CN1009618B - Dispersant salts - Google Patents
Dispersant saltsInfo
- Publication number
- CN1009618B CN1009618B CN86101650.5A CN86101650A CN1009618B CN 1009618 B CN1009618 B CN 1009618B CN 86101650 A CN86101650 A CN 86101650A CN 1009618 B CN1009618 B CN 1009618B
- Authority
- CN
- China
- Prior art keywords
- composition
- acid
- dipersant
- water
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a dispersing agent composition which is prepared by the reaction of phosphorusless carboxyl solubilizing agents with non sulfonic acid type organic acid or inorganic acid, wherein the carboxyl solubilizing agents are prepared by the reaction of at least one poly (alkylidene amine) polybasic carboxylic acid acylating agents accompanied with at least 8 to 500 carbon atoms and at least one substituent based on hydrocarbon. Good thermal stability is achieved when dispersing agent salts are mixed with surfactants and hydrophilic organic solvents, various fillers including black carbon can be dispersed when the composition is used together with an aqueous solution, and different fluids are solubilized.
Description
The present invention has narrated at the dispersible salt of aqueous phase, wherein generally also contains tensio-active agent or hydrophilic organic solvent.Specifically, this salt is the reaction product of non-sulfonic acid organic acid or mineral acid and polycarboxylic acid acylating agent, and this acylating agent has one at least based on hydrocarbon, contains the substituting group of 8 to 500 carbon atoms approximately.
Authorize the United States Patent (USP) of Lowe and narrated a kind of composition as lubricating oil additive for the 3rd, 634, No. 241, its preparation at first is the C that can form imide (Carboximide) key
20-C
400Aliphatic hydrocarbon succsinic acid or derivatives thereof and C
2-C
30, N
2-N
10Alkylidene group polyamine reaction generates a kind of imide, then with itself and C
12-C
40The hydrocarbon sulfonate reaction, product is a sulfonate.
The United States Patent (USP) of authorizing people such as Elliott has been narrated the reaction product of polyalkylene amine sulfonic acid and alkenyl succinic anhydrides or acid for the 3rd, 725, No. 434.
The United States Patent (USP) of authorizing people such as Kahn has been narrated by condensation reaction for the 3rd, 185, No. 704 and has been prepared benzamide type by the mono-alkenyl succinimide.
Authorize the United States Patent (USP) of Brasch and narrated with aliphatic monocarboxylic acid the oily soluble dispersion agent of di-carboxylic acid or acid anhydrides and monomer alkylene imine prepared in reaction for the 3rd, 452, No. 002.Should synthetic can use acid catalyst, for example HCl.
Authorize the product that the United States Patent (USP) of O ' Halloran has disclosed by alkenyl succinic, polyalkylene amine and second kind of acid-respons for the 3rd, 390, No. 086, generation be a kind of acid amides.
Authorize the United States Patent (USP) of Conlisk and narrated various types of washing composition the 3rd, 352, No. 788, as the liquid adhesive of activated carbon composition.
The United States Patent (USP) of authorizing Wilson has been narrated for the 4th, 439, No. 491 and has been adopted wetting agent to make graphite or carbon avoid the method for oxidation.
The United States Patent (USP) of authorizing Krillic narrated for the 3rd, 948, No. 784 adopt cationic polyelectrolyte clean industry grind and cutting in the method for used lubricant that can be water-soluble.
United States Patent (USP) the 3rd, 341,454,3,522,177 and 3,801, narrated the method that in graphitiferous lubricant, adds polyoxyalkylated phenol for No. 504.
The United States Patent (USP) of authorizing Murphy has been narrated the lubricating composition that contains dispersion agent and emulsion splitter that has improved for the 3rd, 509, No. 052, and this dispersion agent is the derivative of the succsinic acid that replaces, and substituting group has 50 aliphatic carbon atoms at least.
The United States Patent (USP) of authorizing people such as Lesuer has been narrated preparation is used as the oily molten product of dispersion agent in lubricating composition method for the 3rd, 172, No. 892, and wherein dispersion agent contains the amber acid or anhydride of replacement.
The United States Patent (USP) of authorizing Lesuer has been narrated for the 3rd, 502, No. 677 and be used as the nitrogenous of additive and phosphorated succinic acid derivative in lubricating composition.
United States Patent (USP) the 4th, 447,348 and 4,448, the composition of narrating hydroxy acid type solubilizing agent No. 703 wherein contains tensio-active agent, this solubilizing agent is by the alkyl of N-(carboxyl substituted) amine and acylation reaction make.
Therefore the above-mentioned patent that belongs to prior art does not all propose or the dispersible aqueous composition of advise containing salt powder and tensio-active agent or hydrophilic organic solvent.
Therefore one aspect of the present invention has provided a kind of dipersant composition that contains tensio-active agent or organic solvent that can be water-soluble, and it has good thermostability and dissolves in water.
The present invention provides the above-mentioned composition that is used at Aquo System carbon blacks, pigment, organic filler and analogue on the other hand.
In a word, contain (A) and reaction product (B) at the dispersible dipersant composition of aqueous phase, wherein
(A) be mineral acid or the organic acid that does not contain sulfonic acid,
(B) be phosphorated carboxyl solubilizing agent not, this solubilizing agent is by (B
1) at least a polycarboxylic acid acylating agent (having at least 8 at least one substituting group based on hydrocarbon to about 500 carbon atoms) and (B
2) at least a poly-(alkylene amines) reaction obtains,
Wherein the dipersant composition contains a kind of tensio-active agent or hydrophilic organic solvent at least.
