TW200831661A - Urea grease composition - Google Patents

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: R11NHCONHR12NHCONHR13…(A), (where R11 and R13are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R11and R13 is a dodecyl group and R12is a diphenylmethane group); and a diurea compound as shown by the General Formula (B) below: R21NHCONHR22NHCONHR23…(B), (where R21 and R23 are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R21 and R23 is an oleyl group, and R22 is a diphenylmethane group).

Description

200831661 IX. Description of the invention: [Technical field to which the meal belongs] The present invention relates to a novel urea grease composition which has excellent noise performance, has a long lubricating life at = temperature, and also provides a basic food for the grease. Such as rhyme stability and heat resistance and appropriate oil separation properties. [Prior Art] Publication of urea compounds as thickening ^ ^ .....q~

It is based on its heat resistance and oxidative stability. Because it has been developed at high temperatures, the lubrication life of conventional lithium greases is several times to ten times or more. The grease of urea is now widely used in many applications. However, virtually all commercially available urea greases have poor noise performance and are often not available for use in a variety of machines and devices that require quiet today. The current situation is limited in the scope of application. For example, 'for common household appliances', in order to ensure a quiet living environment, such as mouth knife deer _ A ® ", washing machine, refrigerator compressor, air-conditioning compression, and fans, electric fans and peaches" "one exhaust fan and air purification pen ° y, /, there are voice countermeasures. Low beta sound full grease with excellent noise performance is actively used in the grease of these appliances. Guide, used in the bearing, ;] q sentence ramp device Size of household appliances, in addition to the type of the threat of the 2nd and 4th, in the more ancient: 乂: two rounds out 'so it is demanded. The use of 7 degrees with a long lubrication life has become - extremely long, the door ... good noise performance The urea compound acts as a thickener and the lubrication gambling system is very effective and is expected to develop more than 6 200831661 v

The basic properties of the shaft 豕 door/moon 曰, such as shear stability (leakage resistance), high temperature stability and proper oil separation properties, are naturally required. In the A-car industry, the demand for quiet has also increased year by year. Specifically, the noise of the high-quality four η sedan and its anti-Qing Shi have been studied in detail. The sound reduction requirements for individual parts are very strict. Here, the demand for high-quality grease for bearings and excellent sound performance is also increasing year by year. Especially for the bearing of the bow 丨 零件 part, it has become a very strong demand at a higher temperature. The use of a urea compound having excellent chewing performance as a thickener and having a (4) slippery grease is very effective and is expected to develop a preferred product. When the above grease is used in household appliances, the basic properties of the two-bearing grease such as shear stability (resistance to shallow leakage), high temperature stability and proper oil separation properties are naturally necessary. References relating to the noise properties of urea greases in prior uranium technology include patent documents 1, 2 and 3 from the applicant of the present invention. The present disclosure describes a thickener comprising a mixture of the following diurea compounds (1) and (Η) as shown by the following formula: (0 R31NHCONHR32NHCONHR33 (ii) R34NHCONHR35NHCONHR36 (wherein the R32 system Diphenyl decyl group, each of flank 31 and R33 is a linear or branched saturated alkyl group having 8 carbon atoms, R35 is a phenyl or dimethyl group, and R34 and R36 are each substituted by an alkyl group. An aromatic group or an aromatic group substituted by a dentate). The present invention discloses a thickener, 7 200831661 which comprises a mixture of the above diurea compounds (1) and (ϋ), Wherein in the above formulas (i) and (ii), R32 is a diphenylene group, R3! and each of a straight or branched saturated alkyl group or an unsaturated alkyl group having 18 carbon atoms, and R35 is a Phenyl group and R34 and R36 are each a linear or branched saturated alkyl group having 8 carbon atoms. V v 曰 专利 专利 第 第 第 第 第 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 And a mixture comprising diurea compounds (1) and (0), wherein in the above formulas (i) and (11), 'R32 represents a methylphenyl group, R31 and R33 are each a linear or branched saturated or unsaturated alkyl group having 16 to 18 stone antiatoms, R35 is a diphenylmethyl group and each of KM is a linear or branched chain having 8 carbon atoms. Saturated base.

References regarding the nature of noise include Japanese Laid-Open Patent Publication No. 3-28299 (199!). This patent document describes a grease composition which is incorporated as a thickener with a base oil containing a main component of an alkyl diphenyl ether oil, which is a diurea compound and is in the above formula (i), R32 is an aromatic hydrocarbon group having 6 to 15 carbon atoms, and the proportion of the alkyl group having 8 to a carbon atoms and the alkyl group having 8 carbon atoms in the ratio of rSi and R33 60 to 1% by mole. 公开 Patent Publication No. 2_80493 (199 〇) (Table 2, page 6) describes a composition for a tapered roller bearing in which 5% by weight is added Oxidatively modified polyolefin and/or acid modified polyolefin blended with urea grease. 纟2 shows stearylamine with X carbon atoms and stearylamine (X A base) with 8 carbon atoms Amine) and MDI (diphenylmethyl I, indole cyanide Iδθ) as a raw material urea thickener and its proof material thickener 8 200831661 shows excellent effects such as machine stability, α 戍鲰% 疋, wet male cut Stability and pressure transferability. Japanese published patent No. %·% No.... Chuan description - species of genomic compound 'wherein the above formula Among them, R32, 3,3, dimethyl-4,4,: a biphenyl group and R and R have a mixture of an alkyl group and an oil group of 8 to 18 carbon atoms. However, this technique has the following disadvantages: Poor permeability and the inability to obtain a grease with a permeability of about 25 除非 unless the use of the thick 曰 曰 thick d ', and the degree of oil separation at high temperatures is large. Japan's open patents 58th 185693? Tiger (1983) description - species One of the improved urea-type greases is a diurea-type grease comprising one of alkenyls, a metal salt of a benzenesulfonic acid, and a metal salt of petroleum sulfonic acid. For the diurea type grease, it is mentioned that diisomeric acid esters and monoamines can be used and for such monoamines, aliphatic amines such as stearylamine and oleyl amine and aromatic amine can be generally used. Such as cyclohexylamine, which reveals excellent grease performance compared to prior art greases. In addition, a study has been found to improve the noise enthalpy of urea greases. For example, Japanese Patent Publication Case No. 2_4895 (199〇) describes a method for producing a urea grease, wherein the urea run The arpeggio nature of the fat can be carried out by adding an isocyanate and an amine to the base oil, and performing the reaction at a temperature of 6 Torr to 2 〇〇C. In the mixture of the obtained urea compound and the base oil, a kneading device is used for dispersion treatment. Then, it is heated to a temperature of 160 to 180 at a temperature increase rate of 〇·5 to 2. 〇/min. The improvement is obtained by means of 〇. 公开 Patent Publication No. 3-190996 (1991) describes an excellent acoustic property. A method for producing a grease, wherein the base oil of the isocyanide 9 200831661 acid ester and the base oil of the dissolved or dispersed amine are pressurized in a reaction vessel, and reacted by collision and mixing with each other Or let it react by increasing the pressure and direct it into the rotating mixing blade. Further, Japanese Laid-Open Patent Publication No. 3-231993 (1991) describes a method for producing a low-noise urea grease comprising 2 to 30% by weight of a urea composition (wherein in the above formula (1), R3! And a mixture of R33 with a saturated alkyl group of 8 to 18 carbon atoms and R32 is a phenyl, diphenylmethyl or dimethyl phenyl group) and 98 to 70% by weight of a base oil is heated to 170 Up to 2 30 C to make the urea compound completely soluble in the base oil in the first process and after the first process, at least 5. The second process of cooling at a rate of (:/min. None of the above-mentioned Patent Documents 1 to 1 has any description of the composition of the urea grease of the present invention. As described in the above-mentioned patent documents, many Examples are the use of TDI or 3,3,_dimethyl- 4,4,_biphenyl diisocyanate (TODI) as the isocyanate starting material to provide urea with excellent noise properties. Further, an example of a manufacturing method in which two or more different types of greases are mixed by a kneading device or a high-pressure tank to prevent the urea compounds from agglomerating, and then heating and dissolving the greases is provided. As the production of glandular grease becomes larger and the demand for grease with excellent twins is stronger on the market, it is continually seeking a cleaner working environment for the manufacture of such doors (7) and the ultimate in noise properties. Commercially available products. The users of the Noon Festival seek low-cost high-performance grease. The expensive urea grease used as a raw material in TOD is not competitive in the market price. , 200831661 = Moreover, as for the manufacture of grease, it is also necessary to consider the increase in the amount of manufacturing, and the careful handling of (4) TDI raw materials (which are under the Labor Safety and Health Act, the second class of specific chemicals) and in order to improve the noise of the shellfish. Strengthen the device and extend the manufacturing process time.

