CN104981536A - Process for preparing urea grease - Google Patents

Process for preparing urea grease Download PDF

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Publication number
CN104981536A
CN104981536A CN201480007940.1A CN201480007940A CN104981536A CN 104981536 A CN104981536 A CN 104981536A CN 201480007940 A CN201480007940 A CN 201480007940A CN 104981536 A CN104981536 A CN 104981536A
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China
Prior art keywords
compound
formula
urea
product
grease
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CN201480007940.1A
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Chinese (zh)
Inventor
S·德格林
A·赫拉维尔
E·科恩
A·马西
H·B·米德
D·范兹维坦
T·维瑟
R·J·威尔金森
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of CN104981536A publication Critical patent/CN104981536A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02—Mixtures of base-materials and thickeners
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides for a process for preparing urea grease. The process is carried out in the presence of a base oil and avoids the use of diisocyanate reagents.

Description

Prepare the method for urea-base grease
Invention field
The present invention relates to the method preparing urea-base grease.
background of invention
Urea-base grease is used to multiple application, comprises bearing in constant-velocity joint bearing, ball joint bearing, wheel bearing, alternator, cooling fan, ball screw, the linear guide rod of lathe, the sliding area of Architectural Equipment and steel equipment and gear and other industrial machinery multiple.Urea-base grease has excellent thermotolerance and scale resistance usually, and can extend bearing life.
Urea-base grease contains low-molecular-weight organic compound, and sometimes referred to as polyureas, it synthesizes usually from isocyanic ester and amine.Vulcabond and monoamine can be used for formation two urea:
Vulcabond and diamines can be used for formation four urea:
Vulcabond, alcohol and diamines can be used for forming triuret-carbamate:
Urea-base grease can be formed by carrying out these reactions in base oil, and directly provide lubricating grease product thus, wherein urea thickening material is dispersed in whole base oil.
The reaction of vulcabond and amine does not require any heat, and at room temperature carries out with good speed.There is no the byproduct of reaction that must remove.But vulcabond reagent is high toxicity and volatile, require special process and treatment unit.Expect the alternative route for the production of urea-base grease finding to avoid using vulcabond reagent.
summary of the invention
Therefore, the invention provides the method preparing urea-base grease, it is included in wherein by one or more steps that the compound of the compound of formula (I), formula (II) and the compound of formula (III) react.
Wherein R 1and R 2be selected from the alkyl with 1 to 30 carbon atoms, or R 1and R 2be connected and form the alkylen group with 1 to 30 carbon atoms, R 3be selected from the alkyl comprising 2 to 30 carbon atoms, and R 4it is the alkylene comprising 2 to 30 carbon atoms;
Wherein at least one reactions steps is carried out under the existence of base oil.
The inventive process provides urea-base grease, but avoid using vulcabond reagent.Urea synthesis without vulcabond describes in the Ph D dissertation " Isocyanate-freesynthesis of (functional) polyureas; polyurethanes andurethane-containing copolymers " of Luc Ubaghs, but the preparation of the unexposed urea-base grease of this file.The present inventor has been found that can by preparing urea-base grease by the reaction of the compound of formula (I), (II) and (III), and wherein at least one reactions steps is carried out under the existence of base oil.
accompanying drawing is sketched
Fig. 1 shows the reacting flow chart of urea-base grease produced according to the present invention.
Fig. 2 shows the reacting flow chart of urea-base grease produced according to the present invention.
Fig. 3 shows the reacting flow chart of urea-base grease produced according to the present invention.
Fig. 4 shows the reacting flow chart of urea-base grease produced according to the present invention.
detailed Description Of The Invention
Term " alkyl " used in this specification sheets refers to and comprises hydrogen and carbon and can be aliphatic series, aromatics or alicyclic monovalent organic groups, such as, but be not limited to, aralkyl, alkyl, aryl, cycloalkyl, alkyl-cycloalkyl or its combination, and can be saturated or olefinic is undersaturated (conjugation or unconjugated one or more double key carbon).Term " alkylene " used in this specification sheets refers to and comprises hydrogen and carbon and can be aliphatic series, aromatics or alicyclic divalent organic group, such as, but be not limited to, aralkyl, alkyl, aryl, cycloalkyl or alkyl-cycloalkyl, and can be saturated or olefinic is undersaturated (conjugation or unconjugated one or more double key carbon).