According to design of the present invention, said composition relates to the not dipersant of phosphorated carboxyl solubilizing agent.This salt is made by carboxyl solubilizing agent and various acid-respons.Although this class acid is normally water miscible, this might not be that essential, appropriate requirement is that dipersant should be dispersible at aqueous phase.Acid generally can be any acid (organic or inorganic acid) that can form dipersant that can be water-soluble substantially, and the example of mineral acid has nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hydrochloric acid, silicic acid, boric acid, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, permanganic acid, chromic acid, dichromic acid, just-partially-and tetra-sodium, hydrofluoric acid, Hydrogen bromide, hydroiodic acid HI and hydrosulphuric acid etc., wherein hydrochloric acid is preferable.Organic acid generally comprises multifunctional or monofunctional acid, so that keep it water-soluble.Non-sulfonic acid organic acid generally contains 1 to 10 carbon atom, and 1 to 4 carbon atom is preferable, and they can be saturated or undersaturated aliphatics or aromatic acid.The example of carboxylic acid has aliphatic carboxylic acid, as formic acid, and acetate, propionic acid, butyric acid and analogue.Also can adopt di-carboxylic acid, as oxalic acid, propanedioic acid, succsinic acid and pentanedioic acid.And undersaturated carboxylic acid (as toxilic acid) also can use.In general, acetate and formic acid are better.Carboxylic acid acylating agent (B
1)
The acylating agent that is used for preparing present composition solubilizing agent (B) is known the intermediate that this acylating agent of known discovery can be used for the additive of lubricant and fuel and prepares them for those skilled in the art.As seen the United States Patent (USP) of listing below, the patent No. is respectively: 4,448,703,4,447,348,3; 219,666,3,272,746,3,381,022,3; 254,025,3,278,550,3,288,714,3; 271,310,3,373,111,3,346; 354,3,272,743,3,374,174,3; 307,928 and 3,394,179, the content about the carboxylic acid acylating agent in these patents is incorporated this paper at this.
In general; these carboxylic acid acylating agents' preparation is with olefin polymer or chlorating olefin polymer and undersaturated carboxylic acid or derivatives thereof (as vinylformic acid, fumaric acid, maleic anhydride and analogue) reaction; the normally many carboxylic acylating agents of these acylating agents are as hydrocarbyl substituted succinic and acid anhydrides.These acylating agents have at least one carbon atom and are about 8 to 500 the substituting group based on alkyl.Say that generally this substituting group is about 8 to 196 or 200 carbon atoms, be about 8 to 100 carbon atoms preferably.Also will explain in more detail below,, then not need tensio-active agent or water-miscible organic solvent when the substituting group carbonatoms is 30 or less than 30 the time.
Term used herein " based on hydrocarbon ", " based on the substituting group of hydrocarbon " and similar phraseology; mean a kind of substituting group within the scope of the present invention, its carbon atom is directly connected to the rest part of acylating agent molecule and mainly has the alkyl characteristic.This class substituting group comprises:
(1) hydrocarbon substituent, be aliphatics (for example alkyl or alkenyl), alicyclic (cycloalkyl for example, cycloalkenyl) substituting group, aromatic series-, aromatic proton and the analogue and the cyclic substituents of aliphatics-and alicyclic-replace, wherein ring is another part Cheng Huan (being that any two substituting groups of pointing out can form an alicyclic radical together) by molecule;
(2) hydrocarbon substituent of Qu Daiing does not promptly contain those substituting groups of alkyl, and they do not change the character of main hydrocarbyl substituent within the scope of the present invention; Those of skill in the art understand this class group, as halogen (particularly chlorine and fluorine), alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group, sulfoxylic acid base (sulfxy) etc.;
(3) hetero atom substituents, both these substituting groups mainly had alkyl character within the scope of the present invention, but contained other atom that is different from carbon atom on ring or chain, and these rings or chain are made of carbon atom in other cases.Suitable heteroatoms is apparent to one skilled in the art, such as sulphur, oxygen, nitrogen.The example of this class heterocyclic substituent has pyridyl, furyl, thiophenyl, imidazolyl etc.
Generally speaking, per ten carbon atoms contain no more than three groups or heteroatoms in based on the substituting group of hydrocarbon, no more than one better.Typical case is not have such group or heteroatoms to exist, thereby is pure hydrocarbyl substituent.
In general, the substituting group based on hydrocarbon that exists in the acylating agent that the present invention uses does not contain acetylene series unsaturated hydrocarbons key, if there is unsaturated ethylene linkage, and the general no more than ethylene linkage of each C-C in the substituting group then.Substituting group is normally fully saturated, thereby does not contain unsaturated ethylene linkage.
As mentioned above, the substituting group based on hydrocarbon that exists in the acylating agent of the present invention can be obtained by olefin polymer or chlorinated olefin polymer.The olefinic monomer of preparation olefin polymer is to be characterized as polymerizable olefins and the monomer that contains one or more unsaturated thiazolinyls.They can be monoolefine monomer (as ethene, propylene, butene-1, iso-butylene and octene-1) or multi-olefin monomer (usually being two-olefinic monomer, as divinyl-1,3 and isoprene).These monomers generally are terminal olefines, and promptly the alkene feature is to have group
=CH
2But some internal olefin also can be used as monomer (alkene in the middle of being sometimes referred to as).General use side alkene simultaneously when using in the middle of this class olefinic monomer, the prepared olefin polymer that goes out is an interpolymer.Substituting group based on alkyl also comprises aromatic base (particularly phenyl) and alicyclic radical, and such group can come from the polymerizable cyclic olefin of polymerisable cyclic olefin or alicyclic replacement.But olefin polymer does not contain such group usually.Yet by 1, the olefin polymer that the multipolymer of 3-diene and vinylbenzene (as divinyl-1,3 and vinylbenzene or to t-butyl styrene) obtains is an exception to this routine.
General this olefin polymer is homopolymer or the multipolymer that contains 2 to 16 carbon atom end alkyl alkene approximately.A more typical class olefin polymer is selected from 2 to 6 carbon atoms, particularly the terminal olefine homopolymer and the multipolymer of 2 to 4 carbon atoms.
Be used to prepare the terminal olefine monomer of olefin polymer (obtaining substituting group thus) and the object lesson of middle olefinic monomer has ethene based on hydrocarbon, propylene, butene-1, butene-2, iso-butylene, amylene-1, hexene-1, ester alkene-1, octene-1, soil alkene-1, decylene-1, amylene-2, tetrapropylene, diisobutylene, tri-isobutylene, divinyl-1,2, divinyl-1,3, pentadiene-1,2, pentadiene-1,3, isoprene, hexadiene-1,5,2 chlorobutadiene-1,3,2-methyl-heptene-1,3-cyclohexyl butene-1,3,3-dimethyl pentene-1, SDVB, the vinyl acetate vinyl carbinol, acetate 1-ethylene methacrylic ester, vinyl cyanide, ethyl propenoate, ethyl vinyl ether and methyl vinyl ketone.Wherein pure alkyl monomer is the typical case, and the terminal olefine monomer is more typical.