The present invention provides a urea grease composition which has excellent noise performance, long lubricity at temperatures, and basic properties such as male cut stability and heat resistance and proper oil separation properties. By carefully identifying the difficulties and needs in the market and by increasing the urea in the urea grease composition (IV), the detailed study and analysis of the structural components of the crucible and the in-depth study, the inventors have found that they are limited to the specific The gland thickener is blended with the urea grease composition in the structural component of the urea, resulting in excellent noise performance and long lubrication life at high temperatures... Bu also provides the basic properties of the grease. Excellent urea-lubricating composition with heat resistance and suitable oil separation properties. It thus reaches the present invention. In other words, the present invention provides a urea grease composition comprising: a diurea compound as shown in the following formula (A):

RuNHCONHR12NHCONHR13 (A), wherein R and R are selected from the group consisting of a hydrocarbon group having 6 to 20 carbon atoms, and at least one of R11 and RU is dodecyl and = diphenylmethylalkyl; And a diurea compound of the following formula (B): R21NHC0NHR22NHC0NHR23 (B) 200831661 ^ (wherein R, R23 are selected from the group consisting of a hydrocarbon group having 6 to 20 carbon atoms, RU and R23 At least one is an oil group and R22 is a diphenylmethyl group. The proportion of the dodecyl group in R11 and Ru of the above formula (A) is preferably from 2 to 70 mol% and/or the proportion of the oil group in the above formula (b) and R23 is 5 Up to 70% by mole. Further, it is preferably a hydrocarbon group which is not a dodecyl group having 6 to 20 carbon atoms in R" and Ri3 of the above formula (A) and/or 6 in the fragrant and R of the above formula (B) The non-oil-based hydrocarbon groups of up to 20 carbon atoms are all octyl groups. The proportion of the dodecyl group in R11 and R13 of the above formula (A) is more preferably from 3 to 55 mol% and/or the proportion of the oil group in r2i and r23 of the above formula (B) is 5 to 55 mol%, and the proportion of octyl groups in R11, R13, R21 and R23 is from 1 90 to 90 mol%. In another aspect, the present invention provides a urea grease composition comprising: • a diurea compound as shown by the following formula: (a) RiNHCONHR^NHCONHR1 and (b) R3NHCONHR2NHCONHR3 and additionally comprising the following formula One or more diurea compounds are shown: (d) R1NHCONHR2NHCONHR4 and/or (e) R3NHCONHR2NHCONHR4, 12 200831661 w (wherein R2 is a diphenyldecyl group, R1 is a hydrocarbyl group having an octyl group as a main component, and R3 has a hydrocarbon group having 14 to 20 carbon atoms and containing at least 20 mol% of an oil group and a hydrocarbon group having an R4 group having a dodecyl group as a main component). In still another aspect, the present invention provides a urea grease composition comprising: a diurea compound as shown by the following formula: (a) R^HCONH^NHCONHR1 and (b) R3NHCONHR2NHCONHR3 and (c) R^HCONHR^HCONHR3 and additionally comprises one or more diurea compounds as shown by the following formula: (d) R^HCONHR^HCONHR4 and/or (e) R3NHCONHR2NHCONHR4, (wherein R2 is diphenyldecyl, R1 It is an alkyl group having an octyl group as a main group of 10, a hydrocarbon group having 14 to 20 carbon atoms and containing at least 20 mol% of an oil group, and a hydrocarbon group having a tetradecyl group as a main component of the R4 group. The present invention further provides a urea grease composition comprising: a diurea compound represented by the above formula (a); and a diurea compound (1) selected from the group consisting of diurea compounds of the following groups General formula (b), (c), (d) and (e) (2) above formula (b), (c) and (d) (3) above formula (b), (c) and (e) ), 13 200831661 - and the molar ratio of the diurea compound represented by the above formula (a) to the molar ratio of the diurea compound is 20 to 80 mol%. Moreover, the present invention provides a urea grease composition comprising: a diurea compound as shown by the following formula: (c) R^HCONHR^HCONHR3 and additionally comprising one or more diureas as shown by the following formula Compound: (d) R^HCONHR^HCONHR4 and/or • (e) R3NHC0NHR2NHC0NHR4, (wherein R2 is a diphenylmethylalkyl group, R1 is a hydrocarbyl group having an octyl group as a main component, and R3 has 14 to 20 carbon atoms and A hydrocarbon group having at least 20 mol% of an oil group and a hydrocarbon group having a tetradecyl group as a main component. In still another aspect, the present invention provides a urea grease composition comprising: a diurea compound as shown by the following formula: (c) R^HCONHR^HCONHR3 ❿ and (b) R3NHCONHR2NHCONHR3 and additionally comprising One or more diurea compounds represented by the following formula: (d) f^NHCONHR^NHCONHR4 and/or (e) R3NHCONHR2NHCONHR4, (wherein R2 is a diphenylmethylalkyl group, and R1 is a hydrocarbon group having an octyl group as a main component, R3 is a hydrocarbon group having 14 to 20 carbon atoms and containing at least 20 moles of hydrocarbon bases of 200831661 " Ear% oil base and R4 system having twelve groups as a main component. Moreover, the present invention provides a urea grease composition comprising: (i) a diurea compound represented by the above formula (c); and (ii) a genus diuretic compound selected from the group consisting of the following: Diurea compound (1) The above formula (b), (d) and (e) (2) the above formula (b) and (d) (2) the above formula (b) and (e) # and as described above The diurea compound represented by the formula (c) is 20 to 80 mol% relative to the molar ratio of the diurea compound. The compound represented by the above formula (A) can be generally obtained according to the following reaction formula: [Formula 1] OCN-R12-NCO + RuNH2 + R13NH2 4 runhconhr12nhconhr13+ r11nhconhr12nhconhr11+ r13nhconhr12nhconhr13 • (wherein R11, R12 and R13 are as described above General). Further, the compound represented by the above formula (B) can be produced in a similar manner to the compound of the formula (A): [Formula 2] OCN-R22-NCO+R21NH2+R23NH2 -> r21nhconhr22nhconhr23+r21nhconhr22nhconhr21+ r23nhconhr22nhconhr23 ( Wherein R21, R22 and R23 are as described above). 15 200831661 The compounds corresponding to the above 〇CN-R 2_NCO and ocn-r22-nco are all diphenylmethane-4,4, diisocyanate. Using R11NH2 and R13NH2 to introduce R11 and R' in the compound of the above formula (A) and introducing R21 and R23 in the above-mentioned hydrate of the general formula (7) using 仏 and ^ [embodiment] The present invention The compounds of the formulae (A) and (B) and the formula (... to b) are explained in detail below. The twelve bases of any of the above R11 and R 3 are particularly resistant to the heat resistance of the urea grease and the durability of the urea grease at a high temperature can be prolonged by the presence thereof. However, if both R11 and R13 are twelve bases, even if the heat resistance is good, the noise performance is poor. Therefore, if any of Rl i and rU is an eleven group, the other may be a hydrocarbon group having 6 to 20 carbon atoms and preferably an oleyl group or an octyl group. Particular examples of materials which supply twelve bases are preferred, including linear-grade dodecylamines. A urea thickener comprising a mixture of a busy amine and an oleylamine or octylamine phenyl decane-4,4'-diisocyanate has excellent thermal stability and a grease composition using the thickener at a high temperature The next is not easy to change, so the effect on extending the lubrication life is very large. The total number of moles of the substituents of RU and Rl3 in the above formula (4) may be from 2 to 7 mol%, preferably from 4 to 50 mol%. At least one of the above R and R towels is an oil base, particularly a positive oil base. The presence of the oil base not only imparts the (4) sound properties of the urea grease composition, but also makes the adsorption property of the urea grease composition to the metal surface forming the sliding portion of the machine part better. Therefore, the lubricating property is further improved. The 16 200831661 / can be 5 to 7 mole % of R 2 and R 23 based on the above formula (7)), and preferably 8 to 55 mole %. In the present invention, at least one of an oil base and a dodecyl group, particularly a n-dodecyl group, must be incorporated into the diurea grease composition, but it is preferred to incorporate an octyl group, particularly an n-octyl group.

If an oil base and a dodecyl group are added and an octyl group is additionally incorporated, particularly an n-octyl group, the proportion of the dodecyl group in R11 and R13 of the above formula (A) is from 3 to 55 mol% and The ratio of the oil base to r£1 and R23 of the above formula is 5 to 55 mol/0, and the proportion of octyl in R", r2i and R23 is suitable for 1 〇 to 9. The molar ratio of the thickeners encompassed by the general formulas (A) and (B) of the present invention is such that it accounts for 2 〇 to 1 (8) mol% of the total thickener. The thickener of the diurea compound represented by the general formulae (A), (B) and (4) to (4) is preferably blended in an amount of 2 to 3 g% by weight relative to the mineral oil or synthetic oil forming the lubricating oil or a mixture thereof. If the mineral oil or synthetic oil of the dimodal compound phase material as a thickener forms a lubricating oil or a mixture thereof is less than 2% by weight, the thickening effect becomes too small to make the grease too soft and There is (for example, the risk of cutting. If it exceeds 3% by weight, the lubricating boring becomes too hard and its flow resistance is increased, so it is impossible to obtain due to an increase in friction torque and a decrease in permeability. Lubricating effect is sufficient. Moreover, the cost is increased. For the lubricating base oil of the present invention, the general lubricating oil and the base oil of the grease can be used. It is not subject to any particular limitation, but the example can refer to mineral oil and / or synthetic oils and vegetable oils. Special examples of synthetic oils: GTL derived base oils (made by Fischer_Tr〇psch method), such as olefin oligomers and polybutenes, polyalkylene glycols such as polyethylene Glycols and polypropylene glycols, diacetates such as di-2-ethylhexyl azelaic acid vinegar and di-2-ethylhexyl adipate vinegar, polyol esters such as trimethylolpropane vinegar and pentaerythritol Vinegar, perfluorinated, polysulfate, and polyphenyl sulfonate, typical examples of vegetable oils may refer to cannabis oil and rapeseed oil. Examples may be provided by these base oils, either alone or in mixtures, without limiting the invention. Further, additives such as antioxidants and rust inhibitors, reagents and extreme pressure additives, and antiwear agents and solid lubricants or metal deactivators and polymers may be additionally added to the composition of the present invention. For example, the antioxidant includes 2, 6_di-t-butyl-4-methylphenol, 2, 6_di·t-butyl _p-cresol, ρ,ρ,-dioctyl-phenylamine, fluorenyl-phenyl-α-naphthylamine and thiodiphenylamine. The rust inhibitor includes paraffin oxide, a metal salt of a carboxylic acid, a metal salt of a sulfonic acid, a carboxylic acid ester, a sulfonate, a salicylate, a succinate, a sorbitan ester, and various amine salts. The oily agent and the extreme pressure additive and the antiwear agent include vulcanization. Zinc dialkyl dithiophosphate, zinc sulfide diallyl dithiophosphate, zinc dialkyl dithiocarbamate, diallyl dithiodithiocarbamate, molybdenum dialkyl disulfide Sulfated monoallyl dithiochromate, molybdenum dialkyl dithiocarbamate, molybdenum monopropyl propyl dithiocarbamate, organic molybdenum complex, sulfurized olefin, diphenyl phosphate, triphenyl Phosphorus thiophosphate, triterpene phosphate, other acid filled vinegar and sulfurized fats and oils. Solid lubricants include molybdenum disulfide, graphite, nitriding, melamine cyanurate, PTFE (polytetrafluoroethylene), bismuth disulfide, and graphite fluoride. Metal deactivators include anthraquinone, anthracene, di- linalyl-hydrazine, 2-diaminopropane, benzotriazole, benzimidazole, benzothiazole, and thiadiazole. Examples of the polymer may mention polybutene, polyisobutylene (p〇lyis〇butene), 200831661 - polyisobutylene (P〇1yisobutylene), polypentadiene and polymethacrylate. The invention can provide a novel urea grease composition, which has excellent sound performance, long life at high temperature and high dropping point, and also provides basic properties such as food cutting stability and heat resistance and proper oil separation. nature. EXAMPLES The present invention is explained in detail by way of examples and comparative examples, but the present invention is limited by these examples in the present manner. The thickeners used in the examples and comparative examples in Tables 1 to 5 below and the abbreviations of the base ingredients are described below. Isocyanate A is diphenylmethane_4,4, diisocyanate having a molecular weight of 250.26 〇 isocyanate B-toluene diisocyanate having a molecular weight of 17416. For the amine starting material: Amine A is a linear primary amine having an average molecular weight of 128.7, wherein the main m-forming knife (at least 90%) is a saturated alkyl group having 8 carbon atoms (industrial grade octylamine); a linear primary amine having a molecular weight of 255., wherein the main component (at least 70%) is an unsaturated alkyl group having 18 carbon atoms (industrial grade oleylamine); and the amine C series has an average molecular weight of 184. A chain primary amine wherein the major component (at least 90%) is a saturated alkyl group having 12 carbon atoms (industrial grade undecylamine). Moreover, the mineral oils shown in the examples and the comparative examples are 10 (12 200831661' dynamic viscosity system 10.12 cm 2 / sec, and synthetic oil A means lOOt: the lower dynamic viscosity is 12.70 cm 2 / sec. Α-olefin oil, synthetic oil B means an alkyl diphenyl ether oil having an kinetic viscosity of 10.69 cm 2 /sec at 100 Å. A, b in the column of the thickener in the thickeners provided in Tables 1 to 4. , c, d and e each refer to a urea compound which can be represented by the following formula: (a) r^NHCONHR^NHCONHR1 (b) R3NHCONHR2NHCONHR3 (c) R^HCONH^NHCONHR3 • (d) R^HCONHR^HCONHR4 (e) R3NHCONHR2NHCONHR4 (wherein R 2 is a diphenylmethylalkyl group, R 1 is a hydrocarbon group having 6 to 10 carbon atoms and having an octyl group as a main component, and R 3 is a hydrocarbon group having 14 to 20 carbon atoms and containing at least 20 mol % of an oil group And R4 is a hydrocarbon group having a n-dodecyl group as a main component.) Further, a and b in the column of the thickener of the comparative example provided in Table 5 refer to the above compounds provided in the examples of Tables 1 to 4. And Tables 1 to 4 • The thickeners provided in the examples provided are f, g, h, i and j. Urea compounds: (f) R4NHCONHR2NHCONHR4 (g) R^HCONHR'NHCONHR1 (h) R3NHCONHR5NHCONHR3 (i) R4NHCONHR5NHCONHR4 (1) i^NHCONHR^NHCONHR4, (wherein R5 is a phenyl group and R1 has 6 to 10 carbons The atom has a hydrocarbyl group having an octyl group as a main component, and R3 is a hydrocarbon group having 14 to 20 carbon atoms and containing at least 20 mol% of an oil group, and R4 is a hydrocarbon group having a n-dodecyl group as a main component. The tests performed on the properties of the examples and the comparative examples were carried out by the method: 1. Permeability: JIS K2220 2. Dropping point: JIS K2220 3. Oil separation: JIS K2220 Method B, conditions were 100. 〇 and 24 hours. 4. Noise test: Measured by the method of Japanese Patent No. 53-2357 (1978) 5. Shell rolling test: ASTM D1831 6. Bearing life test: ASTM D3336 The grease of the present invention is based on the ratios shown in Tables 1 and 2 at the lubricating base. The urea compound (thickener) is synthesized in the oil and blended in the additive. The lubricating base oil and the isocyanate A of the component A (diphenylmethane _4 4, diisocyanate) are fed into a closed prototype grease tank. In the device while stirring This was heated to 60 C. Add lubricating base oil is mixed into the eight-amine (technical grade octyl Fee) of component B1 and reacted with component A. A urea compound 'a' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylmethane)-NHC〇NH-(octyl) The second is the heat of the inner grain to nearly 8 〇C by the heat of reaction. Keep this temperature for 1 ' minutes' then feed the component B2 of the amine B (technical grade 21 200831661 • oil-based amine) which has been previously mixed and dissolved in the lubricating base oil into the tank and react with the isocyanate A of the remaining component A . A urea compound 'b' as shown in the following formula was obtained. (Oil based)-NHCONH-(diphenylmethane)-NHCONH-(Oil based) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine B which have been previously mixed and dissolved in the lubricating base oil Ingredient B3 of (industrial grade oleylamine) is fed to the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'c' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylsulfonium)-NHCONH-(oil based) • Then, after stirring for 5 minutes, the amine A (industrial grade octylamine) which has been previously mixed and dissolved in the lubricating base oil The component B4 of the amine C (industrial grade dodecylamine) is fed to the tank and reacted with the isocyanate VIII of the remaining component A. A urea compound 'd' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) After stirring for 5 minutes, the amine B (industrial grade oleylamine) and amine which have been previously mixed and dissolved in the lubricating base oil Component B5 of C (industrial grade dodecylamine) is fed to the tank and reacted with the isocyanate A of the remaining component A. The urea compound 'e' shown by the following formula is obtained. (Oil-based)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) Then, after rapidly restarting the heating, the temperature was raised to 170 ° C and the temperature was maintained for nearly 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling was started and during the cooling process at 125 ° C, 1.0% by mass of an additional proportion of octyldiphenylamine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 1. 22 200831661 Example 2 Feeding the lubricating base oil and the isocyanate A (diphenylmethane-4,4'-diisocyanate) of component A into a closed prototype grease tank unit and heating the mixture to 60° while stirring C. Component B1 of amine A (technical grade octylamine) which has been incorporated into the lubricating base oil is added and reacted with component A. A urea compound 'a' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyl) The contents were raised to nearly 80 °C via heat of reaction. This temperature was maintained for 10 minutes, and then the component B2 of the amine B (technical grade oleylamine) which had been previously mixed and dissolved in the lubricating base oil was fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'b' as shown in the following formula was obtained. (Oil based)-NHCONH-(diphenylmethane VNHCONH-(oil based) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine B (industrial grade) which have been previously mixed and dissolved in the lubricating base oil The component B3 of the oleylamine) is fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'c' as shown in the following formula is obtained. # (octyl)-NHCONH-(diphenylmethane)-NHCONH - (Oil-based) Then, after stirring for 5 minutes, the component B4 of the amine A (industrial grade octylamine) and the amine C (industrial grade dodecylamine) which have been previously mixed and dissolved in the lubricating base oil are fed into the The can is reacted with the isocyanate A of the remaining component A. A urea compound 'd' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylnonane)-NHCONH-(dodecyl) Then, quickly re- After the heating is started, the temperature is raised to 1 70 ° C and the temperature is maintained for nearly 30 minutes to complete the reaction. After the temperature is maintained for 30 minutes 23 200831661, the cold portion is started to be cooled at 125 ° C, and 1% by mass is used. An additional proportion of octyldiphenylamine antioxidant is added to the grease. Let it progress to ~ 80 ° after two-roll honing The grease was processed to obtain the grease of Example 2. Example 3 The lubricating base oil and the isocyanate a (diphenylnonane-4,4,-diisocyanate) of component A were fed into a closed prototype grease tank apparatus. This was heated to 60 C while stirring. Component B1 of amine A (technical grade octylamine) which had been mixed in the lubricating base oil was added and reacted with component A. A urea compound 'a' represented by the following formula was obtained. (octyl)-NHCONH-(diphenylmethane)_NHC〇NH (octyl) increases the content to nearly 8 (rc via reaction heat). The temperature is maintained for 1 minute and then mixed and dissolved in the lubricating base. The component B2 of the amine B (industrial grade oleylamine) in the oil is fed into the tank and reacted with the isocyanate A of the remaining component a. A urea compound of the formula: b, (oil-based)-NHCONH-( :Phenylnonaneb NHCONH-(Oil-based) A mixture of amine A (industrial grade octylamine) and amine B (industrial grade oleylamine) which have been previously mixed and dissolved in a lubricating base oil after stirring for 5 minutes. B3 is fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'c' as shown in the following formula is obtained. Octyl)-NHCONH-(diphenylnonane)-NHCONH- (oleyl). After 5 minutes of mixing, the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil and The component of the amine c (industrial grade dodecylamine) is pseudo-incorporated into the can and reacted with the isocyanate VIII of the remaining component A. The urea compound 'e' as shown in the following 24 200831661 # is obtained. (Oil-based)-NHCONH- (Diphenylmethane)-NHCONH-(dodecyl) Then, after quickly restarting the heating, the temperature was raised to 170 ° C and the temperature was maintained for nearly 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling was started and during the cooling process at 125 ° C, 1.0% by mass of an additional proportion of octyldiphenylamine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 3.实例 Example 4 The lubricating base oil and the isocyanate A (diphenylmethane-4,4'-diisocyanate) of component A were fed into a closed prototype grease tank apparatus and heated to 60 ° C while stirring. Component B1 of amine A (technical grade octylamine) which has been incorporated into the lubricating base oil is added and reacted with component A. A urea compound 'a' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylnonane)-NHCONH-(octyl) The contents were raised to nearly 80 °C via heat of reaction. This temperature was maintained for 10 minutes, and then component B2 of the amine B (technical grade oleylamine) which had been previously mixed and dissolved in the lubricating base oil was fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'b' as shown in the following formula was obtained. (Oil-based)-NHCONH·(diphenylnonane)-NHCONH-(Oil-based) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine C which have been previously mixed and dissolved in the lubricating base oil Component B4 (industrial grade dodecylamine) is fed to the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'd' as shown in the following formula is obtained. 25 200831661 (octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) After stirring for 5 minutes, the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil The component B5 of the amine C (industrial grade dodecylamine) is fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'e' shown by the following formula is obtained. (Oil-based)-NHCONH.(diphenylmethane)-NHCONH-(dodecyl) Then, after quickly restarting the heating, the temperature was raised to 170 ° C and the temperature was maintained for nearly 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling was started and during the cooling process at 125 ° C, 1.0% by mass of an additional proportion of octyldiphenylamine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 4. Example 5 A lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) of component A were fed into a closed prototype grease tank apparatus and heated to 60 ° C while stirring. Component B1 of amine A (technical grade octylamine) which has been incorporated into the lubricating base oil is added and reacted with component A. The urea compound 'a' shown by the following formula was obtained. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyl) The contents were raised to nearly 80 °C via heat of reaction. This temperature was maintained for 10 minutes, and then component B2 of the amine B (technical grade oleylamine) which had been previously mixed and dissolved in the lubricating base oil was fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'on' as shown in the following formula is obtained. (Oil based)-NHCONH-(diphenylmethane)-NHCONH-(Oil based) 26 200831661 * Then, after stirring for 5 minutes, the amine A (industrial grade octylamine) which has been previously mixed and dissolved in the lubricating base oil And the component B4 of the amine C (industrial grade dodecylamine) is fed into the tank and reacted with the isocyanate A of the remaining component A. The urea compound shown in the following formula, d, was obtained. (Xinky) - Leg 〇: 〇 leg - (diphenyl decane) _NHC 〇 NH- (tweldium base) Then quickly restart the heating, increase the temperature to i 7 〇 and keep the temperature close to 30 Minutes to complete the reaction. After maintaining this temperature for 3 minutes, • Start cooling and add an additional proportion of octyldiphenylamine antioxidant to the grease during the cooling process at 125 °C. After further cooling to 80 C, the grease was processed in a three-roll honing machine to obtain the grease of Example 5. Examples 6 and 7 The lubricating base oil and the isocyanate I of the component a (monophenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease tank device at the blending ratio shown in Table 2. This was heated to 6 Torr while stirring. Hey. The component B1 of the amine A (industrial grade octylamine) which has been mixed into the run-base oil is added and reacted with the component A. A urea compound, a, is obtained as shown in the following formula. (octyl)-NHCONH_(diphenylmethane)_nhC〇NH-(octyl) The content is raised to nearly 8 (rc by reaction heat). The temperature is maintained for 1 minute and then mixed and dissolved in the lubricating base. The component B2 of the amine B (industrial grade oleylamine) in the oil is fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound of the formula: b, (oil-based)-NHC〇NH is obtained. -(diphenylmethane)_nhc〇NH-(oil base) Then, after 5 minutes of scramble, the amine B (industrial grade oleylamine) and amine c (which have been previously mixed and dissolved in the lubricating base oil 27 200831661) The industrial grade dodecylamine is fed into the tank and reacted with the isocyanate a of the remaining component A. A urea compound, e, (oil-based)-NHCONH-(diphenylmethane)_νΗ (: ΟΝΗ•(12 base) Then, after quickly restarting the heating, raise the temperature to i 7 (rc and keep the temperature for nearly 30 minutes to complete the reaction. After maintaining the temperature for 3 minutes, start cooling and cool the process at 125X. During this period, an additional proportion of octyldiphenylamine antioxidant of ι·〇% by mass is added to the grease. After entering the cold section to 80 C, the grease was processed in a three-roll honing machine to obtain the greases of Examples 6 and 7. Example 8 The lubricating base oil and the isocyanate A of the component A (diphenylacetone- 4,4,_Diisocyanate) is fed into a closed prototype grease tank unit and heated to 60 ° C while stirring. Adding amine A (work-grade octylamine) that has been mixed into the lubricating base oil Component B 1 is reacted with component A. A urea compound 'a' represented by the following formula is obtained. _ (octyl)_NHCONH-(diphenylnonane)-NHCONH-(octyl) The content is raised to near by reaction heat 80 ° C. Maintain this temperature for 1 , minutes, then the component B 2 of the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil is thrown into the tank and is different from the remaining component A. The cyanic acid is reacted with A. The gland compound 'b' is obtained as shown in the following formula. (Oil-based)-NHCONH-(diphenylmethane)-NHCONH-(Oil-based) Then, after 5 minutes of disruption, it will be Amine A (industrial grade octylamine) and amine c (industrial grade dodecylamine) mixed and dissolved in a lubricating base oil are incorporated into the tank 28 200831661 Central Asia and remaining The isocyanate A reaction of A. The gland compound 'd' is obtained as shown in the following formula: (octyl)-NHCONH-(diphenylmethane)_nHCONH-(dodecyl) and then rapidly restarting the heating, the temperature is raised to丨7〇.〇 Maintain the temperature for nearly 30 minutes to complete the reaction. After maintaining the temperature for 3 minutes, start cooling and add 1 〇% by mass of octyldiphenyl during the 125° cooling process. An amine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 8. Example 9 A lubricating base oil and an isocyanate a of component A (diphenylnonane-4,4, monoisocyanate) were fed into a closed prototype grease tank apparatus and heated to 60 C while stirring. Amine A (technical grade octylamine) and amine B (technical grade oleylamine) which have been previously mixed and dissolved in a lubricating base oil are added from a funnel and reacted with guanidine isocyanate. A urea compound as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylnonane)_NHC〇NH_(oleyl), and the content of the reaction is raised to nearly 8 〇 by the heat of reaction. The temperature was maintained at that time and then the amine b (technical grade 2 amine) which had been previously mixed and dissolved in the lubricating base oil was fed into the tank from the funnel and reacted with the remaining isocyanate A. A urea compound, b, as shown in the following formula was obtained. (Oil based)-NHCONH-(diphenylmethane)_NHC〇NH-(Oil based) After stirring for 5 minutes, it is premixed and dissolved in the lubricating base oil of the upper amine A (industrial grade octylamine) and Amine c (industrial grade dodecylamine) is fed from a funnel into a crucible and reacted with the remaining isocyanate A. A uread 29 200831661 - 'd' is obtained as shown in the following formula. (octyl)-NHCONH-(diphenylmethane)_nHC0NH-(dodecyl) After stirring for 5 minutes, the amine B (industrial grade oleylamine) and amine c which have been previously mixed and dissolved in the lubricating base oil (Industrial grade dodecylamine) was passed from a funnel into a δH-tank and reacted with the isocyanate A of the remaining component A. A pulse compound ' e ' as shown in the following formula is obtained. (Oil-based)-NHCONH-(diphenylmethane)_Lic〇NH_ (tweldium base) Then, after quickly restarting the heating, the temperature was raised to 17 Torr. 〇和保 _ Hold the temperature for nearly 30 minutes to complete the reaction. After maintaining this temperature for 30 minutes, the cooling started at 125. During the underarm cooling process, an additional proportion by mass of octyldiphenylamine antioxidant is added to the grease. After the step was cooled to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 9. Example 1 0 Lubricate the base oil and the isocyanate A (diphenylmethane-4,4,-diisocyanate S" human-sealed prototype grease tank unit and heat the mixture to 60 C while stirring. Adding (iv) a (industrial grade octylamine) and amine B (industrial grade oleylamine) which have been mixed into the lubricating base oil and reacting with isocyanate A. A urea compound of the formula: c, (octyl)-NHC is obtained. 〇NH-(:phenylpyrene)_NHC〇NH (oil-based) 八 Increase the content to nearly 8 经由 via reaction heat... Maintain this temperature up to ι〇. It will be mixed beforehand and dissolved in the lubricating base oil. The amine b (industrial grade 2-amine) is fed into the tank from a funnel and reacted with the remaining isocyanate _ A to obtain a urea compound as shown in the following formula, b. Further 30 200831661 (Oil based)-NHC〇 NH-(diphenylmethane)-NHCONH- (oil base) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine c (industrial grade ten) which have been previously mixed and dissolved in the lubricating base oil The diamine is introduced into the tank by a funnel and reacted with the remaining isocyanate A. A urea compound 'd' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenyl Burn)-NHCONH-(tweldium base) Then, after 'quickly restarting the heating, increase the temperature to 17 〇 °c and keep the temperature for nearly 30 minutes to complete the reaction. After maintaining the temperature for 3 minutes, start cooling and During the cooling process of 125 art, 1% by mass of the external proportion of octyldiphenylamine antioxidant was added to the grease. After further cooling to 80 ° C, it was processed in a three-roll honing machine. The grease was used to obtain the grease of Example 10. Example 11 The lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype at the blending ratio shown in Table 3. The grease tank device is heated to 6 Torr while stirring. Amine A (industrial grade octylamine) and amine B (industrial grade oleylamine) which have been mixed into the lubricating base oil are added by a funnel and Isochloric acid A is reacted to obtain a urea compound of the formula: c, (octyl)-NHCONH-(:phenylmethyl)-indole (::ΟΝΗ-(oleyl)) Raise to nearly 8 (rc. Keep this temperature for ι〇 minutes, then combine the amine B that has been previously mixed and dissolved in the lubricating base oil (Industrial grade oleylamine) is fed into the tank from a funnel and reacted with the remaining isocyanate A. A urea compound of the formula: b, (oil-based)-NHCONH-(diphenylnonane)-NHC0NH_ is obtained. Oil base) 31 200831661 After stirring for another 5 minutes, the amine B (industrial grade oleylamine) and the amine c (industrial grade dodecylamine) which have been previously mixed and dissolved in the lubricating base oil are fed into the tank from the funnel. And reacting with the remaining isocyanate A. A urea compound 'e' as shown in the following formula is obtained. (Oil-based)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) and then the temperature is raised after rapidly restarting the heating. The reaction was completed up to 17 Torr and maintained at this temperature for approximately 3 minutes. After maintaining the temperature for 3 minutes, cooling was started and an additional proportion of octyldiphenylamine antioxidant was added to the grease during the cooling process at 125 °C. The grease was processed in a three-roll honing machine after further cooling to 80 ° C to obtain the grease of Example 11. Example 12 A lubricating base oil and isocyanate A (diphenylsulfonium-4,4,dioxalic acid vinegar) were placed in a closed prototype grease tank apparatus and heated to 60 C while stirring. Amine (technical grade octylamine) and amine B (technical grade oleylamine) which have been mixed into the lubricating base oil are added from the funnel and reacted with isocyanate a. A urea compound, c, is obtained as shown in the following formula. (octyl)-NHCONH-(diphenylmethane)-NHCONH- (oleyl) The contents were raised to nearly 80 °C via heat of reaction. Maintaining the temperature for 1 minute, then feeding the amine A (industrial grade octylamine) and amine C (industrial grade dodecylamine) which have been previously mixed and dissolved in the lubricating base oil into the tank by the funnel and The remaining isocyanate A is reacted. A urea compound, d, is obtained as shown in the following formula. (octyl)-NHCONH-(diphenylnonane)_nHCONH-(dodecyl), after stirring for 5 minutes, the amine-grade oleylamine which has been previously mixed and dissolved in the lubricating base oil 32 200831661) The amine-grade dodecylamine is fed from the funnel into the tank and reacted with the remaining isocyanate A. A urea compound ' e ' as shown in the following formula is obtained. (Oil based)-NHCONH-(diphenylmethane)_NHc〇Nh• (tweldium base) Then, after quickly restarting the heating, the temperature is raised to 1 Torr. . The temperature was maintained for approximately 30 minutes to complete the reaction. After the temperature was maintained for a minute, cooling was started and during the cooling process at 125 ° C, 1 〇% by mass of an octyl diphenylamine antioxidant in an external ratio was added to the grease. After further cooling to 8 Torr, the grease was treated in a three-roll honing machine to obtain the grease of Example 12. Example 13 A lubricating base oil and isocyanate A (diphenylmethane-4,4, diisoxyl ester) were fed into a closed prototype grease tank apparatus and heated to 60 while stirring. (: Amine A (industrial grade octylamine) and amine B (industrial grade oleylamine) which have been mixed in a lubricating base oil are added from a funnel and reacted with isocyanate A. A urea compound of the following formula, C, is obtained. (Xinyl)-NHCONH-(diphenylmethane)_NHC〇NH gas oil base) The second step is to increase the inner grain to nearly 80 °C by the heat of reaction. Maintain this temperature for 1 〇 minutes, then add the amine A (industrial grade octyl) and amine C (industrial grade dodecylamine) that have been previously mixed and dissolved in the lubricating base oil into the tank from the funnel and Isocyanate A is reacted. A urea compound, a heart, is obtained as shown in the following formula. (octyl)-NHCONH-(diphenylmethane)_NHCONH•(dodecyl) Then, after quickly restarting the heating, the temperature was raised to and maintained at this temperature for nearly 30 minutes to complete the reaction. The temperature was maintained for 3 minutes. 33 200831661 - Thereafter, cooling was started and an additional proportion of octyldiphenylamine antioxidant of 1% by mass was added to the grease during the 125t: lower cooling process. After advancing the cold section 80 C, the grease was processed in a two-roll honing machine to obtain the grease of Example 13. Example 14 Feeding a lubricating base oil and isocyanate A (dipyridyl _ 4,4,-diisocyanate) into a closed prototype grease tank apparatus and heating the mixture to agitation while stirring 6 (TC. Amine a (industrial grade octylamine) and amine B (industrial grade oleylamine) which have been mixed into the lubricating base oil are added by a funnel and reacted with isocyanate A. A urea represented by the following formula is obtained. Compound, C, (octyl)-NHCONH-(diphenylmethane)_NHc〇NH_ (oleyl) The content is raised to nearly 8 〇〇c via heat of reaction. The temperature is maintained for 1 , minutes and then Amine B (industrial grade oleylamine) and amine C (industrial grade dodecylamine) mixed and dissolved in a lubricating base oil are fed into the tank from a funnel and reacted with the remaining isocyanate A. A urea of the following formula is obtained Compound, e, (oleyl)-NHCONH-(diphenylmethane (tityl) • Then, after quickly restarting the heating, raise the temperature to i 7 〇 and keep the temperature for nearly 30 minutes to complete the reaction. After maintaining the temperature for 3 minutes, start cooling and add an additional ratio of octyldiphenyl by 1% by mass during the cooling process at 125 °C. The amine amine antioxidant was added to the grease. After advancing the cold portion to 80 C, the grease was treated in a three-roll honing machine to obtain the grease of Example 14. Example 15 Lubricating base oil and isocyanate of component A A (diphenylmethane_4,4,34 200831661 diisocyanate) is fed into a closed prototype grease tank unit and heated to 6 (TC) when dropped. Add amine A that has been mixed into the lubricating base oil. (industrial grade octylamine) and reacted with isocyanate A. A urea compound 'a' as shown in the following formula is obtained. (octyl)-NHCONH-(diphenylnonane)_NHCONH-(oleyl) The material is raised to approximately 80 ° C. The temperature is maintained for 1 minute, and then the amine B (technical grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil is fed into the tank and reacted with the remaining isocyanate A. A urea compound of the formula: b, (oleyl)-NHCONH-(diphenylmethane)-NHCONH- (oleyl). After stirring for 5 minutes, it is previously mixed and dissolved in a lubricating base oil. Amine A (industrial grade octylamine) and amine c (industrial grade dodecylamine) are fed into the tank and remaining Cyanate vinegar A reaction. Obtain a urea compound as shown in the following formula, d, (octyl)-NHCONH-(diphenylmethane bribe (7) brain - (tweldium base) Then, after quickly restarting heating, the temperature will be Raise to 17 〇 〇 and keep the temperature for nearly 30 minutes to complete the reaction. After maintaining this temperature for 3 〇 minutes, start cooling and at 125. During the 〇 cooling process, ι 〇 mass% γ, proportion of xin A base-based amine amine antioxidant is added to the grease. After cooling it to 8 (TC, the grease is treated in a three-roll honing machine to obtain the grease of Example 15. - f Example 16 妒t The blending ratio shown in Table \ is used to feed the lubricating base oil and the isocyanide-A (monophenylmethane_4,4'-diisocyanate) of component A into a closed prototype lubrication 35 200831661 This was heated to 60 ° C while stirring. The amine A (technical grade octylamine) which has been mixed with the hydrazine and is reacted with isocyanate A. A urea compound, a, was obtained as shown in the following formula. (octyl)-NHCONH-(diphenylmethane)_NHC〇NH_ (oleyl) The contents were raised to nearly 8 Torr via heat of reaction. Hey. The temperature was maintained for 1 minute, and then the amine B (technical grade oleylamine) which had been previously mixed and dissolved in the lubricating base oil was poured into the tank and reacted with the remaining isocyanate A. The urea compound shown in the following formula, b, was obtained. (Oil based)-NHCONH-(:Phenylmethyl)_NHC〇NH_(Oil based) Then, after stirring for 5 minutes, the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil and Amine c (industrial grade dodecylamine) is fed to the tank and reacted with the isocyanate a of the remaining component A. A pulse compound ' e ' as shown in the following formula is obtained. (Oil-based)-NHC〇NH-(diphenylmethane)_NHC〇NH-(dodecyl) Then, after the heating was quickly restarted, the temperature was raised to 17 Torr. The temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 3 minutes, the cold portion was started and an additional proportion of octyldiphenylamine antioxidant of 1 〇 mass ❶ /0 was added to the grease during the cooling process at 125 °C. After further cooling to 80 C, the grease was processed in a three-roll honing machine to obtain the grease of Example 16. Example 17 A lubricating base oil (mixture of mineral oil and synthetic oil A) and isocyanate A (diphenylmethane-4,4, diisocyanate) were fed into a closed prototype grease tank I and this was stirred while stirring. Heat to 60. (: Adding amine A (technical grade octylamine) which has been mixed into the lubricating base 36 200831661 oil and reacting with isocyanate a. A urea compound 'a, which is represented by the following formula, is obtained. (octyl)-NHCONH_(diphenyl Methane)-NHCONH- (oil based) raises the contents to nearly 80 ° C via heat of reaction. Maintains this temperature for 10 minutes, then the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil The component B2 is fed into the tank and reacted with the isocyanate A of the remaining component a. A urea compound of the formula: b, (oil-based)-NHCONH-(diphenylsulfonium)-NHCONH- (oil base) is obtained. After 5 minutes of mixing, the amine A (industrial grade octylamine) and the amine C (industrial grade dodecylamine) which have been previously mixed and dissolved in the lubricating base oil are fed into the tank and with the remaining component A. Isocyanate A is reacted. A urea compound 'd, as shown in the following formula, is obtained. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) Then, after rapid heating restart, the temperature is raised to 1 7 〇 and keep the temperature for nearly 30 minutes to complete the reaction. Keep the temperature for 3 〇 minutes and then start cooling and 125. (: During the lower cooling process, an additional proportion of octyldiphenylamine antioxidant of 1% by mass is added to the grease. It is further cooled to 80T: after treatment in a three-roll honing machine The grease was used to obtain the grease of Example 17. Example 1 8 The lubricating base oil (synthetic oil B) and isocyanate A (diphenylmethane _44, diisocyanate) were fed into a closed prototype grease tank apparatus and Heat this to 60 ° C while stirring. Add the face ^ / ^ τ that has been mixed into the lubricating base oil <Makeup (industrial grade octylamine) and react with isocyanate oxime. A urea compound 37 200831661, a', is obtained as shown in the following formula. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyl) The contents were raised to nearly 8 °C via heat of reaction. This temperature was maintained for 10 minutes, and then component B2 of the amine B (technical grade oleylamine) which had been previously mixed and dissolved in the lubricating base oil was fed into the tank and reacted with the isocyanate A of the remaining component A. A urea compound 'b' as shown in the following formula was obtained. (Oil based)-NHCONH-(diphenylmethane)-NHCONH-(Oil based) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine C which have been previously mixed and dissolved in the lubricating base oil (Industrial grade dodecylamine) is fed into the tank and reacted with the isocyanate A of the remaining component A. The urea compound shown in the following formula, d, was obtained. (octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) Then, after rapidly restarting the heating, the temperature was raised to 170 ° C and the temperature was maintained for nearly 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling was started and during the cooling process at 125 ° C, an additional proportion of 1.0% by mass of octyldiphenylamine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain the grease of Example 18. Comparative Example 1 The lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease tank apparatus at the blending ratio shown in Table 5 and this was stirred while stirring. The material was heated to 6 ° C. Amine A (technical grade octylamine) which has been mixed into the lubricating base oil is added from the funnel and reacted with isocyanate A. A urea compound 'a' as shown in the following formula was obtained. 38 200831661 (辛基)-Jane (: 〇丽-(diphenylmethane)_NHC0NH_ (oleyl) The content is raised to nearly 8 (rc via reaction heat). The temperature is maintained for 1 , minutes and then mixed beforehand and The amine industrial grade dodecylamine dissolved in the lubricating base oil is fed into the tank by a funnel and reacted with the remaining isocyanate a. A urea compound of the formula: f, (t-dodecyl)-NHCONH-( :Phenylmethane)_NHC〇NH_(dodecyl) Then, after quickly restarting the heating, raise the temperature to ^ and keep the temperature for nearly 30 minutes to complete the reaction. Keep the temperature for 3 minutes and then start cooling. During the lower cooling process, 1% by mass of an additional proportion of octyldiphenylamine antioxidant was added to the grease. After further cooling to 8 CTC, the solution was processed in a three-roll honing machine. The grease was used to obtain the grease of Comparative Example 1. Further, in Comparative Example 2, the lubricating base oil and the isocyanate oxime (diphenylnonane-4,4, diisocyanate) were fed into a sealed prototype grease tank apparatus while stirring. Heat this to 60 ° C. Add in the funnel Lubricates the amine B (industrial grade oleylamine) in the base oil and reacts with isocyanate A. A urea compound 'b' as shown in the following formula is obtained. (Oil-based)-NHCONH-(diphenylmethane)-NHCONH-( Oil base) Increases the contents to nearly 8 (TC by reaction heat). The temperature is maintained for i 〇 minutes, then the amine c (industrial grade undecylamine) which has been previously mixed and dissolved in the lubricating base oil is introduced into the funnel silver. The tank is reacted with the remaining isocyanate A. A urea compound of the formula: f, (t-dodecyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) 39 200831661 • Then, fast After restarting the heating, the temperature was raised to i 7 ° C and the temperature was maintained for nearly 30 minutes to complete the reaction. After the temperature was maintained for 3 minutes, cooling was started and cooled during the cooling process at 125 ° C. An additional proportion of octyl-based amine amine antioxidant was added to the grease. After further cooling to 80 ° C, the grease was treated in a three-roll honing machine to obtain a grease of Comparative Example 2. Control f example 3 feed the lubricating base oil and isocyanate B (toluene diisocyanate) The closed prototype grease tank apparatus was heated while stirring to 60 ° C. Amine A (technical grade octylamine) which had been mixed into the lubricating base oil was added from the funnel and reacted with isocyanate ig B. A urea compound of the formula: g, (octyl)-NHCONH-(methylphenyl)-NHCONH-(octyl) K is raised from the heat of reaction to nearly 8 ° C. The temperature is maintained. i 〇 minutes, then the amine B (industrial grade oleylamine) which has been previously mixed and dissolved in the lubricating base oil is fed into the tank from the funnel and reacted with the remaining isocyanate B. A urea compound of the following formula is obtained, h ,.吁 (Oil-based)-NHCONH·(methylphenylene)-NHCONH- (oil-based) After stirring for 5 minutes, the amine A (industrial grade octylamine) and amine which have been previously mixed and dissolved in the lubricating base oil c (industrial grade dodecylamine) was fed into the tank from a funnel and reacted with the remaining isocyanate B. A urea compound 'j ' as shown in the following formula was obtained. (octyl)-NHCONH-(methylphenylene)-NHCONH-(dodecyl) Then, after rapidly restarting the heating, the temperature was raised to j 7 Torr and the temperature was maintained for nearly 30 minutes to complete the reaction. Keep this temperature for 3 minutes. 200831661 Cool down and during the cooling process under (10), i. The mass% of the octyl diphenylamine antioxidant is added to the grease. After further cooling to 8 (TC, in a three-roll honing machine, the grease of Comparative Example 3 was obtained. The grease was processed in the machine to obtain m 4 - ^ lubricating base oil and isocyanate B (toluene) In a diisocyanate-type grease tank device and heating it to the grip during the mixing process.

The amine A (technical grade octylamine) which has been mixed into the lubricating base oil is reacted with iso d曰B. An gland compound as shown in the following formula is obtained, ^. (octyl)-NHCONH-(methylphenylene)_NHc〇NH_(octyl) Μ Increases the (10) to nearly 8 (rc by reaction heat). After maintaining this temperature, it will be mixed beforehand and dissolved in the lubricating base oil. 35c (industrial grade: base amine) is fed into the tank by a funnel and reacted with the remaining isocyanate B. A urea compound of the formula: Γ(t-dodecyl)-NHCONH·(methylphenylene)_NHC is obtained. 〇NH (tweldium base) Then, after quickly restarting the heating, raise the temperature to 17 〇. 〇 and keep the temperature for nearly 30 minutes to complete the reaction. Keep the temperature for 3 〇 minutes to start cooling and cool at i25 °c During the process, the octyl diphenylamine antioxidant of the mass ratio of Y, y, and y is added to the grease. After it is ~V 々 to 80 C, it is processed in a three-roll honing machine. The grease was used to transfer the grease of Comparative Example 4. Compound JIA Example 5 The lubricating base oil and isocyanate B (methyl diisocyanate) were fed into a closed prototype grease tank device and heated to 6 when stirred. 〇r. Add 200831661 into the amine B (industrial grade oleylamine) which has been mixed into the lubricating base oil and react with isocyanate B A urea compound is obtained as shown in the following formula, h (oleyl)-NHCONH- (f phenyl phenyl broth (3) (oil-based) increases the content to nearly 8 (rc by reaction heat). The temperature is maintained for W minutes, Then, an amine c (industrial grade dodecylamine) which has been previously mixed and dissolved in a lubricating base oil is fed into the tank from a funnel and reacted with the remaining isocyanate B. A urea compound of the following formula, hydrazine, is obtained.

(tweldium base)-NHC〇NH_(methylphenylene)_NHc bribe (twelve base) Then, after quickly restarting the heating, increase the temperature to i7〇t and keep the crucible/dish for nearly 30 minutes to complete the reaction. . After the temperature was maintained for 3 minutes, cooling was started and a mascarpine-weight ratio of octyldiphenylamine antioxidant was added to the grease during the cooling process at 125 °C. Let π V "P to 8 〇 C and then treat this in a two-roll honing machine; lick grease to obtain the grease of Comparative Example 5. 42 200831661

44,8 CO rH 00 1 1 Bu Os CN ΓΛ 1 1 inch ο 1 1 la 12.0 la/(b + d) = 75/25 m vo r<l 252 v〇〇00 335 353 mr-H 〇〇j Inch 44.6 CO Inch 1 1 OO VsO —<N CSION (N(N 寸1 1 〇〇(N 0> + + C? C^ ίί OO VO <N 00 in 〇i-H r-S 358 310 ο ο OO m 44.2 36.5 inches u^) V〇(N — m 1 1 (N On (N<N inch divination 1 〇12.0 /^S <υ X) ^ cd II IT) in (N (N inch) o 329 317 1 <N 44.9 36.5 inches^sO<NO〇v〇—(N 1 1 inch 1卜1 1 〇12.0 "Ο ^ m c3 !l CN VO CN u-> i〇(N inch o 〇r*H 335 350 1 F—Η 44.7 36.5 〇 inch (N inch—(N inch 〇—(NO(N—CN 寸卜1 詹〇〇(N ^—4 α> + Λ ι〇(NG\ v〇〇OO Ο 00 inch inch mm OO s < Mm «3 ξ5 s55 φ<ρα < ffl 容_#: ? Λ〇Φ €κ system I ±1 /^s P νβΠΥς w 〜, _ Ik 4ttt w ο CN Μ % ψ 蒎 蒎 々 々 ( ( (S| 5 _! 2 P ο rH Μ 舍; 嚤 蟑 〇 〇 〇 〇 31 31 31 31 31 31 31 31 31

(N< Ο r—( 37.7 1 OO v 〇〇 On i—HC\J 〇 & \ <N m 1 1 704 1 1 ; 1 800 12.0 c/(b + d) =75/25 ”23 5 257 in 〇OO 355 350 1 ON IT) r- CO 1 inch v〇〇 inch ON —(N OO \〇—(N (N On (N 704 should be 1 800 12.0 c/(b + d + e) = 75/25 238 255 Divination fH 358 353 821 〇〇39.7 12.2 24.2 1 1 -- 1 1 704 1 1 800 1 12.0 J a/(b + d) = 25/15 255 241 Bu 359 368 756 Bu 40.3 24.3 16.1 1 1 1 1 in oo v〇OO 704 I 1 800 12.0 a/(b + e) = 50/50 256 247 On (N οο 349 371 1 Ό OO cn inch 36.4 rH OO 瞧1 1 1 n inch m Inch 704 1 1 800 12.0 a/(b + e) = 75/25 258 248 1—Η 342 357 772 Example < m ®I 畹< % /^N m Amine A (g) Amine B (g Amine A (g) Amine c (g) 漤 < 41 PQ % ¥ Thickener blending ratio (mole%) Permeability P ~, /^s 4tiL m Order / ^ \ ο CN Μ % 啦 Shell scroll Test room temperature, 24 hours 150 〇 C, 24 hour bearing life test, 150 ° C life hour amine B (g) amine c (g) Lubricant 200831661

1 '< Divination 15.2 inches m 1 1 rH ^-< 1—( 1 1 760 1 1 800 〇a/(b + d) = 75/25 387 238 卜 ON rH > 440 424 720 inch Ό In m I 1 Os Ό ^O; 1 1 m Ό Ον Ό —(Ν 704 1 1 800 12.0 c/e = 25/75 1 254 238 VO 〇oo 384 336 734 ro rH ι—Η On CO 1 1 v〇 On inch OO rH Ν Ό Ό ... 艺艺1 704 1 I 800 1 12.0 I c/d = 75/25 248 259 inch 〇 ON 351 346 742 (NH 〇〇CO 1 1 14.6 28.9 卜 On r^cn m inch cn Inch 704 1 Painting 800 12.0 c / (d + e) = 75/25 253 255 inch 〇 (N 353 341 1 rH 3 6.6 1 oo 14.6 29.0 1 1 m inch m inch 704 1 瞧 800 ο (Ν τ-Η c /(b + e) = 75/25 256 249 yr\ 〇rH 351 353 1 < am ® I 畹< Fanfanamine A (g) Amine B (g) Amine A (g) Amine C (g) / ^S < φ m fl /-Ν _ thickener blending ratio (mol%) Si 〇◦ /^S _ surface (vw^ 4Hi w Φ Ο <NM coffee shell rolling test room temperature, 24 hours 150 〇C, 24-hour bearing life test, 1 50 °C life hours 'V mu 雄雄 ca^ cts^ Lubricating oil 200831661

200831661

200831661

[Simple description of the diagram] (none) [Description of main component symbols] (none) 48

Claims (1)

200831661 - X. Patent application scope: 1 · A urea grease composition comprising: a diurea compound as shown in the following formula (A): RnNHCONHR12NHCONHR13 ··_ (A), (wherein R11 and R13 are selected a group free of a group consisting of a hydrocarbon group of 6 to 2 carbon atoms, at least one of RU and Rl3 is a dodecyl group and a fluorene group; and) • as in the following formula (B) a diurea compound: R21NHCONHR22NHCONHR23 · (B), wherein R21 and R23 are selected from the group consisting of a hydrocarbon group having 6 to 2 carbon atoms, and at least one of R2! and R23 Oil based and R22 is diphenyl fluorenyl). The urea grease composition according to the scope of the patent application of the present invention, wherein the proportion of the twelve base in the RU and R13 of the above formula (A) is 2 to 7 mol% and/or The proportion of the oil base in the above formula (B) and R23 is 5 to 70 mol%. 3. The urea grease composition according to the scope of claim 2 or 2, wherein the RU of the above formula (A) and the R" have a hydrocarbon group of 6 to 2 carbon atoms which is not a 12 base group and/or The non-oleyl hydrocarbon group having 6 to 20 carbon atoms in the above formula () ru and R23 is an octyl group. 4. The urea grease composition according to item 3 of the patent application, wherein the ratio of the berthyl group to the Rn or RU of the above formula (A) is from 3 49 200831661 - to 55 mol %, The proportion of the oil base in R21 and R23 of the above formula (B) is 5 to 55 mol%, and the proportion of the octyl groups in R11, R13, R21 and R23 is 10 Up to 90% by mole. 5. A urea grease composition comprising: a diurea compound as shown by the following formula: (a) R^HCONH^NHCONHR1 and (b) R3NHCONHR2NHCONHR3 • and additionally comprising one of the following formulas Or a plurality of diurea compounds: (d) R^HCONH^NHCONHR4 and/or (e) R3NHCONHR2NHCONHR4, (wherein R2 is diphenyldecylalkyl, R1 is a hydrocarbyl group having an octyl group as a main component, and R3 has 14 to 20 a hydrocarbon atom having at least 20 mol% of an oil group and a hydrocarbon group having a tetradecyl group as a main component. 6. A urea grease composition comprising: _ a diurea compound of the formula: (a) R^NHCONHR^NHCONHR1 and (b) R3NHCONHR2NHCONHR3 and (c) i^NHCONHR^NHCONHR3 and additionally comprising One or more diurea compounds as shown by the following formula: (d) RiNHCONHR^NHCONHR4 50 200831661 and/or (e) R3NHCONHR2NHCONHR4, (wherein R2 is a diphenylmethyl group, a hydrocarbon group having an octyl group as a main component, R3 is a hydrocarbon group having 14 to 20 carbon atoms and containing at least 2 mole% of an oil group, and R4 is a hydrocarbon group having a dodecyl group as a main component). a urea grease composition comprising: (1) a diurea compound represented by the above formula (a); and (a) a genus selected from the group consisting of diurea compounds of the following groups Urea compound (1) The above formula (b), (c), (d) and (e) (2) the above formula (b), (c) and (d) (3) the above formula (b), (c) and (e), and the molar ratio of the diurea compound represented by the above formula (a) to the sum of the diurea compound is from 20 to 80 mol%. 8 _ - a gland grease composition comprising: a diurea compound as shown by the following formula: (c) R^HCONH^NHCONHR3 and additionally comprising one or more diurea compounds as shown by the following formula: (d) R]NHCONHR2NHCONHR4 and/or (e) R3NHCONHR2NHCONHR4, (wherein RM is a diphenylmethyl group, a hydrocarbon group having a mercapto group as a main component, and R3 has 14 to 20 carbon atoms and contains at least 2 The hydrocarbyl group of the 〇mol% oil group and the hydrocarbon group of the R4 system having a twelfth group as a main component). ' 51 200831661 9. A urea grease composition comprising: a diurea compound as shown by the following formula: (c) R]NHCONHR2NHCONHR3 and (b) R3NHCONHR2NHCONHR3 and additionally comprising one or more of the following formulas Diurea compound: (d) R^HCONH^NHCONHR4 and / or (e) R3NHCONHR2NHCONHR4, (wherein RM is a diphenylmethyl group, a hydrocarbon group having an octyl group as a main component, R3 is a hydrocarbon group having 14 to 20 carbon atoms and containing at least a mol% of an oil group, and the R4 system has twelve Base for rabbits, signed as the main component of von's hydrocarbon group). A urea grease composition comprising: (i) a diurea compound represented by the above formula (c); and (ii) a genus selected from the group consisting of - ΗΕ ^ t 〒 < Diurea compound of a urea compound (1) The above formula (b), (d) and (e) (2) the above formula (b) and (d) (3) the above formula (b) and (e) And, according to the above formula (c), the diurea is in the range of from 20 to 80 moles per gram of the molar ratio of the compound to the diurea compound. 11 A method for improving noise performance, which utilizes a pulse-known composition according to any one of claims 1 to 10 of the prior application. 1 2 _ - The use of the urea grease composition according to the previous patent application, which is used to improve the noise performance. Eleven, circle: (none) 53