CN104212612B - A kind of Calcium naphthenate base six polyurea grease and preparation method thereof - Google Patents
A kind of Calcium naphthenate base six polyurea grease and preparation method thereof Download PDFInfo
- Publication number
- CN104212612B CN104212612B CN201310214545.8A CN201310214545A CN104212612B CN 104212612 B CN104212612 B CN 104212612B CN 201310214545 A CN201310214545 A CN 201310214545A CN 104212612 B CN104212612 B CN 104212612B
- Authority
- CN
- China
- Prior art keywords
- calcium naphthenate
- grease
- preparation
- polyurea
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- DJHXIBTWAABUPK-UHFFFAOYSA-N CNC(C(I)=C)=O Chemical compound CNC(C(I)=C)=O DJHXIBTWAABUPK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
The invention discloses a kind of Calcium naphthenate base six polyurea grease, it is characterised in that with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 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, and described polyurea compound is six polyurea compounds.The invention also discloses Calcium naphthenate base six polyurea grease of the preparation method of Calcium naphthenate base six polyurea grease and preparation thereof.Calcium naphthenate base six polyurea grease of the present invention, there is excellent anticorrosive property and resistance to saltfog, but also there is performances such as being better than the heat-resisting quantity of sulfonic acid calcio six polyurea grease, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, there is longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, constant product quality.
Description
Technical field
The present invention relates to grease, in particular it relates to a kind of Calcium naphthenate base six polyurea grease and preparation method thereof.
Background technology
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffusibility, it is used as the detersive of lubricating oil, it is widely used in the additive of IC engine lubricating oil, its technical development mainly makes its high alkalization, it is simply that calcium carbonate is distributed in flux oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Overbased calcium alkyl-salicylate be mostly from the distillate that crude distillation obtains extract acidic components, through and Ca (OH)2Reaction, the contour alkalization technology of carbonating and obtain, about prepare Patents have CN1465560 etc..
Utilize calcium sulfonate with high base number for raw material production grease, because it has the high temperature performance of excellence, mechanical stability, colloid stability, oxidation stability, water-resistance, anticorrosive property and antirust wear resistence, since putting goods on the market, cause the extensive concern of domestic and international grease industry, but, although high base number composite calcium sulfonate base grease has very excellent combination property, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause that it is not promoted rapidly, simultaneously, along with people are more and more higher to the requirement of environmental conservation, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment is also increasingly subject to the concern of people.Find a kind of performance similar with calcium sulfonate with high base number but the grease of the problems referred to above can be avoided to become the big problem that people face at present.
Summary of the invention
It is an object of the invention to provide a kind of performance similar with sulfonate with high base number grease of calcium, cost is low, grease that preparation technology is simple and environmentally-friendly and preparation method thereof.
The present inventor finds under study for action, with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 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, and described polyurea compound is six polyurea compounds.The performance of this grease is similar with sulfonate with high base number grease of calcium, and cost is low, and preparation technology is simple and environmentally-friendly.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of Calcium naphthenate base six polyurea grease, it is characterised in that with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 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, and described polyurea compound is six polyurea compounds.
Preferably, with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 30-55 weight %；Six polyurea compounds of 1.5-15 weight %；The base oil of 35-60 weight %.
Second aspect, the preparation method that the invention provides Calcium naphthenate base six polyurea grease as above, it is characterized in that, the method includes: by non-newtonian fluid calcium naphthenate, six polyurea compounds and part basis oil mix homogeneously, refine at 180-230 DEG C of constant temperature, cooling, add surplus base oil, add necessary additive, obtain finished product.
The third aspect, the preparation method that the invention provides a kind of Calcium naphthenate base six polyurea grease, it is characterised in that the method includes:
(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, further heat up dehydration, then lower the temperature；
(2) in step (1) products therefrom, add part basis oil and diisocyanate, be then sequentially added into monoamine, diamidogen and diisocyanate and react；
(3) step (2) is reacted gained mixture and be warmed up to 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
Fourth aspect, the invention provides Calcium naphthenate base six polyurea grease prepared by method as above.
Calcium naphthenate base six polyurea grease of the present invention, not only the same with sulfonic acid calcio six polyurea grease, there is excellent anticorrosive property and resistance to saltfog, but also there is performances such as being better than the heat-resisting quantity of sulfonic acid calcio six polyurea grease, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, there is longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, constant product quality.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
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 grease of embodiment 2 preparation.
The XRD crystal formation that Fig. 3 is the calcium carbonate in the grease of embodiment 2 preparation measures.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides a kind of Calcium naphthenate base six polyurea grease, this grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, contains isocyanates and six polyurea compounds of amine reaction generation simultaneously.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of Calcium naphthenate base six polyurea grease, with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 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, and described polyurea compound is six polyurea compounds.
Preferably, with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 30-55 weight %；Six polyurea compounds of 1.5-15 weight %；The base oil of 35-60 weight %.
The infrared absorption peak of the mainly carbonate that calcium carbonate occurs in infrared spectrum, is divided into 4 regions: ν 1-1450cm-1；ν2-1080cm-1；ν3-870cm-1With ν 4-710cm-1.ν 1 bands of a spectrum are carbonate (CO3 2-) antisymmetric stretching vibration absworption 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 bands of a spectrum are the in-plane bending vibration absworption peaks of carbonate.It is said that in general, the crystal form of calcium carbonate can be distinguished by the difference of these absworption peaks.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-1And 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 of its infrared band slightly difference.
Described non-newtonian fluid calcium naphthenate is at infrared spectrum 1082cm-1Left and right, 856cm-1Left and right, 712cm-1Left and right, 700cm-1There is the characteristic absorption peak of aragonite calcium carbonate in place, and total base number is 250mgKOH/g-500mgKOH/g, it is preferable that 300mgKOH/g-450mgKOH/g.Described non-newtonian fluid calcium naphthenate is to be obtained by transforming agent conversion by newton body calcium naphthenate.And containing unformed calcium carbonate in newton body calcium naphthenate, at infrared spectrum 1076cm-1Left and right, 860cm-1There is unformed calcium carbonate characteristic absorption peak at left and right place.Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total base number is 250mgKOH/g-500mgKOH/g, it is preferable that 300mgKOH/g-450mgKOH/g, and after changing into non-newtonian fluid calcium naphthenate, its base number is constant.
In the present invention, described six polyurea compounds preferably have a structure that
Wherein, R1Can being alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, it is preferred to 10-18, and aryl can be the phenyl of phenyl or replacement, it is preferable that the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.
Wherein, R2Can being alkylidene or arlydene, the carbon number of alkylidene can be 2-12, it is preferred to 2-8, and arlydene can be phenylene or biphenylene.
Wherein, R3Can being arlydene, alkylidene or cycloalkylidene, the carbon number of arlydene, alkylidene or cycloalkylidene can be 6-30, it is preferred to 6-20, R3It is more preferably With-(CH2)6-at least one.
Above-mentioned six polyurea compounds can adopt the thinkable various methods of those skilled in the art institute to obtain, for instance can prepare according to the CN103060067A method recorded.
Described lube base oil can be mineral oil, artificial oil, vegetable oil or their mixture, and 100 DEG C of dynamic viscosities are 4-150mm2/ s, it is preferable that 10-60mm2/s.Artificial oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Grease of the present invention can also contain various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent etc..Wherein, the preferred arylamine kind antioxidant of antioxidant, account for the 0.01-5% of grease gross weight, it is preferable that 0.1-2.5%, it is possible to be at least one in diphenylamines, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, it is preferable that di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of grease gross weight, preferred 0.8-8%, it is possible to be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum bisuphide, politef, D2EHDTPA molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium sulfide, fluorographite, calcium carbonate and zinc oxide；Antirust agent accounts for the 0.01-4.5% of grease gross weight, it is preferable that 0.1-2%, it is possible to be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the preparation method that the invention provides Calcium naphthenate base six polyurea grease as above, the method includes: by non-newtonian fluid calcium naphthenate, six polyurea compounds and part basis oil mix homogeneously, refine at 180-230 DEG C of constant temperature, cooling, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, for non-newtonian fluid calcium naphthenate, six polyurea compounds and base oil as it has been described above, do not repeat them here.