Normally poly-(iso-butylene) class of olefin polymer is by containing the butylene of 35% to 75% weight and the iso-butylene C of about 30% to 60% weight approximately
4Refining of petroleum is stayed and part is carried out polymerization in the presence of lewis acid catalyst (as aluminum chloride or boron difluoride) and obtain.These polyisobutene contain the isobutylene repeat units of the following structure of major part (promptly greater than repeating unit sum 80%):
Under the typical situation, the substituting group based on alkyl among the carboxylic acid acylating agent that the present invention adopts is alkyl, alkyl or the alkenyl that is about 8 to 500 carbon atoms, can represent with " hyd " this mark.Useful acylating agent comprises the succsinic acid reagent based on the substituent replacement of alkyl that has about 8 to 100 carbon atoms.
Usually reagent (the B for preparing solubilizing agent (B)
1) be the succsinic acid or derivatives thereof of the replacement that can express by following formula:
Wherein n is 1 to 4.0 integer, preferably 1.This succinic acid acylating agent can be by maleic anhydride, and toxilic acid or fumaric acid and above-mentioned olefin polymer carry out prepared in reaction according to the method shown in the above-mentioned patent.In general, this reaction only relates to these two kinds of reactants of heating under 150 ℃ to 200 ℃ temperature.Also can adopt the mixture of above-mentioned olefin polymerization and the mixture of unsaturated monocarboxylic acid and di-carboxylic acid.Poly-(alkylene amines) (B
2)
With B
1Acylating agent and (B
2) poly-(alkylene amines) prepared in reaction carboxyl solubilizing agent (B).Common B
1Acylating agent is by poly-(alkylene amines) compound coupling.A under any circumstance very important requirement is a reaction product, and promptly carboxyl solubilizing agent (B) contains a unhindered amina at least." unhindered amina " is meant has a hydrogen to be substituted on the amido.
The polyamine class of preparation the present invention (B) product comprises that mainly the overwhelming majority meets the alkylenamines of following formula,
N 1 to about 10 integer preferably wherein, D is hydrogen or is hydrocarbon substantially, is preferably with more than about 30 carbon atoms " alkylene " base preferably 10 or less than the low-grade alkylidene of 10 carbon atoms.Alkylene amines mainly comprises benzylidene amino, ethyleneamines, butylidene amine, propylidene amine, pentylidene amine, hexylidene amine, inferior ester group amine, octylene amine, the ring-type higher homologue of other polymethylene amine and this class amine is as the piperazine of piperazine and aminoalkyl group replacement.Its object lesson has: ethylene diamine, Triethylenetetramine (TETA), trimethylene diamine, decamethylene diamine, eight methylene diamine, two (heptamethylene) triamine, tri propylidene tetramine, tetren, trimethylene diamines, five ethylidene, six ammonia, two (trimethylene) triamine, 2-heptyl-3-(2-aminopropyl) tetrahydroglyoxaline, 4-methyl-tetrahydroglyoxaline, 1, two (2-amino-ethyl) tetrahydroglyoxalines of 3-, pyrimidine, 1-(2-aminopropyl)-piperazine, 1,4 pair of (2-amino-ethyl) piperazine and 2-methyl isophthalic acid-(the amino butyl of 2-) piperazine.By two kinds of condensations or the multiple alkylene amines that exemplifies above and the higher homologue that obtains also is useful.Usually adopt the mixture more than two kinds to replace top amine.
What usually use is ethylene-amines.(Interscience publisher, New York (1950)) are entitled as in " ethyleneamines " literary composition and have described such amine in greater detail on " chemical technology complete works " book the 5th volume 898-905 of Kirk and othmer page or leaf.This compounds can very easily be prepared by two enparas and ammonia react.Reaction product then is more or less complicated alkylene amines mixture, comprising the cyclic condensation product, as piperazine.These mixtures can be used in the method for the present invention.On the other hand, use pure alkylene amines also can obtain gratifying product.In view of the reason of the efficient of the product of economic reasons and acquisition, specially suitable alkylene amines by ethylene dichloride and ammonia react and the mixture of forming the ethyleneamines that is equivalent to tetren.
The higher homologue that above-mentioned alkylene amines is obtained by amino condensation also is an available.One will understand that the condensation by amino produces higher amines when shifting out ammonia.Acylating agent (B
1) and poly-(alkylene amines) (B
2) be reacted into carboxyl solubilizing agent (B)
Acylating agent (B
1) and poly-(alkylene amines) (B
2) reaction generally be to the lowest decomposition temperature of compound of reaction and/or product, to carry out in about 80 ℃ of temperature.General temperature of reaction is with 100 ℃ to about 300 ℃, and is better with 125 ℃ to 250 ℃ approximately, adopts the mixture of acylating agent usually.
Acylating agent generally is about 0.33 to 1.3 equivalent (B with the ratio of poly-(alkylene amines)
1) acylating agent/whenever amount (B
2) amine.The number of the carboxyl functional group that the molecular weight of acylating agent is existed removes the equivalent that can determine acylating agent, and for example, the equivalent of succinyl oxide or two (alkyl) ester acylating agent is half of its molecular weight.The equivalent of amine is to be equivalent to (the B that obtained divided by the gross weight of amine by the nitrogen-atoms sum that exists
2) the amine amount.
Except acylating agent (B
1) in addition, in generating the reaction mixture of solubilizing agent, also can exist one or more low-molecular-weightly to have 1 to the monobasic that is less than 18 carbon atoms approximately or polycarboxylic acid acylating agent (as the lipid acid of 10 to 18 carbon atoms) or substituted this succinyl oxide of tetrapropylene.In this case, the mole number of existing rudimentary acylating agent is less than acylating agent (B at least
1) mole number, and rudimentary acylating agent and acylating agent (B
1) total yield still within above-mentioned ratio range.
Typically rudimentary (MW) monobasic carboxylic acylating agent comprises saturated and undersaturated lipid acid, for example lauric acid, stearic acid, oleic acid, tetradecanoic acid, linolic acid and analogue.If can buy these sour acid anhydrides and lower alkyl esters thereof also can use.The mixture that uses two or more these reagent also is fully feasible.Kirk-othmer " needed (claimed) technology complete works " and in the 811-856 page or leaf (nineteen sixty-five second edition, John Wiley and sons company, New York), extensive discussions this class acid.Acylating agent comprises acetate, propionic acid, butyric acid, vinylformic acid and phenylformic acid and these sour acid anhydride and lower alkyl esters.