The invention provides the method preparing urea-base grease.The compound of the compound of formula (I), formula (II) and the compound of formula (III) are reacted:
R 1and R 2be selected from the alkyl with 1 to 30 carbon atoms, or R 1and R 2be connected and form the alkylen group with 1 to 30 carbon atoms.R 1and R 2preferably only comprise hydrocarbyl group or the alkylen group of hydrogen and carbon atom, but possibly, R 1and R 2also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent, if particularly R 1or R 2in one or more are words of aromatic yl group.The R be applicable to 1and R 2be selected from the aryl with 6 to 12 carbon atoms and the alkyl with 1 to 12 carbon atoms, or R 1and R 2be connected and form the alkylidene group with 1 to 12 carbon atoms.Preferably, R 1and R 2be selected from phenyl and have 6 to 12 carbon atoms replacement phenyl group and there is the alkyl group of 1 to 12 carbon atoms, or R 1and R 2be connected and form the alkylidene group with 1 to 6 carbon atoms.The phenyl replaced comprises phenyl (preferably at contraposition or ortho position) that methyl substituted or ethyl replaces or the phenyl that oxyethyl group replaces.Most preferably, R 1and R 2all phenyl or R 1and R 2be connected and form ethylene group, namely the compound of formula (I) is diphenyl carbonate or ethylene carbonate.Compatibly select R 1and R 2make R 1-OH and R 2-OH (or HO-R 1-R 2-OH) be the compound that easily can remove from reaction mixture.
R 3be selected from the alkyl comprising 2 to 30 carbon atoms.R 3preferably only comprise hydrogen and carbon atom, but possibly, R 3also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent, if particularly R 3the words of aromatic yl group.Preferably, R 3there is the aryl of 6 to 12 carbon atoms or comprise the alkyl of 2 to 18 carbon atoms.Most preferably, the compound of formula (II) is selected from octylame, amino dodecane (lauryl amine), tetradecy lamine (Semen Myristicae amine), cetylamine, stearylamine (tallow amine, also referred to as stearylamine), oleyl amine, aniline, benzylamine, para-totuidine, p-Chlorobenzoic acid amide or waste water.
R 4it is the alkylene comprising 2 to 30 carbon atoms.R 4preferably only comprise hydrogen and carbon atom, but possibly, R 4also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent, if particularly R 4the words of arylene group.Preferably, R 4comprise the arylidene of 6 to 12 carbon atoms or comprise the alkylidene group of 2 to 12 carbon atoms.Most preferably, the compound of formula (III) is selected from the arylidene comprising 6 to 12 carbon atoms.The compound of preferred formula (III) is as follows:
In an embodiment of method of the present invention, the compound of the compound of formula (I), formula (II) and the compound of formula (III) are reacted in one step under the existence of base oil.But in preferred embodiment, reaction is carried out in two steps, and second step carries out under the existence of base oil.First preferred embodiment in, the method preparing urea-base grease comprises the following steps:
(a1) compound of the compound of formula (I) and formula (II) is reacted:
With
(b1) compound of the product of step (a1) and formula (III) is reacted:
Wherein step (b1) is carried out under the existence of base oil.Second preferred embodiment in, the method preparing urea-base grease comprises the following steps:
(a2) compound of the compound of formula (I) and formula (III) is reacted:
With
(b2) compound of the product of step (a2) and formula (II) is reacted:
Wherein step (b2) is carried out under the existence of base oil.
First preferred embodiment in, react in the compound of step (a1) Chinese style (I) and the compound of formula (II):
If R 1and R 2be connected and form alkylen group, so just only having a kind of product.If R 1and R 2be hydrocarbyl group (and not being connected), so will produce alcohol by product in step (a1), and preferably before step (b1), remove this by product.
Two urea greases are applicable to, by being reacted in step (a1) by the compound of formula (I) with (II), being reacted to prepare by the compound of the product of step (a1) and formula (III) subsequently in step (b1).