It will be understood by those skilled in the art that the amount sum of the amount of part basis oil and surplus base oil is the total amount of base oil used, in the present invention, the weight ratio of part basis oil and surplus base oil is preferably 1:0.1-0.5.
For non-newtonian fluid calcium naphthenate, can be obtained by transforming agent conversion by newton body calcium naphthenate, such as, by newton body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, more than 90 DEG C and less than or equal to 110 DEG C, preferred 95-110 DEG C, constant temperature 40-100 minute, then heat to 150-170 DEG C of dehydration.
The third aspect, the invention provides the another kind of preparation method of Calcium naphthenate base six polyurea grease as above, including:
(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, further heat up dehydration, then lower the temperature；
(2) in step (1) products therefrom, add part basis oil and diisocyanate, be then sequentially added into monoamine, diamidogen and diisocyanate and react；
(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
In step (1), by newton body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, more than 90 DEG C and less than or equal to 110 DEG C, it is preferable that 95-110 DEG C, constant temperature 40-100 minute, it is warming up to 150-170 DEG C of dehydration, is then cooled to 100-120 DEG C.
The weight ratio of newton body calcium naphthenate and part basis oil is preferably 1:0.1-1.
Described newton body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total base number is 250mgKOH/g-500mgKOH/g, it is preferable that 300mgKOH/g-450mgKOH/g.
Described transforming agent at least one in water, fatty alcohol, aliphatic ether, fatty acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, cycloalkanes amine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and alkyl benzene sulphonate, it is preferable that at least one in water, isopropanol, methanol, ethanol, propanol, n-butyl alcohol, ketone, formaldehyde, glycol dimethyl ether, acetic acid, propanoic acid, butanoic acid, aphthenic acids, stearic acid, 12-hydroxy stearic acid and DBSA.It is more preferably A, B, C tri-class material, A class material is ethanol, propanol, at least one in butanol and 12-hydroxy stearic acid, B class material is acetic acid, at least one in propanoic acid and butanoic acid, C class material is water, and feed postition is preferably A class material and adds prior to B class material, namely ethanol it is initially charged, propanol, at least one in butanol and 12-hydroxy stearic acid, after mixing homogeneously with newton body calcium naphthenate, add acetic acid, at least one in propanoic acid and butanoic acid, for the addition sequence of C class material water without particular/special requirement, can first add, can add later, can also add together with A class material or B class material.
The addition of transforming agent is the 4-32% of newton body calcium naphthenate weight, it is preferable that 15-25%.When transforming agent is preferably A, B, C tri-class material, A class material is at least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material is at least one in acetic acid, propanoic acid and butanoic acid, when C class material is water, the weight ratio of A class material and B class material and C class material is preferably 1:0.1-10:1-10, more preferably 1:0.5-8:1-8.For in A class material and B class material select concrete material and each material between amount ratio without particular/special requirement, as long as total amount can obtain better effect in above-mentioned scope.
In step (2), step (1) products therefrom adds part basis oil and diisocyanate, is then sequentially added into monoamine, diamidogen and diisocyanate and reacts, be namely prepare six polyurea compounds in step (1) products therefrom.
Prepare the method for six polyurea compounds without particular/special requirement, it is possible to adopt various methods commonly used in the art.Such as, in the present invention, part basis oil and diisocyanate can be added in the product of step (1), add monoamine, stir 2-8 minute, add diamidogen, stir 2-8 minute, adding the diisocyanate being dissolved in part basis oil, stir 2-8 minute, the mol ratio of each added diisocyanate, monoamine, diamidogen and diisocyanate is 2:2:2:1.
In step of the present invention (2), the diisocyanate of twice addition can be the same or different, in order to easy to operate, it is preferable that the diisocyanate of twice addition is identical.
Described diisocyanate structure is OCN-R3-NCO, R3Can be carbon number it be 6-30, it is preferable that the arlydene of 6-20, alkylidene or cycloalkylidene, it is preferred to -(CH2)6-etc..Such as described diisocyanate can be toluene di-isocyanate(TDI) (TDI), methyldiphenyl diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), at least one in dicyclohexylmethyl diisocyanate (HMDI) and an xylylene diisocyanate (XDI) etc..
Described monoamine can be fatty amine, aliphatic cyclic amine or arylamine, and structural formula is R1-NH2、R1’-NH2, R therein1、R1’Can being alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8-24, it is preferable that 10-18, and aryl can be the phenyl of phenyl or replacement, it is preferable that the phenyl of phenyl or C1-C3 alkyl or halogen substiuted.Preferred monoamine can be chosen from the arylamine of aniline, m-chloroaniline, parachloroanilinum, para-totuidine, and/or is selected from the fatty amine of lauryl amine, tetradecy lamine, cetylamine, 18-amine..
Described diamidogen can be fatty amine or arylamine, and structural formula is NH2-R2-NH2, R therein2Can being alkylidene or arlydene, the carbon number of alkylidene can be 2-12, it is preferable that 2-8, and arlydene can be phenylene or biphenylene.Preferred diamidogen can be chosen from p-phenylenediamine, o-phenylenediamine, 4,4-benzidine aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6-hexamethylene diamine straight-chain fatty amine.
In step (3), first 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 surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassed.
In the present invention, in step (1), the total amount of part basis oil used is preferably 1:0.1-1:0.1-1 with the weight ratio of surplus base oil in step (3) to part basis oil used with step (2).
Fourth aspect, Calcium naphthenate base six polyurea grease that the preparation method that present invention also offers is provided by third aspect present invention prepares.
Compared with Calcium naphthenate base six polyurea grease that the preparation method provided by second aspect prepares, Calcium naphthenate base six polyurea grease that the preparation method that the third aspect provides prepares has better heat-resisting quantity, water-resistance and adhesiveness, 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 %=(is overbased or overbased calcium alkyl-salicylate raw materials quality+transforming agent gross mass)/grease gross mass × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.
In embodiment, overbased and overbased calcium alkyl-salicylate raw material is from Xinjiang Land Fine Petrochemical Co., Ltd, it is also possible to prepared by 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 for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total base number is 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm2The HVI150BS lubricating base oil of/s, stirring, heat to 80 DEG C, constant temperature 10 minutes；Adding 1.8kg n-butyl alcohol, temperature controls at about 80 DEG C, stirs 10 minutes；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation；It is warmed up to 160 DEG C under stirring, keeps 60 minutes, dehydration, cool to 120 DEG C；10kg100 DEG C of kinematic viscosity of addition is 11mm2The 4.77kgMDI that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, adds 7.69kg 18-amine., stirs 6 minutes, adds 0.86kg ethylenediamine, stirs 6 minutes, and adding with 5kg100 DEG C of kinematic viscosity is 11mm2The 2.38kgMDI that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, 120 DEG C of constant temperature 20 minutes, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, adds HVI500SN lubricating base oil 15kg；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassed obtain finished product.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 30.6%；Six polyureas 14.4%；Lubricating base oil 55.0%.
Embodiment 2
The present embodiment is for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Volume be 160L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add overbased calcium alkyl-salicylate that 33kg total base number is 400mgKOH/g and 15kg100 DEG C of kinematic viscosity is 31mm2The HVI150BS lubricating base oil of/s, stirring, heat to 60 DEG C, constant temperature 10 minutes；Adding 0.56kg ethanol, temperature controls at about 60 DEG C, stirs 10 minutes；Add 3.36kg propanoic acid and 3.36kg water, stir 10 minutes；In 100 DEG C of constant temperature 70 minutes, material retrogradation；It is warmed up to 150 DEG C under stirring, keeps 60 minutes, dehydration, cool to 110 DEG C；5kg100 DEG C of kinematic viscosity of addition is 11mm2The 0.34kgHDI that the HVI500SN lubricating base oil of/s dissolves, stirs 2 minutes, adds 0.37kg lauryl amine, stirs 2 minutes, adds 0.22kg p-phenylenediamine, stirs 2 minutes, and adding with 5kg100 DEG C of kinematic viscosity is 11mm2The 0.17kgHDI that the HVI500SN lubricating base oil of/s dissolves, stirs 2 minutes, 110 DEG C of constant temperature 15 minutes, is finally warmed up to 180 DEG C of constant temperature 20 minutes.Then, it is cooled to 150 DEG C, adds HVI500SN lubricating base oil 10kg；Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassed obtain finished product.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 50.2%；Six polyureas 1.5%；Lubricating base oil 48.3%.
Embodiment 3
The present embodiment is for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total base number is 450mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm2The HVI150BS lubricating base oil of/s, stirring, heat to 50 DEG C, constant temperature 10 minutes；Adding 0.2kg normal propyl alcohol, 0.2kg n-butyl alcohol and 3.2kg water, temperature controls at about 50 DEG C, stirs 10 minutes；Add 2.96kg acetic acid, stir 10 minutes；In 110 DEG C of constant temperature 40 minutes, material retrogradation；It is warmed up to 170 DEG C under stirring, keeps 60 minutes, dehydration, cool to 100 DEG C；3kg100 DEG C of kinematic viscosity of addition is 11mm2The 2.68kgXDI that the HVI500SN lubricating base oil of/s dissolves, stirs 8 minutes, adds 1.52kg para-totuidine, stirs 8 minutes, adds 1.06kg propane diamine, stirs 8 minutes, and adding with 3kg100 DEG C of kinematic viscosity is 11mm2The 1.34kgXDI that the HVI500SN lubricating base oil of/s dissolves, stirs 8 minutes, 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, adds HVI500SN lubricating base oil 6kg；Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassed obtain finished product.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 40.7%；Six polyureas 8.0%；Lubricating base oil 51.3%.
Embodiment 4
The present embodiment is for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Volume be 110L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total base number is 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm2The HVI150BS lubricating base oil of/s, stirring, heat to 80 DEG C, constant temperature 10 minutes；Adding 1.8kg n-butyl alcohol, temperature controls at about 80 DEG C, stirs 10 minutes；Add 1.56kg n-butyric acie and 3.2kg water, stir 10 minutes；In 95 DEG C of constant temperature 100 minutes, material retrogradation；It is warmed up to 160 DEG C under stirring, keeps 60 minutes, dehydration.
Another volume be 50L and with heating, stirring, circulation, cooling normal-pressure reaction kettle in add with 10kg100 DEG C of kinematic viscosity be 11mm2The 4.77kgMDI that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, adds 7.69kg 18-amine., stirs 6 minutes, adds 0.86kg ethylenediamine, stirs 6 minutes, and adding with 5kg100 DEG C of kinematic viscosity is 11mm2The 2.38kgMDI that the HVI500SN lubricating base oil of/s dissolves, stirs 6 minutes, 120 DEG C of constant temperature 20 minutes, obtains six polyureas.
Six polyureas of gained are all squeezed in a upper still, stirs, be finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, it is cooled to 160 DEG C, adds HVI500SN lubricating base oil 15kg；Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassed obtain finished product.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 30.6%；Six polyureas 14.4%；Lubricating base oil 55.0%.
Embodiment 5
The present embodiment is for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, the difference is that, it being initially charged 1.56kg n-butyric acie, temperature controls at about 80 DEG C, stirs 10 minutes, adds 1.8kg n-butyl alcohol and 3.2kg water, stirs 10 minutes.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 30.6%；Six polyureas 14.4%；Lubricating base oil 55.0%.
Embodiment 6
The present embodiment is for illustrating Calcium naphthenate base six polyurea grease prepared by the present invention.
Calcium naphthenate base six polyurea grease is prepared according to the method for embodiment 1, the difference is that, 1.8kg n-butyl alcohol is replaced with 3.2kg ketone, 1.56kg n-butyric acie and 3.2kg water are replaced with 3.36kg aphthenic acids.Assay is in Table 1.
In the grease that the present embodiment obtains, with grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 30.6%；Six polyureas 14.4%；Lubricating base oil 55.0%.
Comparative example 1
Sulfonate with high base number calcio six polyurea grease is prepared by the method for embodiment 1, the difference is that, the calcium sulfonate with high base number that overbased calcium alkyl-salicylate total base number is 320mgKOH/g replaces, and each performance data of grease finished product obtained is in Table 1.
In the grease that this comparative example obtains, with grease weight for benchmark, consist of: non-newtonian fluid sulfoacid calcium 30.6%；Six polyureas 14.4%；Lubricating base oil 55.0%.
The each grease properties of sample data of table 1
Each indication test method: dropping point: GB/T3498；Drawing cone in-degree: GB/T269；Corrosion: GB/T7326；Anticorrosive 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 and can be seen that, the dropping point of Calcium naphthenate base six polyurea grease of the present invention is far above sulfonic acid calcio six polyurea grease, water drenches number of dropouts much smaller than sulfonic acid calcio six polyurea grease, Stencil oil-dividing value is much smaller than sulfonic acid calcio six polyurea grease, tetra-ball machine test value is more than sulfonic acid calcio six polyurea grease, the bearing lubrication life-span is much larger than sulfonic acid calcio six polyurea grease, the heat-resisting quantity of Calcium naphthenate base six polyurea grease of the present invention is described, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, lubricating life is superior to sulfonic acid calcio six polyurea grease, and Calcium naphthenate base six polyurea grease of the present invention is the same with sulfonic acid calcio six polyurea grease has the performances such as excellent anticorrosive property and resistance to saltfog.
Embodiment 1 and embodiment 4 are compared it can be seen that Calcium naphthenate base six polyurea grease prepared of original position, there is better heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear；Embodiment 1 and embodiment 5 are compared it can be seen that A class material adds prior to B class material in transforming agent, Calcium naphthenate base six polyurea grease of preparation, there is better water-resistance and adhesiveness, colloid stability, and there is longer lubricating life；Embodiment 1 and embodiment 6 are compared and can be seen that, transforming agent is A, B, C tri-class material, A class material is at least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material is at least one in acetic acid, propanoic acid and butanoic acid, C class material is water, Calcium naphthenate base six polyurea grease of preparation, has better heat-resisting quantity, water-resistance and adhesiveness, colloid stability and extreme pressure anti-wear, and has longer lubricating 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 at 1076-1077cm-1Left and right, ν3Bands of a spectrum are 860cm-1Left and right.It is illustrated as amorphous calcium carbonate.
Figure it is seen that containing 1082cm in the infrared spectrum of calcium carbonate in the grease of embodiment 2 preparation-1Left and right, 855cm-1Left and right, 700cm-1Left and right, 713cm-1The absworption peaks such as left and right, for the characteristic absorption peak of aragonite calcium carbonate, illustrate that the amorphous calcium carbonate in overbased calcium alkyl-salicylate converts for aragonite calcium carbonate.
As can be seen from Figure 3, the XRD crystal formation of the calcium carbonate in the grease of embodiment 2 preparation measures, intensity peak is had near angle 26 °, 27 °, 46 °, 33.5 °, 36 °, 38 °, 43 °, consistent with aragonite standard spectrogram, there is aragonite calcium carbonate in sample after conversion is described.
Calcium naphthenate base six polyurea grease of the present invention, not only the same with sulfonic acid calcio six polyurea grease, there is excellent anticorrosive property and resistance to saltfog, but also there is performances such as being better than the heat-resisting quantity of sulfonic acid calcio six polyurea grease, water-resistance and adhesiveness, colloid stability, extreme pressure anti-wear, there is longer lubricating life.The preparation of greases technique of the present invention is simple and environmentally-friendly, and cost is low, constant product quality.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing; but; the present invention is not limited to the detail in above-mentioned embodiment; in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (21)
1. Calcium naphthenate base six polyurea grease, it is characterised in that with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 20-60 weight %；The polyurea compound of 0.5-25 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, and described polyurea compound is six polyurea compounds.
2. grease according to claim 1, wherein, with grease weight for benchmark, including following components: the non-newtonian fluid calcium naphthenate of 30-55 weight %；Six polyurea compounds of 1.5-15 weight %；The base oil of 35-60 weight %.
3. grease according to claim 1 and 2, wherein, described non-newtonian fluid calcium naphthenate is converted by newton body calcium naphthenate and obtains, and its total base number is 250-500mgKOH/g.
4. grease according to claim 1 and 2, wherein, described six polyurea compounds have a structure that
Wherein, R1It is alkyl, cycloalkyl or aryl, R2It is alkylidene or arlydene, R3It is arlydene, alkylidene or cycloalkylidene.
5. grease according to claim 4, wherein, R1It is the phenyl of phenyl or replacement, or carbon number is the alkyl or cycloalkyl of 8-24；R2Be phenylene or biphenylene or carbon number it is the alkylidene of 2-12；R3Be carbon number it is the arlydene of 6-30, alkylidene or cycloalkylidene.
6. grease according to claim 5, 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.
7. the preparation method of Calcium naphthenate base six polyurea grease described in any one in claim 1-6, it is characterized in that, the method includes: by non-newtonian fluid calcium naphthenate, six polyurea compounds and part basis oil mix homogeneously, refine at 180-230 DEG C of constant temperature, cooling, add surplus base oil, add necessary additive, obtain finished product.
8. the preparation method of Calcium naphthenate base six polyurea grease described in any one in claim 1-6, it is characterised in that the method includes:
(1) by newton body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation, further heat up dehydration, then lower the temperature；
(2) in step (1) products therefrom, add part basis oil and diisocyanate, be then sequentially added into monoamine, diamidogen and diisocyanate and react；
(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
9. preparation method according to claim 8, wherein, in step (1), by newton body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, more than 90 DEG C and less than or equal to 110 DEG C of constant temperature 40-100 minute, it is warming up to 150-170 DEG C of dehydration, is then cooled to 100-120 DEG C.
10. preparation method according to claim 8, wherein, in step (2), the product of step (1) adds part basis oil and diisocyanate, adds monoamine, stir 2-8 minute, add diamidogen, stir 2-8 minute, add the diisocyanate being dissolved in part basis oil, stirring 2-8 minute, the mol ratio of each added diisocyanate, monoamine, diamidogen and diisocyanate is 2:2:2:1.
11. preparation method according to claim 8, wherein, in step (3), first 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 surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stirring, circulating filtration, homogenizing, degassed.
12. preparation method according to claim 8, wherein, described newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total base number is 250-500mgKOH/g.
13. preparation method according to claim 8, wherein, described transforming agent at least one in water, fatty alcohol, aliphatic ether, fatty acid, aphthenic acids, fatty aldehyde, aliphatic ketone, fatty amine, cycloalkanes amine, cyclic alkanol, cycloalkanes ether, carbon dioxide, aromatic alcohol, aromatic amine and alkyl benzene sulphonate, the addition of transforming agent is the 4-32% of newton body calcium naphthenate weight.
14. preparation method according to claim 13, wherein, described transforming agent is A, B, C tri-class material, A class material is at least one in ethanol, propanol, butanol and 12-hydroxy stearic acid, B class material is at least one in acetic acid, propanoic acid and butanoic acid, C class material is water, and the addition of transforming agent is the 15-25% of newton body calcium naphthenate weight.
15. preparation method according to claim 14, wherein, A class material adds prior to B class material.
16. preparation method according to claim 8, wherein, the structural formula of described monoamine is R1-NH2, 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.
17. preparation method according to claim 16, wherein, described monoamine is chosen from the arylamine of aniline, m-chloroaniline, parachloroanilinum and/or para-totuidine and/or the fatty amine selected from lauryl amine, tetradecy lamine, cetylamine and/or 18-amine..