The polynary carboxylic acylating agent of useful lower molecular weight (MW) is the phthalic acid that replaces of toxilic acid, fumaric acid, methylene-succinic acid, methylfumaric acid, succsinic acid, phthalic acid, alkyl, propanedioic acid, pentanedioic acid, hexanodioic acid, citraconic acid, propene dicarboxylic acid, chloromaleic acid, xitix etc., and these sour acid anhydrides (if available words) and lower alkyl esters and these sour esters also can be used as rudimentary MW acylating agent equally.
Also can use the lower molecular weight MW acylating agent of certain substituted succsinic acid and acid anhydride.Discussed in the 847-849 page or leaf of the kirkothmer article that a lot of these class acylating agents are all drawn in the above.This class acylating agent generally is expressed from the next:
Wherein R is C
1To about C
10Alkyl.R* is aliphatic or alicyclic hydrocarbon radical preferably, and is wherein unsaturated less than 10% C-C, and 4-butyl-cyclohexyl is arranged for example, two (isobutyl-s), decyl etc.The toxilic acid or derivatives thereof is carried out alkylation with halohydrocarbon, and to produce the substituted succsinic acid of this class and its derivative be known for those skilled in the art, there is no need to go through at this point.
The acyl halide of above-mentioned low MW monobasic and polycarboxylic acid can be used as low MW acylating agent of the present invention.Its preparation is by the acid of this class or its acid anhydrides and halogenating agent (as phosphorus tribromide, phosphorus pentachloride, phosphoryl chloride or thionyl chloride) are reacted.As long as the ester of this class acid should acid, chloride of acid or acid anhydride and alcohol or phenolic compound reaction.Useful especially is the pure and mild alkenols of low alkyl group, as methyl alcohol, ethanol, vinyl carbinol, propyl alcohol, hexalin etc.Usually can promote esterification with basic catalyst (as sodium hydroxide or alkoxide, phenates) or an acidic catalyst (as sulfuric acid or toluenesulphonic acids).The reaction of acid (A) and carboxyl solubilizing agent (B).
The dipersant composition is by the reaction formation of acid (A) and carboxyl solubilizing agent (B).Although this reaction can at room temperature be carried out, usually need the reacting by heating thing, to improve speed of response.General temperature of reaction with 0 ℃～150 ℃, about 15 ℃～100 ℃ cater to the need, about 25 ℃～80 ℃ best.
The consumption of acid is generally not crucial, can excessively use.General every mole of carboxyl solubilizing agent (B) is used 0.5 normal acid at least, uses at least usually that (angelic acid, the reaction of not phosphorous carboxyl solubilizing agent are by at (B
2) increase a hydrogen atom on the unhindered amina of poly-(alkylene amines).Dipersant composition (A) and reaction product (B), it is a kind of at the dispersible salt of aqueous phase.This dipersant almost can ad infinitum disperse in water usually.
Tensio-active agent
Normal and the tensio-active agent logotype of dipersant of the present invention, tensio-active agent not only is used for reducing the viscosity of salt dispersive composition, also can help to disperse or various particles of solubilising or fluid.Tensio-active agent generally also makes water have stability.The dipersant composition of per 100 parts of weight is generally used the tensio-active agent of 5 parts of weight at least, so that increase the stability of system and improve the water-soluble of dipersant, weight is at least 20 parts better.The percent by weight content of tensio-active agent is about 5%～95%.
Tensio-active agent generally is hydrophilic, can be anionic, cationic or non-ionic type.The tensio-active agent of various these classes is well known in the art.For example see " washing composition and emulsifying agent " (North America version in 1978 of Mo Cutcheon, publish by Mc Cutcheon portion of U.S. GLenRocR.N.J.MC publishing company), see the 17-33 page or leaf especially, this with article in this part of tensio-active agent with reference to incorporating this paper into.
In these tensio-active agents, generally use nonionic surface active agent, many these class tensio-active agents are known, the product that wherein has epoxy alkane to handle is as phenol, alcohol, ester, amine and the acid amides with ethylene oxide treatment.The ethylene oxide/propylene oxide segmented copolymer also is useful nonionic surface active agent.Glyceryl ester and sugar ester also are known nonionogenic tensides.
To the useful typical nonionic surface active agent class of derivative of the present invention is the alkylphenol of handling with epoxy alkane, for example the oxyethane alkylphenol condensation of Rohm Haas company sale.Object lesson is Triton X-100, and wherein per molecule on average contains 9 to 10 ethylene oxide units, and the HLB value is about 13.5, and molecular weight is about 628.Many nonionic surface active agent that other is suitable for also are known, for example see the article of above-mentioned MoCutoheon and by MartinJ.Sohiok(M.Drekker company, New York, editor's in 1967 paper " nonionic surface active agent ", wherein the content of this respect is incorporated this paper in this reference.
As mentioned above, anionic and cationic surfactant also can use by the solubilizing agent (A) in the present invention.These tensio-active agents generally are hydrophilic.Aniorfic surfactant has the negative electricity polar group, and cationic surfactant has the positive electricity polar group." chemical technology complete works " second edition of Kirk-Othmer, the 19th the 507th page of volume and the above-mentioned complete works (1969, JohnWiley and Son company, New York) of editing and publishing under one's name in MoCutoheon portion have later been done general survey to useful tensio-active agent.The argumentation cationic with regard to it and aniorfic surfactant of these two parts of reference is incorporated this paper in this reference.
Useful aniorfic surfactant is the metal carboxylate soap class that is widely known by the people, organo-sulfate, sulphonate, sulfuration carboxylic acid and salt and phosphoric acid salt.Useful cationic surfactant comprises nitrogenous compound, as amine oxide and the quaternary ammonium salt of knowing.Amphoterics comprises the material and the analogue of amino acid pattern.Various cationic and anionic dispersing agents can be obtained by industry member, particularly can be by U.S. Rohm and Haas company and the acquisition of U.S. combinating carbide company, further information about negatively charged ion and cats product can be recognized in following article: " aniorfic surfactant ", II part and III part, by W, M.Linfielod edits, published by New York Marcel Dekker company in 1976: " cationic surfactant ", edit (Marcel Dekker company by E.Jungerman, New York, 1976).These two parts of bibliographys are incorporated this paper into regard to the content reference of its this respect.
Hydrophilic organic solvent
Can use hydrophilic organic solvent substitution list surface-active agent, perhaps use jointly with tensio-active agent.That is to say without tensio-active agent, and use the hydrophilic organic solvent stabilising system.Its consumption generally changes according to the type of dipersant, generally is at least 5%(weight), preferably be at least 10%(weight).Hydrophilic solvent is known to those skilled in the art.Solvent is oxidation solvent preferably.One class oxidation solvent comprises the derivative of the list of 1.2-ethylidene glycol and dialkyl ether, 1.2-.Object lesson has 1.2-ethylidene glycol monobutyl ether, 1.2-ethylidene glycol monobutyl ether acetate ester, 1.2-ethylidene glycol monoethyl ether acetate, 1.2-ethylidene glycol list ether, 1.2-ethylidene glycol dibutyl ether, 1.2-ethylidene glycol monohexyl ether, 1.2-ethylidene glycol monomethyl ether acetate and 1.2-ethylidene glycol monophenyl ether.The solvent of these types generally can the Cellosolve trade(brand)name be buied, and they are made by Union Carbide Corporation.Another kind of oxidation solvent is various aliphatic alcohol, as vinyl carbinol and various 1 solubility alkanol to about 4 carbon atoms, and as methyl alcohol, ethanol, propyl alcohol, Virahol and the trimethyl carbinol.Another kind of oxidation solvent-ketone also can use, as acetone and methylethylketone.Also can use various solubility keto-alcohols, as Pyranton.The hydrophilic organic solvent of these and other type can be used to replace various tensio-active agent of the present invention, or use common with it.
Further conceive according to the present invention, if (B
1) acylating agent has approximately 8 to 30, better is about the substituting group based on alkyl of 8 to 12 carbon atoms, then do not need tensio-active agent and hydrophilic solvent.It is believed that this is that hydrocarbon partly is easy to disperse event because along with the hydrocarbon chain carbon number reduces.Therefore, as long as (B
1) hydrocarbon substituent on the acylating agent is little, the dipersant composition just need not to contain any tensio-active agent or hydrophilic organic solvent.
In fact dipersant composition of the present invention no matter whether contain tensio-active agent or hydrophilic organic solvent, all can use, perhaps wherein contain a certain amount of water, transform emulsion or other system so that form, water wherein is in discontinuous phase, and perhaps water wherein forms external phase.Form the type that the actual used water amount that transforms emulsion or external phase will depend on tensio-active agent, hydrophilic organic solvent, dispersion agent and analogue naturally.The type that forms solution often depends on needed concentration in water, perhaps this fact of water not fully.
Particle and fluid
Aqueous dipersant composition can remain on various particles or liquid in the solution.General available any particle that needs to be suspended, disperse or rise similar effect.For example various clays, talcum, coal, sulphur, silicon oxide, pigment, filler and fiber.This disperser composition unwanted particle of people that is specially adapted to suspend, as cigarette ash, carbon black cigarette ash particularly.When making carbon black, cigarette ash is unavoidably produced as paying product.Because cigarette ash can not be separated in fact at all, thus generally cigarette ash is mixed in the syrup or the lignosulfonate/naphtalene sulfonate aqueous solution, dry then.But in drying process, syrup or lignosulfonate/naphtalene sulfonate can be degraded, and produce the carbon black granules that is difficult for redispersion.According to the present invention, this carbon black dust is easy to be disperseed by the dipersant composition.When drying, the carbon black composition that produces free from dust, unrestricted flow and be highly dispersed.Various products are starved of the particle resemble the carbon black as tire, roof material, pigment and analogue.Another kind of particle is a fiber, and is very little usually, when needs with its suspension or be dispersed in the solution.Therefore, when needs remain on cellulose particulates or plastics in the solution, can in the slurrying operation, use the dipersant composition that contains tensio-active agent or organic hydrophilic solvent.The example of other fiber comprises glass, i.e. analogues such as glass fibre, polyester, nylon, carbon fiber, regenerated fiber, polypropylene fibre.As for fluid, various liquid (as dyestuff, oil and analogue) all can be maintained in the solution.And all gases such as carbonic acid gas and analogue also can be maintained in the solution, for example remains in the solution with form of foam.
Therefore,, just can use this dipersant, optional simultaneously tensio-active agent or the hydrophilic organic solvent of using as long as need or remain in the aqueous solution with particle or fluid dispersion.
Can understand the present invention better with reference to following example.
Embodiment 1
In 1 liter of container, add 240 gram polyisobutenyl succsinic acid tetrens, 12 gram formic acid and 64 gram Tritonx-100(tensio-active agent).Mixture under agitation is heated to about 85 ℃, then during several hours in (2～4 hours according to appointment), slowly add 444 the gram water, keep temperature to be about 85 ℃ simultaneously, under agitation mixture is cooled to room temperature.Obtain required dipersant thus.
Embodiment 2
By the mode of similar example 1, prepare required dipersant with same component (but acid is concentrated hydrochloric acid).The consumption of carboxyl solubilizing agent is 150 grams, concentrated hydrochloric acid 13 grams, and tensio-active agent 40 grams, the water yield that adds in the general time is 178 grams.
Embodiment 3
Mode (but acid is acetate) by similar example 1 is prepared required dipersant.The amount of carboxyl solubilizing agent is 600 grams, acetate 30 grams, and tensio-active agent 160 grams, amount of water is 1110 grams in for some time.
Embodiment 4
Mode by similar example 1 is prepared dipersant.With hydrophilic or organic solvent substitution list surface-active agent, specifically be carboxyl solubilizing agent with 840 gram examples 1,420 gram ethylene glycol monobutyl ethers and 21 gram acetate.These three components are mixed, be heated to about 85 ℃ at short notice, obtain required dipersant thus.Then 15 these salt of gram are added in the container, add 85 gram water again and mix, obtain amber liquid (amber soluton) clearly.
Embodiment 5
By the mode of similar example 1, with the 5 gram carboxyl solubilizing agent that propose in the 5 gram examples 1,5 gram ethylene glycol monobutyl ethers and 1 gram acetate heating mix, and slowly add 39 gram water simultaneously.Obtain required dipersant.This solution is still clear after 24 hours.
Embodiment 6
According to example 5 identical modes, adopt prescription equally, but use 2.5 gram acetate, prepare dipersant.Though the acid amount has increased, and obtains solution clearly, solution is still clear after 24 hours.
