CN101541933A

CN101541933A - Urea grease composition

Info

Publication number: CN101541933A
Application number: CNA2007800401857A
Authority: CN
Inventors: 田中启司; 筱田宪明; 加藤哲也
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2006-09-21
Filing date: 2007-09-21
Publication date: 2009-09-23
Anticipated expiration: 2027-09-21
Also published as: WO2008034892A8; BRPI0717042A2; CN101541933B; WO2008034892A3; KR20090058025A; JP4976795B2; RU2451719C2; EP2066769A2; WO2008034892A2; KR101438853B1; US20100029526A1; AR062906A1; TW200831661A; RU2009114834A; JP2008074978A

Abstract

The present invention aims to offer a urea grease composition which excels in noise performance, has long life at high temperatures and, further, also provides the basic performance of greases such as shear stability and heat resistance, as well as appropriate oil separation properties. The present invention provides a urea grease composition comprising: a diurea compound as shown by the General Formula (A) below: R<11>NHCONHR<12>NHCONHR<13>.... (A), (where R<11> and R<13> are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R<11> and R<13> is a dodecyl group and R<12> is a diphenylme thane group); and a diurea compound as shown by the General Formula (B) below: R<21>NHCONHR<22>NHCONHR<23>.... (B), (where R<21 > and R<23> are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R<21> and R<23> is an oleyl group, and R<22> is a diphenylmethane group).

Description

Urea grease composition

Technical field

The present invention relates to a kind of novel urea grease composition, this urea grease composition noiseproof feature is outstanding, have the long lifetime at high temperature and also provide this performance of grease base as shear stability and thermotolerance and suitable separating of oil character in addition.

Background technology

Use carbamide compound to be their thermotolerance and oxidative stability as the most important characteristic of the urea grease of thickening material.Because developed lubricating life at high temperature in numerous purposes than the lubricating life of common lithium soap grease long several times to ten times or the lubricating grease that more manys times, so urea grease is extensive use of at present.

Yet almost all urea greases on the market all have relatively poor noiseproof feature and often have the situation of many machine and equipments that they can not be used for needing peace and quiet at present.Present situation is that the scope of using is restricted.

For example, under the situation of the household electrical appliance of being familiar with, in order to ensure comfortable and quiet living environment, the anti-noise measure is indispensable in equipment such as suction cleaner, washing machine, compressor for refrigeration, compressor of air conditioner and fan, electric fan and dim blower fan, moisture eliminator, exhaust fan and air purifier.In the bearing grease that in the rotatable parts of these electrical equipment, uses, actively using lower noise lubricating grease with good noiseproof feature.

In addition, because these household electrical appliance also require to be accompanied by temperature increase and the higher output that equipment size reduces, therefore depend on the type of electrical equipment except noiseproof feature, the long lifetime under higher temperature has become very intensive requirement.The carbamide compound that use has good noiseproof feature is very effective and the better product of expectation exploitation as thickening material with having long-life lubricating grease.Naturally, the fundamental property of bearing grease such as shear stability (anti-leakage property), at high temperature stability and suitable separating of oil character will be indispensable.

In automotive industry, also be enhanced year by year to quiet requirement.Especially, noise in the high quality car and anti-noise measure have been carried out comprehensive research.Noise in its single parts lowered the requirement be strict.Here, also be enhanced year by year for the requirement of the high quality lubricating grease that uses in the bearing with good noiseproof feature.Particularly under the situation to the bearing that uses in the engine parts, the long lifetime under comparatively high temps has become very intensive requirement.The carbamide compound that use has good noiseproof feature is very effective and the better product of expectation exploitation as thickening material with having long-life lubricating grease.Naturally, identical with the above-mentioned lubricating grease that is used for household electrical appliance, the fundamental property of bearing grease such as shear stability (anti-leakage property), at high temperature stability and suitable separating of oil character will be indispensable.

Reference about noise character in the prior art of urea grease comprises the patent document 1,2 and 3 that is proposed by the applicant.

Japan special permission publication 1-139696 (1989) has described and has comprised by two carbamide compounds (i) of following general formula and the thickening material of mixture (ii):

(i)R ³¹NHCONHR ³²NHCONHR ³³

(ii)R ³⁴NHCONHR ³⁵NHCONHR ³⁶

(R wherein ³²Be diphenylmethyl groups, R ³¹And R ³³The straight or branched saturated alkyl group of respectively doing for oneself and having 8 carbon, R ³⁵Be benzylidene group or dibenzylidene group, and R ³⁴And R ³⁶The aromatic yl group that aromatic yl group that the alkyl of respectively doing for oneself replaces or halogen replace).

Japan special permission publication 2-77494 (1990) has described the thickening material that comprises above-mentioned two carbamide compounds (i) and mixture (ii), wherein at above-mentioned general formula (i) with (ii), and R ³²Be dibenzylidene group, R ³¹And R ³³Representative has the saturated alkyl or the unsaturated alkyl of the straight or branched of 18 carbon, R separately ³⁵Be the diphenylmethyl groups, and R ³⁴And R ³⁶The straight or branched saturated alkyl of respectively doing for oneself and having 8 carbon.

Japan special permission publication 6-17080 (1994) discloses the thickening material that comprises two carbamide compounds (i) and mixture (ii), wherein at above-mentioned general formula (i) with (ii), and R ³²Represent the benzylidene group, R ³¹And R ³³The straight or branched saturated alkyl or the unsaturated alkyl of respectively doing for oneself and having 16-18 carbon, R ³⁵Be the diphenylmethyl groups, and R ³⁴And R ³⁶The straight or branched saturated alkyl group of respectively doing for oneself and having 8 carbon.

The document that relates to noise character comprises Japan special permission publication 3-28299 (1991).The document has been described grease composition, wherein as thickening material with contain alkyl diphenyl base ether oil as the base oil blending of basal component be two carbamide compounds, wherein, in above-mentioned general formula (i), R ³²For having the aromatic hydrocarbyl group of 6-15 carbon, R ³¹And R ³³For straight chained alkyl group with at R with 8-18 carbon ³¹And R ³³Described in have 8 carbon the shared ratio of alkyl group be 60-100mol%.

Japan special permission publication 2-80493 (1990) (the 6th page, table 2) has described a kind of composition that uses in tapered roller bearing, wherein add and mixed oxidation modification polyolefine and/or the acid modified polyolefin of 0.5-5wt% in urea grease.The table 2 of this patent has shown and has used the octylame with 8 carbon, stearylamine (octadecane amine) and the MDI (ditan-4 with 18 carbon, 4 '-vulcabond) make the urea thickening material of raw material, and it confirms that described thickening material shows good effect such as mechanical stability, wet shear stability and pressure transferability.

Japan special permission publication 3-243696 (1991) has described two carbamide compounds, wherein in above-mentioned general formula (i), and R ³²Be 3,3 '-dimethyl-4,4 '-diphenylene group and R ³¹And R ³³Be the alkyl group with 8-18 carbon and the mixture of oleyl group.But there is following shortcoming in this technology: unless penetration degree is relatively poor and use a large amount of thickening materials otherwise can not obtain penetration degree and be about 250 lubricating grease, and at high temperature separating of oil degree is very big.

Japan special permission publication 58-185693 (1983) has described improved two ureas lubricating grease, the two ureas lubricating grease that wherein make contain in the metal-salt of the metal-salt of alkenyl succinimide, alkyl benzene sulphonate (ABS) and mahogany acid one or both or multiple.It is mentioned for two ureas lubricating grease, can use vulcabond and monoamine and for monoamine, can use fatty amine such as stearylamine and oleyl amine and aromatic amine such as cyclo-hexylamine usually.It discloses with the lubricating grease of prior art and has compared, and this lubricating grease has extraordinary noise character.

In addition, can find example for the research preparation method of the noise character of improving urea grease.For example, Japan special permission publication 2-4895 (1990) has described the preparation method of urea grease, wherein by in base oil, adding isocyanic ester and amine, under 60-120 ℃ temperature, implement reaction, by using kneader device the mixture of the carbamide compound of gained and base oil is carried out dispersion treatment and is heated to 160-180 ℃ with the temperature rise rate of 0.5-2 ℃/min subsequently having improved noise character.

Japan special permission publication 3-190996 (1991) has described the preparation of greases method with good noise character, wherein will be wherein in reaction vessel dissolve or be dispersed with the base oil of isocyanic ester and wherein dissolved or the base oil that is dispersed with amine pressurizes, make their reactions by making them collide mutually and mix, or by pressure boost with they are caused rotation mix oar and make their reactions.

In addition, Japan special permission publication 3-231993 (1991) has described the preparation method of lower noise urea grease, and this method is made up of first process and second process, wherein in first process, with the carbamide compound of the above-mentioned general formula (i) of 2-30wt% (R wherein ³¹And R ³³For having the saturated alkyl group of 8-18 carbon, and R ³²Be benzylidene group, diphenylmethyl groups or dimethyl diphenylene group) and the mixture heating up of the base oil of 98-70wt% to 170-230 ℃, so that carbamide compound is dissolved in the base oil fully, in second process after first process is finished, implement cooling with the speed of at least 5 ℃/min.In above-mentioned patent documentation 1-10, the none concrete proposals urea grease composition of the present invention.

Described as above-mentioned patent documentation, have a plurality of examples, wherein for the isocyanic ester raw material, used tolylene diisocyanate (TDI) or 3,3 '-dimethyl-4,4 '-diphenylene vulcabond (TODI) to be to provide superior noise character to urea grease.In addition, also provide preparation method's example, wherein after reaction process, used kneader device or autoclave to mix two or more inhomogeneous lubricating grease, made carbamide compound not assemble and postheating and dissolving lubricating grease.

Along with the quantitative change of the urea grease that is produced on the big and market to the increase in demand of lubricating grease with superior noise character, seeking to produce better noise character in the Working environment of more cleaning of lubricating grease and the final Industrial products.

Many users seek high-performance lubricating grease at a low price.In complex process, use the urea grease of expensive raw material TODI on market, to strive unexpectedly.

And about the production of lubricating grease, also because the increase of its turnout, so be necessary more carefully to handle the TDI raw material (in industrial safety and healthy rules (Industial Safety andHealth Law), it is classified as the special chemical substance of 2 classes), with in order to improve noise character qualitatively, be necessary to consider the number of times of ruggedized equipment and amplification production process.

Summary of the invention

The invention provides a kind of urea grease composition, the noiseproof feature of described urea grease composition is outstanding, have the long lifetime at high temperature and also provide this performance of grease base as shear stability and thermotolerance and suitable separating of oil character in addition.

After the careful problem of assert in the market and demand, and by complete investigation and analysis and the structural constituent of studying urea thickening material in the urea grease composition in large quantities, the inventor has been found that by being limited to some specific urea thickening material in the structural constituent scope that adds urea in urea grease composition, obtain good urea grease composition, this urea grease composition noiseproof feature is outstanding, have the long lifetime at high temperature and also provide this performance of grease base as shear stability and thermotolerance and suitable separating of oil character in addition.Therefore they have obtained the present invention.

In other words, the invention provides a kind of urea grease composition, it comprises:

Two carbamide compounds by following general formula (A) expression

R ¹¹NHCONHR ¹²NHCONHR ¹³ (A)

(R wherein ¹¹And R ¹³For being selected from the group of alkyl, R with 6-20 carbon ¹¹And R ¹³In at least one be dodecyl, and R ¹²Be the diphenylmethyl groups); With two carbamide compounds by following general formula (B) expression:

R ²¹NHCONHR ²²NHCONHR ²³ (B)

(R wherein ²¹And R ²³For being selected from the group of alkyl, R with 6-20 carbon ²¹And R ²³In at least one is the oleyl group, and R ²²Be the diphenylmethyl groups).

Preferably, R in above-mentioned general formula (A) ¹¹And R ¹³In the shared ratio of dodecyl group be 2-70mol%, and/or in above-mentioned general formula (B) R ²¹And R ²³The middle shared ratio of oleyl group is 5-70mol%.

In addition, R in the preferred above-mentioned general formula (A) ¹¹And R ¹³In R in alkyl except that the dodecyl group and/or the above-mentioned general formula (B) with 6-20 carbon ²¹And R ²³The alkyl with 6-20 carbon beyond the middle oil removing alkenyl group is an octyl group.

Even R in above-mentioned general formula (A) more preferably ¹¹Or R ¹³The middle shared ratio of dodecyl group is 3-55mol%, R in above-mentioned general formula (B) ²¹And R ²³In the shared ratio of oleyl group be 5-55mol% and at R ¹¹, R ¹³, R ²¹And R ²³The middle shared ratio of octyl group is 10-90mol%.

In yet another aspect, the invention provides a kind of urea grease composition, it comprises:

Two carbamide compounds of following general formula:

(a) R ¹NHCONHR ²NHCONHR ¹With

(b) R ³NHCONHR ²NHCONHR ³With

In addition by two carbamide compounds of following general formula:

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

(R wherein ²Be diphenylmethyl groups, R ¹For with the alkyl of octyl group as its main composition, R ³For having 14-20 carbon and comprise the alkyl of the oleyl group of 20mol% at least, and R ⁴For with the alkyl of dodecyl group) as its main composition.

Aspect another one, the invention provides a kind of urea grease composition, it comprises:

Two carbamide compounds by following general formula:

(a) R ¹NHCONHR ²NHCONHR ¹With

(b) R ³NHCONHR ²NHCONHR ³With

(c) R ¹NHCONHR ²NHCONHR ³With

In addition by two carbamide compounds of following general formula:

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

In addition, the invention provides a kind of urea grease composition, it comprises:

(i) a kind of two carbamide compounds by above-mentioned general formula (a) expression; With

(ii) two carbamide compounds, it is to be selected from two following carbamide compounds:

(1) above-mentioned general formula (b), (c), (d) and (e)

(2) above-mentioned general formula (b), (c) and (d)

(3) above-mentioned general formula (b), (c) and (e),

With two carbamide compounds of above-mentioned general formula (a) expression be 20-80mol% with respect to the mol ratio of two carbamide compound total amounts.

Two carbamide compounds by following general formula:

(c) R ¹NHCONHR ²NHCONHR ³With

Two carbamide compounds of representing by following general formula in addition:

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

Two carbamide compounds by following general formula:

(c) R ¹NHCONHR ²NHCONHR ³With

(b) R ³NHCONHR ²NHCONHR ³With

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

(i) two carbamide compounds of representing by above-mentioned general formula (c); With

(ii) two carbamide compounds, it is to be selected from two following carbamide compounds

(1) above-mentioned general formula (b), (d) and (e)

(2) above-mentioned general formula (b) and (d)

(3) above-mentioned general formula (b) and (e),

With two carbamide compounds of above-mentioned general formula (c) expression be 20-80mol% with respect to the mol ratio of two carbamide compound total amounts.

The compound of above-mentioned general formula (A) expression is usually according to following reaction formula preparation:

[formula 1]

OCN-R ¹²-NCO+R ¹¹NH ₂+R ¹³NH ₂→R ¹¹NHCONHR ¹²NHCONHR ¹³+R ¹¹NHCONHR ¹²NHCONHR ¹¹+R ¹³NHCONHR ¹²NHCONHR ¹³

(R wherein ¹¹, R ¹²And R ¹³As previously mentioned).

The compound of above-mentioned general formula (B) expression also can prepare in the mode similar to compound shown in the general formula (A):

[formula 2]

OCN-R ²²-NCO+R ²¹NH ₂+R ²³NH ₂→R ²¹NHCONHR ²²NHCONHR ²³+R ²¹NHCONHR ²²NHCONHR ²¹+R ²³NHCONHR ²²NHCONHR ²³

(R wherein ²¹, R ²²And R ²³As previously mentioned).

Corresponding to above-mentioned OCN-R ¹²-NCO and OCN-R ²²The compound of-NCO be ditan-4,4 '-vulcabond.

In order in the compound of above-mentioned general formula (A), to introduce R ¹¹And R ¹³, used R ¹¹NH ₂And R ¹³NH ₂With in order in the compound of above-mentioned general formula (B), to introduce R ²¹And R ²³, used R ²¹NH ₂And R ²³NH ₂

Below at general formula (A) and (B) and the compound of general formula (a) to (e) describe the present invention in detail.

At above-mentioned R ¹¹And R ¹³Any in, dodecyl group and particularly just-the dodecyl group provides thermotolerance to urea grease, and its existence can prolong the urea grease life-span at high temperature.Yet, if R ¹¹And R ¹³Be the dodecyl group, even thermotolerance is good, noiseproof feature also is poor.Therefore, if R ¹¹And R ¹³In any when being the dodecyl group, then another can and be preferably the oleyl group or the octyl group group for the alkyl of 6-20 carbon.Provide the object lesson of the raw material of dodecyl group to preferably include straight chain dodecyl primary amine.Comprise lauryl amine and oleyl amine or octylame and ditan-4,4 '-the urea thickening material of the mixture of vulcabond has good thermostability, at high temperature be difficult for changing with the grease composition that uses this urea thickening material, thereby the effect of prolongs life is very big.With respect to R in the above-mentioned general formula (A) ¹¹And R ¹³Total mole number, the dodecyl group can account for 2-70mol% and be preferably 4-50mol%.

Above-mentioned R ²¹And R ²³In at least one for oleyl group at least and especially for just-the oleyl group.The existence of oleyl group not only provides good noiseproof feature to urea grease composition, and the adsorption property of metallic surface that urea grease composition forms the slipper of machine part relatively becomes better and therefore further improved lubricating quality.R in above-mentioned general formula (B) ²¹And R ²³In, the oleyl group can account for 5-70mol% and be preferably 8-55mol%.

In the present invention, indispensable is to add oleyl group and dodecyl group at least in two urea grease compositions, particularly just-and the dodecyl group, but preferably also add the octyl group group, particularly just-the octyl group group.

If added oleyl group and dodecyl group and also added the octyl group group, particularly just-the octyl group group, R in then suitable the is above-mentioned general formula (A) ¹¹And R ¹³The middle shared ratio of dodecyl group is R in 3-55mol% and the other above-mentioned general formula (B) ²¹And R ²³The middle shared ratio of oleyl group is 5-55mol%, and at R ¹¹, R ¹³, R ²¹And R ²³The middle shared ratio of octyl group group is 10-90mol%.

The usage ratio by general formula (A) and the thickening material (B) contained as feature of the present invention can be so that they account for the 20-100mol% of total thickening material.

Comprise by above-mentioned general formula (A), (B) and (a) to the thickening material of two carbamide compounds of (e) expression preferably can be by amount adding with respect to the 2-30wt% of the mineral oil that forms lubricating oil or synthetic oil or its mixture.If form mineral oil or synthetic oil or its mixture of lubricating oil relatively, be less than 2wt% as two carbamide compounds of thickening material, then thickening effectiveness becomes too little and lubricating grease may become too soft, thereby has the risk of for example leaking.If it surpasses 30wt%, then lubricating grease may become too hard and its resistance to flow increases, and makes because friction torque increases and penetrating power reduction and can not obtain sufficient lubricant effect.Cost also increases simultaneously.

For the lubricating base oil among the present invention, can use those that are used as lubricating oil and grease base oil usually.They are not particularly limited, but can mention mineral oil and/or synthetic oil and vegetables oil as an example.The object lesson of synthetic oil has GTL deutero-base oil (being produced by Fischer-Tropsch process), polyolefine such as alpha-olefin low polymers and polybutene, polyalkylene glycol such as polyoxyethylene glycol and polypropylene glycol, diester as two-2-ethylhexyl sebate and two-2-ethylhexyl adipic acid ester, polyol ester such as trihydroxymethylpropanyl ester and pentaerythritol ester, perfluoroalkyl ethers, silicone oil and polyphenylene ether; Can mention Viscotrol C and rapeseed oil with exemplary as vegetables oil.Can provide separately or use the example of these base oils, but they do not limit the present invention with the form of mixture.

In addition, might further in composition of the present invention, add additive such as antioxidant and rust-preventive agent, oiliness improver and extreme-pressure additive and anti-wear agent and solid lubricant or metal passivator and polymkeric substance.For example antioxidant comprises 2,6-two-tertiary butyl-4-methylphenol, 2,6-two-tertiary butyl-p-Cresol, P, P '-dioctyl diphenylamine, N-phenyl-and thiodiphenylamine.Rust-preventive agent comprises the metal-salt of paraffinic hydrocarbons oxide compound, carboxylic acid, metal-salt, carboxylicesters, sulphonate, salicylate, succinate, Isosorbide Dinitrate and the various amine salt of sulfonic acid.Oiliness improver and extreme-pressure additive and anti-wear agent comprise the sulfurized zinc dialkyl dithiophosphate, the sulfurized diallyl disulfide is for zinc phosphate, the sulfurized zinc dialkyl dithiocarbamate, the sulfurized diallyl disulfide is for carbaminate, the sulfurized molybdenum dialkyl-dithiophosphate, the sulfurized diallyl disulfide is for molybdenum phosphate, the sulfurized molybdenum dialkyldithiocarbamacompositions, the sulfurized diallyl disulfide is for the carboxylamine molybdenum, the organic-molybdenum mixture, sulfurized alkene, triphenylphosphate, triphenyl-thiophosphate, Tritolyl Phosphate, other phosphoric acid ester and sulfurized fat and oily.Solid lubricant comprises molybdenumdisulphide, graphite, boron nitride, melamine cyanurate, PTFE (tetrafluoroethylene), tungsten disulfide and fluorographite.Metal passivator comprises N, N '-two salicylidene-1, benzotriazole, benzoglyoxaline, benzothiazole and thiadiazole.As the example of polymkeric substance, can mention polybutene, polyisobutene, polyisobutene, polyisoprene and polymethacrylate.

By the present invention, a kind of novel urea grease composition might be provided, and this urea grease composition noiseproof feature is outstanding, have long high temperature service life and high dropping point and also provide this performance of grease base as shear stability and thermotolerance and suitable separating of oil character in addition.

Embodiment

Describe the present invention below by embodiment and Comparative Examples, but these embodiment limit the present invention never in any form.

Abbreviation about the feed composition of the thickening material that uses in embodiment and Comparative Examples and base oil is described below among the table 1-5.

Isocyanic ester A be ditan-4,4 '-vulcabond, molecular weight is 250.26.

Isocyanic ester B is a tolylene diisocyanate, and molecular weight is 174.16.

For the amine raw material:

Amine A is that molecular-weight average is 128.7 straight chain primary amine, the saturated alkyl group (industrial octylame) that its main composition (at least 90%) is 8 carbon;

Amine B is that molecular-weight average is 255.0 straight chain primary amine, the unsaturated alkyl group (industrial oleyl amine) that its main composition (at least 70%) is 18 carbon; With

Amine C is that molecular-weight average is 184.6 straight chain primary amine, the saturated alkyl group (industrial lauryl amine) that its main composition (at least 90%) is 12 carbon.

In addition, be 10.12mm in the kinematic viscosity of the mineral oil shown in embodiment and the Comparative Examples under 100 ℃ ²/ s, and synthetic oil A refers to poly-alpha-olefin oil, its kinematic viscosity at 100 ℃ is 12.70mm ²/ s and synthetic oil B refer to alkyl diphenyl base ether oil, and its kinematic viscosity at 100 ℃ is 12.69mm ²/ s.

In the thickening material mol% hurdle that table provides among the 1-4, a, b, c, d and e represent the carbamide compound that can be expressed from the next respectively:

(a)R ¹NHCONHR ²NHCONHR ¹

(b)R ³NHCONHR ²NHCONHR ³

(c)R ¹NHCONHR ²NHCONHR ³

(d)R ¹NHCONHR ²NHCONHR ⁴

(e)R ³NHCONHR ²NHCONHR ⁴

(R wherein ²Be diphenylmethyl groups, R ¹For with the alkyl of octyl group group as 6-10 carbon of its main composition, R ³For having 14-20 carbon and comprise the hydrocarbyl group of 20mol% oleyl group at least, and R ⁴For with just-the dodecyl group is as the alkyl of its main composition).

In addition, in the thickening material mol% hurdle of the Comparative Examples that in table 5, provides, a and b represent in the thickening material mol% hurdle at the given above-claimed cpd of embodiment of table 1-4 and the embodiment that provides in table 1-4, and f, g, h, i and j represent the carbamide compound represented by following general formula respectively:

(f)R ⁴NHCONHR ²NHCONHR ⁴

(g)R ¹NHCONHR ⁵NHCONHR ¹

(h)R ³NHCONHR ⁵NHCONHR ³

(i)R ⁴NHCONHR ⁵NHCONHR ⁴

(j)R ¹NHCONHR ⁵NHCONHR ⁴

(R wherein ⁵Be benzylidene group, R ¹For with the alkyl of octyl group group as 6-10 carbon of its main composition, R ³For having 14-20 carbon and comprise the hydrocarbyl group of 20mol% oleyl group at least, and R ⁴For with just-the dodecyl group is as the alkyl of its main composition).

Implement test as follows to the character of embodiment and Comparative Examples:

1. penetration degree: JIS K2220

2. dropping point: JIS K2220

3. separating of oil: JIS K2220 method B, condition is 100 ℃ and 24 hours.

4. noise testing: the method for pressing Japanese Patent 53-2357 (1978) is measured.

5. stability (Shell roll): ASTM D1831

6. bearing life test: ASTM D3336

By the synthetic carbamide compound in lubricating base oil of ratio shown in use table 1 and 2 is thickening material, and by blend in additive, obtains lubricating grease of the present invention.

Embodiment 1

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, be incorporated as B component 3 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine B (industrial oleyl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, be incorporated as B component 4 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.Behind the restir 5 minutes, in still, be incorporated as B component 5 and in lubricating base oil, mixed in advance and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of the additional scale of 1.0 quality %.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 1.

Embodiment 2

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, be incorporated as B component 3 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine B (industrial oleyl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, be incorporated as B component 4 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 2.

Embodiment 3

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, be incorporated as B component 3 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine B (industrial oleyl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, be incorporated as B component 5 and in lubricating base oil, mixed in advance and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 3.

Embodiment 4

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, be incorporated as B component 4 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.Behind the restir 5 minutes, in still, be incorporated as B component 5 and in lubricating base oil, mixed in advance and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 4.

Embodiment 5

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, be incorporated as B component 4 and in lubricating base oil, mixed in advance and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 5.

Embodiment 6 and 7

In the blend ratio shown in the table 2, in the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 6 and 7.

Embodiment 8

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Be incorporated as B component 1 and blended amine A (industrial octylame) in lubricating base oil, and react with component A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 8.

Embodiment 9

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Add in advance mixing and lysed amine A (industrial octylame) and amine B (industrial oleyl amine) in lubricating base oil by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.After further stirring 5 minutes, in still, add in advance mixing and lysed amine A (industrial octylame) and amine C (industrial lauryl amine) in lubricating base oil by loading hopper, and react with remaining isocyanic ester A.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.Behind the restir 5 minutes, in still, add in advance by loading hopper and in lubricating base oil, to mix and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 9.

Embodiment 10

Adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add amine A (industrial octylame) and the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Behind the restir 5 minutes, in still, add in advance mixing and lysed amine A (industrial octylame) and amine C (industrial lauryl amine) in lubricating base oil, and react with remaining isocyanic ester A by loading hopper.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 10.

Embodiment 11

In the blend ratio shown in the table 3, adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add amine A (industrial octylame) and the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Behind the restir 5 minutes, in still, add in advance mixing and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine) in lubricating base oil, and react with remaining isocyanic ester A by loading hopper.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 11.

Embodiment 12

Adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add amine A (industrial octylame) and the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.Behind the restir 5 minutes, in still, add in advance mixing and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine) in lubricating base oil, and react with remaining isocyanic ester A by loading hopper.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 12.

Embodiment 13

Adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add amine A (industrial octylame) and the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 13.

Embodiment 14

Adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add amine A (industrial octylame) and the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' c ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 14.

Embodiment 15

In the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed, and react with isocyanic ester A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 15.

Embodiment 16

In the blend ratio shown in the table 4, in the prototype grease kettle equipment of a sealing, add lubricating base oil and be the isocyanic ester A (ditan-4,4 '-vulcabond) of component A, and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed, and react with isocyanic ester A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Then, stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' e ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 16.

Embodiment 17

In the prototype grease kettle equipment of a sealing, add lubricating base oil (mixture of mineral oil and synthetic oil A) and isocyanic ester A (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed, and react with isocyanic ester A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 17.

Embodiment 18

In the prototype grease kettle equipment of a sealing, add lubricating base oil (synthetic oil B) and isocyanic ester A (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed, and react with isocyanic ester A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, be incorporated as B component 2 then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine) in advance, and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Stir after 5 minutes, in still, add in advance and in lubricating base oil, mix and lysed amine A (industrial octylame) and amine C (industrial lauryl amine), and with remaining be that the isocyanic ester A of component A reacts.Obtain carbamide compound ' d ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of embodiment 18.

Comparative Examples 1

In the blend ratio shown in the table 5, adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' a ' by general formula (octyl group)-NHCONH-(ditan)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' f ' by general formula (dodecyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of Comparative Examples 1.

Comparative Examples 2

Adding lubricating base oil and isocyanic ester A in the prototype grease kettle equipment of a sealing (ditan-4,4 '-vulcabond), and under stirring condition, be heated to 60 ℃.Add the amine B (industrial oleyl amine) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester A.Obtain carbamide compound ' b ' by general formula (oleyl)-NHCONH-(ditan)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine C (industrial lauryl amine), and react with remaining isocyanic ester A.Obtain carbamide compound ' f ' by general formula (dodecyl)-NHCONH-(ditan)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of Comparative Examples 2.

Comparative Examples 3

In the prototype grease kettle equipment of a sealing, add lubricating base oil and isocyanic ester B (tolylene diisocyanate), and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester B.Obtain carbamide compound ' g ' by general formula (octyl group)-NHCONH-(benzylidene)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine B (industrial oleyl amine), itself and remaining isocyanic ester B react.Obtain carbamide compound ' h ' by general formula (oleyl)-NHCONH-(benzylidene)-NHCONH-(oleyl) expression.Behind the restir 5 minutes, in still, add in advance mixing and lysed amine A (industrial octylame) and amine C (industrial lauryl amine) in lubricating base oil, and react with remaining isocyanic ester B by loading hopper.Obtain carbamide compound ' j ' by general formula (octyl group)-NHCONH-(benzylidene)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of Comparative Examples 3.

Comparative Examples 4

In the prototype grease kettle equipment of a sealing, add lubricating base oil and isocyanic ester B (tolylene diisocyanate), and under stirring condition, be heated to 60 ℃.Add the amine A (industrial octylame) in lubricating base oil, mixed by loading hopper, and react with isocyanic ester B.Obtain carbamide compound ' g ' by general formula (octyl group)-NHCONH-(benzylidene)-NHCONH-(octyl group) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine C (industrial lauryl amine), and react with remaining isocyanic ester B.Obtain carbamide compound ' i ' by general formula (dodecyl)-NHCONH-(benzylidene)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of Comparative Examples 4.

Comparative Examples 5

In the prototype grease kettle equipment of a sealing, add lubricating base oil and isocyanic ester B (tolylene diisocyanate), and under stirring condition, be heated to 60 ℃.Add the amine B (industrial oleyl amine) in lubricating base oil, mixed, and react with isocyanic ester B.Obtain carbamide compound ' h ' by general formula (oleyl)-NHCONH-(benzylidene)-NHCONH-(oleyl) expression.Make content be warming up to about 80 ℃ by reaction heat.With this temperature maintenance 10 minutes, in still, add in advance by loading hopper then and in lubricating base oil, mix and lysed amine C (industrial lauryl amine), and react with remaining isocyanic ester B.Obtain carbamide compound ' i ' by general formula (dodecyl)-NHCONH-(benzylidene)-NHCONH-(dodecyl) expression.After restarting heating rapidly, temperature is increased to 170 ℃ then, and keeps about 30 minutes of this temperature to finish reaction.Keeping described temperature after 30 minutes, begin to cool down and in process of cooling under 125 ℃, in lubricating grease, add the octyl diphenylamine (it is an antioxidant) of 1.0 quality % additional scale.After further being cooled to 80 ℃, in three-roll mill, handle lubricating grease, to obtain the lubricating grease of Comparative Examples 5.

Claims

1. urea grease composition, it comprises:

Two carbamide compounds by following general formula (A) expression

R ¹¹NHCONHR ¹²NHCONHR ¹³ (A)，

R wherein ¹¹And R ¹³For being selected from the group of alkyl, R with 6-20 carbon ¹¹And R ¹³In at least one is a dodecyl, and R ¹²Be the diphenylmethyl groups; With

Two carbamide compounds by following general formula (B) expression:

R ²¹NHCONHR ²²NHCONHR ²³ (B)，

R wherein ²¹And R ²³For being selected from the group of alkyl, R with 6-20 carbon ²¹And R ²³In at least one is the oleyl group, and R ²²Be the diphenylmethyl groups.

2. the described urea grease composition of claim 1, wherein R in above-mentioned general formula (A) ¹¹And R ¹³In the shared ratio of dodecyl group be 2-70mol% and/or in above-mentioned general formula (B) R ²¹And R ²³The middle shared ratio of oleyl group is 5-70mol%.

3. claim 1 or 2 described urea grease compositions, wherein R in above-mentioned general formula (A) ¹¹And R ¹³In except that the dodecyl group the alkyl with 6-20 carbon and/or in above-mentioned general formula (B) R ²¹And R ²³The alkyl with 6-20 carbon beyond the middle oil removing alkenyl group is an octyl group.

4. the described urea grease composition of claim 3, wherein R in above-mentioned general formula (A) ¹¹Or R ¹³The middle shared ratio of dodecyl group is 3-55mol%, R in above-mentioned general formula (B) ²¹And R ²³In the shared ratio of oleyl group be 5-55mol% and at R ¹¹, R ¹³, R ²¹And R ²³The middle shared ratio of octyl group is 10-90mol%.

5. urea grease composition, it comprises:

Two carbamide compounds of following general formula:

(a) R ¹NHCONHR ²NHCONHR ¹With

(b) R ³NHCONHR ²NHCONHR ³With

In addition by two carbamide compounds of following general formula:

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

R wherein ²Be diphenylmethyl groups, R ¹For with the alkyl of octyl group as its main composition, R ³For having 14-20 carbon and comprise the alkyl of the oleyl group of 20mol% at least, and R ⁴For with the alkyl of dodecyl group as its main composition.

6. urea grease composition, it comprises:

Two carbamide compounds by following general formula:

(a) R ¹NHCONHR ²NHCONHR ¹With

(b) R ³NHCONHR ²NHCONHR ³With

(c) R ¹NHCONHR ²NHCONHR ³With

In addition by two carbamide compounds of following general formula:

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

7. urea grease composition, it comprises:

(1) above-mentioned general formula (b), (c), (d) and (e)

(2) above-mentioned general formula (b), (c) and (d)

(3) above-mentioned general formula (b), (c) and (e),

8. urea grease composition, it comprises:

Two carbamide compounds by following general formula:

(c) R ¹NHCONHR ²NHCONHR ³With

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

9. urea grease composition, it comprises:

Two carbamide compounds by following general formula:

(c) R ¹NHCONHR ²NHCONHR ³With

(b) R ³NHCONHR ²NHCONHR ³With

(d) R ¹NHCONHR ²NHCONHR ⁴And/or

(e)R ³NHCONHR ²NHCONHR ⁴，

10. urea grease composition, it comprises:

(1) above-mentioned general formula (b), (d) and (e)

(2) above-mentioned general formula (b) and (d)

(3) above-mentioned general formula (b) and (e),

11. use each urea grease composition of aforementioned claim 1-10 to improve the method for noiseproof feature.

12. each urea grease composition of aforementioned claim 1-10 is used to improve the purposes of noiseproof feature.