CN104293416B

CN104293416B - Composite calcium naphthenate-based hexa-polyurea lubricating grease and preparation method thereof

Info

Publication number: CN104293416B
Application number: CN201310300756.3A
Authority: CN
Inventors: 孙洪伟; 董禄虎; 郑会; 何懿峰; 段庆华; 张建荣; 陈政; 刘中其; 姜靓
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-07-17
Filing date: 2013-07-17
Publication date: 2017-02-08
Anticipated expiration: 2033-07-17
Also published as: CN104293416A

Abstract

The invention discloses composite calcium naphthenate-based hexa-polyurea lubricating grease which is characterized by including following components, on the basis of the weight of the lubricating grease, 20-60 wt% of non-Newtonian calcium naphthenate, 1-10 wt% of a calcium salt of a higher fatty acid, 0.5-25 wt% of a polyurea compound and 25-70 wt% of a basic oil. An infrared spectrogram of the non-Newtonian calcium naphthenate has a characteristic absorption peak of aragonite-type calcium carbonate. The polyurea compound is a hexa-polyurea compound. The invention also discloses a preparation method of the composite calcium naphthenate-based hexa-polyurea lubricating grease and the composite calcium naphthenate-based hexa-polyurea lubricating grease prepared through the same. The composite calcium naphthenate-based hexa-polyurea lubricating grease has excellent anti-corrosion property and anti-salt fog property, and has performances comprising a high-temperature-resistant performance, a water-resistant performance, an adhesive performance, a colloid stability and the like, which are better than those of a composite calcium sulfonate-based hexa-polyurea lubricating grease. The composite calcium naphthenate-based hexa-polyurea lubricating grease has a longer lubricating service life.

Description

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

Technical field

The present invention relates to lubricating grease, in particular it relates to a kind of Composite calcium naphthenate base six polyurea grease and its preparation side Method.

Background technology

Overbased calcium alkyl-salicylate has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusivity, can To be used as the detersive of lubricating oil, it is widely used in the additive of IC engine lubricating oil, the development of its technology mainly makes it high-alkali Changing becomes a kind of colloidal dispersion system it is simply that calcium carbonate is distributed in flux oil with the naphthenic acid calcium with surface-active.High Mostly base number calcium naphthenate is the acidic components extracting from the distillate that crude distillation obtains, through and Ca (OH)₂Reaction, carbonating Contour alkalization technology and obtain, about preparation Patents have CN1465560 etc..

Using calcium sulfonate with high base number be raw material produce lubricating grease, because its have excellent high temperature performance, mechanical stability, Colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, have caused domestic and international profit The extensive concern of consistent lubricant industry, although however, high base number composite calcium sulfonate base grease has very excellent combination property, The preparation technology of the high price of its raw materials for production calcium sulfonate with high base number and complexity itself leads to it not promoted rapidly, with When, with the requirement more and more higher to environmental protection for the people, in calcium sulfonate with high base number production process must through sulfonation process to ring The pollution in border is also increasingly subject to the concern of people.Find a kind of performance similar with high base number composite calcium sulfonate base grease but can The lubricating grease avoiding the problems referred to above becomes the big problem that people face at present.

Content of the invention

It is an object of the invention to provide a kind of performance is similar with high base number composite calcium sulfonate base grease, low cost, preparation Process is simple, lubricating grease of environmental protection and preparation method thereof.

The present inventor finds under study for action, on the basis of lubricating grease weight, including following components：20-60 weight % Non-newtonian fluid calcium naphthenate；The calcium salt of the higher fatty acids of 1-10 weight %；The polyurea compound of 0.5-25 weight %；25-70 The base oil of weight %, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the characteristic absorption of aragonite calcium carbonate Peak, described polyurea compound is six polyurea compounds；Described lubricating grease preferably also includes the small molecule inorganic acid of 1-15 weight % And/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 weight %.The performance of this lubricating grease and high base number are combined sulphur Sour calcium-base grease is similar to, and low cost, preparation process is simple, environmental protection.

Therefore, to achieve these goals, on the one hand, the invention provides a kind of Composite calcium naphthenate base six polyureas lubrication Fat it is characterised in that on the basis of lubricating grease weight, including following components：The non-newtonian fluid calcium naphthenate of 20-60 weight %；1- The calcium salt of the higher fatty acids of 10 weight %；The polyurea compound of 0.5-25 weight %；The base oil of 25-70 weight %, wherein, institute The infrared spectrum stating non-newtonian fluid calcium naphthenate has the characteristic absorption peak of aragonite calcium carbonate, described polyurea compound be six gather Carbamide compound.

Preferably, on the basis of lubricating grease weight, described lubricating grease also include 1-15 weight % small molecule inorganic acid and/ Or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 weight %.

Preferably, on the basis of lubricating grease weight, including following components：The non-newtonian fluid calcium naphthenate of 25-55 weight %； The calcium salt of the higher fatty acids of 2-6 weight %；The small molecule inorganic acid of 2-10 weight % and/or the calcium salt of lower fatty acid, and/or The calcium salt of the aromatic acid of 2-10 weight %；Six polyurea compounds of 1.3-15 weight %；The base oil of 35-60 weight %.

Second aspect, the invention provides the preparation method of Composite calcium naphthenate base six polyurea grease as above, It is characterized in that, the method includes：By non-newtonian fluid calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid and/or little point The calcium salt of sub- inorganic acid and/or lower fatty acid, six polyurea compounds and part basis oil mix, in 180-230 DEG C of perseverance Temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.

The third aspect, the invention provides a kind of preparation method of Composite calcium naphthenate base six polyurea grease, its feature It is, the method includes：

（1）By newton body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation；

（2）In step（1）Add lime or calcium hydroxide in products therefrom, add higher fatty acids, aromatic acid and/or little point Sub- inorganic acid and/or lower fatty acid are reacted, and heat up after reaction dehydration, then lowers the temperature；

（3）In step（2）Add base oil and diisocyanate in gained mixture, then sequentially add monoamine, diamines Reacted with diisocyanate；

（4）By step（3）Gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, addition must The additive wanted, obtains finished product.

Fourth aspect, the invention provides the Composite calcium naphthenate base six polyureas lubrication being obtained by method as above Fat.

Composite calcium naphthenate base six polyurea grease of the present invention, not only with Composite calcium-sulfonate-batetrapolyurea six polyurea grease one Sample, has excellent anticorrosive property and resistance to saltfog, but also has the resistance to height better than Composite calcium-sulfonate-batetrapolyurea six polyurea grease The performance such as warm nature, water-resistance and adhesiveness, colloid stability, has longer lubricating life.The preparation of greases of the present invention Process is simple, environmental protection, low cost, product quality is stable.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description

Fig. 1 is the infrared analysis spectrogram of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2.

Fig. 2 is the infrared analysis spectrogram of the calcium carbonate in the lubricating grease of embodiment 2 preparation.

Fig. 3 is that the XRD crystal formation of the calcium carbonate in the lubricating grease of embodiment 2 preparation measures.

Specific embodiment

Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of Composite calcium naphthenate base six polyurea grease, this lubricating grease employs petroleum naphthenic acid Calcium or synthesis calcium naphthenate are raw material, the six polyureas chemical combination simultaneously producing containing the reaction of composite calcium thickening agent, isocyanates and amine Thing.

Present invention also offers above-mentioned preparation of greases method.

On the one hand, the invention provides a kind of Composite calcium naphthenate base six polyurea grease, on the basis of lubricating grease weight, Including following components：The non-newtonian fluid calcium naphthenate of 20-60 weight %；The calcium salt of the higher fatty acids of 1-10 weight %；0.5-25 The polyurea compound of weight %；The base oil of 25-70 weight %, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has The characteristic absorption peak of aragonite calcium carbonate, described polyurea compound is six polyurea compounds.

The infrared absorption peak of the mainly carbonate that calcium carbonate occurs in infrared spectrum, is divided into 4 regions：ν1- 1450cm^-1；ν2-1080cm^-1；ν3-870cm^-1With ν 4-710cm^-1.ν 1 bands of a spectrum are carbonates（CO₃ ^2-）Antisymmetric stretching vibration is inhaled Receive peak, ν 2 bands of a spectrum are carbonate symmetrical stretching vibration absworption peaks, and ν 3 bands of a spectrum are the out-of-plane bending vibration absworption peaks of carbonate, and ν 4 composes Band is the in-plane bending vibration absworption peak of carbonate.In general, can be distinguishing calcium carbonate by the difference of these absworption peaks Crystalline form.The characteristic absorption of different crystal forms calcium carbonate is as follows：ν 3 bands of a spectrum of calcite type are 876cm^-1Left and right, ν 4 bands of a spectrum are 712cm^-1Left and right；ν 2 bands of a spectrum of aragonitic are 1082cm^-1Left and right, ν 3 bands of a spectrum are 856cm^-1Left and right, ν 4 bands of a spectrum are 712cm^-1With 700cm^-1（Weak）；Vaterite-type ν 3 bands of a spectrum are 876cm^-1Left and right, ν 4 bands of a spectrum are 745cm^-1Left and right；Amorphous ν 3 bands of a spectrum are 860cm^-1Left and right.Environment residing for calcium carbonate is different, the peak position slightly difference of its infrared band.

Described non-newtonian fluid calcium naphthenate is in infrared spectrum 1082cm^-1Left and right, 856cm^-1Left and right, 712cm^-1Left and right, 700cm^-1The characteristic absorption peak of aragonite calcium carbonate in place, and total base number is 250mgKOH/g-500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g.Described non-newtonian fluid calcium naphthenate is to be converted by transforming agent by newton body calcium naphthenate Arrive.And contain unformed calcium carbonate in newton body calcium naphthenate, in infrared spectrum 1076cm^-1Left and right, 860cm^-1Have or not at left and right Sizing calcium carbonate characteristic absorption peak.Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, its total base number For 250mgKOH/g-500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g, after changing into non-newtonian fluid calcium naphthenate, its Base number is constant.

In the present invention, higher fatty acids is carbon number is 8-20, preferably the straight chain fatty acid of 10-16 or hydroxy fatty acid, example As at least one in laurate, palmitic acid, stearic acid, 12- hydroxy stearic acid, eicosyl carboxylic acid, preferably 12- hydroxyl is hard Resin acid.

In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 150.Wherein, small molecule is inorganic Acid can be selected from least one in boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be selected from At least one in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid etc., preferably acetic acid.

In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl is joined directly together with aromatic ring, aromatic acid can be replace or not Replace aromatic acid, its substituent can be in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc. extremely Few one kind, the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, for example, it is possible to be selected from unsubstituted or C1- In the phthalic acid of C5 alkyl replacement, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid at least A kind of.It is preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, and methyl substituted biphenyl diformazan At least one in sour, multi-joint phthalic acid etc..

In the present invention, described six polyurea compounds preferably have following structure：

Wherein, 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, the preferably phenyl of phenyl or C1-C3 alkyl or halogen substiuted.

Wherein, R²Can be alkylidene or arlydene, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can To be phenylene or biphenylene.

Wherein, R³Can be arlydene, alkylidene or cycloalkylidene, arlydene, alkylidene or sub- ring The carbon number of alkyl can be 6-30, preferably 6-20, R³More preferably In At least one.

Above-mentioned six polyurea compounds can be obtained using the thinkable various methods of those skilled in the art institute, for example permissible Prepare according to the method that CN103060067A records.

Described lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of motions are glutinous Spend for 4-150mm²/ s, preferably 10-60mm²/s.Artificial oil can be poly-a-olefin oil（PAO）, Esters oil, alkyl-silicone oil, Fischer-Tropsch Artificial oil etc..

Various additives can also be contained, such as antioxidant, extreme pressure anti-wear additives, antirust agent etc. in lubricating grease of the present invention.Its In, antioxidant preferred arylamine kind antioxidant, account for the 0.01-5% of lubricating grease gross weight, preferably 0.1-2.5%, can be diphenylamines, At least one in PA and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine.Extreme pressure anti-wear additives account for lubricating grease The 0.5-12% of gross weight, preferably 0.8-8%, can be two thio Acidic phosphates zinc, two thio dialkyl amido formic acid molybdenums, two Thio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, polytetrafluoroethyl-ne Alkene, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorographite, carbonic acid At least one in calcium and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferably 0.1-2%, can be oil At least one in barium sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.

Second aspect, the invention provides the preparation method of Composite calcium naphthenate base six polyurea grease as above, The method includes：By non-newtonian fluid calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid and/or small molecule inorganic acid and/ Or the calcium salt of lower fatty acid, six polyurea compounds and part basis oil mix, refine in 180-230 DEG C of constant temperature, cooling, Add surplus base oil, add necessary additive, obtain finished product.

In the present invention, inorganic for non-newtonian fluid calcium naphthenate, the calcium salt of higher fatty acids, the calcium salt of aromatic acid, small molecule The calcium salt of acid and/or lower fatty acid, six polyurea compounds and base oil are as described above, will not be described here.

It will be understood by those skilled in the art that the amount of part basis oil is as used with the amount sum of surplus base oil Base oil total amount, in the present invention, part basis oil and the weight ratio preferably 1 of surplus base oil：0.1-1.

For non-newtonian fluid calcium naphthenate, can be obtained by transforming agent conversion by newton body calcium naphthenate, for example, by ox Body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, the transforming agent needed for adding is reacted, and all transforming agents add Afterwards, more than 90 DEG C and be less than or equal to 110 DEG C, preferably 95-110 DEG C, constant temperature 40-100 minute, then heat to 150-170 DEG C Dehydration.

The third aspect, the invention provides a kind of preparation method of Composite calcium naphthenate base six polyurea grease, including：

Step（1）In, newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C add required transforming agent to enter Row reaction, after all transforming agents add, more than 90 DEG C and less than or equal to 110 DEG C, preferably 95-110 DEG C, constant temperature 40-100 divides Clock.

The weight ratio preferably 1 of newton body calcium naphthenate and base oil：0.1-1.

Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total base number is 250mgKOH/g- 500mgKOH/g, preferably 300mgKOH/g-450mgKOH/g.

Described transforming agent is selected from water, fatty alcohol, aliphatic ether, aliphatic acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, ring At least one in alkanamine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and alkyl benzene sulphonate, be preferably selected from water, Isopropanol, methyl alcohol, ethanol, propyl alcohol, n-butanol, ketone, formaldehyde, glycol dimethyl ether, acetic acid, propionic acid, butyric acid, aphthenic acids, hard At least one in resin acid, 12- hydroxy stearic acid and DBSA.More preferably A, B, C tri- class material, A class material For at least one in ethanol, propyl alcohol, butanol and 12- hydroxy stearic acid, B class material be in acetic acid, propionic acid and butyric acid at least One kind, C class material be water, and feed postition be preferably A class material prior to B class material add, that is, be initially charged ethanol, propyl alcohol, At least one in butanol and 12- hydroxy stearic acid, after mixing with newton body calcium naphthenate, add acetic acid, propionic acid and At least one in butyric acid, for the addition sequence no particular/special requirement of C class material water, can first add, can later plus it is also possible to A class material or B class material add together.

The addition of transforming agent is the 4-32%, preferably 15-25% of newton body calcium naphthenate weight.When transforming agent be preferably A, B, C tri- class material, A class material is ethanol, propyl alcohol, at least one in butanol and 12- hydroxy stearic acid, B class material is acetic acid, At least one in propionic acid and butyric acid, when C class material is water, A class material is preferably with the weight ratio of B class material and C class material 1：0.1-10：1-10, more preferably 1：0.5-8：1-8.For the concrete material selecting in A class material and B class material and each thing Amount ratio between matter no particular/special requirement, as long as total amount can obtain more preferable effect within the above range.

Step（2）In, at 85-100 DEG C, add the suspension of lime or calcium hydroxide, add higher fatty acids, stirring 5-20 minute, adds aromatic acid and/or small molecule inorganic acid and/or lower fatty acid, stirs 5-20 minute, is warming up to 150-170 DEG C, preferably keep 30-60 minute to realize being dehydrated, be then cooled to 100-120 DEG C.Wherein, higher fatty acids and aromatic acid and/or The addition sequence of small molecule inorganic acid and/or lower fatty acid can exchange.

In the present invention, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid are as it was previously stated, here is no longer superfluous State.

In the present invention, the H of higher fatty acids and aromatic acid and/or small molecule inorganic acid and/or lower fatty acid⁺Total material Amount and the OH contained by calcium hydroxide^-The amount of total material is equal, and the amount of calcium hydroxide also can excessive 1-10%.

In the present invention, in terms of calcium hydroxide, the addition of the suspension of lime or calcium hydroxide is preferably newton body cycloalkanes The 1-15% of sour calcium weight；With H⁺Material gauge, higher fatty acids and aromatic acid and/or small molecule inorganic acid and/or rudimentary fat The mol ratio of fat acid is preferably 1：1-10.

In the present invention, it is suspended that the suspension of lime or calcium hydroxide refers to that lime or calcium hydroxide are formed in water Liquid, the solid content of suspension is preferably 10-60 weight %.

Step（3）In, in step（2）Add base oil and diisocyanate in gained mixture, then sequentially add list Amine, diamines and diisocyanate are reacted, and are in step（2）Six polyurea compounds are prepared in gained mixture.

Prepare the method no particular/special requirement of six polyurea compounds, can be using various methods commonly used in the art.For example, exist In the present invention, can be in step（2）Add base oil and diisocyanate in gained mixture, add monoamine, stirring 2-8 divides Clock, adds diamines, stirs 2-8 minute, adds the diisocyanate being dissolved in base oil, stirs 2-8 minute, and each time added Diisocyanate, monoamine, diamines and diisocyanate mol ratio be 2:2:2:1.

Step of the present invention（3）In, the diisocyanate adding twice can be the same or different, in order to easy to operate, The diisocyanate that preferably twice adds is identical.

Described diisocyanate structure is OCN-R³- NCO, R³Can be carbon number be 6-30, preferably The arlydene of 6-20, alkylidene or cycloalkylidene, preferably Deng. For example described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), and 1,6- is sub- Hexyl diisocyanate (HDI), dicyclohexylmethyl diisocyanate（HMDI）With an xylylene diisocyanate（XDI）Deng In at least one.

Described monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R¹-NH₂、R^1’-NH₂, R therein¹、R^1’Can To be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, preferably 10-18, aryl can be phenyl or The phenyl replacing, the preferably phenyl of phenyl or C1-C3 alkyl or halogen substiuted.Preferably monoamine can be selected from aniline, m-chloro Aniline, parachloroanilinum, the arylamine of para-totuidine, and/or it is selected from lauryl amine, tetradecy lamine, cetylamine, the fatty amine of octadecylamine.

Described diamines can be fatty amine or arylamine, and structural formula is NH₂-R²-NH₂, R therein²Can be alkylidene or Asia Aryl, the carbon number of alkylidene can be 2-12, preferably 2-8, and arlydene can be phenylene or biphenylene.Preferably diamines can Be selected from p-phenylenediamine, o-phenylenediamine, the aromatic amine of 4,4- benzidine and/or selected from ethylenediamine, propane diamine, 1,6- oneself two The straight-chain fatty amine of amine.

Step（4）In, first in 100-120 DEG C of constant temperature 10-20 minute, finally it is warmed up to 180-230 DEG C of constant temperature 5-20 minute； It is cooled to 150-160 DEG C, adds base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, be circulated throughout Filter, homogenizing, degassing.

In the present invention, step（1）In the total amount of base oil used and step（3）In the total amount of base oil used and step （4）In base oil used total amount weight ratio preferably 1：0.1-1：0.1-1.

Fourth aspect, present invention also offers the composite calcium naphthenate being obtained by the preparation method that third aspect present invention provides Calcium base six polyurea grease.

Compared with Composite calcium naphthenate base six polyurea grease being obtained with the preparation method being provided by second aspect, third party Composite calcium naphthenate base six polyurea grease that the preparation method that face provides is obtained has more preferable heat-resisting quantity, water-resistance and glues Attached property, colloid stability and extreme pressure anti-wear.

Embodiment

The present invention is further illustrated for below example, but and is not so limited the present invention.

In the following Examples and Comparative Examples：

Non-newtonian fluid calcium naphthenate %=（Overbased or overbased calcium alkyl-salicylate material quality+transforming agent gross mass）/ profit Consistent lubricant gross mass × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.

In embodiment, it is limited that overbased and overbased calcium alkyl-salicylate raw material is derived from Xinjiang Lander Speciality Petrochemicals share Company is it is also possible to prepare according to method disclosed in CN101885677A.

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

Embodiment 1

The present embodiment is used for Composite calcium naphthenate base six polyurea grease of present invention preparation is described.

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base number Naphthenate with superhigh base number calcium for 320mgKOH/g and 30kg100 DEG C of kinematic viscosity are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 80 DEG C, constant temperature 10 minutes；Add 1.8kg n-butanol, temperature control, at 80 DEG C about, stirs 10 points Clock；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation；Add solid content For the calcium hydroxide suspension 10.8kg of 20 weight %, stir 10 minutes, add the 12- hydroxy stearic acid of 2.4kg, stir 10 points Clock, adds the terephthalic acid (TPA) of 4.2kg, stirs 10 minutes, is warmed up to 160 DEG C under stirring, keeps 45 minutes, and dehydration cools to 120℃；Adding with 10kg100 DEG C of kinematic viscosity is 11mm²The 4.77kg MDI of the HVI500SN lubricating base oil dissolving of/s, stirs Mix 6 minutes, add 7.69kg octadecylamine, stir 6 minutes, add 0.86kg ethylenediamine, stir 6 minutes, add and use 5kg100 DEG C kinematic viscosity is 11mm²The 2.38kg MDI of the HVI500SN lubricating base oil dissolving of/s, stirs 6 minutes, 120 DEG C of constant temperature 20 Minute, finally it is warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, add HVI500SN lubricating base oil 15kg；Treat Temperature is cooled to 110 DEG C, and circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, consist of：Non-newtonian fluid calcium naphthenate 28.6%；12- hydroxy stearic acid calcium 2.2%；Terephthalic acid (TPA) calcium 4.4%；Six polyureas 13.4%；Lubricating base oil 51.4%.

Embodiment 2

A volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 33kg total base number Overbased calcium alkyl-salicylate for 400mgKOH/g and 15kg100 DEG C of kinematic viscosity are 31mm²The HVI150BS lubricating base oil of/s, Stirring, heats to 60 DEG C, constant temperature 10 minutes；Add 0.56kg ethanol, temperature control, at 60 DEG C about, stirs 10 minutes； Add 3.36kg propionic acid and 3.36kg water, stir 10 minutes；In 100 DEG C of constant temperature 70 minutes, material retrogradation；Solid content is added to be 50 The calcium hydroxide suspension 5.2kg of weight %, stirs 10 minutes, adds the 12- hydroxy stearic acid of 2kg, stirs 10 minutes, adds The boric acid of 2.6kg, stirs 10 minutes, is warmed up to 150 DEG C under stirring, keeps 60 minutes, and dehydration cools to 110 DEG C；Add and use 5kg100 DEG C of kinematic viscosity is 11mm²The 0.34kg HDI of the HVI500SN lubricating base oil dissolving of/s, stirs 2 minutes, adds 0.37kg lauryl amine, stirs 2 minutes, adds 0.22kg p-phenylenediamine, stirs 2 minutes, adds with 5kg100 DEG C of kinematic viscosity For 11mm²The 0.17kg HDI of the HVI500SN lubricating base oil dissolving of/s, stirs 2 minutes, 110 DEG C of constant temperature 15 minutes, finally It is warmed up to 180 DEG C of constant temperature 20 minutes.Then, it is cooled to 150 DEG C, add HVI500SN lubricating base oil 10kg；Treat that temperature cools down To 100 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, consist of：Non-newtonian fluid calcium naphthenate 47.1%；12- hydroxy stearic acid calcium 2.8%；Line borate 3.4%；Six polyureas 1.4%；Lubricating base oil 45.3%.

Embodiment 3

A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base number Naphthenate with superhigh base number calcium for 450mgKOH/g and 30kg100 DEG C of kinematic viscosity are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 50 DEG C, constant temperature 10 minutes；Add 0.2kg normal propyl alcohol, 0.2kg n-butanol and 3.2kg water, temperature control System, at 50 DEG C about, stirs 10 minutes；Add 2.96kg acetic acid, stir 10 minutes；In 110 DEG C of constant temperature 40 minutes, material retrogradation； Cool to 85 DEG C, add the calcium hydroxide suspension 7.8kg that solid content is 40 weight %, stir 10 minutes, add the 12- hydroxyl of 2kg Base stearic acid, stirs 10 minutes, adds the phthalic acid of 3.5kg and the acetic acid of 2kg, stirs 10 minutes, is warmed up under stirring 170 DEG C, keep 30 minutes, dehydration, cool to 100 DEG C；Adding with 3kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN profit of/s The 2.68kg XDI of sliding base oil dissolving, stirs 8 minutes, adds 1.52kg para-totuidine, stir 8 minutes, add 1.06kg third Diamines, stirs 8 minutes, adding with 3kg100 DEG C of kinematic viscosity is 11mm²The HVI500SN lubricating base oil dissolving of/s 1.34kg XDI, stirs 8 minutes, and 100 DEG C of constant temperature 10 minutes is finally warmed up to 230 DEG C of constant temperature 5 minutes.Then, it is cooled to 155 DEG C, add HVI500SN lubricating base oil 6kg；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection Test and the results are shown in Table 1.

In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, consist of：Non-newtonian fluid calcium naphthenate 36.7%；12- hydroxy stearic acid calcium 2.3%；Calcium phthalate 4.7%；Calcium acetate 2.9%；Six polyureas 7.3%；Lubricating base oil 46.1%.

Embodiment 4

A volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add 30kg total base number Naphthenate with superhigh base number calcium for 320mgKOH/g and 30kg100 DEG C of kinematic viscosity are 31mm²The HVI150BS lubrication base of/s Oil, stirring, heat to 80 DEG C, constant temperature 10 minutes；Add 1.8kg n-butanol, temperature control, at 80 DEG C about, stirs 10 points Clock；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation.

Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle at 95 DEG C add Solid content is the calcium hydroxide suspension 7.2kg of 30 weight %, stirs 10 minutes, adds the 12- hydroxy stearic acid of 2.4kg, stirring 10 minutes, add the terephthalic acid (TPA) of 4.2kg, stir 10 minutes, obtain 12- hydroxy stearic acid calcium and terephthalic acid (TPA) calcium.

The 3rd volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add use 10kg100 DEG C kinematic viscosity is 11mm²The 4.77kgMDI of the HVI500SN lubricating base oil dissolving of/s, stirs 6 minutes, adds 7.69kg ten Eight amine, stir 6 minutes, add 0.86kg ethylenediamine, stir 6 minutes, adding with 5kg100 DEG C of kinematic viscosity is 11mm²/ s's The 2.38kg MDI of HVI500SN lubricating base oil dissolving, stirs 6 minutes, and 120 DEG C of constant temperature 20 minutes obtains six polyureas.

The 12- hydroxy stearic acid calcium of gained and terephthalic acid (TPA) calcium are all squeezed in first kettle, stirs, stirring Under be warmed up to 160 DEG C, keep 45 minutes, dehydration, then cool to 120 DEG C, will be whole for six polyureas of the 3rd reactor gained Squeeze in this kettle, stir, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, add HVI500SN profit Sliding base oil 15kg；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Assay is shown in Table 1.

Embodiment 5

Method according to embodiment 1 prepares Composite calcium naphthenate base six polyurea grease, except for the difference that, is initially charged 1.56kg N-butyric acie, temperature control, at 80 DEG C about, stirs 10 minutes, adds 1.8kg n-butanol and 3.2kg water, stirs 10 minutes.Inspection Test and the results are shown in Table 1.

Embodiment 6

Method according to embodiment 1 prepares Composite calcium naphthenate base six polyurea grease, except for the difference that, by positive for 1.8kg fourth Alcohol replaces with 3.2kg ketone, and 1.56kg n-butyric acie and 3.2kg water are replaced with 3.36kg aphthenic acids.Assay is shown in Table 1.

Comparative example 1

Prepare high base number composite calcium sulfonate base six polyurea grease, except for the difference that, high base number cycloalkanes as described in Example 1 Sour calcium total base number is that the calcium sulfonate with high base number of 320mgKOH/g replaces, and each performance data of lubricating grease finished product obtaining is shown in Table 1.

In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, consist of：Non-newtonian fluid sulfoacid calcium 28.6%； 12- hydroxy stearic acid calcium 2.2%；Terephthalic acid (TPA) calcium 4.4%；Six polyureas 13.4%；Lubricating base oil 51.4%.

The each lubricating grease properties of sample data of table 1

Each indication test method：Dropping point：GB/T3498；Work cone penetration：GB/T269；Corrosion：GB/T7326；Anticorrosion Property：GB/T5018；Water drenches number of dropouts：SH/T0109；Stencil oil-dividing：SH/T0324；Tetra-ball machine test：SH/T0202；Ball bearing Lubricating life：ASTMD3336.

Embodiment 1 and comparative example 1 are compared Composite calcium naphthenate base six polyurea grease as can be seen that the present invention Dropping point be higher than Composite calcium-sulfonate-batetrapolyurea six polyurea grease, water drench number of dropouts be much smaller than Composite calcium-sulfonate-batetrapolyurea six polyurea grease, Stencil oil-dividing value is much smaller than Composite calcium-sulfonate-batetrapolyurea six polyurea grease, and the bearing lubrication life-span is much larger than Composite calcium-sulfonate-batetrapolyurea six polyureas Lubricating grease, illustrates the heat-resisting quantity of Composite calcium naphthenate base six polyurea grease, water-resistance and adhesiveness, the colloid peace of the present invention Qualitative, lubricating life is superior to Composite calcium-sulfonate-batetrapolyurea six polyurea grease, and the Composite calcium naphthenate base six polyureas profit of the present invention Consistent lubricant has the performances such as excellent anticorrosive property and resistance to saltfog as Composite calcium-sulfonate-batetrapolyurea six polyurea grease.

Embodiment 1 and embodiment 4 are compared the Composite calcium naphthenate base six polyureas lubrication as can be seen that preparation in situ Fat, has more preferable water-resistance and adhesiveness, colloid stability, and has longer lubricating life；By embodiment 1 and embodiment 5 are compared as can be seen that A class material adds prior to B class material in transforming agent, the Composite calcium naphthenate base six polyureas profit of preparation Consistent lubricant, has more preferable water-resistance and adhesiveness, colloid stability, and has longer lubricating life；By embodiment 1 and enforcement Example 6 is compared as can be seen that transforming agent is A, B, C tri- class material, and A class material is that ethanol, propyl alcohol, butanol and 12- hydroxyl are hard At least one in resin acid, B class material is acetic acid, at least one in propionic acid and butyric acid, and C class material is water, preparation compound Calcium naphthenate-based hexapolyurea lubricating grease, has more preferable water-resistance and adhesiveness, colloid stability, and has the longer lubrication longevity Life.

It will be seen from figure 1 that the ν of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2₂Bands of a spectrum are in 1076- 1077cm^-1Left and right, ν₃Bands of a spectrum are 860cm^-1Left and right.Illustrate as amorphous calcium carbonate.

Figure it is seen that embodiment 2 preparation lubricating grease in the infrared spectrum of calcium carbonate in contain 1082cm^-1Left Right, 855cm^-1Left and right, 700cm^-1Left and right, 713cm^-1The absworption peaks such as left and right, are the characteristic absorption peak of aragonite calcium carbonate, explanation Amorphous calcium carbonate in overbased calcium alkyl-salicylate converts for aragonite calcium carbonate.

From figure 3, it can be seen that embodiment 2 preparation lubricating grease in calcium carbonate XRD crystal formation measure, 26 ° of angle, 27 °, 46 °, 33.5 °, 36 °, 38 °, 43 ° nearby have intensity peak, consistent with aragonite standard spectrogram, deposit after conversion is described in sample In aragonite calcium carbonate.

Describe the preferred embodiment of the present invention above in association with accompanying drawing in detail, but, the present invention is not limited to above-mentioned reality Apply the detail in mode, in the range of the technology design of the present invention, multiple letters can be carried out to technical scheme Monotropic type, these simple variant belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can The combination of energy no longer separately illustrates.

Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it equally should be considered as content disclosed in this invention.

Claims

1. a kind of Composite calcium naphthenate base six polyurea grease is it is characterised in that on the basis of lubricating grease weight, including with the following group Point：The non-newtonian fluid calcium naphthenate of 20-60 weight %；The calcium salt of the higher fatty acids of 1-10 weight %；0.5-25 weight % Polyurea compound；The base oil of 25-70 weight %, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has aragonitic The characteristic absorption peak of calcium carbonate, described polyurea compound is six polyurea compounds.

2. lubricating grease according to claim 1, wherein, on the basis of lubricating grease weight, described lubricating grease also includes 1-15 The small molecule inorganic acid of weight % and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 weight %.

3. lubricating grease according to claim 2, wherein, on the basis of lubricating grease weight, including following components：25-55 weight The non-newtonian fluid calcium naphthenate of amount %；The calcium salt of the higher fatty acids of 2-6 weight %；The small molecule inorganic acid of 2-10 weight % And/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 weight %；Six polyurea compounds of 1.3-15 weight %； The base oil of 35-60 weight %.

4. the lubricating grease according to any one in claim 1-3, wherein, described non-newtonian fluid calcium naphthenate is by newton The conversion of body calcium naphthenate obtains, and its total base number is 250-500mgKOH/g.

5. the lubricating grease according to any one in claim 1-3, wherein, described higher fatty acids is 8-20's for carbon number Straight chain fatty acid or hydroxy fatty acid.

6. lubricating grease according to claim 5, wherein, described higher fatty acids be selected from laurate, palmitic acid, stearic acid, At least one in 12- hydroxy stearic acid, eicosyl carboxylic acid.

7. the lubricating grease according to Claims 2 or 3, wherein, the molecular weight of small molecule inorganic acid or lower fatty acid is less than Equal to 150.

8. lubricating grease according to claim 7, wherein, described small molecule inorganic acid be selected from boric acid, phosphoric acid, in sulfuric acid extremely Few one kind, at least one in acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid for the described lower fatty acid.

9. the lubricating grease according to Claims 2 or 3, wherein, described aromatic acid is substituted or unsubstituted aromatic acid, substituent For at least one in alkyl, thiazolinyl, alkynyl, aryl, haloalkyl or halogenated aryl, the molecular weight of described aromatic acid is less than or equal to 550.

10. according to the lubricating grease described in claim 9, wherein, described aromatic acid is selected from unsubstituted or the replacement of C1-C5 alkyl neighbour At least one in phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.

11. lubricating grease according to any one in claim 1-3, wherein, described six polyurea compounds have following knot Structure：

Wherein, R¹It is alkyl, cycloalkyl or aryl, R²It is alkylidene or arlydene, R³It is arlydene, alkylidene or cycloalkylidene.

12. lubricating grease according to claim 11, wherein, R¹It is phenyl or substituted phenyl, or carbon number is the alkyl of 8-24 Or cycloalkyl；R²It is the phenylene or biphenylene or carbon number alkylidene for 2-12；R³Be carbon number be the arlydene of 6-30, alkylene Base or cycloalkylidene.

13. lubricating grease according to claim 12, wherein, R¹It is phenyl or the phenyl of C1-C3 alkyl or halogen substiuted, or Carbon number is the alkyl or cycloalkyl of 10-18, R²It is phenylene or biphenylene, or carbon number is the alkylidene of 2-8；R³It is selected from With-(CH₂)₆- at least one.

The preparation method of Composite calcium naphthenate base six polyurea grease described in any one in 14. claims 1-13, it is special Levy and be, the method includes：By non-newtonian fluid calcium naphthenate, the calcium salt of higher fatty acids, six polyurea compounds and part basis At least one mixing in oil and the calcium salt selected from aromatic acid, the calcium salt of small molecule inorganic acid and the calcium salt of lower fatty acid is all Even, refine in 180-230 DEG C of constant temperature, cooling, add surplus base oil, add necessary additive, obtain finished product.

The preparation method of Composite calcium naphthenate base six polyurea grease described in any one in 15. claims 1-13, it is special Levy and be, the method includes：

(1) by newton body calcium naphthenate and base oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation；

(2) add lime or calcium hydroxide in step (1) products therefrom, add higher fatty acids and selected from aromatic acid, little point At least one in sub- inorganic acid and lower fatty acid is reacted, and heat up after reaction dehydration, then lowers the temperature；

(3) add base oil and diisocyanate in step (2) gained mixture, then sequentially add monoamine, diamines and two Isocyanates is reacted；

(4) step (3) gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds base oil, add necessary Additive, obtains finished product.

16. preparation methods according to claim 15, wherein, in step (1), newton body calcium naphthenate, base oil are mixed Conjunction is heated to 50-80 DEG C, adds required transforming agent to be reacted, after all transforming agents add, more than 90 DEG C and less than etc. In 110 DEG C of constant temperature 40-100 minutes.

17. preparation methods according to claim 15, wherein, in step (2), at 85-100 DEG C, add lime or hydrogen The suspension of calcium oxide, adds higher fatty acids, stirs 5-20 minute, adds selected from aromatic acid, small molecule inorganic acid and rudimentary fat At least one in fat acid, stirs 5-20 minute, is warming up to 150-170 DEG C of dehydration, is then cooled to 100-120 DEG C.

18. preparation methods according to claim 15, wherein, in step (3), add in step (2) gained mixture Base oil and diisocyanate, add monoamine, stir 2-8 minute, add diamines, stir 2-8 minute, add and be dissolved in basis Diisocyanate in oil, stirs 2-8 minute, the rubbing of diisocyanate added by each time, monoamine, diamines and diisocyanate That ratio is 2:2:2:1.

19. preparation methods according to claim 15, wherein, in step (4), first divide in 100-120 DEG C of constant temperature 10-20 Clock, is finally warmed up to 180-230 DEG C of constant temperature 5-20 minute；It is cooled to 150-160 DEG C, add base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassing.

20. preparation methods according to claim 15, wherein, described newton body calcium naphthenate be petroleum naphthenic acid calcium and/ Or synthesis calcium naphthenate, its total base number is 250-500mgKOH/g.

21. preparation methods according to claim 15, wherein, described transforming agent is selected from water, fatty alcohol, aliphatic ether, fat Acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, cycloalkanes amine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and At least one in alkyl benzene sulphonate, the addition of transforming agent is the 4-32% of newton body calcium naphthenate weight.

22. preparation methods according to claim 21, wherein, described transforming agent is A, B, C tri- class material, and A class material is At least one in ethanol, propyl alcohol, butanol and 12- hydroxy stearic acid, B class material is at least in acetic acid, propionic acid and butyric acid Kind, C class material is water, and the addition of transforming agent is the 15-25% of newton body calcium naphthenate weight.

23. preparation methods according to claim 22, wherein, A class material adds prior to B class material.

24. preparation methods according to claim 15, wherein, the structural formula of described monoamine is R¹-NH₂, wherein, R¹It is benzene Base or the phenyl of C1-C3 alkyl or halogen substiuted, or the alkyl or cycloalkyl for 10-18 for the carbon number.

25. preparation methods according to claim 24, wherein, described monoamine is arylamine or fatty amine, and described arylamine is selected from At least one in aniline, m-chloroaniline, parachloroanilinum and para-totuidine, described fatty amine be selected from lauryl amine, tetradecy lamine, 16 At least one in amine and octadecylamine.

26. preparation methods according to claim 15, wherein, the structural formula of described diamines is NH₂-R²-NH₂, wherein, R²It is Carbon number is the alkylidene of 2-8, or phenylene or biphenylene.

27. preparation methods according to claim 26, wherein, described diamines be selected from p-phenylenediamine, o-phenylenediamine, 4,4- The aromatic amine of benzidine and/or be selected from ethylenediamine, propane diamine, the straight-chain fatty amine of 1,6- hexamethylene diamine.

28. preparation methods according to claim 15, wherein, the structure of described diisocyanate is OCN-R³- NCO, R³It is Carbon number is arlydene, alkylidene or the cycloalkylidene of 6-30.

29. preparation methods according to claim 28, wherein, described diisocyanate is selected from toluene di-isocyanate(TDI), first Base diphenyl diisocyanate, 1,6- hexylidene diisocyanate, dicyclohexylmethyl diisocyanate and an xyxylene two At least one in isocyanates.