Above-mentioned example 1 to the complete soln in the example 6 all is satisfactory stability, leave standstill at least one day after, do not see obviously that component separates.
Embodiment 7
According to the mode of similar example 1, carboxyl solubilizing agent and the 10 gram ethylene glycol monobutyl ether heating that propose in the 5 gram examples 1 are mixed.Need not acid.Add 35 gram tap water then at short notice, continue heating simultaneously.Again with this solution cooling.Take place after 6 hours obviously to separate.
Therefore, obviously, need not acid can not obtain suitable dipersant.
Every kind of dipersant in the example 1 to 6 is mixed with the cigarette ash of carbon black.The dispersant solution amount that comprises water is about 4%(weight), amount of carbon blacks is about 96%(weight).After each component thorough mixing, mixture is dry down about 450～500 °F.Remaining carbon black mixt is very tiny, but does not wherein contain any powder or dust, and can unrestricted flow.Therefore every kind of dipersant can both be produced the carbon black system of high degree of dispersion according to the present invention.
Point out that as top although it is very wide to form the water yield variation range of Aquo System, this system contains a spot of water usually.So Aquo System contains the water of 20% weight at least, be the water that contains 40% weight at least better.Form spissated or basic water Aquo System thus.
These concentrated aqueous systems and basic water Aquo System can select to add other conventional additives that is usually used in the basic water function fluid.They comprise functional additive, sanitas, shear stable agent, sterilant, dyestuff, water-softening chemicals, odor mask, antifoams and analogue.
Enriched material is similar to basic water function fluid, but moisture less, contains other component of larger proportion.Dilute with water just can be converted into basic water function fluid.Usually dilute with the hybrid technology of standard, this practice is very convenient, because enriched material can be moved to point-of-use before adding water.Therefore can save the freight charges of most of water yield in the basic water function fluid.Only need to carry and form the essential water yield of enriched material (this is mainly by whether being easy to handle and factors decision such as comfort level).
The present invention also comprises the method for preparing Aquo System, and this system comprises enriched material and basic water function fluid, wherein contains other conventional additives that is usually used in the basic water function fluid.The preparation method may further comprise the steps:
(1) mixes with above-mentioned conventional additives composition of the present invention simultaneously or sequentially, form dispersion or solution.
(2) optionally with this dispersion or solution and water combination, form said aqueous concentrates: and/or
(3) dilute with water dispersion or solution or enriched material, water consumption to make in the enriched material or in the basic water function fluid composition of the present invention and other functional additive reach required concentration.
Above-mentioned mixing step utilizes conventional equipment, generally carries out under room temperature or comparatively high temps (generally be lower than 100 ℃, be usually less than 50 ℃).As mentioned above, after enriched material forms, be sent to the place to use, dilute with water generates required basic water function fluid again.In other cases, final basic water function fluid can be directly forms in being used for preparing the same equipment of enriched material or dispersion or solution.
Spendable functional additive is the insoluble additive of oily molten water that typically works in conventional base oil system, as E, P agent, wear preventive additive, load-carrying additive, friction modifier, lubricant etc.They also can play slipproofing agent, membrane-forming agent and friction modifier.As everyone knows, this class additive can have above-mentioned two or more functions: for example E, P agent often have the function of load-carrying additive.
" the insoluble functional additive of oily molten water " this term means a kind of functional additive, and its meltage in 25 ℃ of following 100 ml waters is no more than about 1 gram, but dissolves 1 gram in 25 ℃ of following every liter of mineral oil at least.
These functional additives also can comprise some solid lubricant, as graphite, molybdenumdisulphide, tetrafluoroethylene and relevant solid polymer.
These functional additives can comprise that also friction polymer forms thing.Say that simply these are at potential forming polymer material, they are dispersed in the liquid vehicle with lower concentration, carry out surface aggregate when friction or contact, and form the protectiveness polymeric film on this surface.Polymerization be considered to since the heat that friction generates and may since the catalysis on new exposed surface and/or chemical action cause.The object lesson of this material has the dilinoleic acid that can form the polyester friction polymer film and the composition of 1,2 ethylene glycol.These materials are known, can recognize in the literature, as " shearing " (Wear) magazine 26 volume 369-392 pages or leaves, the application for patent 2,339,065 that West Germany publishes.Wherein incorporate this paper in this reference about the discussion of friction polymer formation thing.
Typical these functional additives are the metal-salt or the amine salt of known organosulfur, phosphorus, boron or carboxylic acid, and are identical with the additive that uses in the base oil fluid, or type is identical.The salt that typical this class salt is following acid: the aromatic series of 1～22 carbon atom or aliphatic carboxylic acid; Sulfur acid is as alkyl or aromatic sulphonic acid and analogue; Phosphoric acid is as phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, phosphate ester acid and similar sulfur-bearing homologue, as thiophosphoric acid and phosphorodithioic acid and relevant acid ester; Boronic acid containing comprises boric acid, acid borate and analogue.Useful functional additive also comprises the metal dithionite carbaminate, as molybdenum dithiocarbamate and antimony; And butyl disulfide tin, tributyltin oxide, phosphoric acid salt and phosphite; The boric acid amine salt, clorafin; Oxidation trialkyltin, molybdenum phosphate and clorafin.
This class functional additive major part in the present technique field is known.For example, in following document, can see description: " progress of petroleum chemistry and oil refining " the 8th volume for additive useful in conventional base oil system and Aquo System of the present invention, (edit by John J.Mcketta, New York Interscience publisher, 1963) the 31st～38 page of content that comprises; " chemical technology complete works " 12 volume (second edition, New York Interscience publisher, 1967) the 575th page and subsequent content of Kirk-Othmer; " lubricant additive " of M.W.RanneY (NoYes Data company, Park Ridge, N.J., 1973); " lubricating oil additive " of C.V.Smalheer and R.K.Smith (Lezius-Hiles company, Ohio, USA Clevelanel).These reference are incorporated this paper with regard to the disclosure that it can be used for functional additive in the system of the present invention in this reference.
In typical Aquo Systems more of the present invention, functional additive is the known sulfur-bearing that can be used for the base oil system or chloro-sulphur E, P, agent.They comprise chlorinated aliphatic, as clorafin; Organic sulfide and polysulfide, as benzyl disulphide, two (zephiran chloride) disulphide, the dibutyl tetrasulfide, the sulfuration Sperm whale oil vulcanizes oleic methyl esters, sulfenyl phenolate, sulfuration limonene, sulfuration terpenes and sulfuration diels-alder adduct; Phosphosulfurized hydrocarbon is as the reaction product of phosphoric sulfide and rosin or Witconol 2301; Phosphorus ester is as phosphorous acid two hydrocarbon and trialkyl, i.e. dibutyl phosphite, phosphorous acid two heptyl esters, phosphorous acid two cyclohexyls, phosphorous acid amyl group phenyl ester, phosphorous acid diamyl phenyl ester, tridecyl phosphite, the substituted phenol phosphorous acid ester of phosphorous acid distearyl ester and polypropylene; Metal sulfo-amino hydrochlorate is as dioctyl zinc dithiocarbamate and heptylphenol dithiocarbamic acid barium; The II family metal-salt of phosphorodithioic acid is as the zinc salt of dicyclohexyl zinc dithiophosphate and phosphorodithioic acid.
Functional additive also can be a membrane-forming agent, as synthetic or natural emulsion or its emulsion in water.Such latex comprises caoutchouc latex and polystyrene divinyl synthetic latex.
Functional additive also can be knock-compound or noise elimination agent (antisquawk), its example has acyl ammonia metal dithionite for phosphate composition, and as Deutsches Reichs-Patent 1,109,302 are disclosed; Amine salt-azo methene composition is disclosed as british patent specification 893,977; Perhaps United States Patent (USP) 3,002, the 014 phosphorodithioic acid amine that discloses.Noise elimination agent example has United States Patent (USP) 3,156,652 and 3,156, the 653 N-acyl group-sarkosines that disclosed and its derivative; United States Patent (USP) 2,913,415 and 2,982,734 sulfide aliphatic acid that discloses and its esters; United States Patent (USP) 3,039, the ester of 967 dimer (fatty acid) yls that disclose.Above-mentioned patent is incorporated this paper with regard to its disclosure about knock-compound and noise elimination agent (they can be used for the functional additive of Aquo System of the present invention) in this reference.
The object lesson that can be used for Aquo System functional additive of the present invention comprises the following product that can buy on market.
The table I
Functional additive trade(brand)name chemical name supplier
Anglamo132 chloro sulfuration hydrocarbon Lubrizol '
Anglamo175 dialkyl group zinc phosphate Lubrizol '
Molyvan L sulfo-phosphomolybdate Varderbilt
2
Lubrizol-5315 sulfuration ring carboxylicesters Lubrizol '
Emcol TS230 acid phosphoric acid ester Witco
3
1.Lubrizol company, Ohio, USA Wickliffe.
2.R.T.Vanderbilt company, the New York, United States New York.
3.Witco chemical company, organic product portion, Texas, USA Houston.
Also can use the mixture of above-mentioned work post or multiple functional additive arbitrarily.
The functional additive that generally contains significant quantity in the system that contains of the present invention, for example, if desire to make functional additive mainly as load-carrying additive, its consumption then is the amount of load-carrying additive.
Aquo System of the present invention contains a kind of anticolodal usually at least, to prevent the two corrosion of ferrous metal metal (as copper, bronze, brass, titanium, aluminium and analogue) or they.Sanitas itself can be an organic or inorganic.Although the effect of sanitas also can be played in the water fast, generally speaking, sanitas can fully dissolve in water, so that satisfied preservative activity to be provided.Sanitas is not necessarily water-soluble.The many suitable inorganic corrosion inhibitor that can be used for Aquo System of the present invention is known those of skill in the art.Comprising at Burns and Bradley " the maintenance coating of metal " (Reinhold) publishing company, second edition) sanitas described in 596～605 pages in the 13rd chapter.This part content about sanitas is incorporated this paper in this reference.The example of useful inorganic corrosion inhibitor comprises alkali metal nitrites salts, two and tripolyphosphate sodium salt, potassiumphosphate or di-potassium, alkali metal borate and their mixture.Many suitable organic anti-corrosive agent are known to those skilled in the art.Object lesson comprises the alkylamine of alkylamine and carboxyl substituted, neutral acid compound such as neutral phosphoric acid salt and alkyl phosphate, neutral lipid acid (containing 8 to 22 carbon atoms according to appointment), neutral aromatic carboxylic acid (as the 4-p t butylbenzoic acid), neutral naphthenic acid and neutral hydrocarbyl sulfonate, the mixing salt ester of the inferior acid amides of alkylation amber also is an available.Useful especially amine comprises alkanolamine, as thanomin and diethanolamine, also can use the mixture of any two kinds or multiple foregoing preservatives.The corrosion of metal when concentration that sanitas usually exists can prevent to contact with aqueous composition effectively.
Some Aquo System of the present invention (especially for the system of metal forming or cutting) also can contain at least a polyvalent alcohol that has retrograde solubility in water.This class polyvalent alcohol raises and the solubleness minimizing with water temperature.Therefore they also can resemble the surface lubricant in cutting or handle in the operation and work, because along with the friction between metal processing piece and the instrument causes liquid heat, polyvalent alcohol with reverse dissolution degree can " be separated out " on work piece surface, has improved the oilness of workpiece thus.
Aquo System of the present invention also can comprise at least a sterilant, this series bactericidal agent is known to those skilled in the art, " functional materials " book that the visible above-mentioned Mccutcheob of specific examples publishes, title is " biocide ", the 9-20 page or leaf, wherein the content of Xu Shu the relevant sterilant that can be used for aqueous composition of the present invention or system is incorporated this paper in this reference.These sterilant generally are water miscible, and its dissolved degree will make it play the effect of sterilant at least.
Aquo System of the present invention also can comprise other material: dyestuff (as the acid green dyestuff), water-softening chemicals (as disodium edta or nitrilotriacetic acid(NTA)), odor mask (as lemongrass, lemon oil and analogue), antifoams (siloxanes antifoams as the well-known).
When needs used composition at low temperatures, Aquo System of the present invention also can contain antifreeze additive.Can use 1,2-diethyl two these class materials of pure and mild similar polyoxyalkylene polyol are as frostproofer.Obviously, its consumption depends on the degree that needs anti-frost protection, and this is known to one of ordinary skill in the art.
Should be noted that above-mentioned many components that are used to prepare Aquo System of the present invention all are industrial products, they can give this system more than one performance.Therefore a kind of component may provide multiple function, has reduced the needs that other is added component thus, and perhaps finishing does not need.For example, E.P agent (as tributyltin oxide) also can play sterilant.
