all values is percetage by weight.Other additive used in each embodiment For identical and include low HLB emulsifier, soap, corrosion inhibitor and Biocide.

Table 1: additive bag

All additive bags described in upper table are by mixing composition and along with gentle agitation is by mixture with listed order Be heated to 50 DEG C about 1 hour and prepare.

Then each additive is used to pack standby emulsion.Each emulsion sample makes the concentration of additive bag exist by adding water Each emulsion sample is identical (5 weight %) and prepares.Each emulsion sample is strongly shaken in graduated cylinder, then makes It stands 24 hours, then by the amount of visible frost in the amount of visible oil in sample or percent and sample or percent And evaluate stability.Visible oil and frost are the fewest, and emulsion is the most stable, so additive bag is the most effective, so emulsifying agent additive The most effective.If it has 0% or trace amount and not more than 0.5% white after 24 hours, then preparaton is considered as to connect It is subject to.

Also some emulsion sample are carried out industrial foam test.In this experiment, 200ml emulsion embodiment is put into In Sunbeam cake mixer and high speed shear 300 seconds.Then after closing mixer, record the time of foam collapse, with Second represent, and to record this time be lather collapse and/or collapse time.The time of foam collapse is the shortest, and result is the best, but 60 seconds Or less result is typically considered acceptable.

Result of the test is summarized in following table.

Table 2: result

Result above shows that additive of the present invention provides acceptable stability and emulsifying agent performance, also provides for allowing simultaneously The interpolation motility of salt formation on the spot.

By quoting above referenced each file, any prior art including its priority of requirement is incorporated herein, The most whether it is expressly recited.Mentioning of any file is not to recognize that this document obtains the qualification of prior art or with any power Limit constitutes the general knowledge of technical staff.Except embodiment China and foreign countries, or as additionally explicitly pointed out, be described material in this description The quantity of amount, reaction condition, molecular weight, carbon number etc. is to be understood that as being modified by wording " about ".It is to be understood that described herein The upper and lower bound of amount, scope and ratio can combine independently.Similarly, the scope of each element of the present invention and amount can with any its Scope or the amount of its element are used together.

As used herein, " comprise " with the transitional term of " including ", " containing " or " feature is ... " synonym be inclusive or Open, and it is not excluded for other unstated elements or method step.But, in each description " comprised " in this article, meaning Being intended to alternately embodiment, this term also includes phrase " substantially by ... composition " and " Consists of ", wherein " Consists of " Do not include any unstated elements or step, and " substantially by ... composition " allows the combination including that substantial effect is not considered Other of the basic and new features of thing or method does not describes element or step.

Although show some representative embodiment and details to illustrate the present invention, skilled in the art realises that can not Deviate the scope of the present invention and make various changes and improvements herein.On this point, the scope of the present invention is only by following power Profit claim limits.

Claims

1. comprise (i) and replace the functional group of acylating agent with (ii) derived from the second alkyl replacement acylating agent derived from the first alkyl The additive of functional group, wherein functional group (i) and (ii) are by the functional groups derived from aklylene glycol；

Wherein the first alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing at least about 20 carbon atoms；And wherein the second alkyl Replace acylating agent and comprise the hydrocarbyl substituent containing less than about 20 carbon atoms.

Additive the most according to claim 1, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturated carboxylic acid Product；Wherein said long chain hydrocarbon has the number-average molecular weight of greater than about 400.

3., according to the additive of claim 1 or claim 2, wherein the first alkyl replaces acylating agent and comprises polyisobutene succinic Anhydride, polyisobutylene group has the number-average molecular weight of greater than about 400.

Additive the most as claimed in one of claims 1-3, wherein the second alkyl replaces acylating agent and comprises long chain hydrocarbon with list not The product of saturated carboxylic acid；Wherein said long chain hydrocarbon has the number-average molecular weight of less than about 280.

Additive the most as claimed in one of claims 1-4, wherein the second alkyl replaces acylating agent and comprises hexadecene base amber Amber anhydride.

Additive the most as claimed in one of claims 1-5, wherein aklylene glycol comprises and has formula HO [(CH (R))_x– O–]_mThe glycol of H, wherein each R independently be H or has the alkyl of 1-6 carbon atom, and each x independently be 2 to about 10 Integer, and the integer that m is 1 to about 10.

Additive the most as claimed in one of claims 1-6, wherein aklylene glycol is linear alkylene glycol.

Additive the most as claimed in one of claims 1-7, wherein aklylene glycol comprise PEG, poly-(1,3-third Glycol) or ethylene glycol and the copolymer of 1,3-propylene glycol.

Additive the most as claimed in one of claims 1-8, wherein aklylene glycol comprises and has formula HO (CH₂)_xOH's Glycol, wherein x is the integer of 2 to about 10.

Additive the most according to claim 9, wherein aklylene glycol comprises ethylene glycol.

11. additives as claimed in one of claims 1-7, wherein the first alkyl replaces acylating agent and comprises polyisobutene succinic Anhydride, polyisobutylene group has the number-average molecular weight of greater than about 750；

Wherein the second alkyl replaces acylating agent and comprises hexadecenyl succinic anhydride；And

Wherein aklylene glycol comprises ethylene glycol.

12. according to the additive any one of claim 1-11, itself and the neutralization component reaction comprising amine.

13. methods preparing emulsifier component, it includes step:

I. make the first alkyl replace acylating agent, the second alkyl replaces acylating agent and aklylene glycol reaction；

Wherein the first alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing at least about 20 carbon atoms；And

Wherein the second alkyl replaces acylating agent and comprises the hydrocarbyl substituent containing less than about 20 carbon atoms；

Generation comprises (i) and replaces the functional group of acylating agent derived from described first alkyl and (ii) takes derived from described second alkyl For the intermediate of the functional group of acylating agent, wherein functional group (i) and (ii) are by the functional group derived from described aklylene glycol In conjunction with；

II. described intermediate is provided to be used as emulsifier component precursor；Thereafter

III. by making described intermediate, with neutralizing component reaction, described intermediate be changed into emulsifier component.

14. methods according to claim 13, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturated carboxylic acid Product；Wherein said long chain hydrocarbon has the number-average molecular weight of greater than about 400；And

Wherein the second alkyl replaces acylating agent and comprises the product of long chain hydrocarbon and single unsaturated carboxylic acid；Wherein said long chain hydrocarbon has There is the number-average molecular weight of less than about 280；

Wherein aklylene glycol comprises and has formula HO [(C (R))_x–O–]_mThe glycol of H, wherein each R independently be H or Having the alkyl of 1-6 carbon atom, each x independently be the integer of 2 to about 10, and the integer that m is 1 to about 10.

15. according to claim 13 or the method for claim 14, wherein aklylene glycol comprise PEG, poly-(1,3- Propylene glycol) or ethylene glycol and the copolymer of 1,3-propylene glycol.

16. according to claim 13 or the method for claim 14, and wherein aklylene glycol comprises and has formula HO (CH₂)_x–OH Glycol, wherein x is the integer of 2 to about 10.

17. methods according to claim 14, wherein the first alkyl replaces acylating agent and comprises the equal molecule of number with greater than about 750 The polyisobutylene succinic anhydride of amount；

Wherein aklylene glycol comprises ethylene glycol.

18. according to the method any one of claim 13-17, wherein neutralizes component and comprises amine.

19. methods customizing emulsifier component in the composition, described method includes step:

III. by making described intermediate, with neutralizing component reaction, described intermediate be changed into emulsifier component；

Produce customization emulsifier component.

20. methods according to claim 19, wherein the first alkyl replaces acylating agent and comprises long chain hydrocarbon and single unsaturated carboxylic acid Product；Wherein said long chain hydrocarbon has the number-average molecular weight of greater than about 400；And

Wherein aklylene glycol comprises and has formula HO (CH₂)_xThe glycol of OH, wherein x is the integer of 2 to about 10.

21. according to claim 19 or the method for claim 20, wherein neutralizes component and comprises amine.

22. emulsifier components prepared by a kind of method, described method includes step:

23. emulsifier components according to claim 22, wherein said neutralization component comprises amine.