If four urea greases expect product, so react in step (a1) Chinese style (I) and the compound of (II) compound that is other and formula (IV):
Wherein R 5it is the alkylene comprising 2 to 30 carbon atoms.Then the product of step (a1) and the compound of formula (III) react in step (b1):
R 5preferably only comprise hydrogen and carbon atom, but possibly, R 5also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent.R 5preferably comprise the arylidene of 6 to 12 carbon atoms or comprise the alkylidene group of 2 to 12 carbon atoms.The compound of preferred formula (IV) comprises quadrol, propylene diamine, butanediamine, pentamethylene diamine and hexanediamine.
If triuret-carbamate lubricating grease expects product, so step (a1) Chinese style (I) and (II) compound in addition and the compound of formula (V) and the compound of formula (VI) react:
Wherein R 6and R 7independently selected from the alkyl comprising 2 to 30 carbon atoms.
Then the product of step (a1) and the compound of formula (III) react in step (b1):
R 6preferably only comprise hydrogen and carbon atom, but possibly, R 6also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent.R 6preferably comprise alkylidene group or the alkenylene of 2 to 24 carbon atoms.The compound of preferred formula (V) comprises 1-lauryl alcohol (lauryl alcohol), 1-tetradecyl alcohol (tetradecyl alcohol), Cetyl OH (spermaceti (or palm) alcohol), 1-stearyl alcohol (stearyl alcohol), cis-9-octadecene-1-ol (oleyl alcohol), 9-18 carbon diene-1-alcohol (unsaturated Palmitoleyl alcohol (palmitoleyl alcohol)), 12-18 carbon diene-1-alcohol (linoleyl alcohol).
R 7preferably only comprise hydrogen and carbon atom, but possibly, R 7also hetero atom substituents can be comprised, such as halogen, nitro, hydroxyl or alkoxy substituent.R 7preferably comprise the arylidene of 6 to 12 carbon atoms or comprise the alkylidene group of 2 to 12 carbon atoms.The compound of preferred formula (VI) comprises quadrol, propylene diamine, butanediamine, pentamethylene diamine and hexanediamine.
The product of step (a1) is being used for before step (b1), preferably the compound of any unreacted formula (I) of removing and (II), any solvent that may use and any by product (particularly R 1-OH and R 2-OH compound).Removing compatibly uses vacuum to realize.
Second preferred embodiment in, react in the compound of step (a2) Chinese style (I) and the compound of formula (III):
If R 1and R 2be connected and form alkylen group, so just only having a kind of product.If R 1and R 2be hydrocarbyl group (and not being connected), so will produce alcohol by product in step (a2), and preferably before step (b2), remove this by product.
Two urea greases are applicable to, by being reacted in step (a2) by the compound of formula (I) with (III), being reacted to prepare by the compound of the product of step (a2) and formula (II) subsequently under the existence of base oil in step (b2).
If four urea greases expect product, so react in step (a2) Chinese style (I) and the compound of (III) compound that is other and formula (IV):
Wherein R 5it is the alkylene comprising 2 to 30 carbon atoms.Preferred R 5group is as described in the present invention first preferred implementation.In step (a2), the compound of formula (I) will react with the compound of formula (III), and the compound of formula (I) will react with the compound of formula (IV).In step (b2), the reaction product of step (a2) is then reacted with the compound of formula (II):
If triuret-carbamate lubricating grease expects product, so react in other and formula (V) and (VI) the compound of compound of step (a2) Chinese style (I) and (III):
Wherein R 6and R 7independently selected from the alkyl comprising 2 to 30 carbon atoms.Preferred R 6and R 7group is as described in first embodiment of the invention.In step (a2), the compound of formula (I) will react with the compound of formula (III), the compound of formula (I) will react with the compound of formula (V), and the compound of formula (I) will react with the compound of formula (VI).In step (b2), the reaction product of step (a2) is then reacted with the compound of formula (II):
Before the product of step (a2) is used for step (b2), the preferably compound of any unreacted formula (I) of removing and (III), any solvent that may use and any by product (particularly R 1-OH and R 2-OH compound).Removing compatibly uses vacuum or sufficient solvent wash to realize.
Preferred reaction conditions in step (a1) and (a2) will be subject to the impact of the selection of compound (I).If compound (I) is diphenyl carbonate, so step (a1) or (a2) preferably do not use solvent or carry out under the existence of solvent such as toluene or dimethyl formamide.Reaction is preferably carried out under the existence of catalyzer such as diphenyl phosphonic acid.Phenol will produce as byproduct of reaction.Phenol by-product should such as by using vacuum removing.If compound (I) is methylcarbonate, so expect to use catalyzer such as dibutyl methoxyl group tin, dibutyl tin laurate or stannous octoate (II).Other catalyzer spendable comprise potassium tert.-butoxide, acetylacetone copper (II), DABCO BL11 and DABCO LV33.
Preferred reaction conditions in step (b1) and (b2) will be subject to the impact of the selection of compound (I).If compound (I) is diphenyl carbonate, so preferably reactant is heated at least 90 DEG C, more preferably from about 100 DEG C.Reaction is preferably carried out in the absence of a catalyst.If compound (I) is methylcarbonate, so preferably reactant is heated at least 130 DEG C, more preferably from about 140 DEG C.Reaction is preferably carried out under the existence of catalyzer such as dibutyl tin laurate.The present inventor has been found that extra heating is normally necessary, so that the reaction product of step (b1) or (b2) is converted into lubricating grease.Preferably the reaction product of step (b1) or (b2) is heated at least 170 DEG C, then cools.
The base oil be present at least one reactions steps can be mineral origin, synthesis source or its combination.The base oil of mineral origin can be mineral oil, such as, produced by solvent refined or hydrotreatment those.The base oil in synthesis source can comprise the mixture of C10-C50 hydrocarbon polymer usually, such as, and the polymkeric substance of alpha-olefin, synthetic ester lubricant, ether-type synthetic oil and combination thereof.Base oil can also comprise the high alkane product that Fischer-Tropsch method obtains.
The mineral base oil example be applicable to comprises alkane base oil and cycloalkanes base oil.The ratio of the carbon that alkane base oil has usually in aromatic structure (Ca) is 1 to 10%, in cycloalkane structure (Cn) be 20 to 30% and in chain alkyl structure (Cp) be 60 to 70%.The ratio of the carbon that cycloalkanes base oil has usually in aromatic structure (Ca) is 1 to 20%, in cycloalkane structure (Cn) be 30 to 50% and in chain alkyl structure (Cp) be 40 to 60%.
The example of the base oil be applicable to comprises middle viscous mineral oil, high viscosity mineral oil and combination thereof.Middle viscous mineral oil generally has 5mm at from 100 DEG C 2/ s centistoke (cSt) is to 15mm at 100 DEG C 2in/s (cSt) scope, preferably 6mm at from 100 DEG C 2/ s (cSt) is to 12mm at 100 DEG C 2in/s (cSt) scope, and more preferably 7mm at from 100 DEG C 2/ s (cSt) is to 12mm at 100 DEG C 2viscosity in/s (cSt) scope.High viscosity mineral oil generally has 15mm at from 100 DEG C 2/ s (cSt) is to 40mm at 100 DEG C 2in/s (cSt) scope, and preferred 15mm at from 100 DEG C 2/ s (cSt) is to 30mm at 100 DEG C 2viscosity in/s centistoke (cSt) scope.
Can be easy to use be applicable to mineral oil example comprise Shell Group member company sell called after " HVI ", " MVIN " or " HMVIP " those.Also polyalphaolefin and the base oil of the type prepared by the hydroisomerization of wax can be used, those of called after " XHVI " (trade mark) that such as ShellGroup member company sells.
At least one reactions steps is carried out under the existence of base oil, and preferred end reaction step is carried out under the existence of base oil.The product urea-base grease of method of the present invention comprises urea thickening material and base oil.Preferably, based on the gross weight of urea-base grease, the weight percent of the urea that urea-base grease comprises from the scope of 2 % by weight to 25 % by weight, more preferably from the scope of 3 % by weight to 20 % by weight, with most preferably from the scope of 5 % by weight to 20 % by weight.
The product of method of the present invention is urea-base grease.Preferably, the basic lubricating grease obtained from step (b1) or step (b2) stands further finishing (finishing) process, such as homogenize, filtration and degassed.
Prepared according to the methods of the invention urea-base grease can comprise one or more additives of normally used amount in the application field, to give urea-base grease some desired character, comprise, such as, oxidative stability, stickiness, extreme pressure character, corrosion-inhibiting, minimizing friction and wear and combination thereof.Additive preferably joined basic lubricating grease before finishing.Most preferably, by basic lubricating grease homogenize, then add additive, then lubricating grease is stood further homogenize.
The additive be applicable to comprises one or more extreme pressure/antiwear agents, such as zinc salt, such as phosphorodithioic acid dialkyl group zinc or phosphorodithioic acid diaryl zine, boric acid ester, the thiadiazoles be substituted, what obtained by dialkoxy amine and the reaction of the organophosphate be substituted is polymerized nitrogen/phosphorus compound, phosphamide, sulfuration natural or synthesizes whale oil, sulfurized lard, sulfuration ester, sulfide aliphatic acid ester and the similar sulfidic material of originating, organophosphate, such as, according to formula (OR) 3p=O, wherein R is alkyl, aryl or aralkyl, and triphenyl-thiophosphate; One or more high alkalinity containing metal washing composition, such as alkyl sodium salicylate or magnesium, or alkyl aryl sulphonic acid calcium or magnesium; One or more are without ash content dispersant additives, the reaction product of such as polyisobutylene succinic anhydride and amine or ester; One or more antioxidants, such as hindered phenol or amine, such as phenyl αnaphthylamine, pentanoic or alkylated diphenylamine; One or more rust-inhibiting additives, the oxygen-containing hydrocarbon of such as optional calcium neutralization, the calcium salt of alkylated benzenes sulfonic acid and the calcium salt of alkylated benzenes mahogany acid and succinic acid derivative, or friction modified additive; One or more viscosity index improvers; One or more depression of pour point additives; With one or more sizing agents.Also solid material such as graphite, the MoS that grinds can be added 2, talcum, metal-powder and various polymkeric substance such as polyethylene wax, give special properties.
Based on the gross weight of urea-base grease, prepared according to the methods of the invention urea-base grease can comprise 0.1 % by weight to 15 % by weight, preferably 0.1 % by weight to 5 % by weight, more preferably 0.1 % by weight to 2 % by weight, even more preferably one or more additives of 0.2 % by weight to 1 % by weight.
The urea-base grease that method according to the present invention is produced is applicable to the application of typical urea-base grease, such as, bearing in the sliding area of constant-velocity joint bearing, ball joint bearing, wheel bearing, alternator, cooling fan, ball screw, the linear guide rod of lathe, Architectural Equipment and steel equipment and gear and other industrial machinery multiple.
In alternate embodiments of the present invention, can prepare urea-base grease by the following method, described method is included in wherein by one or more steps that the compound of the compound of formula (I), formula (II) and the compound of formula (III) react:
Wherein R 1and R 2be selected from the alkyl with 1 to 30 carbon atoms, or R 1and R 2be connected and form the alkylen group with 1 to 30 carbon atoms, R 3be selected from the alkyl comprising 2 to 30 carbon atoms, and R 4it is the alkylene comprising 2 to 30 carbon atoms; With comprise wherein gained urea product and be dispersed in the step in base oil.In this modification of the present invention, synthesize urea from compound (I), (II) and (III), then by urea powder dispersion in base oil to form lubricating grease.
Illustrate that the reacting flow chart of four kinds of proposed urea-base grease synthesis is shown in Fig. 1,2,3 and 4.
Fig. 1 shows the method that wherein diphenyl carbonate (2) does not use solvent to react in a nitrogen atmosphere with quadrol (4) and octylame (1).After the completion of reaction, excessive phenol is removed in a vacuum.By under the same conditions and introduce methylenediphenyl diamines (6) under the existence of base oil, and then two kinds of intermediates (3,5) are combined into final four ureas (7).Reaction product is heated to 170 DEG C to form four urea greases.
Fig. 2 shows and wherein octylame (1) and quadrol (4) is joined the method in ice-cooled ethylene carbonate (8) aqueous solution.Reaction is by (Bu 2sn (OMe) 2) catalysis.After the short reaction times, under vacuo except desolventizing and excessive amine, and separated product 9 and 10.In further ligation, by (Bu at 150 DEG C 2sn (OMe) 2) catalysis and under the existence of base oil, product 9 is connected with methylenediphenyl diamines (6) with 10.Remove the ethylene glycol obtained in a vacuum.Reaction product is heated to 170 DEG C to form four urea greases.
Fig. 3 shows wherein methylcarbonate (1) and 4, the method that 4 '-methylene dianiline (MDA) (2) reacts at 80 DEG C under the existence of potassium tert.-butoxide.Methyl alcohol will remove as by product.Diphenylcarbamate product (3) and octylame (4) react under the existence of base oil and dibutyl tin laurate at 100 DEG C, and to provide lubricating grease product, it is two ureas in base oil.Reaction product is heated to 170 DEG C to form two urea greases.
Fig. 4 shows wherein diphenyl carbonate (1) and 4, the method that 4 '-methylene dianiline (MDA) (2) reacts at 100 DEG C under the existence of diphenyl phosphonic acid.Phenol will remove as by product.Diphenylcarbamate product (3) and octylame (4) react under the existence of base oil at 100 DEG C, and to provide lubricating grease product, it is two ureas in base oil.Reaction product is heated to 170 DEG C to form two urea greases.
Embodiment
The present invention is further explained in detail hereinafter by embodiment and comparing embodiment, but the present invention is not limited by any way by these embodiments.
embodiment 1a: step (a2)---the synthesis of Diphenylcarbamate
The mixture of diphenyl carbonate (2 equivalent), 4,4'-methylene dianiline (MDA)s and diphenyl phosphonic acid (5-10%) reacts spend the night (solid melts, then solid is formed again) at 100 DEG C.
By adding dme, filtration and processing product with dme washing.Obtaining yield is the Diphenylcarbamate of 91-94%.
embodiment 1b: step (a2)---the synthesis of Diphenylcarbamate
The mixture of diphenyl carbonate (2 equivalent), 4,4'-methylene dianiline (MDA)s and diphenyl phosphonic acid (10%) reacts (1ml/g diphenyl carbonate) at 100 DEG C in toluene.Mixture reflux, after 14 hours, the only raw material of surplus 7%.
embodiment 1c: step (b2)---the synthesis of two ureas in base oil
5g Diphenylcarbamate in base oil (14.5g) and octylame react and spend the night at 110 DEG C.With 5x15ml washing with acetone product.Add extra base oil (14.5g), and mixture is stirred 10 minutes at 100 DEG C, cool to room temperature.Lubricating grease is not formed after cooling.Sample is heated to 100 DEG C again, and stirs under 1000rpm and spend the night.Still lubricating grease is not formed.Material stirred 30 minutes again at 170 DEG C and cools, forming lubricating grease.Measure the character that lubricating grease is also shown in Table 1.
embodiment 1d: step (b2)---the synthesis of two ureas in base oil
By the 101g Diphenylcarbamate prepared according to embodiment 1a in base oil (506g) and octylame (60g) at 96 DEG C heated overnight.Cooling mixture with acetone (4x500ml) stirring, sedimentation decant to remove phenol and by product (be 95% pure according to NMR).Use rotatory evaporator dry substance, be heated to 170 DEG C, then cool to form lubricating grease.Measure the character that lubricating grease is also shown in Table 1.
embodiment 2: the one kettle way two step synthesis of two ureas in base oil
Diphenyl carbonate (150g), 4,4'-methylene dianiline (MDA)s (69g), and the mixture of diphenyl phosphonic acid (7.5g) reacts at 90 DEG C.Solid melts is for stirring the mixture.After some hours, it becomes solid again.Reaction is stirred spend the night (mechanical stirring) at 90 DEG C.
In next morning, mixture becomes solid.Add base oil (198g), and mixture is stirred 1 hour at 90 DEG C.Add extra base oil (303.3g).Then octylame (90.5g) is added.Mixture starts to become milky white/pink colour.By mixture 104 DEG C of heating 6.30 hours.Mixture is suspended and decant in acetone (11).Repeat for several times until remove all phenol.Use rotatory evaporator dry substance, add 130g base oil, mixture be heated to 170 DEG C and cool to obtain lubricating grease.Measure the character that lubricating grease is also shown in Table 1.
embodiment 3a: step (a2)---the synthesis of diamino-methyl formate
4,4'-methylene dianiline (MDA) and potassium tert.-butoxide (4.4 equivalent) are heated 0.5 hour in methylcarbonate (pure) at 80 DEG C, to provide diamino-methyl formate (89%) after filtration and water washing.
embodiment 3b: step (b2)---the synthesis of two ureas in base oil
The diamino-methyl formate prepared according to embodiment 3a (65g) and octylame and dibutyl tin laurate (adding during a few days) are reacted 7, to provide two urea products and some single ureas in base oil at 140 DEG C.Isolate 498g lubricating grease.Measure the character that lubricating grease is also shown in Table 1.
embodiment 3c: step (b2) and washing with acetone
Evaporate from the lubricating grease sample (40-50g) of embodiment 3b with washing with acetone, to obtain 31g, purity is 97%.Measure the character that lubricating grease is also shown in Table 1.
the synthesis of embodiment 4: two urea and the dispersion subsequently in base oil
Diphenyl carbonate (10g), 4,4'-methylene dianiline (MDA)s (4.6g), and the mixture of diphenyl phosphonic acid (0.5g) reacts and spends the night at 100 DEG C.By its cool to room temperature after mixture solidified.By carrying out processing reaction with diethyl ether (3x25ml) washing.Leach white mass and drying.Diamino-methyl formate and octylame are reacted 2 hours at 105 DEG C.Use washed with dichloromethane product, then by crystallization purified product from dimethyl formamide.
5g urea product is suspended in base oil (20g).Mixture is heated 30 minutes at 170 DEG C, then cools to provide lubricating grease.
Grease characteristic
The penetration degree of untapped lubricating grease and the penetration degree of worked grease is measured according to ASTMD 217.Calculate Δ penetration degree (difference of untapped and used penetration degree).Dropping point is measured according to IP 396.Value illustrates in Table 1:
table 1
Expect that Δ penetration degree is low as far as possible, and some lubricating grease achieve low value.Worked penetration value scope is from 247 to 340, and it will provide the lubricating grease of the classification usually falling into NLGI rank 1,2 or 3.Expect that dropping point is high as far as possible, and some lubricating grease obtain the dropping point more than 300.

Claims (8)

1. prepare a method for urea-base grease, it is included in wherein by one or more steps that the compound of the compound of formula (I), formula (II) and the compound of formula (III) react:
Wherein R 1and R 2be selected from the alkyl with 1 to 30 carbon atoms, or R 1and R 2be connected and form the alkylen group with 1 to 30 carbon atoms, R 3be selected from the alkyl comprising 2 to 30 carbon atoms, and R 4it is the alkylene comprising 2 to 30 carbon atoms;
Wherein at least one reactions steps is carried out under the existence of base oil.
2. the method preparing urea-base grease according to claim 1, it comprises the following steps:
(a1) compound of the compound of formula (I) and formula (II) is reacted:
With
(b1) compound of the product of step (a1) and formula (III) is reacted:
H 2N-R 4-NH 2
(III)
Wherein step (b1) is carried out under the existence of base oil.
3. the method preparing urea-base grease according to claim 1, it comprises the following steps:
(a2) compound of the compound of formula (I) and formula (III) is reacted:
With
(b2) compound of the product of step (a2) and formula (II) is reacted:
R 3-NH 2
(II)
Wherein step (b2) is carried out under the existence of base oil.
4. according to the method in claim 2 or 3, wherein there is catalyzer in step (a1), step (a2), step (b1) and/or step (b2).
5. the method according to claim 2,3 or 4, is wherein heated at least 170 DEG C by the reaction product of step (b1) or (b2), then cools.
6. the method according to arbitrary aforementioned claim, wherein based on the gross weight of described urea-base grease, the weight percent of the urea that described urea-base grease comprises is from the scope of 2 % by weight to 25 % by weight.
7. the method according to arbitrary aforementioned claim, wherein said lubricating grease stands one or more and is selected from homogenize, filtration and degassed finishing.
8. one or more additives are wherein joined in described lubricating grease by the method according to arbitrary aforementioned claim.
CN201480007940.1A 2013-02-08 2014-02-07 Process for preparing urea grease Pending CN104981536A (en)

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