According to patent law, best mode and better embodiment have been proposed here, scope of the present invention is proposed by appended claims.
Claims (20)
1, can be at aqueous phase dispersive water-soluble salt disperser composition, comprising:
The reaction product of at least 0.5 equivalent (A)/mol (B), wherein
(A) be mineral acid or 1-10 carbon organic acid, except the sulfonic acid organic acid and
(B) be not phosphorous carboxyl solubilizing agent, its method for making is with (B1) at least a following formula poly carboxylic acid acylating agent
Wherein hyd is a 30-200 carbon alkyl or alkenyl substituting group, and n is the integer of 1-4, with poly-(alkylene amines) reaction of at least a following formula
Wherein n is the integer of 1-10, and D is hydrogen or maximum 30 carbon alkyl, and alkylidene group contains 1-10 carbon, and dipersant comprises at least a tensio-active agent, the mixture of hydrophilic organic solvent or tensio-active agent and hydrophilic organic solvent, its amount is 5wt% at least, in composition.
2, according to the dipersant composition of claim 1, tensio-active agent wherein is cationic, anionic or non-ionic hydrophilic tensio-active agent.
3, according to the dipersant composition of claim 2, wherein the D of (B2) poly-(alkylene amines) contains 8 carbon atoms or still less.
4, according to the dipersant composition of claim 3, (A) organic acid wherein is the simple function organic acid of 1 to 4 carbon atom.
5, according to the dipersant composition of claim 4, wherein (B1) hyd substituting group contains 30 to 100 carbon atoms.
6, according to the dipersant composition of claim 1, wherein (A) mineral acid is hydrochloric acid or phosphoric acid.
7, according to the dipersant composition of claim 1, acylating agent wherein is the polyisobutenyl succinyl oxide.
8, according to the dipersant composition of claim 1, acylating agent wherein is a polyisobutenyl succinic anhydride.
9, according to the dipersant composition of claim 1, wherein contain water.
10, according to the dipersant composition of claim 2, wherein contain water, the water yield will make it form discontinuous phase.
11, dipersant composition according to Claim 8, the water yield wherein make it form discontinuous phase.
12, according to the dipersant composition of claim 1, wherein contain water, and water forms external phase.
13, according to the dipersant composition of claim 2, wherein contain water, and water forms external phase.
14, according to the dipersant composition of claim 4, wherein contain water, and water forms external phase.
15, according to the dipersant composition of claim 6, wherein contain water, and water forms external phase.
16, according to the dipersant composition of claim 7, wherein contain water, and water forms external phase.
17, according to the dipersant composition of claim 1, wherein contain water and divided particles, this particle is selected from carbon black, pigment, fiber, filler or their composition.
18,, wherein contain water and at least a dispersive liquid according to the dipersant composition of claim 1.
19,, wherein contain water and at least a dispersive gas according to the dipersant composition of claim 1.
20, according to the dipersant composition of claim 14 or 16, wherein contain divided particles, this particle is selected from carbon black, pigment, fiber, filler and their composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86101650.5A CN1009618B (en) | 1984-12-27 | 1986-02-14 | Dispersant salts |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68678684A | 1984-12-27 | 1984-12-27 | |
| CN86101650.5A CN1009618B (en) | 1984-12-27 | 1986-02-14 | Dispersant salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101650A CN86101650A (en) | 1987-08-26 |
| CN1009618B true CN1009618B (en) | 1990-09-19 |
Family
ID=25742184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101650.5A Expired CN1009618B (en) | 1984-12-27 | 1986-02-14 | Dispersant salts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009618B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049211A (en) * | 2010-10-26 | 2011-05-11 | 苏州博纳化学科技有限公司 | Organic-inorganic composite dispersing agent as well as preparation method and application thereof |
| US9243203B2 (en) * | 2012-11-30 | 2016-01-26 | Chevron Oronite Company Llc | Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation |
| CN107206337A (en) * | 2014-12-19 | 2017-09-26 | 阿克苏诺贝尔化学品国际有限公司 | General dispersant |
-
1986
- 1986-02-14 CN CN86101650.5A patent/CN1009618B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86101650A (en) | 1987-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1045308C (en) | Water soluble metal working fluids | |
| CN1049532A (en) | Corrosion-inhibiting compositions and functional liquid thereof | |
| CN1078229C (en) | Method for preparing bitumen/polymer compsn., and use thereof | |
| EP0152677B1 (en) | Aqueous systems containing organo-borate compounds | |
| CN102643706B (en) | Nanoparticle additives and the lubricant formulations containing this nanoparticle additives | |
| CN1006717B (en) | Water-based functional fluid thickening combination or surfactants and hydrocarbyl-substituted acid and/or anhgdride/amine terminated poly (oxyalkylene) reaction products | |
| CN1319648A (en) | Preparation of lubricant additive | |
| CN1532269A (en) | Method for lubricating diamond-like carbon coated surfaces | |
| CN1028876C (en) | Hydrocarbyl-substituted succinic acid and/or anhydride/amine Terminated poly (oxyalkylene) reaction products, and Aqueous systems containing-same | |
| CN86103481A (en) | Sulfur-containing compositions and multifunctional additive for lubricating oils, lubricating oil and contain the metal working lubricant of above-mentioned substance | |
| CN1616613A (en) | Power transmission fluids having extended friction durability | |
| CN1346875A (en) | Lubircation of plunger engine | |
| CN1357609A (en) | Lubricant oil composition | |
| CN1009618B (en) | Dispersant salts | |
| US4642330A (en) | Dispersant salts | |
| CN1441038A (en) | Lubrication oil composition | |
| EP0207967B1 (en) | Dispersant salts | |
| JPS62500727A (en) | Aqueous systems containing aminosulfonic acid derivatives of carboxylic acids | |
| CN1131183A (en) | Lubricant additive and lubricating grease composition containing the same | |
| CN1106859A (en) | Molybdenum-containing friction-reducing additives | |
| US3809647A (en) | Grease composition | |
| GB2032951A (en) | Carboxylic Solubilizer/ Surfactant Combinations and Aqueous Compositions Containing Same | |
| CN1539935A (en) | Grease compsns. | |
| CN87106648A (en) | Blended overbase complex antifouland compositions and application thereof | |
| CN1940039A (en) | Grease composition for pivot assembly bearing and bearing for pivot assembly |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |