CN103695076B - A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof.On the basis of grease weight, this grease includes following components: 1) non-newtonian fluid calcium naphthenate 10 70%；2) calcium salt 1 10% of higher fatty acids；3) calcium salt of aromatic acid；4) four polyureas 0.5 30%；5) lubricating base oil 10 80%.Described grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, contains composite calcium thickening agent and four polyurea compounds simultaneously.This grease has fabulous extreme pressure anti-wear and overlength lubricating life, the most also has the performances such as excellent adhesiveness, water-resistance, colloid stability, high dropping point, thermostability, anticorrosive property, resistance to saltfog.

Description

A kind of Composite calcium naphthenate base four polyurea grease and preparation method thereof

Technical field

The present invention relates to lubricant, be specifically a kind of Composite calcium naphthenate base four polyurea grease And preparation method thereof.

Background technology

Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellence Diffusibility, be used as the detersive of lubricating oil, be widely used in the interpolation of IC engine lubricating oil Agent, the development of its technology mainly makes its high alkalization, it is simply that the calcium carbonate ring with surface activity Acid calcium is distributed in flux oil become a kind of colloidal dispersion system.Overbased calcium alkyl-salicylate be mostly from The acidic components extracted in the distillate that crude distillation obtains, warp and Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about preparation Patents have CN 1465560 etc..

Utilize that calcium sulfonate with high base number is raw material production grease has the high and low temperature of excellence because of it Energy, mechanical stability, colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust Wear resistence, since putting goods on the market, has caused the extensive concern of domestic and international grease industry, but, Although high base number composite calcium sulfonate base grease has the most excellent combination property, but its production is former High price and complicated preparation technology itself of material calcium sulfonate with high base number cause it not by rapidly Promoting, meanwhile, along with people are more and more higher to the requirement of environmental conservation, calcium sulfonate with high base number produces During must through sulfonation process the pollution of environment is also increasingly subject to the concern of people.Find one Performance is similar with high base number composite calcium sulfonate but the grease of the problems referred to above can be avoided to become people The big problem of faced at present.

Summary of the invention

The invention provides a kind of Composite calcium naphthenate base four polyurea grease, this grease uses Petroleum naphthenic acid calcium or synthesis calcium naphthenate are raw material, contain composite calcium thickening agent and four poly-simultaneously Carbamide compound.

The present invention also provides for above-mentioned preparation of greases method.

The calcium naphthenate-based tetrapolyurea lubricating grease that the present invention provides, on the basis of grease weight, bag Include following components:

1) non-newtonian fluid calcium naphthenate 10-70%, preferably 20-60%, most preferably 30-55%；

2) the calcium salt 1-10% of higher fatty acids, preferably 2-6%, most preferably 2.2-4.2%；

3) the calcium salt 1-15% of aromatic acid, preferably 2-12%, most preferably 3-10%；

4) four polyureas 0.5-30%, preferably 1-20%, most preferably 2-10%；

5) lubricating base oil, 10-80%, preferably 20-70%, most preferably 30-60%.

Described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm^-1-886cm^-1There is crystal formation carbon in place Acid calcium characteristic absorption peak, total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g.Described non-newtonian fluid calcium naphthenate is by newton body aphthenic acids Calcium is converted by transforming agent and obtains.And containing unformed calcium carbonate in newton body calcium naphthenate, red 860cm in outer spectrogram^-1-865cm^-1There is characteristic absorption peak in place.Described newton body calcium naphthenate is Petroleum naphthenic acid calcium or synthesis calcium naphthenate, its total base number is 250mgKOH/g -450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, change into non-newtonian fluid ring After alkanoic acid calcium, its base number is constant.

Described higher fatty acids be carbon number be straight chain fatty acid or the hydroxyl of 8-20, preferably 10-16 Fatty acid, such as lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic One or more mixture in acid, preferably 12-hydroxy stearic acid.

Described aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, other substituent group Can be the alkyl or aryl etc. of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, Molecular weight is less than or equal to 550.Described aromatic acid preferred binary aromatic acid, for example, it is possible to selected from unsubstituted Or the substituted phthalic acid of C1-C5 alkyl, M-phthalic acid, p-phthalic acid, biphenyl two One or more in formic acid, polyphenyls dioctyl phthalate.Preferably phthalic acid, M-phthalic acid, P-phthalic acid, biphenyl dicarboxylic acid, and methyl substituted biphenyl dicarboxylic acid, polyphenyls dioctyl phthalate One or more in Deng.

Grease of the present invention can also contain little molecule mineral acid and/or the calcium of little molecules of fatty acids Salt.The molecular weight of described little molecule mineral acid or little molecules of fatty acids is less than or equal to 150.Wherein, Little molecule mineral acid can be selected from the mixture of one or more in boric acid, phosphoric acid, sulphuric acid etc., Preferred boric acid and/or phosphoric acid；Little molecules of fatty acids can be selected from acetic acid, ethanedioic acid, propanoic acid, the third two The mixture of one or more in acid, butanoic acid, succinic acid etc., preferably acetic acid.

Described four polyureas have a structure that

R therein¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl be permissible It is 8 ~ 24, preferably 10 ~ 18, aryl can be phenyl or substituted phenyl, preferably phenyl or C1 ~ C3 Alkyl or the phenyl of halogen substiuted.

R therein²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2 ~ 12, excellent Selecting 2 ~ 8, arlydene can be phenylene or biphenylene.

R therein³Can be carbon number be 6 ~ 30, the arlydene of preferably 6 ~ 20, alkylidene or sub-ring Alkyl, preferably methylphenylene, diphenylmethylene, dicyclohexylmethylene, a dimethyl Asia At least one in phenyl and hexylidene.

Described lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, 100 ° of C dynamic viscosities are 4-150mm²/ s, preferably 10-60mm²/s.Artificial oil can be poly-α- Alkene oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch synthesis oil etc..

Grease of the present invention can also contain various additives, such as antioxidant, antiwear additive, antirust Agent etc..Wherein antioxidant preferred arylamine kind antioxidant, accounts for the 0.1%-5% of grease gross weight, excellent Select 0.2%-1%, can be diphenylamines, phenyl-a-naphthylamine, di-iso-octyldiphenylamine or they Mixture, preferably di-iso-octyldiphenylamine.Antiwear additive can be dithio Acidic phosphates zinc, two Sulfur for dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formate, triphenylphosphorothionate, Organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, politef, D2EHDTPA molybdenum, chlorination Paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium sulfide, fluorographite, carbon Acid calcium and zinc oxide；Antirust agent can be barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzene A pair of horses going side by side triazole, zinc naphthenate and alkenyl succinic acid.

The preparation method of described Composite calcium naphthenate base four polyurea grease, including:

(1) in reactor A by newton body calcium naphthenate, part basis oil and transforming agent mixing, Heating, makes material retrogradation become smectic；

(2) in aforesaid reaction vessel, add Calx or calcium hydroxide, be separately added into higher fatty acids And aromatic acid, heat up dehydration；

(3) in the product of reactor A or in reactor B, part basis oil is added different with two Cyanate, is initially charged diamidogen and reacts, and adds monoamine and reacts, wherein diisocyanate, Diamidogen is 2:1:2 with the mol ratio of monoamine；

(4) by the material mix homogeneously in reactor A, or the material of reactor A and B is closed Mix homogeneously after and, is warmed up to 200-220 ° of C constant temperature refining, cooling, adds surplus base oil, Add necessary additive, obtain finished product.

Specifically, preparation method of the present invention can complete in a reactor, it is possible to use Two reactors.

Specifically, in step (1), newton body calcium naphthenate, the mixing of part basis oil are added Heat, to 50-90 ° of C, preferably constant temperature 10-30 minute, is sequentially added into required transforming agent and reacts, Stirring about 10 minute after adding the most every time, react fully, all transforming agents rise after adding Temperature, preferably 60-100 ° of C constant temperature 0.5-3 hour, makes material retrogradation become smectic.Described newton Body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, its total base number 250-450mgKOH/g, preferably 300-400mgKOH/g.

Described transforming agent is selected from the fatty alcohol of C1-C5, fatty acid, aliphatic ketone, fatty aldehyde, fat Fat amine, cycloalkanes amine, cyclic alkanol, ether, and calcium carbonate, boric acid, phosphonic acids, carbon dioxide, benzene One or more in phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate, water etc., excellent Select the one in DBSA, C16-C62 aphthenic acids, methanol, butanol, acetic acid and water Or it is several.The addition of transforming agent is the 2-30% of newton body calcium naphthenate weight, preferably 6-22%.

In step (2), add Calx or the suspension of calcium hydroxide at 85-100 ° of C, 85-100 ° of C adds higher fatty acids, stirs 5-20 minute, adds aromatic acid, it is also possible to adding must The little molecule mineral acid wanted and/or little molecules of fatty acids, stir 5-20 minute, be warmed up to 105-120 ° of C, preferably keeps 30-60 minute, and dehydration cools to 90 ° of C-105 ° of C；The highest Level fatty acid can exchange with aromatic acid addition sequence.

Described higher fatty acids be carbon number be straight chain fatty acid or the hydroxyl of 8-20, preferably 10-16 Fatty acid, such as lauric acid, Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic One or more mixture in acid, preferably 12-hydroxy stearic acid.

Described aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, other substituent group Can be the alkyl or aryl etc. of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, Molecular weight is less than or equal to 550.Described aromatic acid preferred binary aromatic acid, for example, it is possible to selected from unsubstituted Or the substituted phthalic acid of C1-C5 alkyl, M-phthalic acid, p-phthalic acid, biphenyl two One or more in formic acid, polyphenyls dioctyl phthalate.Preferably phthalic acid, M-phthalic acid, P-phthalic acid, biphenyl dicarboxylic acid, and methyl substituted biphenyl dicarboxylic acid, polyphenyls dioctyl phthalate One or more in Deng.

The molecular weight of described little molecule mineral acid or little molecules of fatty acids is less than or equal to 150.Wherein, Little molecule mineral acid can be selected from the mixture of one or more in boric acid, phosphoric acid, sulphuric acid etc., Preferred boric acid and/or phosphoric acid；Little molecules of fatty acids can be selected from acetic acid, ethanedioic acid, propanoic acid, the third two The mixture of one or more in acid, butanoic acid, succinic acid etc., preferably acetic acid.

The total thing of H+ of higher fatty acids and aromatic acid and little molecule mineral acid and/or little molecules of fatty acids The amount of the amount of matter material total with the OH-contained by calcium hydroxide is equal, and the amount of calcium hydroxide also can excess 1%-10%。

In step (3), in the product of step (2) or in another reactor, add part basis Oil and diisocyanate, stir, and adds diamidogen, reacts 2-8 minute, adds monoamine, instead Answering 2-8 minute, the mol ratio of diisocyanate, diamidogen and monoamine is 2:1:2, monoamine, diamidogen and Diisocyanate can be first dissolved in part basis oil.

Described diisocyanate structure is OCN-R³-NCO, R³Can be carbon number be 6 ~ 30, Arlydene, alkylidene or the cycloalkylidene of preferably 6 ~ 20, preferably methylphenylene, diphenyl Asia Methyl, dicyclohexylmethylene, dimethylphenylene and hexylidene etc..The most described two isocyanides Acid esters can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), 1,6- Hexamethylene diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI), or benzene two methylene At least one in group diisocyanate (XDI) etc..

Described monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R¹-NH₂, its In R¹Can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8 ~ 24, Preferably 10 ~ 18, aryl can be phenyl or substituted phenyl, preferably phenyl or C1 ~ C3 alkyl or The phenyl of halogen substiuted.Preferably monoamine can be selected from aniline, m-chloroaniline, parachloroanilinum, The arylamine of para-totuidine, and/or selected from lauryl amine, tetradecy lamine, cetylamine, the fatty amine of 18-amine..

Described diamidogen can be fatty amine or arylamine, and structural formula is NH₂-R²-NH₂, therein R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2 ~ 12, preferably 2 ~ 8, sub-virtue Base can be phenylene or biphenylene.Preferably diamidogen can be selected from p-phenylenediamine, adjacent benzene two Amine, the aromatic amine of 4,4 '-benzidine and/or selected from ethylenediamine, propane diamine, 1,6-hexamethylene diamine straight Chain fatty amine.

In step (4), will heat up after the product mix homogeneously of step (2) and step (3), Preferably 100-120 ° C constant temperature 10-20 minute, is finally warmed up to 200-220 ° of C constant temperature 5-10 and divides Clock；It is cooled to 150-160 ° of C, adds surplus lubricating base oil, treat that temperature is cooled to 100-120 ° of C, Adding necessary additive, stirring, circulating filtration, homogenizing, degassing obtain finished product.

Grease of the present invention compared with prior art, has excellent extreme pressure anti-wear and long lubrication longevity Life, meanwhile, also has excellent adhesiveness, water-resistance, colloid stability, high dropping point, heat peace The performances such as qualitative, anticorrosive property, resistance to saltfog.This product preparation process is simple, and product quality is steady Fixed.

Accompanying drawing explanation

Fig. 1 is the infrared spectrum of the grease of embodiment 2 preparation.It can be seen that 873cm^-1-886cm^-1There is crystal form calcium carbonate characteristic absorption peak in place.Meanwhile, exist 3300cm^-1-3323cm^-1The peak at place is the stretching vibration absworption peak of-NH-in four polyureas molecules.

Fig. 2 is the infrared analysis spectrogram of four polyureas in the grease of embodiment 2 preparation.From figure It can be seen that 3310 ~ 3323cm^-1The stretching vibration that peak is-NH-in four polyureas molecules at place absorbs Peak, 1630cm^-1The peak at place is the vibration absorption peak of-CO-in four polyureas molecules.

Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of four polyureas in the grease of embodiment 2 preparation.From In figure it can be seen that the peak of about δ=155HZ is the chemical shift of-CO-in four polyureas molecules.

Fig. 4 is the Electrospray Ionization Mass Spectrometry spectrogram of four polyureas in the grease of embodiment 2 preparation. It can be seen that the mass-to-charge ratio of sample is 1100.4m/z, this phase with four polyurea compounds Molecular mass is matched.

Detailed description of the invention

In embodiment, the computational methods of each constituent content are as follows:

Non-newtonian fluid calcium naphthenate %=(overbased or overbased calcium alkyl-salicylate raw materials quality+conversion Agent gross mass)/grease gross mass.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.

The calcium salt of higher fatty acids and the calcium salt content of aromatic acid are with the higher fatty acids added and aromatic acid Response calculation completely.

In embodiment, overbased and overbased calcium alkyl-salicylate raw material is from the fine oil of Xinjiang Lander Chemical inc, it is also possible to according to CN101885677A (a kind of highly basic calcium naphthenate Preparation method) disclosed in method prepare.

In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..

Embodiment 1

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(30kg)；Aphthenic acids (pure acid number 120mgKOH/g, acid content 70%, 2.8kg)； Methanol (1kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)；12-hydroxy stearic acid (2kg)； P-phthalic acid (3.5kg) 18-amine. (1.08kg)；Ethylenediamine (0.12kg)；MDI(1kg)； 500SN(17kg)。

It is 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down at a volume Middle addition 30kg total base number is naphthenate with superhigh base number calcium and 100 ° of C of 30kg of 400mgKOH/g Kinematic viscosity is 31mm²The HVI150BS lubricating base oil of/s, stirring, heat to 80 ° of C, Constant temperature 10 minutes；Adding 2.8kg aphthenic acids, temperature controls, at 80 ° of about C, to stir 10 minutes； Add 1kg methanol, stir 10 minutes；Add acetic acid and the water of acetic acid weight 4 times of 0.56kg Solution, stirs 10 minutes；It is warmed up to 85 ° of C, constant temperature 90 minutes, material retrogradation；Add 1.8kgCa(OH)₂And with 4 times of water-reducible suspensions, stir 10 minutes；Add 2kg12-hydroxyl Base stearic acid, stirs 10 minutes；Add 3.5kg p-phthalic acid, stirring, be warmed up under stirring 110 ° of C, keep 60 minutes, dehydration；Cool to 90 ° of C addition 1kg MDI and quickly stir 4 points Clock, quickly stirring is lower adds 0.12kg ethylenediamine, stirs 4 minutes, adds 1.08kg 18-amine. Stirring 4 minutes, added MDI, ethylenediamine are 2:1:2 with the mol ratio of 18-amine., 120 ° of C Constant temperature 20 minutes, is finally warmed up to 200 ° of C constant temperature 5 minutes.Then, it is cooled to 160 ° of C, It is 11mm that addition accounts for 100 ° of C kinematic viscositys of grease weight 18kg²The HVI500SN profit of/s Sliding base oil；Treating that temperature is cooled to 110 ° of C, circulating filtration, homogenizing, degassing obtain finished product.Inspection Test and the results are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.5%；Four polyureas 2.5%；Lubricating base oil 52.8%；12-hydroxy stearic acid Calcium 2.4%；P-phthalic acid calcium 4.8%.

Embodiment 2

Raw material components: naphthenate with superhigh base number calcium (total base number is 420mgKOH/g, 30kg)； 150BS(30kg)；DBSA (2.8kg)；Isopropanol (1kg)；Acetic acid (0.56kg)； Ca(OH)₂(1.8kg)；12-hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；18 Amine (1.08kg)；Ethylenediamine (0.12kg)；MDI(1kg)；500SN(17kg).

It is 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down at a volume Middle addition 30kg total base number is naphthenate with superhigh base number calcium and 100 ° of C of 30kg of 420mgKOH/g Kinematic viscosity is 31mm²The HVI150BS lubricating base oil of/s, stirring, heat to 50 ° of C, Constant temperature 10 minutes；Adding 2.8kg DBSA, temperature controls, at 50 ° of about C, to stir Mix 10 minutes；Add 1kg isopropanol, stir 10 minutes；Add acetic acid and the acetic acid of 0.56kg The aqueous solution that weight is 4 times, stirs 10 minutes；Being warmed up to 95 ° of C, constant temperature 90 minutes, material becomes Thick one-tenth smectic；Add 1.8kgCa (OH)₂And with 4 times of water-reducible suspensions, stir 10 minutes； Add 2kg12-hydroxy stearic acid, stir 10 minutes；Add 3.5kg p-phthalic acid, stir, It is warmed up to 110 ° of C under stirring, keeps 60 minutes, dehydration.

It is 30L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down at another volume 18kg100 ° of C kinematic viscosity of middle addition is 11mm²The HVI500SN lubricating base oil of/s and 1kg MDI is warming up to 110 ° of C, and quickly stirring is lower adds 0.12kg ethylenediamine, stirs 4 minutes, adds 1.08kg 18-amine. stirs 4 minutes, and added MDI, ethylenediamine with the mol ratio of 18-amine. are 2:1:2,120 ° of C constant temperature 20 minutes, obtain four polyureas.

Gained four polyureas is all squeezed in a upper still, stirs, be finally warmed up to 200 ° of C Constant temperature 10 minutes.Then, still cooling is turned；Treat that temperature is cooled to 90 ° of C, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

A small amount of four polyureas are prepared again, with petroleum ether (boiling point 60 ~ 90 by above-mentioned steps 2 same method DEG C) washing, it being filtrated to get precipitation, gained precipitation the most i.e. obtains four polyurea compounds.It is red Outer spectrogram, nuclear magnetic resonance spectroscopy spectrogram, Electrospray Ionization Mass Spectrometry spectrogram see respectively Fig. 2, Fig. 3, Fig. 4.

The four polyureas molecular structural formulas contained in component are:

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non-newtonian fluid ring Alkanoic acid calcium 37.5%；Four polyureas 2.5%；Lubricating base oil 52.8%；12-hydroxy stearic acid calcium 2.4%； P-phthalic acid calcium 4.8%.

Embodiment 3

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(20kg)；N-butyl alcohol (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； Stearic acid (1.9kg)；Phthalic acid (3.5kg)；Lauryl amine (0.88kg)；Ethylenediamine (0.14kg)； MDI(1.18kg)；500SN(27kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be use n-butyl alcohol, stearic acid, phthalic acid, lauryl amine replace aphthenic acids, 12-hydroxyl Stearic acid, p-phthalic acid, 18-amine. and each number of components also respective change, the grease obtained The each performance data of finished product is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.5%；Four polyureas 2.5%；Lubricating base oil 52.9%；Calcium stearate 2.3%； Calcium phthalate 4.8%.

Embodiment 4

Raw material components: overbased calcium alkyl-salicylate (total base number is 320mgKOH/g, 30kg)；150BS (25kg)；DBSA (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Ca(OH)₂ (1.8kg)；12-hydroxy stearic acid (2kg)；M-phthalic acid (3.5kg)；18-amine. (1.25kg)； Ethylenediamine (0.14kg)；TDI(0.81kg)；500SN(22kg).

High base number Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be use 320mgKOH/g overbased calcium alkyl-salicylate, DBSA, M-phthalic acid, Toluene di-isocyanate(TDI) (TDI) replace 400mgKOH/g overbased calcium alkyl-salicylate, aphthenic acids, P-phthalic acid, MDI and each number of components also respective change, each performance of grease finished product obtained Data are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.5%；Four polyureas 2.5%；Lubricating base oil 52.8%；12-hydroxy stearic acid Calcium 2.4%；M-phthalic acid calcium 4.8%.

Embodiment 5

Raw material components: overbased calcium alkyl-salicylate (total base number is 360mgKOH/g, 30kg)；150BS (15kg)；Aphthenic acids (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； 12-hydroxy stearic acid (2kg)；2-methyl isophthalic acid, 4-phthalic acid (3.8kg)；18-amine. (1.08kg)； Ethylenediamine (0.12kg)；MDI(1kg)；500SN(7kg).

High base number Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different It is to use 360mgKOH/g overbased calcium alkyl-salicylate, 2-methyl isophthalic acid, 4-phthalic acid and base oil Consumption change so that each material rate occur bigger change, the grease obtained become The each performance data of product is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 52.1%；Four polyureas 3.5%；Lubricating base oil 34.4%；12-hydroxy stearic acid Calcium 3.3%；2-methyl isophthalic acid, 4-phthalic acid calcium 6.7%.

Embodiment 6

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(25kg)；Aphthenic acids (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； 12-hydroxy stearic acid (2kg)；4,4 '-biphenyl dicarboxylic acid (5.1kg)；18-amine. (3.24kg)； Ethylenediamine (0.36kg)；MDI(3kg)；500SN(18.6kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be use 4,4 '-biphenyl dicarboxylic acid replaces p-phthalic acid, and 18-amine., ethylenediamine, MDI Being varied from the amount of base oil, each performance data of grease finished product obtained is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 36.4%；Four polyureas 7.2%；Lubricating base oil 47.6%；12-hydroxy stearic acid calcium 2.3%；4,4 '-biphenyl dicarboxylic acid calcium 6.5%.

Embodiment 7

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； PAO 40(30kg)；Aphthenic acids (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； 12-hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.08kg)；Second two Amine (0.12kg)；MDI(1kg)；PAO 10(9kg)；Dithio Acidic phosphates zinc (2kg)； Molybdenum dialkyldithiocarbamacompositions (1kg)；Tungsten disulfide (2kg)；Two tungsten selenide (2kg)； Right, right '-di-iso-octyldiphenylamine (0.2kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be use full synthetic oil poly & Alpha ,-olefin oil PAO 10 (100 ° of C kinematic viscositys are 10mm²/ s) and (100 ° of C kinematic viscositys are 40mm to PAO 40²/ s) respectively replace 500SN and 150BS, and Addition additive dithio Acidic phosphates zinc before homogenizing, molybdenum dialkyldithiocarbamacompositions, two Tungsten sulfide, two tungsten selenide, right, right '-di-iso-octyldiphenylamine, each performance of grease finished product obtained Data are shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.8%；Four polyureas 2.5%；Lubricating base oil 44.2%；12-hydroxy stearic acid Calcium 2.4%；P-phthalic acid calcium 4.9%；Dithio Acidic phosphates zinc 2.3%；Dialkyl disulfides For carbamic acid molybdenum 1.1%；Tungsten disulfide 2.3%；Two tungsten selenide 2.3%；Right, right '-diisooctyl Diphenylamines 0.2%.

Embodiment 8

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(15kg)；Aphthenic acids (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； 12-hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.08kg)；Second two Amine (0.12kg)；MDI(1kg)；500SN(33kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be free from antioxidant pair, right '-di-iso-octyldiphenylamine and base oil consumption are varied from, and obtain The each performance data of grease finished product is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.1%；Four polyureas 2.4%；Lubricating base oil 53.3%；12-hydroxy stearic acid Calcium 2.4%；P-phthalic acid calcium 4.8%.

Embodiment 9

Raw material components: overbased calcium alkyl-salicylate (total base number is 360mgKOH/g, 30kg)；150BS (20kg)；Aphthenic acids (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(5.2kg)；12-hydroxyl Stearic acid (2kg)；Boric acid (2.32kg)；P-phthalic acid (7.6kg)；18-amine. (1.08kg)； Ethylenediamine (0.12kg)；MDI(1kg)；500SN(28kg)；Right, right '-diisooctyl hexichol Amine (0.2kg).

High base number Composite calcium naphthenate base four polyurea grease is prepared by the method for example 9, different Being the increase in phosphoric acid and base oil consumption is varied from, each performance data of grease finished product obtained is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 34.2%；Four polyureas 2.2%；Lubricating base oil 49.2%；12-hydroxy stearic acid Calcium 2.2%；Calcium pyroborate 2.4%；P-phthalic acid calcium 9.6%；Right, right '-di-iso-octyldiphenylamine 0.2%。

Embodiment 10

Raw material components: overbased calcium alkyl-salicylate (total base number is 360mgKOH/g, 30kg)；150BS (15kg)；Aphthenic acids (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(3kg)；12-hydroxyl Stearic acid (2kg)；P-phthalic acid (3.5kg)；Acetic acid (2kg)；18-amine. (1.08kg)； Ethylenediamine (0.12kg)；MDI(1kg)；500SN(33kg).

High base number Composite calcium naphthenate base four polyurea grease is prepared by the method for example 9, different Being the increase in acetic acid and base oil consumption is varied from, each performance data of grease finished product obtained is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 36.0%；Four polyureas 2.4%；Lubricating base oil 51.8%；12-hydroxy stearic acid Calcium 2.3%；P-phthalic acid calcium 4.7%；Calcium acetate 2.8%.

Embodiment 11

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(30kg)；Aphthenic acids (2.8kg)；Methanol (1kg)；Acetic acid (0.56kg)；Ca(OH)₂ (1.8kg)；12-hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；Para-totuidine (0.61kg)； Ethylenediamine (0.17kg)；MDI(1.42kg)；500SN(17kg)；Right, right '-diisooctyl two Aniline (0.2kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be to replace 18-amine. with para-totuidine, each performance data of grease finished product obtained is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.4%；Four polyureas 2.5%；Lubricating base oil 52.7%；12-hydroxy stearic acid Calcium 2.4%；P-phthalic acid calcium 4.8%；Right, right '-di-iso-octyldiphenylamine 0.2%.

Embodiment 12

Raw material components: naphthenate with superhigh base number calcium (total base number is 400mgKOH/g, 30kg)； 150BS(15kg)；DBSA (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)； 12-hydroxy stearic acid (2kg)；P-phthalic acid (3.5kg)；18-amine. (1.03kg)；1,6- Hexamethylene diamine (0.22kg)；MDI(0.95kg)；500SN(33kg)；Right, right '-diisooctyl two Aniline (0.2kg).

Overbased Composite calcium naphthenate base four polyurea grease is prepared by the method for example 1, different Be with DBSA, 1,6-hexamethylene diamine replace ethylenediamine replace aphthenic acids and ethylenediamine and Base oil consumption changes, and each performance data of grease finished product obtained is shown in Table 1.

In the grease that the present embodiment obtains, on the basis of grease weight, consist of: non newtonian Body calcium naphthenate 37.0%；Four polyureas 2.4%；Lubricating base oil 53.2%；12-hydroxy stearic acid Calcium 2.4%；P-phthalic acid calcium 4.8%；Right, right '-di-iso-octyldiphenylamine 0.2%.

Comparative example 1

Raw material components: calcium sulfonate with high base number (total base number is 320mgKOH/g, 30kg)；150BS (30kg)；DBSA (2.8kg)；Acetic acid (0.56kg)；500SN(20.2kg)； Right, right '-di-iso-octyldiphenylamine (0.2kg).

It is 160L and with the normal-pressure reaction kettle heating, stirring, circulate, cool down at a volume Middle addition 30kg total base number is calcium sulfonate with high base number and 100 ° of C motions of 30kg of 320mgKOH/g Viscosity is 31mm²The HVI150BS lubricating base oil of/s, stirring, heat to 80 ° of C, Constant temperature 10 minutes；Adding 2.8kg DBSA, temperature controls, at 80 ° of about C, to stir Mix 10 minutes；Add acetic acid and the aqueous solution of acetic acid weight 4 times of 0.56kg, stir 10 minutes； 85 ° of C constant temperature 30 minutes, material retrogradation became smectic；It is warmed up to 110 ° of C under stirring, keeps 60 Minute, dehydration；Finally it is warmed up to 200 ° of C constant temperature 5 minutes.It is cooled to 160 ° of C, adds and account for profit The lubricating base oil 500SN of consistent lubricant weight 20.2kg；Treat that temperature is cooled to 110 ° of C, add and account for profit Consistent lubricant weight 0.2kg pair, right '-di-iso-octyldiphenylamine stirred after 10 minutes, circulating filtration, homogenizing, Degassing obtains finished product.Assay is shown in Table 1.

Comparative example 2

Raw material components: calcium sulfonate with high base number (320mgKOH/g, 30kg)；150BS(30kg)； DBSA (2.8kg)；Acetic acid (0.56kg)；Ca(OH)₂(1.8kg)；12-hydroxyl Stearic acid (2kg)；Boric acid (2.32kg)；18-amine. (1.5kg)；MDI(0.7kg)；500SN (18kg)；Right, right '-di-iso-octyldiphenylamine (0.2kg).

High base number composite calcium sulfonate base two polyurea grease is prepared, except for the difference that by the method for example 1 Use total base number is the calcium sulfonate with high base number of 320mgKOH/g and does not contains diamidogen, the grease obtained The each performance data of finished product is shown in Table 1.

Table 1 each grease properties of sample data

Continued

Claims (24)

1. Composite calcium naphthenate base four polyurea grease, on the basis of grease weight, including Following components:

1) non-newtonian fluid calcium naphthenate 10-70%；2) the calcium salt 1-10% of higher fatty acids；3) The calcium salt 1-15% of aromatic acid；4) four polyureas 0.5-30%；5) lubricating base oil 10-80%, its In, described non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm^-1-886cm^-1There is crystal formation carbon in place Acid calcium characteristic absorption peak, described higher fatty acids be carbon number be straight chain fatty acid or the hydroxyl of 8-20 Base fatty acid, described aromatic acid is that at least 1 carboxyl is joined directly together with aromatic ring and molecular weight is less than The carboxylic acid of 550, other substituent group is the alkyl of hydrogen, alkyl, thiazolinyl, alkynyl, aryl, halo Or aryl.

2. according to the grease described in claim 1, wherein on the basis of grease weight, including Following components:

1) non-newtonian fluid calcium naphthenate 20-60%；2) the calcium salt 2-6% of higher fatty acids；3) The calcium salt 2-10% of aromatic acid；4) four polyureas 1-20%；5) lubricating base oil 20-70%.

3., according to the grease described in claim 1, described non-newtonian fluid calcium naphthenate total base number is 250mgKOH/g-450mgKOH/g。

4. according to the grease described in claim 1, described higher fatty acids selected from lauric acid, One or more mixing in Palmic acid, stearic acid, 12-hydroxy stearic acid, eicosyl carboxylic acid Thing.

5., according to the grease described in claim 1, described aromatic acid is selected from unsubstituted or C1-C5 In the substituted phthalic acid of alkyl, M-phthalic acid, p-phthalic acid, biphenyl dicarboxylic acid one Plant or several.

6. according to the grease described in claim 1, wherein possibly together with little molecule mineral acid and/or The calcium salt of little molecules of fatty acids, described little molecule mineral acid and/or little molecules of fatty acids molecular weight are less than Equal to 150.

7. according to the grease described in claim 1, described little molecule mineral acid selected from boric acid, The mixture of one or more in phosphoric acid, sulphuric acid, described little molecules of fatty acids selected from acetic acid, The mixture of one or more in ethanedioic acid, propanoic acid, malonic acid, butanoic acid, succinic acid.

8. four according to the grease described in claim 1, wherein, described polyureas have following knot Structure:

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³Be arlydene, Alkylidene or cycloalkylidene.

9. according to the grease described in claim 8, wherein, R¹It is phenyl or substituted phenyl, Or the alkyl or cycloalkyl that carbon number is 8～24；R²It is phenylene or biphenylene or carbon number is 2～12 Alkylidene；R³Be carbon number be arlydene, alkylidene or the cycloalkylidene of 6～30.

10. according to the grease described in claim 8, wherein, R¹It is phenyl or C1～C3 alkane Base or the phenyl of halogen substiuted, or the alkyl or cycloalkyl that carbon number is 10～18, R²Be phenylene or Biphenylene, or the alkylidene that carbon number is 2～8；R³Selected from methylphenylene, diphenylmethylene, At least one in dicyclohexylmethylene, a dimethylphenylene and hexylidene.

The preparation of described Composite calcium naphthenate base four polyurea grease of one of 11. claim 1～10 Method, including:

(1) in reactor A by newton body calcium naphthenate, part basis oil and transforming agent mixing, Heating, makes material retrogradation become smectic；

(2) in aforesaid reaction vessel, add Calx or calcium hydroxide, be separately added into higher fatty acids And aromatic acid, heat up dehydration；

(3) in the product of reactor A or in reactor B, part basis oil is added different with two Cyanate, is initially charged diamidogen and reacts, and adds monoamine and reacts, wherein diisocyanate, Diamidogen is 2:1:2 with the mol ratio of monoamine；

(4) by the material mix homogeneously in reactor A, or the material of reactor A and B is closed Mix homogeneously after and, is warmed up to 200-220 DEG C of constant temperature refining, cooling, adds surplus base oil, Add necessary additive, obtain finished product.

12. according to the preparation method described in claim 11, in step (1), by newton body Calcium naphthenate, part basis oil Hybrid Heating to 50-90 DEG C, be sequentially added into required transforming agent and enter Row reaction, all transforming agents heat up after adding, 60-100 DEG C of constant temperature 0.5-3 hour, make thing Material retrogradation is smectic.

13. according to the preparation method described in claim 11, in step (2), at 85-100 DEG C Add Calx or the suspension of calcium hydroxide, add higher fatty acids at 85-100 DEG C, stir 5-20 Minute, add aromatic acid, and the little molecule mineral acid of necessity and/or little molecules of fatty acids, stirring 5-20 minute, it is warmed up to 105-120 DEG C, dehydration.

14. according to the preparation method described in claim 11, in step (3), in step (2) Product in or another reactor in add part basis oil and diisocyanate, stir 2-8 minute, Add diamidogen under stirring, react 2-8 minute, add monoamine, react 2-8 minute.

15. according to the preparation method described in claim 11, in step (4), by step (2) (3) heat up after product mix homogeneously, 100-120 DEG C of constant temperature 10-20 minute, finally It is warmed up to 200-220 DEG C of constant temperature 5-10 minute；It is cooled to 150-160 DEG C, adds surplus lubrication Base oil, treats that temperature is cooled to 100-120 DEG C, adds necessary additive, stirring, is circulated throughout Filter, homogenizing, degassing.

16. according to the preparation method described in claim 11, and described newton body calcium naphthenate is stone Oil calcium naphthenate or synthesis calcium naphthenate, its total base number is 250-450mgKOH/g.

17. are selected from C1-C5 according to the preparation method described in claim 11, described transforming agent Fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, cycloalkanes amine, cyclic alkanol, ether, And calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, C8-C20 One or more in alkyl benzene sulphonate, C16-C62 aphthenic acids, water, the addition of transforming agent is The 2-30% of newton body calcium naphthenate weight.

18. are selected from dodecyl according to the preparation method described in claim 11, described transforming agent One or more in benzenesulfonic acid, C16-C62 aphthenic acids, methanol, butanol, acetic acid and water, turn The addition of agent is the 6-22% of newton body calcium naphthenate weight.

19. according to the preparation method described in claim 11, wherein, and described monoamine structural formula For R¹-NH₂, R therein¹Being alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8～24, aryl is phenyl or substituted phenyl.

20. according to the preparation method described in claim 11, and wherein, described monoamine is to be selected from The arylamine of aniline, m-chloroaniline, parachloroanilinum and/or para-totuidine, and/or selected from lauryl amine, The fatty amine of tetradecy lamine, cetylamine and/or 18-amine..

21. according to the preparation method described in claim 11, wherein, and described diamine structures formula For NH₂-R²-NH₂, R therein²Being alkylidene or arlydene, the carbon number of alkylidene is 2～12, Arlydene is phenylene or biphenylene.

22. according to the preparation method described in claim 11, and wherein, described diamidogen is selected from right Phenylenediamine, o-phenylenediamine, 4, the aromatic amine of 4 '-benzidine, and/or selected from ethylenediamine, propane diamine, The straight-chain fatty amine of 1,6-hexamethylene diamine.

23. according to the preparation method described in claim 11, wherein, and described diisocyanate Structure is OCN-R³-NCO, R³Be carbon number be arlydene, alkylidene or the cycloalkylidene of 6～30.

24. according to the preparation method described in claim 11, and wherein, described diisocyanate selects From toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1, hexamethylene-diisocyanate, bicyclo- Hexyl methane diisocyanate, or at least one in XDI.