18. preparation method according to claim 8, wherein, the structural formula of described diamidogen is NH2-R2-NH2, wherein, R2Be carbon number it is the alkylidene of 2-8, or phenylene or biphenylene.
19. preparation method according to claim 18, wherein, described diamidogen be chosen from p-phenylenediamine, o-phenylenediamine, 4,4-benzidines aromatic amine and/or selected from ethylenediamine, propane diamine, 1,6-hexamethylene diamine straight-chain fatty amine.
20. preparation method according to claim 8, wherein, the structure of described diisocyanate is OCN-R3-NCO, R3Be carbon number it is the arlydene of 6-30, alkylidene or cycloalkylidene.
21. preparation method according to claim 20, wherein, described diisocyanate at least one in toluene di-isocyanate(TDI), methyldiphenyl diisocyanate, hexamethylene diisocyanate, dicyclohexylmethyl diisocyanate and an xylylene diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310214545.8A CN104212612B (en) | 2013-05-31 | 2013-05-31 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310214545.8A CN104212612B (en) | 2013-05-31 | 2013-05-31 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104212612A CN104212612A (en) | 2014-12-17 |
| CN104212612B true CN104212612B (en) | 2016-07-06 |
Family
ID=52094523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310214545.8A Active CN104212612B (en) | 2013-05-31 | 2013-05-31 | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104212612B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102417855A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof |
| CN103571571A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof |
-
2013
- 2013-05-31 CN CN201310214545.8A patent/CN104212612B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070173420A1 (en) * | 2004-02-23 | 2007-07-26 | Kenichi Iso | Grease composition and rolling device |
| CN102417855A (en) * | 2010-09-27 | 2012-04-18 | 中国石油化工股份有限公司 | Calcium sulfonate tetra-polyurea lubricating grease and preparation method thereof |
| CN103571571A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Calcium naphthenate-based hexapolyurea lubricating grease and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104212612A (en) | 2014-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106032488B (en) | Lubricant composition and preparation method thereof | |
| CN106032486B (en) | Lubricant composition and preparation method thereof | |
| CN106032482B (en) | Lubricant composition and preparation method thereof | |
| CN104212535B (en) | A kind of calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
| CN104212612B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN104560318B (en) | A kind of polyurea grease of calcium naphthenate zirconium base six and preparation method thereof | |
| CN104293449B (en) | A kind of Composite calcium naphthenate base grease and preparation method thereof | |
| CN104212611B (en) | A kind of Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN104293452B (en) | A kind of Composite calcium naphthenate base polyurea grease and preparation method thereof | |
| CN104212610B (en) | A kind of calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN104293451B (en) | A kind of Composite calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
| CN104293450B (en) | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof | |
| CN106032480B (en) | Lubricant composition and preparation method thereof | |
| CN104293416B (en) | Composite calcium naphthenate-based hexa-polyurea lubricating grease and preparation method thereof | |
| CN104560273B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base octa-polyurea lubricating grease and preparation method thereof | |
| CN104449956B (en) | A kind of high base number composite calcium-base polyurea grease and preparation method thereof | |
| CN104450109B (en) | A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof | |
| CN106032484B (en) | Lubricant composition and preparation method thereof | |
| CN104560317B (en) | A kind of complex calcium sulfonate calcium naphthenate zirconium base polyurea grease and preparation method thereof | |
| CN104560320B (en) | A kind of composite calcium naphthenate calcium zirconium base polyurea grease and preparation method thereof | |
| CN104560272B (en) | A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base six and preparation method thereof | |
| CN104560325B (en) | A kind of polyurea grease of composite calcium naphthenate calcium zirconium base six and preparation method thereof | |
| CN104560316B (en) | A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base four and preparation method thereof | |
| CN104450115B (en) | A kind of sulfoacid calcium calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN104560321B (en) | A kind of polyurea grease of sulfoacid calcium calcium naphthenate zirconium base six and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |