CN106032483B - A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof - Google Patents

A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof Download PDF

Info

Publication number
CN106032483B
CN106032483B CN201510105354.7A CN201510105354A CN106032483B CN 106032483 B CN106032483 B CN 106032483B CN 201510105354 A CN201510105354 A CN 201510105354A CN 106032483 B CN106032483 B CN 106032483B
Authority
CN
China
Prior art keywords
calcium
acid
weight
newtonian fluid
content
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
Application number
CN201510105354.7A
Other languages
Chinese (zh)
Other versions
CN106032483A (en
Inventor
何懿峰
孔锡奎
孙洪伟
段庆华
张建荣
刘中其
郑会
姜靓
陈政
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201510105354.7A priority Critical patent/CN106032483B/en
Publication of CN106032483A publication Critical patent/CN106032483A/en
Application granted granted Critical
Publication of CN106032483B publication Critical patent/CN106032483B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Lubricants (AREA)

Abstract

The present invention relates to lubricating grease fields, disclose a kind of composite sulfuration alkyl phenol calcium-base grease, contain base oil and thickening agent, thickening agent contains the calcium salt of non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids, thickening agent also optionally contains non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, one of calcium salt of small molecule inorganic acid and/or lower fatty acid is a variety of, the content of base oil is 10-80 weight %, the content of non-newtonian fluid sulfurized alkylphenol calcium is 10-70 weight %, the content of the calcium salt of higher fatty acids is 1-20 weight %, the content of remaining each optional components is respectively 0-70 weight %, 0-70 weight %, 0-70 weight %, 0-70 weight %, 0-15 weight %, 0-15 weight %.Also disclose preparation method.Lubricating grease of the invention has excellent performance, and preparation process is simple and environmentally-friendly, stable product quality.

Description

A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof
Technical field
The present invention relates to lubricating grease, and in particular, to a kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof.
Background technique
SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER has preferable detergent-dispersant performance, good acid neutralization capacity and excellent diffusion Property, it is used as the detersive of lubricating oil, is widely used in modulation medium and high classes I. C. engine oil, is particularly suitable for supercharged diesel engine For oil to reduce the carbon deposit of top land and the additive of marine cylinder oil, technology development mainly makes its height alkalization, be exactly Calcium carbonate, which is distributed in flux oil with the sulfurized alkylphenol calcium with surface-active, becomes a kind of colloidal dispersion system.High base number Sulfurized alkylphenol calcium is that alkyl phenol is reacted with CaO, vulcanized, carbonated contour alkalization technology and obtain, and the correlation in relation to preparation is specially Benefit has CN101423483 etc..
It is that raw material produces lubricating grease using calcium sulfonate with high base number, because it is with excellent antirust and anticorrosive property, from investment Since market, the extensive concern of domestic and international lubricating grease industry is caused, however, although high base number composite calcium sulfonate base grease has Very excellent antirust and anticorrosive property, but hardening is easy in storage process, and its raw materials for production calcium sulfonate with high base number is high Price and complicated preparation process itself cause it not promoted rapidly, meanwhile, the requirement with people to environmental protection is got over Come higher, necessary sulfonation process is also increasingly subject to the concern of people to the pollution of environment in calcium sulfonate with high base number production process. It finds a kind of antirust and anticorrosive property is similar with high base number composite calcium sulfonate base grease but can reduce the lubrication of the above problem Rouge becomes the big problem that people face at present.
Summary of the invention
The object of the present invention is to provide one kind to have good antirust and anticorrosive property, storage good security and its raw material system Standby simple process, lubricating grease of environmental protection and preparation method thereof.
The present inventor has found that sulfurized alkylphenol calcium may hold at high temperature due to containing active sulfur under study for action Elemental sulfur easily is precipitated and generates corrosion, therefore, when as detersive, the antirust and anticorrosive property of sulfurized alkylphenol calcium are far below Sulfoacid calcium, but when sulfurized alkylphenol calcium is prepared lubricating grease as thickening agent, but it can get and high base number composite calcium sulfonate Ji Run Consistent lubricant quite even preferably antirust and anticorrosive property, and storage good security.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of composite sulfuration alkyl phenol calcium base lubrications Rouge, the lubricating grease contain base oil and thickening agent, and the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium and higher aliphatic The calcium salt of acid, the thickening agent also optionally contain non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid salicylic acid Calcium, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or a variety of, On the basis of the weight of the lubricating grease, the content of base oil is 10-80 weight %, the content of non-newtonian fluid sulfurized alkylphenol calcium For 10-70 weight %, the content of the calcium salt of higher fatty acids is 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-70 weight % is measured, the content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, non- The content of newton body calcium oleate is 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, small molecule inorganic acid and/or The content of the calcium salt of lower fatty acid is 0-15 weight %.
Preferably, on the basis of the weight of the lubricating grease, the content of base oil is 20-70 weight %, non-newtonian fluid sulphur The content for changing alkyl phenol calcium is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, non-newtonian fluid sulfonic acid The content of calcium is 0-50 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, and non-newtonian fluid calcium salicylate contains Amount is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, The content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 2-10 weight %.
Second aspect, the present invention provides the preparation methods of composite sulfuration alkyl phenol calcium-base grease as described above, should Method includes: to be uniformly mixed thickening agent and part basis oil, refines in 180-230 DEG C of constant temperature, surplus base oil is added, be added Necessary additive, obtains finished product, and the thickening agent contains the calcium salt of non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids, institute It states thickening agent and also optionally contains non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid Calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or a variety of.
The third aspect, the present invention provides a kind of preparation method of composite sulfuration alkyl phenol calcium-base grease, this method packets It includes:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional ox will be contained Body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/ Or high base number material and part basis the oil mixing of non-newtonian fluid calcium oleate, obtain mixture；
(2) reaction of at least partly composite calcium is optionally carried out: addition lime or calcium hydroxide, addition higher fatty acids, Optional aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, are reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) it is warming up to 180-230 DEG C of constant temperature refining, surplus base oil is added, necessary additive is added, obtains finished product.
Preferably, in step (2), the reaction of at least partly composite calcium is carried out.
Fourth aspect, the present invention provides the composite sulfuration alkyl phenol calcium-base grease as made from method as described above.
Composite sulfuration alkyl phenol calcium-base grease of the invention has quite even more excellent with complex calcium sulfonate grease Good antirust and anticorrosive property, and there is excellent storage stability, also there is the thickening better than complex calcium sulfonate grease Property, mechanical stability, water-resistance, colloid stability, abrasion resistance and extreme pressure anti-wear, and also there is excellent heat-resisting quantity etc. Performance.The feed preparation process of lubricating grease of the invention is simple and environmentally-friendly, stable product quality.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the overbased sulfurized alkylphenol calcium raw material of embodiment 1 and the infrared analysis spectrogram pair of lubricating grease obtained Than.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of composite sulfuration alkyl phenol calcium-base grease, this lubricating grease uses synthesis alkyl monosulfide Phenol calcium and optional calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, optional petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, Optional salicylate calcium, optional natural calcium oleate and/or synthesis calcium oleate is raw material, is thickened simultaneously containing composite calcium Agent.
The present invention also provides above-mentioned preparation of greases methods.
On the one hand, the present invention provides a kind of composite sulfuration alkyl phenol calcium-base grease, lubricating grease contains base oil and thick Agent, thickening agent contain the calcium salt of non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids, and thickening agent also optionally contains non-ox Body sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule One of calcium salt of inorganic acid and/or lower fatty acid is a variety of, and on the basis of the weight of lubricating grease, the content of base oil is The content of 10-80 weight %, non-newtonian fluid sulfurized alkylphenol calcium are 10-70 weight %, and the content of the calcium salt of higher fatty acids is 1-20 weight %, the content of non-newtonian fluid sulfoacid calcium are 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 weight % is measured, the content of non-newtonian fluid calcium salicylate is 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, aromatic acid The content of calcium salt be 0-15 weight %, the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 0-15 weight %.
Preferably, on the basis of the weight of lubricating grease, the content of base oil is 20-70 weight %, and non-newtonian fluid vulcanizes alkane The content of base phenol calcium is 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, non-newtonian fluid sulfoacid calcium Content is 0-50 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight %, and the content of non-newtonian fluid calcium salicylate is 0-50 weight %, the content of non-newtonian fluid calcium oleate are 0-50 weight %, and the content of the calcium salt of aromatic acid is 2-10 weight %, small point The content of the calcium salt of sub- inorganic acid and/or lower fatty acid is 2-10 weight %.
In the present invention, " optionally containing " refers to can be containing the component or without containing the component, that is, non-newtonian fluid Sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule are inorganic One of calcium salt of acid and/or lower fatty acid or it is a variety of be optional component, composite sulfuration alkyl phenol calcium Ji Run of the invention It may include the component in consistent lubricant, can not also include the component.
Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid salicylic acid Calcium, non-newtonian fluid calcium oleate or combinations thereof object are in infrared spectrum 873cm-1-886cm-1There is crystal form calcium carbonate characteristic absorption in place Peak.Non-newtonian fluid sulfurized alkylphenol calcium is converted by newton body sulfurized alkylphenol calcium, non-newtonian fluid sulfurized alkylphenol calcium Total base number be 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid sulfoacid calcium is by newton body sulfoacid calcium What conversion obtained, the total base number of non-newtonian fluid sulfoacid calcium is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non newtonian Body calcium naphthenate is converted by newton body calcium naphthenate, and the total base number of non-newtonian fluid calcium naphthenate is 250- 450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium salicylate is converted by newton body calcium salicylate, The total base number of non-newtonian fluid calcium salicylate is 250-450mgKOH/g, preferably 300-400mgKOH/g；Non-newtonian fluid calcium oleate It is to be converted by newton body calcium oleate, the total base number of non-newtonian fluid calcium oleate is 250-450mgKOH/g, preferably 300- 400mgKOH/g.And newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, newton body calcium naphthenate, newton body calcium salicylate, ox Contain unformed calcium carbonate in body calcium oleate, in infrared spectrum 860cm-1-865cm-1There is unformed calcium carbonate feature and inhales in place Receive peak.Newton body sulfurized alkylphenol calcium is synthesis sulfurized alkylphenol calcium, total base number 250-450mgKOH/g, preferably 300- 400mgKOH/g；Newton body sulfoacid calcium is calcium mahogany sulfonate and/or calcium alkylbenzenesulfonate, total base number 250-450mgKOH/g, Preferably 300-400mgKOH/g；Newton body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, total base number are 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium salicylate is salicylate calcium, and total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g；Newton body calcium oleate be natural calcium oleate and/or synthesis calcium oleate, Its total base number is 250-450mgKOH/g, preferably 300-400mgKOH/g.Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulphur The base number for the high base number material that sour calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate mix For the weight average value of the base number of each component.
In the present invention, higher fatty acids can be that carbon number is 8-20, preferably the fatty acid of 10-18 or hydroxy fatty acid, Such as can be at least one of lauric acid, palmitinic acid, stearic acid, 12- hydroxy stearic acid, eicosyl carboxylic acid, preferably 12- hydroxy stearic acid.
In the present invention, aromatic acid is the carboxylic acid that at least 1 carboxyl and aromatic ring are connected directly, and aromatic acid can be substituted or not Substituted aromatic acid, substituent group can be in alkyl, alkenyl, alkynyl, aryl, halogenated or perhalogeno alkyl or aryl etc. extremely The molecular weight of few one kind, aromatic acid is preferably smaller than equal to 550.Aromatic acid is preferably binary aromatic acid, for example, can selected from unsubstituted or The alkyl-substituted phthalic acid of C1-C5, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, in multi-joint phthalic acid extremely Few one kind.Preferably phthalic acid, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid and methyl substituted biphenyl two At least one of formic acid, multi-joint phthalic acid etc..
In the present invention, the molecular weight of small molecule inorganic acid or lower fatty acid is less than or equal to 250.Wherein, small molecule is inorganic Acid can be selected from least one of boric acid, phosphoric acid, sulfuric acid etc., preferably boric acid and/or phosphoric acid；Lower fatty acid can be selected from At least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid etc., preferably acetic acid.
In the present invention, base oil can be mineral oil, synthetic oil, vegetable oil or their mixture, 100 DEG C of dynamic viscosities For 4-150mm2/ s, preferably 10-60mm2/s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, Fischer-Tropsch Synthetic oil etc..
Various additives, such as antioxidant, extreme pressure anti-wear additives, antirust agent can also be contained in lubricating grease of the invention. Wherein, the preferred arylamine kind antioxidant of antioxidant, accounts for the 0.01-5% of lubricating grease total weight, preferably 0.1-2.5%, can be hexichol At least one of amine, phenyl-α-naphthylamine and di-iso-octyldiphenylamine, preferably di-iso-octyldiphenylamine；Extreme pressure anti-wear additives account for profit The 0.5-12% of consistent lubricant total weight, preferably 0.8-8% can be two thio Acidic phosphates zinc, two thio dialkyl amido first Sour molybdenum, two thio dialkyl amido lead formates, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenum disulfide, Polytetrafluoroethylene (PTFE), thiophosphoric acid molybdenum, chlorinated paraffin, dibutyl dithiocaarbamate antimony, tungsten disulfide, selenium disulfide, fluorination At least one of graphite, calcium carbonate and zinc oxide；Antirust agent accounts for the 0.01-4.5% of lubricating grease total weight, preferably 0.1-2%, It can be in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid at least It is a kind of.
Second aspect, the present invention provides the preparation methods of composite sulfuration alkyl phenol calcium-base grease as described above, should Method includes: to be uniformly mixed thickening agent and part basis oil, refines in 180-230 DEG C of constant temperature, surplus base oil is added, be added Necessary additive, obtains finished product, and thickening agent contains the calcium salt of non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids, thickening agent Also optionally containing non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, One of calcium salt of the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid is a variety of.
In the present invention, " optionally containing " is as previously mentioned, details are not described herein.
In the present invention, non-newtonian fluid sulfurized alkylphenol calcium, the calcium salt of higher fatty acids, non-newtonian fluid sulfoacid calcium, non newtonian Body calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or rudimentary rouge Calcium salt, base oil and the additive of fat acid are as previously mentioned, details are not described herein.
It will be understood by those skilled in the art that the sum of the amount of part basis oil and the amount of surplus base oil are used Base oil total amount, in the present invention, the weight ratio of part basis oil and surplus base oil is preferably 1:0.1-5.
For non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid bigcatkin willow Sour calcium, non-newtonian fluid calcium oleate or combinations thereof object, can be by newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, newton body ring Alkanoic acid calcium, newton body calcium salicylate, newton body calcium oleate or combinations thereof object pass through transforming agent respectively and convert to obtain, for example, by ox Pause body sulfurized alkylphenol calcium, optional newton body sulfoacid calcium, optional newton body calcium naphthenate, optional newton body salicylic acid Calcium, optional newton body calcium oleate and base oil Hybrid Heating are added required transforming agent and are reacted to 50-80 DEG C, own After transforming agent adds, 80-100 DEG C constant temperature 60-90 minutes, then heat to 110-130 DEG C of dehydration.
In the present invention, " optional " refer to can there is the raw material or no raw material, for example, " optional newton body Sulfoacid calcium ", which refers to, can this raw material of newton body sulfoacid calcium, can also not have this raw material of newton body sulfoacid calcium.
The third aspect, the present invention provides a kind of preparation method of composite sulfuration alkyl phenol calcium-base grease, this method packets It includes:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional ox will be contained Body and/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/ Or high base number material and part basis the oil mixing of non-newtonian fluid calcium oleate, obtain mixture；
(2) reaction of at least partly composite calcium is optionally carried out: addition lime or calcium hydroxide, addition higher fatty acids, Optional aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, are reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) it is warming up to 180-230 DEG C of constant temperature refining, surplus base oil is added, necessary additive is added, obtains finished product.
" optional " as previously mentioned, details are not described herein.
In the present invention, newton body sulfurized alkylphenol calcium, newton body sulfoacid calcium, non-newtonian fluid sulfoacid calcium, newton body aphthenic acids Calcium, non-newtonian fluid calcium naphthenate, newton body calcium salicylate, non-newtonian fluid calcium salicylate, newton body calcium oleate, non-newtonian fluid oleic acid Calcium, higher fatty acids, aromatic acid, small molecule inorganic acid, lower fatty acid are as previously mentioned, details are not described herein.
In step (1) of the present invention, " optional newton body and/or non-newtonian fluid sulfoacid calcium " refers to that sulfoacid calcium is optional Component, sulfoacid calcium can be newton body sulfoacid calcium, or non-newtonian fluid sulfoacid calcium.Remaining is same.
In step (2) of the present invention, " optionally carrying out the reaction of at least partly composite calcium " i.e. include three kinds of situations: (i) not Carry out the reaction of composite calcium, that is, do not have step (2), the reaction of whole composite calciums is only carried out in step (4), that is, The method of the present invention is first added transforming agent and is converted, and carries out the reaction of composite calcium after conversion again；(ii) part composite calcium is carried out Reaction carries out the reaction of part composite calcium in step (2), carries out the reaction of remaining composite calcium, i.e. phase again in step (4) When the reaction for carrying out part composite calcium before conversion in the method for the present invention, the reaction of part composite calcium is carried out again in post-conversion； (iii) reaction for carrying out whole composite calciums, i.e., carry out the reaction of whole composite calciums in step (2), without step (4), That is, the method for the present invention first carries out the reaction of composite calcium, then converted.
This field is generally transforming agent to be first added to be converted, then carry out the reaction of composite calcium when preparing lubricating grease, When such as preparing complex calcium sulfonate grease.But the present inventor has found under study for action, according to above situation (ii) or (iii) method of the invention is carried out, than carrying out method of the invention according to situation (i), i.e., is first carried out all or part of compound Calcium reaction, then converted, it can further improve the performance of lubricating grease obtained.This may be due to first carrying out composite calcium Reaction, can preferably convert the newton body sulfurized alkylphenol calcium of oily to the non-newtonian fluid sulfurized alkylphenol calcium of smectic. It is therefore preferred that carrying out the reaction of at least partly composite calcium in step (2).
When carrying out step (2) and when step (4), it is preferable that at 85-100 DEG C, addition lime or calcium hydroxide it is suspended Higher fatty acids is added in liquid, stirs 5-20 minutes, optional aromatic acid, optional small molecule inorganic acid and/or lower aliphatic is added Acid stirs 5-20 minutes.Wherein, the addition sequence of higher fatty acids and aromatic acid, small molecule inorganic acid and/or lower fatty acid can With exchange.
In the present invention, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/or lower fatty acid H+OH contained by the amount and lime of total material or the suspension of calcium hydroxide-The amount of total material is equal, OH-Amount can also be excessive 1-10%.
In the present invention, in terms of calcium hydroxide, the additional amount of the suspension of lime or calcium hydroxide is preferably high base number material The 1-15% of total weight；With H+Substance meter, higher fatty acids and optional aromatic acid and optional small molecule inorganic acid and/ Or the molar ratio of lower fatty acid is preferably 1:1-10.
In the present invention, the suspension of lime or calcium hydroxide refers to that lime or calcium hydroxide are formed suspended in water Liquid, the solid content of suspension are preferably 10-60 weight %.
In step (3) of the present invention, it is preferable that at 50-80 DEG C, required transforming agent is added in preferred constant temperature 10-30 minutes It is reacted, is stirred 8-12 minutes after preferably adding every kind of transforming agent, after all transforming agents add, in 80-100 DEG C of constant temperature 60- 90 minutes.
The transforming agent be preferably selected from fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, In phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate, aphthenic acids, C16-C24 alkyl phenol and water At least one；Be more preferably selected from the fatty alcohol of C1-C5, the fatty acid of C1-C5, the aliphatic ketone of C1-C5, C1-C5 fatty aldehyde, The fatty amine of C1-C5, the ether of C1-C5, boric acid, the alkyl phosphonic acid of C1-C10, the di alkyl phosphonic acid of C2-C16, C6-C20 aryl Phosphonic acids, the diaryl phosphonic acids of C12-C24, the aromatic alcohol of C7-C20, the aromatic amine of C7-C20, C8-C20 alkyl benzene sulphonate, cycloalkanes At least one of acid, C16-C22 alkyl phenol and water；Still more preferably it is selected from dodecyl benzene sulfonic acid, aphthenic acids, octadecane At least one of base phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water.The additional amount of transforming agent is preferably high base number object Expect the 2-30%, the more preferably 6-22% of high base number material total weight of total weight.
In the present invention, fatty alcohol includes straight chain, branch and cricoid fatty alcohol, fatty acid, aliphatic ketone, fatty aldehyde, fat Amine is similarly.
In step (5) of the present invention, it is preferable that be warming up to 110-130 DEG C, preferably remain 30-60 minutes to realize dehydration.
In step (6) of the present invention, it is preferable that be warming up to 180-230 DEG C of constant temperature 5-30 minutes；Surplus base oil is added, to Temperature is cooled to 100-120 DEG C, and necessary additive is added, stirring, circulating filtration, homogenizing, degassing.
In the present invention, the weight ratio of base oil used is preferably 1:0.1- in base oil used and step (6) in step (1) 5。
Fourth aspect, the present invention also provides composite sulfuration alkane made from the preparation method provided as third aspect present invention Base phenol calcium-base grease.
Compared with the composite sulfuration alkyl phenol calcium-base grease made from the preparation method provided as second aspect, the third aspect Composite sulfuration alkyl phenol calcium-base grease made from the preparation method of offer has better viscous resistance, mechanical stability, water resistant Property, colloid stability, abrasion resistance and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples:
Non-newtonian fluid sulfurized alkylphenol calcium, non-newtonian fluid sulfonic acid in composite sulfuration alkyl phenol calcium-base grease obtained Calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate and non-newtonian fluid calcium oleate total content vulcanized with non-newtonian fluid Alkyl phenol calcium % is indicated, that is,
Non-newtonian fluid sulfurized alkylphenol calcium %=(overbased or SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER raw material weight+superelevation alkali Value or calcium sulfonate with high base number raw material weight+overbased or overbased calcium alkyl-salicylate raw material weight+overbased or high base number water Poplar acid calcium raw material weight+overbased or high base number calcium oleate raw material weight+transforming agent total weight)/lubricating grease total weight × 100%.Transforming agent is included in non-newtonian fluid sulfurized alkylphenol calcium %.
Overbased and SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER is prepared according to patent CN101423483.
Overbased and calcium sulfonate with high base number is prepared according to the method for patent CN101928239A.
Overbased and overbased calcium alkyl-salicylate raw material is purchased from Xinjiang Land Fine Petrochemical Co., Ltd.
Aphthenic acids is purchased from Jinzhou Tie Chen petrochemical industry Co., Ltd.
High base number calcium salicylate is prepared according to the method for patent CN1345921.
High base number calcium oleate is prepared according to document (NLGI Spokeman, 2009,73 (2): 1-17) method.
Embodiment 1
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 40kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity For 11mm2/ s, 7kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 20kg, stirring is warming up to 95 DEG C, The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes；2kg 12- hydroxy stearic acid, stirring is added 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes.The HVI150BS lubricating base oil that 20kg is added is down to material 50 DEG C, constant temperature 10 minutes, 2.8kg 4- octadecylphenol is added, temperature is controlled at 50 DEG C, stirred 10 minutes；2.8kg is added Concentration is the aqueous acetic acid of 20 weight %, is stirred 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation；It is risen under stirring Temperature is kept for 45 minutes to 120 DEG C, dehydration.It is warming up to 200 DEG C of constant temperature 10 minutes, then, is cooled to 160 DEG C, is added 7kg's HVI500SN lubricating base oil；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.Fig. 1 is seen with the comparison of the infrared analysis spectrogram of the calcium carbonate in lubricating grease obtained in overbased sulfurized alkylphenol calcium raw material.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 2
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 420mgKOH/g, 24kg)；Overbased sulfoacid calcium (total base number 420mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 30kg)；4- ten Eight alkylphenols (1.8kg)；Acetic acid (0.56kg)；Boric acid (1kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acid (2kg)； Phthalic acid (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 17kg).
It in a volume is 160L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfoacid calcium of 420mgKOH/g, 24kg total base number be 420mgKOH/g overbased sulfurized alkylphenol calcium and The HVI150BS lubricating base oil of 30kg, stirring are warming up to 85 DEG C, and the calcium hydroxide suspension that solid content is 20 weight % is added 2.25kg is stirred 10 minutes；0.5kg 12- hydroxy stearic acid is added, stirs 10 minutes；0.88kg phthalic acid is added, stirs It mixes 10 minutes.At 60 DEG C, constant temperature 10 minutes；1.8kg 4- octadecylphenol is added, temperature is controlled at 60 DEG C, stirs 10 points Clock；The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes；The boric acid that 5kg concentration is 20 weight % is added Aqueous solution stirs 10 minutes；It is warming up to 85 DEG C, constant temperature 75 minutes, material retrogradation；The hydroxide that solid content is 20 weight % is added Calcium suspension 6.75kg is stirred 10 minutes；1.5kg 12- hydroxy stearic acid is added, stirs 10 minutes；2.62kg neighbour's benzene two is added Formic acid stirs 10 minutes.It is warming up to 110 DEG C under stirring, is kept for 60 minutes, dehydration.It is warming up to 180 DEG C of constant temperature 20 minutes.Then, The HVI500SN lubricating base oil of 17kg is added；100 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Inspection It tests and the results are shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of calcium phthalate Measure %.
Embodiment 3
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 6kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 24kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 20kg)；4- Octadecylphenol (1kg)；Butanol (0.8kg)；Acetic acid (0.56kg)；Boric acid (1kg)；Calcium hydroxide (1.8kg)；Stearic acid (1.9kg)；M-phthalic acid (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 28kg).
It in a volume is 160L and with 6kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER of 320mgKOH/g, 24kg total base number be 400mgKOH/g naphthenate with superhigh base number calcium and The HVI150BS lubricating base oil of 20kg, stirring are warming up to 90 DEG C, and the calcium hydroxide suspension that solid content is 20 weight % is added 9kg is stirred 10 minutes；1.9kg stearic acid is added, stirs 10 minutes；3.5kg M-phthalic acid is added, stirs 10 minutes.80 At DEG C, constant temperature 10 minutes；1kg 4- octadecylphenol and 0.8kg butanol is added, temperature is controlled at 80 DEG C, stirred 10 minutes； The aqueous acetic acid that 2.8kg concentration is 20 weight % is added, stirs 10 minutes；The boric acid water that 5kg concentration is 20 weight % is added Solution stirs 10 minutes；It is warming up to 100 DEG C, constant temperature 60 minutes, material retrogradation；It is warming up to 130 DEG C under stirring, is kept for 30 minutes, Dehydration.Being warming up to 230 DEG C, constant temperature for 5 minutes.Then, the HVI500SN lubricating base oil of 28kg is added；120 are cooled to temperature DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.3 weight % of lubricating base oil；2.3 weight % of calcium stearate；5.0 weight % of M-phthalic acid calcium.
Embodiment 4
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 6kg)；Overbased calcium salicylate (total base number 400mgKOH/g, 33kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 20kg)；4- Octadecylphenol (1.6kg)；Dodecyl benzene sulfonic acid (1.2kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxyl Base stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 28kg), right, right '-di-iso-octyldiphenylamine (0.2kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, overbased vulcanization alkane Base phenol calcium replaces with SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and overbased calcium salicylate；Transforming agent uses 4- octadecylphenol, ten Dialkyl benzene sulfonic acids and acetic acid；And 110 DEG C are cooled to temperature, pair of 0.2kg is added, right '-di-iso-octyldiphenylamine stirs It mixes 10 minutes, then circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 39.6 weight %；54.2 weight % of lubricating base oil；2 weight % of 12- hydroxy stearic acid calcium；4.0 weight % of terephthalic acid (TPA) calcium, It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.
Embodiment 5
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 24kg)；High base number calcium oleate is (total Base number is 320mgKOH/g, 6kg)；(100 DEG C of kinematic viscosity are 31mm to HVI150BS lubricating base oil2/ s, 15kg)；4- 18 Alkylphenol (1.8kg)；Aphthenic acids (total acid number 180mgKOH/g, 1.0kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity For 11mm2/ s, 7kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, overbased vulcanization alkane Base phenol calcium replaces with SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER and high base number calcium oleate；Transforming agent uses 4- octadecylphenol, aphthenic acids Calcium and acetic acid；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 54.0 weight %；35.6 weight % of lubricating base oil；3.4 weight % of 12- hydroxy stearic acid calcium；7.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 6
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 6kg)；Overbased calcium alkyl-salicylate (total base number 400mgKOH/g, 24kg)；(100 DEG C of kinematic viscosity are 41mm to full synthetic oil poly & Alpha ,-olefin oil PAO402/ s, 30kg)；4- octadecylphenol (2kg)；Dodecyl benzene sulfonic acid (0.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)； 12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；(100 DEG C of kinematic viscosity are full synthetic oil poly & Alpha ,-olefin oil PAO 10 11mm2/ s, 17kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 2, unlike, thickening agent increases high-alkali It is worth calcium naphthenate, transforming agent uses 4- octadecylphenol, dodecyl benzene sulfonic acid and acetic acid, uses full synthetic oil poly alpha olefin Oily PAO 40 and PAO 10 replaces HVI150BS and HVI500SN respectively；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 7
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 12kg)；High base number calcium salicylate (total base number 320mgKOH/g, 12kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 6kg)；HVI150BS profit (100 DEG C of kinematic viscosity are 31mm to sliding base oil2/ s, 30kg)；4- octadecylphenol (2.2kg)；(total acid number is aphthenic acids 180mgKOH/g, 0.6kg)；Acetic acid (0.56kg)；Calcium hydroxide (2.2kg)；12- hydroxy stearic acid (10kg)；2- methyl-1, 4- phthalic acid (2.2kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 20kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, overbased vulcanization alkane Base phenol calcium replaces with SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, high base number calcium salicylate and naphthenate with superhigh base number calcium；Transforming agent uses 4- Octadecylphenol, aphthenic acids and acetic acid；Using 2- methyl-1,4- phthalic acid replaces terephthalic acid (TPA)；The dosage of each ingredient As above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 34.5 weight %；51.7 weight % of lubricating base oil；11.0 weight % of 12- hydroxy stearic acid calcium；2- methyl-1,4- phthalic acid 2.8 weight % of calcium.
Embodiment 8
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 10kg)；Overbased sulfoacid calcium (total base number 400mgKOH/g, 10kg)；Naphthenate with superhigh base number calcium (total base number 400mgKOH/g, 10kg)；HVI150BS (100 DEG C of kinematic viscosity are 31mm to lubricating base oil2/ s, 30kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Hydrogen Calcium oxide (1.8kg)；12- hydroxy stearic acid (2kg)；4,4'- biphenyl dicarboxylic acid (5.1kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity are 11mm2/ s, 20kg), right, right '-di-iso-octyldiphenylamine (0.2kg)；Two thio dibutylamino first Sour molybdenum (4kg)；Selenium disulfide (4kg)；Benzotriazole (0.4kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, thickening agent increases superelevation Base number calcium sulfonate and naphthenate with superhigh base number calcium；Terephthalic acid (TPA) is replaced using 4,4'- biphenyl dicarboxylic acid；And it is cooling to temperature To 110 DEG C, pair of 0.2kg is added, right '-di-iso-octyldiphenylamine stirs 10 minutes, the two thio dibutylaminos of 4kg are added Formic acid molybdenum stirs 10 minutes, and the selenium disulfide of 4kg is added, and stirs 10 minutes, and the benzotriazole of 0.4kg is added, and stirs 10 points Clock, then circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 33.4 weight %；50.0 weight % of lubricating base oil；2.1 weight % of 12- hydroxy stearic acid calcium；4,4'- biphenyl dicarboxylic acid calcium 5.9 Weight %；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine；Two thio 4.0 weight % of dibutylamino formic acid molybdenum；Curing 4.0 weight % of selenium；0.4 weight % of benzotriazole.
Embodiment 9
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 320mgKOH/g, 4kg)；Non-newtonian fluid high base number sulphur Sour calcium (20kg)；High base number calcium oleate (total base number 320mgKOH/g, 6kg)；(the 100 DEG C of movements of HVI150BS lubricating base oil Viscosity is 31mm2/ s, 15kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxyl Base stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；(100 DEG C of kinematic viscosity are 11mm to HVI500SN lubricating base oil2/ s, 32kg)。
The preparation of non-newtonian fluid calcium sulfonate with high base number: in a volume being 30L and with heating, stirring, circulation, cooling 100 DEG C of kinematic viscosity of calcium sulfonate with high base number and 5kg that 12kg total base number is 350mgKOH/g are added in normal-pressure reaction kettle is 31mm2The HVI150BS lubricating base oil of/s, stirring, heats to 80 DEG C, constant temperature 10 minutes；2.5kg dodecyl is added Benzene sulfonic acid, temperature are controlled at 80 DEG C or so, are stirred 10 minutes；The acetic acid and 4 times of acetic acid weight of aqueous solution of 0.5kg is added, stirs It mixes 10 minutes；85 DEG C are warming up to, constant temperature 90 minutes, it is spare to obtain non-newtonian fluid sulfoacid calcium at smectic for material retrogradation.
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, overbased vulcanization alkane Base phenol calcium replaces with the non-newtonian fluid calcium sulfonate with high base number and high base number calcium oleate of SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, preparation；Respectively at The dosage divided is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 10
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER (total base number 360mgKOH/g, 10kg)；Calcium sulfonate with high base number is (total Base number is 360mgKOH/g, 8kg)；Overbased calcium alkyl-salicylate (total base number 360mgKOH/g, 4kg)；High base number calcium oleate is (total Base number is 360mgKOH/g, 4kg)；High base number calcium salicylate (total base number 360mgKOH/g, 4kg)；HVI150BS lubrication base (100 DEG C of kinematic viscosity are 31mm to oil2/ s, 30kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (4.2kg)；12- hydroxy stearic acid (2kg)；Boric acid (2.32kg)；Ethanedioic acid (3.02kg)；HVI500SN lubricating base oil (100 DEG C kinematic viscosity is 11mm2/ s, 15kg), right, right '-di-iso-octyldiphenylamine (0.2kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, overbased vulcanization alkane Base phenol calcium replaces with SULFURIZED CALCIUM ALKYL PHENATE WITH HIGH BASE NUMBER, calcium sulfonate with high base number, overbased calcium alkyl-salicylate, high base number calcium salicylate and height Base number calcium oleate；12- hydroxy stearic acid is being added, stirring after ten minutes, is added boric acid, stirs 10 minutes, then add second Diacid stirs 10 minutes；And 110 DEG C are cooled to temperature, pair of 0.2kg, right '-di-iso-octyldiphenylamine, stirring 10 is added Minute, then circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.2 weight %；51.5 weight % of lubricating base oil；2.5 weight % of 12- hydroxy stearic acid calcium；2.7 weight % of line borate；Second two Sour 4.9 weight % of calcium；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.
Embodiment 11
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 2kg)；High base number calcium salicylate (total base number 360mgKOH/g, 8kg)；Overbased calcium oleate (total base number 400mgKOH/g, 20kg)；HVI150BS lubrication (100 DEG C of kinematic viscosity are 31mm to base oil2/ s, 30kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Hydroxide Calcium (3kg)；12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；Acetic acid (2kg)；HVI500SN lubricating base oil (100 DEG C kinematic viscosity is 11mm2/ s, 14kg), right, right '-di-iso-octyldiphenylamine (0.2kg).
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, use three kinds of high base numbers Raw material, i.e. thickening agent increase high base number calcium salicylate and overbased calcium oleate；And terephthalic acid (TPA) is being added, is stirring 10 points Acetic acid is added in Zhong Hou, stirs 10 minutes；And 110 DEG C are cooled to temperature, pair of 0.2kg, right '-diisooctyl hexichol is added Amine stirs 10 minutes, and then circulating filtration, homogenizing, degassing obtain finished product；The dosage of each ingredient is as above.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.5 weight %；50.8 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %；3.1 weight % of calcium acetate；It is right, right ' 0.2 weight % of-di-iso-octyldiphenylamine.
Embodiment 12
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 40kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity For 11mm2/ s, 7kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 20kg, stirring is heated to 50 DEG C, constant temperature 10 minutes；2.8kg4- octadecylphenol is added, temperature is controlled at 50 DEG C, stirred 10 minutes；It is dense that 2.8kg is added Degree is the aqueous acetic acid of 20 weight %, is stirred 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material retrogradation.
It in another volume is 50L and with 3kg is added in heating, stirring, circulation, cooling normal-pressure reaction kettle The calcium hydroxide suspension 9kg that solid content is 20 weight % is added at 100 DEG C, stirs 10 points for HVI500SN lubricating base oil Clock；2kg 12- hydroxy stearic acid is added, stirs 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes, obtains 12- hydroxyl Base calcium stearate and terephthalic acid (TPA) calcium.
Resulting 12- hydroxy stearic acid calcium and terephthalic acid (TPA) calcium are all squeezed into a upper kettle, stirred evenly, is stirred Under be warming up to 120 DEG C, kept for 45 minutes, dehydration is finally warming up to 200 DEG C of constant temperature 10 minutes.Then, 160 DEG C are cooled to, is added Remaining HVI500SN lubricating base oil；110 DEG C are cooled to temperature, circulating filtration, homogenizing, degassing obtain finished product.Examine knot Fruit is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 13
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Raw material components: overbased sulfurized alkylphenol calcium (total base number 400mgKOH/g, 30kg)；HVI150BS lubricates base (100 DEG C of kinematic viscosity are 31mm to plinth oil2/ s, 40kg)；4- octadecylphenol (2.8kg)；Acetic acid (0.56kg)；Calcium hydroxide (1.8kg)；12- hydroxy stearic acid (2kg)；Terephthalic acid (TPA) (3.5kg)；HVI500SN lubricating base oil (100 DEG C of kinematic viscosity For 11mm2/ s, 7kg).
It in a volume is 160L and with 30kg total base number is added in heating, stirring, circulation, cooling normal-pressure reaction kettle For the overbased sulfurized alkylphenol calcium of 400mgKOH/g and the HVI150BS lubricating base oil of 40kg, stirring is warming up to 50 DEG C, Constant temperature 10 minutes, 2.8kg 4- octadecylphenol is added, temperature is controlled at 50 DEG C, stirred 10 minutes；2.8kg concentration, which is added, is The aqueous acetic acid of 20 weight % stirs 10 minutes；It is warming up to 80 DEG C, constant temperature 90 minutes, material slightly retrogradation；100 DEG C are warming up to, The calcium hydroxide suspension 9kg that solid content is 20 weight % is added, stirs 10 minutes；2kg 12- hydroxy stearic acid, stirring is added 10 minutes；3.5kg terephthalic acid (TPA) is added, stirs 10 minutes.It is warming up to 120 DEG C under stirring, is kept for 45 minutes, dehydration.Heating To 200 DEG C constant temperature 10 minutes, then, be cooled to 160 DEG C, the HVI500SN lubricating base oil of 7kg be added；It is cooled to temperature 110 DEG C, circulating filtration, homogenizing, degassing obtain finished product.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Embodiment 14
The present embodiment is for illustrating composite sulfuration alkyl phenol calcium-base grease prepared by the present invention.
Composite sulfuration alkyl phenol calcium-base grease is prepared according to the method for embodiment 1, unlike, by 4- octadecyl benzene Phenol replaces with butanone, and acetic acid is replaced with ethylene glycol monobutyl ether.Inspection result is shown in Table 1.
In the lubricating grease that the present embodiment obtains, on the basis of lubricating grease weight, composition are as follows: non-newtonian fluid sulfurized alkylphenol calcium 38.4 weight %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight of terephthalic acid (TPA) calcium Measure %.
Comparative example 1
Complex calcium sulfonate grease is prepared according to the method for embodiment 1, unlike, overbased sulfurized alkylphenol calcium It is replaced with total base number by the overbased sulfoacid calcium of 400mgKOH/g, obtained each performance data of lubricating grease finished product is shown in Table 1.
In the lubricating grease that this comparative example obtains, on the basis of lubricating grease weight, composition are as follows: 38.4 weight of non-newtonian fluid sulfoacid calcium Measure %；54.2 weight % of lubricating base oil；2.4 weight % of 12- hydroxy stearic acid calcium；5.0 weight % of terephthalic acid (TPA) calcium.
Each lubricating grease properties of sample data of table 1
Each indication test method: dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: GB/T 269；It is rotten Erosion: GB/T 7326；Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant It is spraying: SH/T0643；Stencil oil-dividing: SH/T 0324；Surface hardened layer value: 0370 appendix A of SH/T；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202.
Each lubricating grease properties of sample data of 1 (Continued) of table
Each indication test method: dropping point: GB/T 3498；Work cone penetration and extension work cone penetration: GB/T 269；It is rotten Erosion: GB/T 7326；Anticorrosive property: GB/T 5018；Water drenches number of dropouts: SH/T 0109；Salt spray test: SH/T 0081；Water resistant It is spraying: SH/T0643；Stencil oil-dividing: SH/T 0324；Surface hardened layer value: 0370 appendix A of SH/T；Coefficient of friction: SH/T 0721；Tetra-ball machine test: SH/T 0202.
It will be understood by those skilled in the art that work cone penetration is smaller, grease thickening performance is better；Extend work The difference for making cone penetration and the cone penetration that works is smaller, and the mechanical stability of lubricating grease can be better；Water leaching number of dropouts is smaller, lubricating grease Water-resistance it is better；Salt spray test higher grade, and the antirust and anticorrosive property of lubricating grease are better；Water resistant is worth smaller, lubrication by spraying The adhesiveness and water-resistance of rouge are better；Stencil oil-dividing value is smaller, and the colloid stability of lubricating grease is better；Surface hardened layer value it is absolute It is worth smaller, the storage stability of lubricating grease is better；Coefficient of friction is smaller, and the abrasion resistance of lubricating grease is better；PB, PD value are bigger, The extreme pressure anti-wear of lubricating grease is better.
Embodiment 1 and comparative example 1, which are compared, can be seen that composite sulfuration alkyl phenol calcium-base grease of the invention Antirust and anticorrosive property, storage stability are substantially better than complex calcium sulfonate grease.Moreover, composite sulfuration alkyl of the invention Phenol calcium-base grease have better than the viscous resistance of complex calcium sulfonate grease, mechanical stability, water-resistance, colloid stability, Abrasion resistance and extreme pressure anti-wear.Moreover, composite sulfuration alkyl phenol calcium-base grease of the invention also has excellent high temperature resistant Property.
Embodiment 1 and embodiment 12 are compared as can be seen that the composite sulfuration alkyl phenol calcium base being prepared in situ lubricates Rouge has better viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance and extreme pressure anti-wear；It will implement Example 1, which is compared as can be seen that first carrying out composite calcium with embodiment 12, embodiment 13, reacts, then is converted, obtained compound Sulfenyl phenolate calcium-base grease have better viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance and Extreme pressure anti-wear；Embodiment 1 and embodiment 14 are compared as can be seen that transforming agent is selected from dodecyl benzene sulfonic acid, cycloalkanes At least one of acid, octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, composite sulfuration alkyl phenol obtained Calcium-base grease has better viscous resistance, mechanical stability, water-resistance, colloid stability, abrasion resistance and extreme-pressure anti-wear Property.
Composite sulfuration alkyl phenol calcium-base grease of the invention has quite even more excellent with complex calcium sulfonate grease Good antirust and anticorrosive property, and there is excellent storage stability, also there is the thickening better than complex calcium sulfonate grease Property, mechanical stability, water-resistance, colloid stability, abrasion resistance and extreme pressure anti-wear, and also there is excellent heat-resisting quantity etc. Performance.The feed preparation process of lubricating grease of the invention is simple and environmentally-friendly, stable product quality.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (22)

1. a kind of composite sulfuration alkyl phenol calcium-base grease, the lubricating grease contain base oil and thickening agent, which is characterized in that institute The calcium salt that thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids is stated, the thickening agent also optionally contains non-ox Body sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule One of calcium salt of inorganic acid and/or lower fatty acid is a variety of, and on the basis of the weight of the lubricating grease, base oil contains Amount is 10-80 weight %, and the content of non-newtonian fluid sulfurized alkylphenol calcium is 10-70 weight %, and the calcium salt of higher fatty acids contains Amount is 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-70 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-70 Weight %, the content of non-newtonian fluid calcium salicylate are 0-70 weight %, and the content of non-newtonian fluid calcium oleate is 0-70 weight %, virtue The content of the calcium salt of acid is 0-15 weight %, and the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is that 0-15 is weighed Measure %.
2. lubricating grease according to claim 1, wherein on the basis of the weight of the lubricating grease, the content of base oil is The content of 20-70 weight %, non-newtonian fluid sulfurized alkylphenol calcium are 20-65 weight %, and the content of the calcium salt of higher fatty acids is 2-15 weight %, the content of non-newtonian fluid sulfoacid calcium are 0-50 weight %, and the content of non-newtonian fluid calcium naphthenate is 0-50 weight % is measured, the content of non-newtonian fluid calcium salicylate is 0-50 weight %, and the content of non-newtonian fluid calcium oleate is 0-50 weight %, aromatic acid The content of calcium salt be 2-10 weight %, the content of the calcium salt of small molecule inorganic acid and/or lower fatty acid is 2-10 weight %.
3. lubricating grease according to claim 1 or 2, wherein the non-newtonian fluid sulfurized alkylphenol calcium is by newton body sulphur Change what alkyl phenol calcium converted, the total base number of the non-newtonian fluid sulfurized alkylphenol calcium is 250-450mgKOH/g；It is described non- Newton body sulfoacid calcium is converted by newton body sulfoacid calcium, and the total base number of the non-newtonian fluid sulfoacid calcium is 250- 450mgKOH/g；The non-newtonian fluid calcium naphthenate is converted by newton body calcium naphthenate, the non-newtonian fluid cycloalkanes The total base number of sour calcium is 250-450mgKOH/g；The non-newtonian fluid calcium salicylate is to convert to obtain by newton body calcium salicylate , the total base number of the non-newtonian fluid calcium salicylate is 250-450mgKOH/g；The non-newtonian fluid calcium oleate is by newton body What calcium oleate converted, the total base number of the non-newtonian fluid calcium oleate is 250-450mgKOH/g.
4. lubricating grease according to claim 1 or 2, wherein the higher fatty acids is the fatty acid that carbon number is 8-20.
5. lubricating grease according to claim 4, wherein the higher fatty acids be selected from lauric acid, palmitinic acid, stearic acid, At least one of 12- hydroxy stearic acid, eicosyl carboxylic acid.
6. lubricating grease according to claim 1 or 2, wherein the aromatic acid is substituted or unsubstituted aromatic acid, substituent group For at least one of alkyl, alkenyl, alkynyl, aryl and halogenated alkyl or aryl, the molecular weight of the aromatic acid is less than or equal to 550。
7. lubricating grease according to claim 6, wherein the halogenated alkyl or aryl is the alkyl or virtue of perhalogeno Base.
8. lubricating grease according to claim 6, wherein the aromatic acid is selected from unsubstituted or C1-C5Alkyl-substituted neighbour's benzene At least one of dioctyl phthalate, M-phthalic acid, terephthalic acid (TPA), biphenyl dicarboxylic acid, multi-joint phthalic acid.
9. lubricating grease according to claim 1 or 2, wherein point of the small molecule inorganic acid and the lower fatty acid Son amount is less than or equal to 250.
10. lubricating grease according to claim 9, wherein the small molecule inorganic acid is in boric acid, phosphoric acid, sulfuric acid At least one, the lower fatty acid are selected from least one of acetic acid, ethanedioic acid, propionic acid, malonic acid, butyric acid, succinic acid.
11. the preparation method of composite sulfuration alkyl phenol calcium-base grease, this method described in any one of claim 1-10 Include: to be uniformly mixed thickening agent and part basis oil, refined in 180-230 DEG C of constant temperature, surplus base oil is added, is added necessary Additive, obtain finished product, which is characterized in that the thickening agent contains non-newtonian fluid sulfurized alkylphenol calcium and higher fatty acids Calcium salt, the thickening agent also optionally containing non-newtonian fluid sulfoacid calcium, non-newtonian fluid calcium naphthenate, non-newtonian fluid calcium salicylate, Non-newtonian fluid calcium oleate, the calcium salt of aromatic acid, small molecule inorganic acid and/or lower fatty acid one of calcium salt or a variety of.
12. a kind of preparation method of composite sulfuration alkyl phenol calcium-base grease, which is characterized in that this method comprises:
(1) newton body sulfurized alkylphenol calcium, optional newton body and/or non-newtonian fluid sulfoacid calcium, optional newton body will be contained And/or non-newtonian fluid calcium naphthenate, optional newton body and/or non-newtonian fluid calcium salicylate and optional newton body and/or non- The high base number material and part basis oil of newton body calcium oleate mix, and obtain mixture；
(2) it optionally carries out the reaction of at least partly composite calcium: lime or calcium hydroxide is added, higher fatty acids, optionally is added Aromatic acid, optional small molecule inorganic acid and/or lower fatty acid, reacted；
(3) transforming agent is added, heats up to material retrogradation；
(4) reaction of remaining composite calcium is carried out；
(5) heating dehydration；
(6) it is warming up to 180-230 DEG C of constant temperature refining, surplus base oil is added, necessary additive is added, obtains finished product, with institute On the basis of the weight for obtaining finished product, the content of base oil is 10-80 weight %, and the content of non-newtonian fluid sulfurized alkylphenol calcium is 10- 70 weight %, the content of the calcium salt of higher fatty acids are 1-20 weight %, and the content of non-newtonian fluid sulfoacid calcium is 0-70 weight %, The content of non-newtonian fluid calcium naphthenate is 0-70 weight %, and the content of non-newtonian fluid calcium salicylate is 0-70 weight %, non newtonian The content of body calcium oleate is 0-70 weight %, and the content of the calcium salt of aromatic acid is 0-15 weight %, small molecule inorganic acid and/or rudimentary The content of the calcium salt of fatty acid is 0-15 weight %.
13. preparation method according to claim 12, wherein in step (2), carry out the reaction of at least partly composite calcium.
14. preparation method according to claim 12 or 13, wherein in step (2) and step (4), at 85-100 DEG C, It the suspension of lime or calcium hydroxide is added, higher fatty acids is added, stirs 5-20 minute, optional aromatic acid, optionally is added Small molecule inorganic acid and/or lower fatty acid stir 5-20 minutes.
15. preparation method according to claim 12 or 13, wherein in step (3), at 50-80 DEG C, be added required Transforming agent is reacted, after all transforming agents add, 80-100 DEG C constant temperature 60-90 minutes.
16. preparation method according to claim 12 or 13, wherein in step (5), be warming up to 110-130 DEG C of dehydration.
17. preparation method according to claim 12 or 13, wherein in step (6), be warming up to 180-230 DEG C of constant temperature 5- 30 minutes, be added surplus base oil, be cooled to 100-120 DEG C to temperature, necessary additive be added, stir, circulating filtration, Change, degassing.
18. preparation method according to claim 12 or 13, wherein the newton body sulfurized alkylphenol calcium is synthesis vulcanization Alkyl phenol calcium, the total base number of the newton body sulfurized alkylphenol calcium are 250-450mgKOH/g；The newton body sulfoacid calcium is stone Oily sulfoacid calcium and/or calcium alkylbenzenesulfonate, the total base number of the newton body sulfoacid calcium are 250-450mgKOH/g；The newton body ring Alkanoic acid calcium is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and the total base number of the newton body calcium naphthenate is 250- 450mgKOH/g；The newton body calcium salicylate is salicylate calcium, and the total base number of the newton body calcium salicylate is 250- 450mgKOH/g；The newton body calcium oleate is natural calcium oleate and/or synthesis calcium oleate, the total alkali of the newton body calcium oleate Value is 250-450mgKOH/g.
19. preparation method according to claim 12 or 13, wherein the transforming agent is selected from fatty alcohol, fatty acid, fat Ketone, fatty aldehyde, fatty amine, ether, calcium carbonate, boric acid, phosphonic acids, carbon dioxide, phenol, aromatic alcohol, aromatic amine, C8-C20Alkylbenzene Sulfonic acid, aphthenic acids, C16-C24At least one of alkyl phenol and water, the additional amount of transforming agent are to contain newton body sulfenyl phenolate Calcium, optional newton body sulfoacid calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate and optional newton body The 2-30% of the high base number material total weight of calcium oleate.
20. preparation method according to claim 19, wherein the transforming agent be selected from dodecyl benzene sulfonic acid, aphthenic acids, At least one of octadecyl phenol, methanol, isopropanol, butanol, boric acid, acetic acid and water, the additional amount of transforming agent are to contain ox Pause body sulfurized alkylphenol calcium, optional newton body sulfoacid calcium, optional newton body calcium naphthenate, optional newton body calcium salicylate With the 6-22% of the high base number material total weight of optional newton body calcium oleate.
21. composite sulfuration alkyl phenol calcium-base grease made from the method as described in any one of claim 12-20.
22. lubricating grease according to claim 4, wherein the higher fatty acids is the hydroxy fatty acid that carbon number is 8-20.
CN201510105354.7A 2015-03-11 2015-03-11 A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof Active CN106032483B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510105354.7A CN106032483B (en) 2015-03-11 2015-03-11 A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510105354.7A CN106032483B (en) 2015-03-11 2015-03-11 A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106032483A CN106032483A (en) 2016-10-19
CN106032483B true CN106032483B (en) 2019-01-08

Family

ID=57150292

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510105354.7A Active CN106032483B (en) 2015-03-11 2015-03-11 A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106032483B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106590814B (en) * 2016-12-05 2019-11-19 新乡市瑞丰新材料股份有限公司 A kind of preparation method of calcium sulfonate complex grease
CN107502418B (en) * 2017-08-01 2020-01-31 太原理工大学 Environment-friendly layered potassium magnesium calcium phosphate grease and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181619A (en) * 1978-10-30 1980-01-01 Mobil Oil Corporation Antiwear composition
WO2002012418A3 (en) * 2000-08-10 2002-04-25 Shell Int Research Grease composition with improved rust prevention and abrasion resistance properties
CN101423483A (en) * 2008-06-20 2009-05-06 辽宁天合精细化工股份有限公司 High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN103627496A (en) * 2012-08-28 2014-03-12 中国石油化工股份有限公司 Composite calcium naphthenate-based lubricating grease and preparation method therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181619A (en) * 1978-10-30 1980-01-01 Mobil Oil Corporation Antiwear composition
WO2002012418A3 (en) * 2000-08-10 2002-04-25 Shell Int Research Grease composition with improved rust prevention and abrasion resistance properties
CN101423483A (en) * 2008-06-20 2009-05-06 辽宁天合精细化工股份有限公司 High basic value (TBN400) sulfurized calcium alkyl and preparation method thereof
CN102453598A (en) * 2010-10-22 2012-05-16 中国石油化工股份有限公司 Composite calcium sulfonate-based octaurea lubricating grease, and preparation method thereof
CN103627496A (en) * 2012-08-28 2014-03-12 中国石油化工股份有限公司 Composite calcium naphthenate-based lubricating grease and preparation method therefor

Also Published As

Publication number Publication date
CN106032483A (en) 2016-10-19

Similar Documents

Publication Publication Date Title
CN106032488B (en) Lubricant composition and preparation method thereof
CN106032486B (en) Lubricant composition and preparation method thereof
CN106032483B (en) A kind of composite sulfuration alkyl phenol calcium-base grease and preparation method thereof
CN106032482B (en) Lubricant composition and preparation method thereof
CN104449959B (en) A kind of high base number complex calcium lubricating grease and preparation method thereof
CN106032485B (en) Lubricant composition and preparation method thereof
CN106032478B (en) Lubricant composition and preparation method thereof
CN104450111B (en) A kind of complex calcium sulfonate calcium naphthenate base grease and preparation method thereof
CN106032479B (en) Lubricant composition and preparation method thereof
CN106032480B (en) Lubricant composition and preparation method thereof
CN106032487B (en) Lubricant composition and preparation method thereof
CN106032484B (en) Lubricant composition and preparation method thereof
CN104293449B (en) A kind of Composite calcium naphthenate base grease and preparation method thereof
CN104560276B (en) A kind of complex calcium sulfonate calcium naphthenate zirconium base lubricating grease and preparation method thereof
CN106032481B (en) Lubricant composition and preparation method thereof
CN104450109B (en) A kind of polyurea grease of high base number composite calcium-base four and preparation method thereof
CN106032477B (en) Lubricant composition and preparation method thereof
CN104449956B (en) A kind of high base number composite calcium-base polyurea grease and preparation method thereof
CN104293452B (en) A kind of Composite calcium naphthenate base polyurea grease and preparation method thereof
CN104212611B (en) A kind of Calcium naphthenate base polyurea grease and preparation method thereof
CN104450113B (en) A kind of high base number composite calcium-base octa-polyurea lubricating grease and preparation method thereof
CN104450112B (en) A kind of polyurea grease of high base number composite calcium-base six and preparation method thereof
CN104293451B (en) A kind of Composite calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof
CN104560270B (en) A kind of polyurea grease of complex calcium sulfonate calcium naphthenate zirconium base four and preparation method thereof
CN104449958B (en) A kind of complex calcium sulfonate calcium naphthenate base octa-polyurea lubricating grease 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
GR01 Patent grant
GR01 Patent grant