CN108463542A

CN108463542A - The method for preparing grease of calcium sulfonic acid using the non-aqueous transforming agent of delay addition

Info

Publication number: CN108463542A
Application number: CN201680078416.2A
Authority: CN
Inventors: 安德鲁·J·韦尼克
Original assignee: NCH Corp
Current assignee: NCH Corp
Priority date: 2016-01-07
Filing date: 2016-12-14
Publication date: 2018-08-28
Anticipated expiration: 2036-12-14
Also published as: CN108463542B; WO2017119999A1; EP3400279A4; EP3400279A1

Abstract

A method of the high alkaline calcium sulfonate lubricating grease of the high alkaline calcium sulfonate comprising decrement, water and at least one non-aqueous transforming agent being prepared, wherein the non-aqueous transforming agent of addition at least part after one or more period of delays of the addition of opposite water.Period of delay can be related to adjusting the period needed for the temperature of mixture, period during holding the mixture in certain temperature or temperature range and its multiple and any combinations.With compared with the lubricating grease for adding substantially similar composition prepared by the in the case of of not having delay between water and non-aqueous transforming agent, these grease of calcium sulfonic acid have improved thickener yield and high dropping point, particularly when using high alkaline calcium sulfonate inferior.

Description

The method for preparing grease of calcium sulfonic acid using the non-aqueous transforming agent of delay addition

The citation of related application

This application claims the priority for the Application U.S. Serial No 14/990,473 that on January 7th, 2016 submits, this application is The part continuation application for the Application U.S. Serial No 13/664,574 and 13/664,768 that on October 31st, 2012 submits, and two Person is required to the equity for the U.S.Provisional Serial 61/553,674 that on October 31st, 2012 submits.

1. technical field

The present invention relates to high alkalinity (overbased, the parlkaline) sulfoacid calciums prepared by postponing the non-aqueous transforming agent of addition Lubricating grease (grease, lubricating oil, grease) and the method for manufacturing this lubricating grease, to provide thickener yield The improvement of (thickener yield) and the expection high temperature effectiveness such as proved by dropping point (dropping point), even if working as When oil-soluble high alkaline calcium sulfonate for manufacturing lubricating grease is considered of poor quality.

2. background technology

High alkaline calcium sulfonate lubricating grease lubricating grease classification always set for many years.Manufacture one kind of this lubricating grease Perception method is to be related to " promoting " and the two-step method of " conversion " step.In general, the first step (" promotion ") is the chemistry made as alkali source Measure excessive calcium oxide (CaO) or calcium hydroxide (Ca (OH)₂) and alkyl benzene sulphonate, carbon dioxide (CO₂) and and other components Reaction is to generate the oil-soluble high alkaline calcium sulfonate for being dispersed with amorphous calcium carbonate wherein.These high alkalinity oil-soluble sulfonic acid calcium Normally transparent and bright, has Newtonian rheology.In some cases, they may be slightly muddy, but this variation and there is no harm in Them are hindered to be used to prepare high alkaline calcium sulfonate lubricating grease.For purposes of this disclosure, term " high alkalinity oil-soluble sulfonic acid calcium " and " oil-soluble high alkaline calcium sulfonate " and " high alkaline calcium sulfonate " refer to any high alkalinity sulphur for being suitable for preparing grease of calcium sulfonic acid Sour calcium.Typically, second step (" conversion ") is to promoting the product of step to add one or more transforming agents such as propylene glycol, different Propyl alcohol, water, formic acid or acetic acid are together with suitable base oil (e.g., mineral oil) (if necessary) to keep initial lubricating grease less Firmly, amorphous calcium carbonate is converted to the crystalline calcium carbonate of superfine dispersion.When using acetic acid or other acid as transforming agent, Generally also use water and another non-aqueous transforming agent (third transforming agent, such as alcohol)；Alternatively, water is only added (without third to turn Agent), but then convert and usually occur in pressurizing vessel.It is high-alkali to realize due to the use of excessive calcium hydroxide or calcium oxide Change, thus a small amount of residual oxygen calcium or calcium hydroxide can also be used as oil-soluble high alkaline calcium sulfonate a part exist and It will be dispersed in initial grease structure.The crystal type of calcium carbonate is preferably calcite.This superfine dispersion calcium carbonate ( Referred to as aqueous colloidal dispersion) it is interacted with sulfoacid calcium to form greasy consistency.This high alkalinity produced by two-step method Grease of calcium sulfonic acid be referred to as " simple grease of calcium sulfonic acid (and simple calcium sulfonate grease, it is single Grease of calcium sulfonic acid) ", and it is disclosed in such as U.S. Patent number 3,242,079,3,372,115；3,376,222、3,377,283、 With 3,492,231.

In the prior art it is also known that the two steps are combined into a step by carefully controlling reaction.In the one-step method In, in carbon dioxide and functions simultaneously as accelerating agent and (generate reacting by carbon dioxide and excessive calcium oxide or calcium hydroxide Both and the amorphous calcium carbonate of high alkalization) and transforming agent (crystalline calcium carbonate for converting amorphous calcium carbonate to superfine dispersion) Reagent system in the presence of, moistened to prepare simple sulfoacid calcium by sulfonic acid appropriate and calcium hydroxide or reacting for calcium oxide Consistent lubricant.Therefore, greasy consistency, wherein high alkalinity oil-soluble sulfonic acid calcium (first in two-step method are formed in one step The product of step) it is actually never formed and is detached as individual product.The one-step method is disclosed in for example, U.S. Patent number 3, 661,622,3,671,012,3,746,643 and 3,816,310.

Other than simple grease of calcium sulfonic acid, sulfoacid calcium complex grease is also known in the prior art.Usually By adding strong calcic alkali such as calcium hydroxide or oxidation into the simple grease of calcium sulfonic acid generated by two-step method or one-step method Calcium, and with the Compound-acid of up to stoichiometric equivalents (complexing acid, complex acid) such as 12- hydroxy stearic acids, boron Acid, acetic acid (it can also be transforming agent when being added before conversion) or phosphatase reaction prepare these complex greases.Sulfoacid calcium Complex grease includes sticky reduction, pumping raising and the raising of high temperature effectiveness better than the advantages of report of simple lubricating grease. Sulfoacid calcium complex grease is disclosed in for example, U.S. Patent number 4,560,489,5,126,062,5,308,514 and 5,338, In 467.

Many knowns using two-step method teach while heating and usually add before heating All transforming agents (water and non-aqueous transforming agent).However, some prior art references are disclosed in addition water and are added at least Time interval (although always define unclear or do not define at all) between partial one or more non-aqueous transforming agents.Example Such as, U.S. Patent number 4,560,489 disclose a kind of method (embodiment 1-3), wherein base oil and high alkalinity calcium carbonate are added Then heat adds water to about 150 °F, then before addition acetic acid and methyl cellosolve (the high toxicity monomethyl ether of ethylene glycol) Heat the mixture to about 190 °F.Obtained lubricating grease contains the high alkaline calcium sulfonate more than 38%, and ' 489 patents refer to Go out, disclosed in the desired quantity of high alkaline calcium sulfonate of method be about 41-45%, because according to ' 489 patent uses be less than 38% generates soft grease.The gained lubricating grease of embodiment 1 in ' 489 patents has only about 570 °F of dropping point.' 489 patents Do not illustrate to add the period of delay between water and the non-aqueous transforming agent of addition, but shows be heated to the just time of 190F from 150F It is added immediately after section.Dropping point and thickener yield in ' 489 patents are worthless.

Made using aliphatic acid such as 12- hydroxy stearic acids in addition, U.S. Patent number 5,338,467 and 5,308,514 is disclosed For the transforming agent being used together with methanol with acetic acid, wherein addition aliphatic acid does not postpone, but in addition water and addition acetic acid and There are some time intervals between methanol.The embodiment 1 in embodiment B and ' 467 patents in ' 514 patents all describes a kind of side Method is then adding wherein water and aliphatic acid transforming agent are added in other compositions (including high alkaline calcium sulfonate and base oil) It is heated to about 140-145 °F before adding acetic acid then to add methanol.Then, about 150-160 °F is heated the mixture to until turning Change and completes.The amount of the high alkaline calcium sulfonate in final grease product in two kinds of embodiments is 32.2, this is than desired It is high.These patents do not illustrate to add the period of delay between water and aliphatic acid and addition acetic acid and methanol, but show not specified Heating time after add immediately.Similar side is disclosed in the embodiment A and the embodiment C of ' 514 patents of ' 467 patents Method, other than adding all aliphatic acid after being to convert, therefore the non-aqueous transforming agent being used only is by mixture and water It is heated to the acetic acid and methanol that are added after 140-145F together.In these embodiments, the amount of high alkaline calcium sulfonate even compares Previous embodiment is high by 40%.Other than ideal thickener yield results are not achieved, all these methods all use methanol As transforming agent, this is with environmental gap.These ingredients may be caused to be discharged into air using volatility alcohol as transforming agent, Latter portions as the lubricating grease manufacturing process that many areas in the world are forbidden.If do not discharged, must by washing or Water knockout drum (water trap) recycles alcohol, this leads to detoxication cost.Better thickener is obtained therefore, it is necessary to a kind of The method of yield preferably need not use volatility alcohol as transforming agent.

Better thickener yield is obtained in the embodiment 10 of ' 514 patents, but the use of superfluous lime is considered as obtaining The requirement of these results.In this embodiment, water and superfluous lime are added together with other compositions, is heated the mixture to 180-190F, while it being slowly added acetic acid during heating.The lubricating grease of gained contains 23% high alkaline calcium sulfonate.Although should Thickener yield is better than other, but there are still the rooms for improvement of bigger without using excessive lime, this is ' 514 patents Introduction is requirement.

Other examples that there is thickener yield wherein for 23% or lower ' 514 and ' 467 patents are included in conversion Period use autoclave, or as wherein add between water and non-aqueous transforming agent or both be not present " delay " at other The much bigger part of the prior art.These embodiments include addition water and aliphatic acid transforming agent, mixing 10 minutes without heating, Then acetic acid is added, in autoclave or in no pressure.These patents all do not recognize 10 minutes of addition acetic acid Any benefit or advantage of interval or other heating delays in embodiment discussed above, make on the contrary, these patents concentrate on Use aliphatic acid as transforming agent, and the benefit of addition aliphatic acid is observed as any before conversion, after conversion or both The reason of yield improves.In addition, as discussed below, 10 minutes incorporation time intervals without any heating are not herein " delay " of the middle term used, and it is considered identical as adding ingredient simultaneously, it is understood that it adds each ingredient and needs at least Some times, and cannot occur moment.

Furthermore it is known that the prior art instruct calcium oxide or calcium hydroxide is used to be used as generating sulfoacid calcium lubrication always The alkaline calcium source of fat or as being reacted with Compound-acid to form the required component of sulfoacid calcium complex grease.Known existing skill Art teaches addition calcium hydroxide or calcium oxide needs enough amounts (to be present in high alkalinity oil-soluble sulfonic acid calcium when being added to When a certain amount of calcium hydroxide or calcium oxide) to provide calcium hydroxide or the oxidation of the total amount for being enough fully to react with Compound-acid Calcium.Such as in the Application U.S. Serial No of co-pending 13/664,574 and 13/664, disclosed in 768, it is known that existing skill Art usually instructs calcium carbonate (as individual ingredient or as " impurity " in calcium hydroxide or calcium oxide, in addition to carbonating Exist later except the amorphous calcium carbonate being dispersed in sulfoacid calcium) at least two reasons should be avoided.It is that calcium carbonate is logical first Often it is considered as weak base, is not suitable for being reacted with Compound-acid to form best grease structure.Second the reason is that unreacted Conversion process is interfered in the presence of solid calcium compound (including calcium carbonate, calcium hydroxide or calcium oxide), if before conversion or Conversion is completed then to lead to lubricating grease inferior without removing unreacted solid before.However, applicant have found that addition calcium carbonate As independent element (other than the amount of calcium carbonate contained in high alkaline calcium sulfonate), calcium hydroxy apetite (calcium Hydroxyapatite, calcium hydroxyapatite) or combinations thereof (addition or do not add calcium hydroxide or calcium oxide) as with The ingredient of Compound-acid reaction generates the brand-name grease as described in ' 574 and ' 768 applications.

There are several prior art references to disclose addition crystalline calcium carbonate as independent element (in addition to high alkalinity sulfonic acid Except the amount of calcium carbonate contained in calcium), but these lubricating grease have difference thickener yield (such as teaching in prior art) or Need the nano-sized particles of calcium carbonate.For example, U.S. Patent number 5,126,062 discloses the calcium carbonate conduct of addition 5-15% The independent element of complex grease is formed, it also requires addition calcium hydroxide with Compound-acid to react.In ' 062 patent, addition The calcium carbonate calcic alkali uniquely added that is not intended to react with Compound-acid.In fact, the calcium carbonate of addition does not add particularly Add as the alkaline reactant reacted with Compound-acid.On the contrary, needing calcium hydroxide to be added as being reacted with all Compound-acids Specific calcic alkali.In addition, No. 2 lubricating grease of the NGLI of gained contains the high alkaline calcium sulfonate of 36%-47.4%, this is a large amount of The ingredient of this costliness.In another example, the open CN101993767 of China, which is disclosed, is added in high alkaline calcium sulfonate The addition of the nano-sized particles (size is between 5-300nm) of calcium carbonate, although bibliography does not show to add calcium carbonate Nano-sized particles as reactant, or only individually addition calcic alkali for being reacted with Compound-acid.Use nano-sized particles Increase consistency of grease to keep its robustness, like by converting amorphous calcium carbonate institute contained in high alkaline calcium sulfonate The crystalline calcium carbonate of formation fine dispersions (its can be about 20A to 5000A or according to ' 467 patents be about 2nm extremely 500nm), but compared with the calcium carbonate granule of the addition of large-size, cost can also be significantly increased.The Chinese patent application is very The absolute necessity of the calcium carbonate with real nano particle size of addition is highlighted in big degree.Such as basis in co-pending Shown in the exemplary lubricating grease of the present invention described in ' 574 applications, brand-name grease can be by adding micron order calcium carbonate Formed, without using very expensive nano-scale particle, and when use the calcium carbonate of addition as one kind or with it is unique When the calcic alkali of addition with Compound-acid to react.

There is also use tricalcium phosphate as the prior art references of the additive in lubricating grease.For example, the U.S. is special The all introductions of profit number 4,787,992,4,830,767,4,902,435,4,904,399,4,929,371 use tricalcium phosphate as profit Consistent lubricant additive.However, it is believed that being used with formula Ca without prior art references introduction₅(PO₄)₃The hydroxy-apatite of OH The mathematical equivalent thereof that stone calcium or fusing point are about 1100C manufactures lubricating grease, including sulfonic acid as the calcic alkali for being reacted with acid Calcium-base grease.Several prior art references in the presence of the Showa Shell Sekiyu for belonging to Japan include that the U.S. is special Sharp application publication number 2009/0305920, which depict contain tricalcium phosphate Ca₃(PO₄)₂Lubricating grease and with reference to have formula [Ca₃ (PO₄)₂]3·Ca(OH)₂" hydroxyapatite " source as tricalcium phosphate." hydroxyapatite " this is referred to and being disclosed It is different from the calcium hydroxy apetite disclosed and claimed in ' 768 applications for the mixture of tricalcium phosphate and calcium hydroxide, And there is formula Ca herein₅(PO₄)₃OH or mathematical equivalent thereof, fusing point are about 1100C.Although name has misleading, hydroxyl Base apatite calcium, tricalcium phosphate and calcium hydroxide are individually the different compounds with different chemical formulas, structure and fusing point.When mixed When being combined, two different crystalline compounds tricalcium phosphate (Ca₃(PO₄)₂) and calcium hydroxide (Ca (OH)₂) will not be mutual Reaction otherwise generates different crystalline compounds calcium hydroxy apetite (Ca₅(PO₄)₃OH).Tricalcium phosphate (has formula Ca₃(PO₄)₂) fusing point be 1670C.Calcium hydroxide does not have fusing point, but the son that dries out at 580C is to form calcium oxide. The calcium oxide being thusly-formed has the fusing point of 2580C.Calcium hydroxy apetite (has formula Ca₅(PO₄)₃OH or mathematical equivalent thereof) tool There is the fusing point of about 1100C.Therefore, no matter how inaccurate name may have, calcium hydroxy apetite is not identical as tricalcium phosphate Compound, and it is not the simple blend of tricalcium phosphate and calcium hydroxide.

In addition, it is expected that leading to the thickener yield improved with the composite lubricated oil/fat composition of sulfoacid calcium and its manufacturing method And dropping point.Many known prior art compositions need the high alkaline calcium sulfonate of at least 36% amount (to be produced with final lubricating grease The weight meter of product) to obtain the suitable lubricating grease in No. 2 classification of NGLI, the verified drop at least 575F Point.High alkalinity oil-soluble sulfonic acid calcium is one of the ingredient of most expensive for manufacturing grease of calcium sulfonic acid, it is therefore desirable for reducing the ingredient Amount, while still keeping firmness level's (thus improve thickener yield) needed for final lubricating grease.In order to realize the height used The amount of alkaline sulfoacid calcium is greatly decreased, and many prior art references utilize pressure reactor.Expect to have high alkalinity sulfonic acid Grease of calcium, wherein when consistency is in No. 2 grades of NLGI (or 60 stroke needle penetration (worked 60stroke of work of lubricating grease Penetration, 60 stroke operation needle penetrations, used 60 stroke needle penetration, work 60 stroke of needle penetration, past by 60 times Work needle penetration after multiple) between 265 and 295) in when, the percentage of high alkalinity oil-soluble sulfonic acid calcium is less than 36%, and Dropping point is always 575F or higher, without pressure reactor.Since dropping point is limited about the high temperature effectiveness of lubricating grease First is also to be easiest to determining guidance, therefore, it is considered that higher dropping point is desired.

Invention content

The present invention relates to high alkaline calcium sulfonate lubricating grease and the method for manufacturing this lubricating grease, to provide thickener yield (need less high alkaline calcium sulfonate, while keeping acceptable penetration measurement value) and desired high temperature effectiveness (such as pass through drop Point is proved) improvement.A preferred embodiment according to the present invention, is prepared by reacting and mixing certain compounds Simply (simple, single, primary) grease of calcium sulfonic acid, the compound include：(a) include the amorphous carbonic acid with dispersion The main high alkali compound matter of the high alkalinity oil-soluble sulfonic acid calcium of calcium；(b) optionally, if it is desired, suitable base oil, so as to There is provided acceptable consistency after conversion for product (can add the basis of the addition of any amount before conversion, after conversion or both Oil)；(c) water is as transforming agent；(d) other one or more transforming agents (non-aqueous transforming agent), wherein adding water before conversion And it is added before conversion between other at least part of one or more non-aqueous transforming agents and there are one or more period of delays.Such as this Used in text, " non-aqueous transforming agent " refers to any transforming agent than water, and include can contain some water as diluent or The transforming agent of impurity.

Another preferred embodiment according to the present invention, composite sulfoacid is prepared by reacting and mixing certain compounds Grease of calcium, the compound include：(a) master of the high alkalinity oil-soluble sulfonic acid calcium comprising the amorphous calcium carbonate with dispersion Want high alkali compound matter；(b) optionally, if it is desired, suitable base oil provides so as in post-conversion for product acceptable thick Degree (base oil that the addition of any amount can be added before conversion, after conversion or both)；(c) water is as transforming agent；(d) a kind of Or various other transforming agents (non-aqueous transforming agent)；(d) one or more Compound-acids；(e) it is used for and one or more Compound-acids The calcic alkali of one or more additions of reaction；Added wherein before conversion addition before water and conversion it is at least part of a kind of or There are one or more period of delays between various other non-aqueous transforming agents.It can be added before conversion or after conversion all One or more Compound-acids.Alternatively, it is possible to add one or more Compound-acids before composite calcium sulfonate grease lubricant conversion A part, and add the remainder of one or more Compound-acids in post-conversion.It can add before conversion or after conversion Add all one or more calcic alkali.Alternatively, it is possible to a part for one or more calcic alkali is added before conversion, and Remainder is added in post-conversion.Can use calcium hydroxy apetite, the calcium carbonate of addition, addition calcium hydroxide, addition Calcium oxide or combinations thereof is as the calcic alkali for being reacted with Compound-acid.Preferably, it is not added relative to used before conversion Compound-acid the excessive calcium hydroxide of total amount.

According to another preferred embodiment, one or more period of delays, (addition and at least part were non-before the conversion of water Time between being added before the conversion of water transforming agent) it is that temperature adjusts period of delay or holding period of delay or both.If manufacturing To compensate evaporation loss, then those additions are not used in restarting or determine delay the additional water of addition before being converted during process Phase, and be only used as the water of first time addition to determine the starting point of period of delay.Period of delay may include that multiple temperature adjust delay Phase and/or multiple holding period of delays.For example, it is to heat the mixture to after the water addition centainly that the first temperature, which adjusts period of delay, Temperature or certain temperature range (the first temperature) the time it takes amount.First holding period of delay be be heated or cooled to it is another The time quantum of the first temperature is held the mixture in before temperature or before the non-aqueous transforming agent of addition at least part.Second temperature Degree adjusting period of delay is that mixture is heated or cooled to another temperature or temperature range (second after the first holding period of delay Temperature) the time it takes amount.Second holding period of delay was before being heated or cooled to another temperature or in addition at least one The time quantum of second temperature is held the mixture in before the non-aqueous transforming agent in part.Additional temperature adjusts period of delay or keeps prolonging Slow phase (that is, third temperature adjusts period of delay) follows identical pattern.In general, being kept for period of delay before temperature adjusts period of delay Or later, vice versa, but may have back-to-back (back to back) two holding period of delays or back-to-back two temperature tune The section phase.For example, can be held the mixture in before a kind of non-aqueous transforming agent of addition under environment temperature 30 minutes, (first keeps Period of delay) and another hour can be continually maintained under environment temperature before adding identical or different non-aqueous transforming agent (second is kept for period of delay).In addition, mixture can be heated or cooled to the first temperature, non-aqueous transforming agent (first is added later Temperature adjusts the phase), mixture is then heated or cooled to second temperature, adds identical or different non-aqueous transforming agent later (second temperature adjusts the phase, without any intermediate retention period).In addition, a part of non-aqueous turn need not be added after each period of delay Agent, but period of delay can be skipped before addition or between addition.For example, temperature (the first temperature can be heated the mixture to Adjust period of delay), then kept for a period of time (the first holding delay at such a temperature before adding any non-aqueous transforming agent Phase).

According to a preferred embodiment, the first temperature can be environment temperature or another temperature.Any following temperature It could possibly be higher than or less than previous temperature.Before final conversion temperature (for non-pressurised production) will at about 190 °F to 220 °F or Up to 230 °F, as the temperature usually converted in open kettle.Temperature can be less than 190F, but this before final conversion Kind process conditions normally result in significantly greater length of transformation time, and thickener yield may also reduce.If reaching one A part of non-aqueous transforming agent is added immediately after constant temperature degree or temperature range, then for the specific temperature and non-aqueous turn of the part Agent does not have retention time delay；But if adding another part again after being kept for a period of time in the temperature or temperature range, Then for the temperature, there are soaking time delays with the non-aqueous transforming agent in the part.Period of delay or holding can be adjusted in any temperature A part for one or more non-aqueous transforming agents is added after period of delay, and can adjust period of delay or holding in another temperature The identical or different non-aqueous transforming agent of another part is added after period of delay.

According to another preferred embodiment, the temperature before the final conversion that mixture is heated to about 190F to 230F The non-aqueous transforming agent of at least part is added after range.According to another preferred embodiment, without a certain amount of non-aqueous turn Agent is substantially simultaneously added with water, and there are at least one period of delays before adding any non-aqueous transforming agent.According to another One preferred embodiment, when at least one non-aqueous transforming agent is glycol (such as propylene glycol or hexylene glycol), a part two Alcohol is substantially simultaneously added with water, and another part glycol and any other non-aqueous turn all is added after at least one period of delay Agent.According to another preferred embodiment, when adding acetic acid before conversion, substantially simultaneously added with water, and Another (different) non-aqueous transforming agent is added after period of delay.According to another preferred embodiment, alcohol is not used as non-aqueous turn Agent.

According to a preferred embodiment, after period of delay, in a batch mode (primary all, with retouch below Continuous addition during the period of delay stated is opposite) all or part of non-aqueous transforming agent of addition.However, it should be noted that advising greatly In mould or commercial-scale operation, due to the volume of involved material, complete this non-aqueous transforming agent profit is added batch-wise Some times are needed in consistent lubricant batch.In being added batch-wise, non-aqueous transforming agent is added in lubrication lipoprotein mixture and is spent Time quantum is not considered as period of delay.In this case, any delay before adding the non-aqueous transforming agent or part thereof exists Non-aqueous transforming agent terminates when beginning is added batch-wise.According to another preferred embodiment, in period of delay, (temperature adjusts delay Phase is kept for period of delay) during process, a kind of at least one or a part of non-aqueous transforming agent are added in a continuous manner.In temperature During adjusting period of delay, holding period of delay or both, this continuous addition can pass through with substantially stable flow velocity (flow Rate, flow) it is slowly added non-aqueous transforming agent or is realized by repeat, discrete increment addition.In this case, completely It includes terminating when the addition of non-aqueous transforming agent is completed within period of delay to add non-aqueous transforming agent the time it takes.According to Another preferred embodiment adds a kind of at least part of non-aqueous transforming agent in a batch manner after period of delay, and And add the identical or different non-aqueous transforming agent of at least another part in a continuous manner during period of delay.

Another preferred embodiment according to the present invention, even if when high alkaline calcium sulfonate is considered as " poor quality (poor Quality, ropy) " when, improved thickener yield results are realized using at least one period of delay.Using existing When the sulfoacid calcium technology of technology, commercially available and sale can for manufacturing certain high alkalinity oil-soluble sulfonic acid calcium of calcium sulfonate grease Unacceptable low dropping point can be provided for product.This high alkalinity oil-soluble sulfonic acid calcium is referred to herein as the height of " poor quality " Basic oil-soluble sulfoacid calcium.Other than the high alkaline calcium sulfonate for using commercial lots, when all the components and method are all identical, It is considered as the mesh for the present invention that generating, which has the high alkalinity oil-soluble sulfonic acid calcium of the lubricating grease of higher dropping point (being higher than 575F), " excellent " matter sulfoacid calcium, and it is considered as purposes of the present invention to generate with those of the lubricating grease of relatively low dropping point " bad " matter.Its several example is provided in ' 768 applications being incorporated by reference into.Although having been carried out high-quality and inferior The comparative chemistry of high alkalinity oil-soluble sulfonic acid calcium is analyzed, but thinks that the exact cause of this low dropping point problem has not proved out. Although most of commercially available high alkaline calcium sulfonates are considered good, whether or not using high-quality or inferior sulfonic acid Calcium all it is expected while realizing the thickener yield of raising and higher dropping point.It has been found that when using delay according to the present invention When adding method, the thickener yield improved and higher dropping point can be realized with high-quality or inferior sulfoacid calcium.In fact, working as When using at least some preferred embodiments of the invention, the result even table of the embodiment of high alkaline calcium sulfonate inferior is used Reveal than using those of high-quality high alkaline calcium sulfonate preferably thickener yield.According to another preferred embodiment, when When at least one non-aqueous transforming agent is glycol (for example, propylene glycol or hexylene glycol), after at least one period of delay (not with water one Play addition) all glycol of addition, and use sulfoacid calcium inferior.

When being produced according to the parameter of invention as described herein, the grease of calcium sulfonic acid of high quality always can be prepared, Its thickener yield and dropping point performance are better than those of prior art lubricating grease.It prepares according to the preferred embodiment of the present invention High alkaline calcium sulfonate complex grease has the drop of No. 2 rank consistency of NLGI (or more preferable, i.e., harder) and 575 °F (or higher) Point, wherein when in open container (without pressure) prepare when high alkalinity oil-soluble sulfonic acid calcium percentage be about 10% to 45%.It is highly preferred that when (do not have pressure) manufacture in open container, the profit for preparing according to the preferred embodiment of the present invention The amount of high alkalinity oil-soluble sulfonic acid calcium in consistent lubricant is at least about 10% but about 36% or less, even more preferably about 30% or more It is few, and most preferably about 22% or less.These improved thickener productions can be realized with high-quality and inferior high alkaline calcium sulfonate Rate.When manufacturing lubricating grease in pressurizing vessel, even higher thickener yield may be implemented using the method for the present invention.Most Preferably, the dropping point of 650F is achieved over.Due to the cost reduction of lubricating grease, the low concentration realized through the invention it is high-alkali Property oil-soluble sulfonic acid calcium is ideal.The improved thickener yield realized according to the present invention also can advantageously influence other property Can, such as mobility and pumping, especially at a lower temperature.

The simple lubricating grease of high alkaline calcium sulfonate prepared according to the preferred embodiment of the present invention has No. 2 ranks of NLGI The percentage of the dropping point of consistency and 575 °F (or higher), wherein high alkalinity oil-soluble sulfonic acid calcium is about 30% to 70%, and optimal It is selected as about 45% to 54%.If necessary to softer lubricating grease, then the high alkalinity oil-soluble sulfonic acid calcium of less percentage will be needed, As would be known to one of ordinary skill in the art.Although the invention mainly relates to the lubricating grease prepared in open container, It can also be used in the closed container for wherein completing to heat under stress.It can cause even preferably to thicken using this pressurizing vessel Agent yield.For the purposes of the present invention, open container is any container with or without head cover or hatch, if it is any this Kind head cover or hatch are not airtight, to not will produce significant pressure during heating.This is used during conversion process The open container that kind head cover or hatch are closed will be helpful to keep the necessary water as transforming agent, while allow generally for converting The boiling point of temperature water under the boiling point of water or even higher than.As one of ordinary skill understood, this higher conversion Temperature can cause the further thickener yield of both simple and composite calcium sulfonate grease lubricants to improve.

Specific implementation mode

A preferred embodiment according to the present invention, simple sulfoacid calcium is prepared by reacting and mixing certain compounds Lubricating grease, the compound include：(a) include the main of the high alkalinity oil-soluble sulfonic acid calcium with the amorphous calcium carbonate disperseed High alkali compound matter；(b) optionally, if it is desired, suitable base oil, to provide acceptable consistency in post-conversion for product (base oil that the addition of any amount can be added before conversion, after conversion or both)；(c) water is as transforming agent；(d) a kind of Or various other transforming agents (non-aqueous transforming agent), wherein before conversion add water and add it is at least part of it is one or more its There are one or more period of delays between his non-aqueous transforming agent.

Another preferred embodiment according to the present invention, composite sulfoacid is prepared by reacting and mixing certain compounds Grease of calcium, the compound include：(a) master of the high alkalinity oil-soluble sulfonic acid calcium comprising the amorphous calcium carbonate with dispersion Want high alkali compound matter；(b) optionally, if it is desired, suitable base oil provides so as in post-conversion for product acceptable thick Degree (base oil that the addition of any amount can be added before conversion, after conversion or both)；(c) water is as transforming agent；(d) a kind of Or various other transforming agents (non-aqueous transforming agent), wherein before conversion add water and add it is at least part of it is one or more its There are one or more period of delays between his non-aqueous transforming agent；(e) one or more Compound-acids；(f) with it is one or more multiple Close the calcic alkali of one or more additions of acid reaction.It can be added before composite calcium sulfonate grease lubricant conversion one or more A part for Compound-acid, and the remainder of one or more Compound-acids is added in post-conversion.Can use calcium hydroxy apetite, The calcium carbonate of addition, the calcium hydroxide of addition, addition calcium oxide or combinations thereof as the calcic alkali for being reacted with Compound-acid.

In simple and complex grease, due to the evaporation and volatilization in manufacturing process, some or all ingredients (including turn Agent) it may not be in final finished.Optionally, for simple or complex grease, another embodiment party according to the present invention Formula can add promotion acid before conversion.This promotion acid contributes to grease structure to be formed.For letter according to the present invention List and complex grease are added before conversion and are deposited between water and other at least part of one or more non-aqueous transforming agents of addition In one or more period of delays.It is also optimal described in preferred method of the following article about grease of calcium sulfonic acid produced according to the present invention Mixture is heated to certain temperature or temperature range by selection of land during at least one period of delay or during each period of delay.It is optimal Selection of land, one or more period of delays (time before the conversion of water between addition and the addition of the non-aqueous transforming agent of at least part) are Temperature adjusts period of delay or holding period of delay or both.Period of delay may include that multiple temperature adjust period of delay and multiple holdings delay Phase.For example, the first temperature adjust period of delay be after the water addition the temperature change by mixture to desired temperature or temperature Range (the first temperature) the time it takes section.First heat preservation period of delay was the time quantum for holding the mixture in the first temperature. Second temperature adjusting period of delay is that mixture is heated or cooled to another temperature or temperature range after keeping postponing first (second temperature) the time it takes section.Second heat preservation period of delay was the time quantum for holding the mixture in second temperature.Additionally Temperature adjust period of delay and kept for period of delay (that is, third temperature adjust period of delay) follow identical pattern.First temperature can To be environment temperature or high temperature.Any following temperature could possibly be higher than or less than previous temperature.Temperature will be before final conversion About 190 °F to 220 °F or up to 230 °F, as the temperature usually converted in open kettle.It can be adjusted and be prolonged with temperature in use Slow phase and/or any combinations for being kept for period of delay.

If adding non-aqueous transforming agent or part thereof immediately after reaching certain temperature or temperature range, for the spy Constant temperature degree does not keep period of delay.It can be added after any temperature adjusts period of delay or holding period of delay one or more non- A part for water transforming agent, and it is identical to add another part after another temperature adjusts period of delay or holding period of delay Or different non-aqueous transforming agent.In general, the duration that each temperature adjusts period of delay would be about 30 minutes to 24 hours, or More typically about 30 minutes to 5 hours.However, the duration that any temperature adjusts period of delay will be according to lubricating grease batch Size, the equipment for mixing and heating batch and the temperature difference between start temperature and final temperature and change, such as will be by What those skilled in the art understood.Preferred embodiment about one or more period of delays is below in relation to basis The preferred method for manufacturing lubricating grease of the present invention further discusses.

The height high alkalinity oil-soluble sulfonic acid calcium used these embodiments according to the present invention can be in the prior art Those of any typical case recorded, such as U.S. Patent number 4,560,489,5,126,062,5,308,514 and 5,338,467.It is high Spending high alkalinity oil-soluble sulfonic acid calcium can be according to this known method produced in situ, or commercial products can be used as to buy. This height high alkalinity oil-soluble sulfonic acid calcium, which has, is not less than 200, preferably not less than 300, most preferably about 400 or higher Total alkali number (TBN) value.Such commercially available high alkaline calcium sulfonate includes but not limited to following substance：By Chemtura The Hybase C401 of USA companies supply；By Kimes science and technology international corporation (Kimes Technologies International Corporation the Syncal OB 400 and Syncal OB405-WO) supplied；The Lubrizol supplied by Lubrizol companies 75GR, Lubrizol 75NS, Lubrizol75P and Lubrizol 75WO.High alkaline calcium sulfonate contains with high alkaline calcium sulfonate Weight is calculated as the amorphous calcium carbonate of about 28% to 40% dispersion, is converted into during the process for preparing grease of calcium sulfonic acid Crystalline calcium carbonate.High alkaline calcium sulfonate is also containing the residual oxygen calcium or hydrogen for being calculated as about 0% to 8% with high alkaline calcium sulfonate weight Calcium oxide.The high alkaline calcium sulfonate of most commercial also contains about 40% base oil as diluent, to prevent high alkalinity sulphur Sour calcium is so sticky and it is made to be difficult to handle and process.The amount of base oil in high alkaline calcium sulfonate may make before conversion It is unnecessary that additional base oil (as individual ingredient), which is added, to obtain acceptable lubricating grease.High alkalinity sulphur used Sour calcium may have as high-quality or inferior herein and defined in ' 768 applications.

It can be with according to the amount of the height high alkalinity oil-soluble sulfonic acid calcium in the final complex grease of embodiment of the present invention Variation, but usually 10 to 45%.Preferably, when being prepared (without pressure) in open container, implementation according to the present invention The amount of height high alkalinity oil-soluble sulfonic acid calcium in the final complex grease of mode is about 36% or smaller, even more preferably about 30% or smaller, and most preferably about 22% or smaller, it can get when being prepared in pressure vessel or even smaller percentage. It can be changed according to the amount of the height high alkalinity oil-soluble sulfonic acid calcium in the final simple lubricating grease of embodiment of the present invention, but logical It is often 30 to 70%, more preferably less than 60%, and more preferably less than 55%.

It is usually used and in lubricating grease manufacturing field well known any cycloalkane or paraffin mineral based on oil Oil may be used as base oil according to the present invention.It is added as needed on base oil, due to the high alkaline calcium sulfonate of most commercial Containing about 40% base oil as diluent, overbased sulfonate is so sticky and keeps it not disposable to prevent, because This expectation consistency for depending on desired grease consistency and final lubricating grease after conversion immediately may not be needed addition volume Outer base oil.Synthetic base oil can also be used in the lubricating grease of the present invention.This synthetic base oil include polyalphaolefin (PAO), Diester, polyol ester, polyethers, alkylated benzenes, alkylated naphthalene and silicone fluid.In some cases, if synthetic base oil exists Exist in conversion process, may have adverse effect, as one of ordinary skill understood.In this case, initially Those synthetic base oils should not be added, but the stage that will be eliminated or minimized is being adversely affected to be added to profit (after converting) In consistent lubricant manufacturing process.Cycloalkane and alkene mineral base oil are preferred due to its lower cost and availability.It is based on The final weight of lubricating grease, addition base oil total amount (including the amount initially added and it is any can be in lubricating grease processing slightly Added afterwards to reach the amount of desired consistency) it is usually 30% to 70%, preferably 45% to 70%, most preferably 50% He 70%.Typically, the amount as the base oil of independent element addition will reduce with the amount of high alkaline calcium sulfonate and be increased.

It is added to water as a kind of transforming agent in the preferred embodiment of the present invention.Preferably, the present invention these Other one or more non-aqueous transforming agents are also added in embodiment.Non-aqueous transforming agent includes any transforming agent than water, Such as alcohol, ether, glycol, glycol ethers, glycol polyethers, carboxylic acid, inorganic acid, organic nitrates/salt and contain active hydrogen or tautomerism Any other compound of hydrogen.Non-aqueous transforming agent further includes containing some water as those of diluent or impurity reagent.Although They may be used as non-aqueous transforming agent, but due to environmental problem and with the discharge gas in lubricating grease preparation process or washing alcohol The hazardous waste of class handles related limitation, does not preferably use alcohol such as methanol or isopropanol or other low molecular weights (that is, being more easy to wave Hair) alcohols.The total amount of final weight based on lubricating grease, the water as transforming agent addition is 1.5% to 10%, preferably 2.0% to 5.0%, most preferably 2.2% to 4.5%.Additional water may be added after conversion.Moreover, if sufficiently high At a temperature of converted in open container with most of water that volatilizees in the conversion process, then can add additional water to replace The water of loss.The total amount of final weight based on lubricating grease, one or more non-aqueous transforming agents of addition is 0.1% to 5%, excellent It is selected as 0.5% to 4%, most preferably 1.0% to 3.0%.In general, the amount of used non-aqueous transforming agent will be with high alkalinity sulphur The amount of sour calcium is reduced and is reduced.Depending on used transforming agent, can be removed in them by volatilization during manufacturing process Some or all.The particularly preferably glycol of lower molecular weight such as hexylene glycol and propylene glycol.It should be noted that being begged for according to following An embodiment of the invention of opinion, some transforming agents are also used as Compound-acid to generate sulfoacid calcium complex grease.This Kind material will provide conversion and complex function simultaneously.

Although it is not required, a small amount of promotion acid can be added before conversion according to another implementation of the invention To mixture.Suitable promotion acid such as alkyl benzene sulphonate with the usually long alkyl chains of 8 to 16 carbon can contribute to Effective grease structure is promoted to be formed.Most preferably, which includes the alkyl that length is largely about 12 carbon The mixture of chain length.This benzene sulfonic acid is commonly known as dodecyl benzene sulfonic acid (" DDBSA ").Such commercially available benzene sulphur Acid includes 1298 sulfonic acid of JemPak provided by JemPak GK Inc., the Calsoft LAS- provided by Pilot chemical companies The 99 and Biosoft S-101 that are provided by Stepan chemical companies.When alkyl benzene sulphonate is used in the present invention, based on lubrication The final weight of fat, with about 0.50% to 5.0%, preferably 1.0% to 4.0% before conversion, most preferably 1.3% to It is added in 3.6% amount.If sulfoacid calcium is prepared in situ using alkyl benzene sulphonate, according to the rush of embodiment addition It is other than the acid needed for production sulfoacid calcium into acid.

When another preferred embodiment according to the present invention prepares composite calcium sulfonate grease lubricant, it is additionally added a kind of or more Kind Compound-acid and one or more calcic alkali.Calcic alkali may include calcium hydroxy apetite, the calcium carbonate of addition, addition hydrogen-oxygen Change calcium, addition calcium oxide or it is aforementioned in one or more combinations.It can be before conversion, after the conversion or preceding part of conversion It is partly added behind ground and conversion and calcium hydroxy apetite of the calcic alkali to be reacted with Compound-acid is used as according to the embodiment.It is optimal Selection of land, calcium hydroxy apetite are subdivided into about 1 to 20 micron, preferably from about 1 to 10 micron, most preferably about 1 to 5 micron flat Equal granularity.In addition, calcium hydroxy apetite is by with enough purity, so that abrasive material pollutant such as silica and aluminium oxide contain Measure it is sufficiently low, to be not significantly affected by gained lubricating grease abrasion resistance.It is desirable that obtain optimum efficiency, hydroxy-apatite Stone calcium should be food-grade or United States Pharmacopeia grade.Total weight based on lubricating grease, the amount of the calcium hydroxy apetite of addition be 2.0% to 20%, preferably 4% to 15%, most preferably 5% to 10%, although can convert and complete and Compound-acid if necessary All reactions after add it is more.

According to another implementation of the invention, calcium hydroxy apetite can be not enough to react completely with Compound-acid Amount is added in mentioned component.In this embodiment, it can be added preferably before conversion as the solid insoluble in oil The calcium carbonate of the subdivision of calcic alkali presents in an amount at least sufficient to the portion with any Compound-acid then added not neutralized by calcium hydroxy apetite Divide and fully reacts and neutralize.

It according to another embodiment, can be by calcium hydroxy apetite to be not enough to be added to the amount that Compound-acid reacts completely In mentioned component.In this embodiment, it can be added preferably before conversion as the solid calcic alkali insoluble in oil The calcium hydroxide and/or calcium oxide of subdivision, present in an amount at least sufficient to the calcium hydroxy apetite do not added jointly neutralize it is any then It fully reacts and neutralizes in the part of the Compound-acid of addition.In this embodiment, calcium hydroxide and/or calcium oxide preferably indicate not The hydroxide equivalent basicity that the total amount by the calcium hydroxy apetite, calcium hydroxide and the calcium oxide that add more than 75% provides. In another embodiment, calcium carbonate can also be added together with calcium hydroxy apetite, calcium hydroxide and/or calcium oxide, In calcium carbonate is added before or after being reacted with Compound-acid.When calcium hydroxy apetite, calcium hydroxide and/or calcium oxide amount not When being enough to neutralize the one or more Compound-acids added, preferably be more than be enough to neutralize it is any remaining one or more multiple The amount for closing acid adds calcium carbonate.

These embodiments according to the present invention, individually or with another or a variety of calcic alkali it is used as containing in combination The calcium carbonate of the addition of calcium alkali is subdivided into about 1 to 20 micron of average particle size, preferably from about 1 to 10 micron, most preferably about 1 To 5 microns.In addition, the calcium carbonate added is preferably the crystalline calcium carbonate (being most preferably calcite) with enough purity, with Keep the content of abrasive material pollutant such as silica and aluminium oxide sufficiently low, to be not significantly affected by the wear resistence of gained lubricating grease Energy.It is desirable that obtain optimum efficiency, calcium carbonate should be food-grade or United States Pharmacopeia grade.Final weight based on lubricating grease, adds The amount of the calcium carbonate entered is 2.0% to 20%, preferably 4% to 15%, most preferably 6% to 10%.It is high-alkali in addition to being included in Except the amount of the calcium carbonate of dispersion in property sulfoacid calcium, this tittle is added as individual ingredient.It is according to the present invention another The calcium carbonate of addition is added with anti-with Compound-acid as the calcic alkali composition uniquely added before conversion in preferred embodiment It answers.Additional calcium carbonate can be added with after the completion of the total overall reaction of Compound-acid in post-conversion and in the case of complex grease It is added in the simple or complex grease embodiment of the present invention.However, the calcium carbonate for the addition being mentioned above refers to converting The calcium carbonate added before, and be when preparing complex grease according to the present invention as the one kind reacted with Compound-acid or The calcic alkali uniquely added.

The calcium hydroxide for the addition added before conversion according to another embodiment and/or the calcium oxide of addition should be thin It is divided into about 1 to 20 micron, preferably from about 1 to 10 micron, most preferably about 1 to 5 micron of average particle size.In addition, calcium hydroxide With calcium oxide by with enough purity, so that the content of abrasive material pollutant such as silica and aluminium oxide is sufficiently low, to not The abrasion resistance of gained lubricating grease can be significantly affected.It is desirable that obtain optimum efficiency, calcium hydroxide and calcium oxide should be food Grade or United States Pharmacopeia grade.The total amount of total weight based on lubricating grease, calcium hydroxide and/or calcium oxide is 0.07% to 1.00%, Preferably 0.15% to 0.85%, most preferably 0.18% to 0.40%.In addition to the residual hydrogen-oxygen for including in high alkaline calcium sulfonate Except the amount for changing calcium or calcium oxide, this tittle is added as individual ingredient.Most preferably, do not added before conversion relative to The excessive calcium hydroxide of total amount of Compound-acid used.According to another embodiment, need not add for anti-with Compound-acid Any calcium hydroxide or calcium oxide answered, and the calcium carbonate of addition or calcium hydroxy apetite can be used to be used as this anti- The calcic alkali individually added answered can be used for this reaction in combination.

The Compound-acid used in these embodiments will include at least one, and be preferably two or more following objects Matter：Long-chain carboxylic acid, short chain carboxy acid, boric acid and phosphoric acid.Depending on adding the time, acetic acid and other carboxylic acids can be used as transforming agent or multiple Close acid or both.Similarly, some Compound-acids can be used as transforming agent (such as the 12- hydroxy stearic acids in ' 514 and ' 467 patents). In terms of the weight of final lubricating grease, the total amount of the Compound-acid of addition is preferably 2.8% to 11%.Suitable in accordance with the purpose of the invention Long-chain carboxylic acid include at least 12 carbon atoms aliphatic carboxylic acid.Preferably, long-chain carboxylic acid includes to have at least 16 carbon The aliphatic carboxylic acid of atom.Most preferably, long-chain carboxylic acid is 12- hydroxy stearic acids.Final weight based on lubricating grease, long-chain carboxylic acid Amount be 0.5% to 5.0%, preferably 1.0% to 4.0%, most preferably 2.0% to 3.0%.

Include to have to be not more than 8 carbon atoms, and preferably no more than 4 suitable for short chain carboxy acid in accordance with the purpose of the invention The aliphatic carboxylic acid of atom.Most preferably, short chain carboxy acid is acetic acid.The amount of final weight based on lubricating grease, short chain carboxy acid is 0.05% to 2.0%, preferably 0.1% to 1.0%, most preferably 0.2% to 0.5%.Use is also suitable for for generating long-chain This reaction of short chain carboxy acid expectable and water or reacted for generating the other components of lubricating grease according to the present invention Any compound.For example, the second of Compound-acid to be used as will be formed by being reacted with water present in mixture using acetic anhydride Acid.It equally, will be by reacting to form Compound-acid to be used as with water present in mixture using 12- methyl hydroxystearates 12- hydroxy stearic acids.Alternatively, if enough water is not present in mixture, additional water can be added into mixture To form necessary Compound-acid with this component reaction.

If using boric acid as Compound-acid according to the embodiment, the final weight based on lubricating grease, addition 0.4% To about 4.0%, preferably 0.7% to 3.0%, and most preferably 1.0% to 2.5% amount.First in water dissolving or at Boric acid is added after slurry, or can be added in the absence of water.Preferably, boric acid is added during manufacturing process so that Water there are still.Alternatively, any well known inorganic borate can be used to replace boric acid.Similarly, any have determined that can be used Boration organic compound such as boration amine, boration amide, boration ester, boration alcohol, boration glycol, boration Ether, boration epoxides, boration urea, boration carboxylic acid, boration sulfonic acid, boration epoxides, boration peroxidating Object etc. is used for replacing boric acid.If using phosphoric acid as Compound-acid, the final weight based on lubricating grease, addition 0.4% is to about 4.0%, preferably 1.0% to 3.0%, and most preferably 1.4% to 2.0% amount.Various Compound-acids as described herein Percentage refers to pure reactive compound.If can get any one of these Compound-acids with dilute form, they are still It is applicable to the purposes of the present invention.However, it is necessary to the percentage of this diluted Compound-acid be adjusted, to consider dilution gfactor and make Substantial activity substance reaches specified percentage range.

Other additives generally acknowledged usually in lubricating grease manufacturing field can be also added to the simple lubricating grease of the present invention In embodiment or complex grease embodiment.This additive may include antirust agent and corrosion inhibitor, metal deactivating Agent, matal deactivator, antioxidant, EP agent, antiwear additive, chelating agent, polymer, tackifier, dyestuff, chemistry mark Note, flavor imparting agent and evaporation solvent.Later category is special when manufacturing exposed gear lubricating agent and braided wire rope lubricant It is useful.Including any such additive is interpreted as still within the scope of the invention.

It is preferred that preparing grease of calcium sulfonic acid composition according to invention as described herein method.Unless otherwise indicated, own Percentage is based on the final weight of finished product lubricating grease.It is a kind of to prepare simple lubricating grease or the preferred method of complex grease includes Mixing water, less than 30% containing dispersion amorphous calcium carbonate high alkaline calcium sulfonate (for complex grease) or 30% to The high alkaline calcium sulfonate (for simple lubricating grease) and optional base oil of 70% amorphous calcium carbonate containing dispersion are with shape At the first mixture；After one or more period of delays, at least part of one or more non-aqueous transforming agents are added to One mixture is to form mixture before conversion；And by heating until amorphous carbonic acid contained in high alkaline calcium sulfonate occurs The conversion of calcium to crystalline calcium carbonate converts mixture before conversion in the mixture of conversion.

The preferred method that another kind prepares simple lubricating grease or complex grease include mixing water, less than 45% containing dividing The high alkaline calcium sulfonate (for complex grease) of scattered amorphous calcium carbonate or 30% to 70% containing dispersion it is amorphous The high alkaline calcium sulfonate (for simple lubricating grease) of calcium carbonate and optional base oil are to form the first mixture；At one or more After a period of delay or period, at least part of one or more non-aqueous transforming agents are added to the first mixture to form conversion Preceding mixture；It will to the conversion of crystalline calcium carbonate until amorphous calcium carbonate contained in high alkaline calcium sulfonate occurs by heating Mixture is converted into the mixture of conversion before conversion, and wherein at least one period of delay is to maintain delay period, wherein the first mixing Mixture is maintained at a period of time in certain temperature or certain temperature range before object or conversion.

The preferred method that another kind prepares simple lubricating grease or complex grease include mixing water, less than 22% containing dividing The high alkaline calcium sulfonate (for complex grease) of scattered amorphous calcium carbonate or 30% to 70% containing dispersion it is amorphous The high alkaline calcium sulfonate (for simple lubricating grease) of calcium carbonate and optional base oil are to form the first mixture；At one or more After a period of delay or period, at least part of one or more non-aqueous transforming agents are added to the first mixture to form conversion Preceding mixture；It will to the conversion of crystalline calcium carbonate until amorphous calcium carbonate contained in high alkaline calcium sulfonate occurs by heating Mixture is converted into the mixture of conversion before conversion.

The preferred method that another kind is simple to manufacture lubricating grease includes the following steps：(1) in suitable lubricating grease manufacture container Middle mixing following ingredients：The high alkalinity oil-soluble sulfonic acid calcium, optional of water as transforming agent, the amorphous calcium carbonate containing dispersion Suitable suitable base oil (if necessary) and optional at least part of one or more non-aqueous transforming agents are to form the One mixture；(2) mix or stir the first mixture, at the same hold it in certain temperature or certain temperature range and/or The temperature of the first mixture is adjusted to be heated or be cooled to other one or more during one or more period of delays Temperature or temperature range；It (3) optionally will be at least part of one or more after or during the period one or more period of delays Non-aqueous transforming agent is mixed with the first mixture to form the second mixture；(4) heat the first mixture (or the second mixture, such as Non-aqueous transforming agent is added in fruit in step 3) to conversion temperature, (preferably 190F to 230F is higher than the typical model of 190F to 220F Enclose, for open container) third mixture is formed with the last period in one or more period of delays；(5) after step 4 or During step 4, whole or any remainders (if any) of one or more non-aqueous transforming agents are mixed；(6) lead to It crosses and continues mixing when maintaining the temperature at conversion temperature range (preferably 190F to 230F) to convert third mixture, until complete Crystalline calcium carbonate very fine crushing is converted at amorphous calcium carbonate contained in high alkaline calcium sulfonate.The process generates preferred Simple grease of calcium sulfonic acid.The preferred method also optionally includes the calcium carbonate of step (7) mixing addition and/or (8) mixing promotees Into acid.It can carry out step (7) after converting in any time before conversion or a part can be added before conversion Another part is added after conversion.Step (8) can be carried out in any time before conversion.Most preferably, in opening This method is carried out in container, but can also be carried out in pressurizing vessel.

A kind of preferred method of complex grease constructed in accordance includes the following steps：(1) in suitable lubricating grease Following ingredients are mixed in manufacture container：Water as transforming agent, the height high alkalinity oil of the amorphous calcium carbonate containing dispersion are molten Property sulfoacid calcium, optional suitable suitable base oil (if necessary) and optional at least part of one or more non-aqueous Transforming agent is to form the first mixture；(2) it mixes or stirs the first mixture, while holding it in certain temperature or a constant temperature It spends in range and/or adjusts the temperature of the first mixture to be heated or be cooled in addition during one or more period of delays One temperature of one or more or temperature range；It (3) optionally will at least one after or during the period one or more period of delays The one or more non-aqueous transforming agents divided are mixed with the first mixture to form the second mixture；(4) heat the first mixture (or Second mixture, if non-aqueous transforming agent is added in step 3) to conversion temperature, (preferably 190F to 230F is higher than 190F extremely The typical range of 220F, for open container) in the last period formation third mixture of one or more period of delays；(5) After step 4 or during the step 4, mix one or more non-aqueous transforming agents whole or any remainders (if there is If)；(6) third is converted by continuing mixing when maintaining the temperature at conversion temperature range (preferably 190F to 230F) Mixture, until completing amorphous calcium carbonate contained in high alkaline calcium sulfonate is converted into crystalline calcium carbonate very fine crushing；(7) Mix one or more calcic alkali；(8) optionally mixing promotes acid；(9) one or more suitable Compound-acids are mixed.The mistake Journey generates preferred composite calcium sulfonate grease lubricant.Step (7) can be carried out before conversion or after conversion, or can be in conversion The some parts or whole of the preceding one or more calcic alkali of addition, and one or more calcic alkali can be added after conversion Some parts or whole.Step (8) can be carried out in any time before conversion.It can be carried out before conversion or after conversion Step (9), or some parts or whole of one or more Compound-acids can be added before conversion, and can be after conversion Add some parts or whole of one or more Compound-acids.Most preferably, this method is carried out in open container, but can also It is carried out in pressurizing vessel.

According to several other embodiments, the method for manufacturing complex grease is same as described above, in addition to step (7) be related to Except one of lower：(a) calcium hydroxy apetite fine crushing is mixed before conversion, as the calcic alkali uniquely added；(b) according to one A embodiment, by calcium hydroxy apetite and calcium carbonate fine crushing to be enough fully to react and neutralize with the Compound-acid then added Amount mixing；(c) Compound-acid by calcium hydroxy apetite and calcium hydroxide and/or calcium oxide fine crushing to be enough with then be added The amount mixing fully reacted and neutralized, wherein according to another implementation of the invention, calcium hydroxide and/or calcium oxide are preferred Worked as with the hydroxide that the total amount by the calcium hydroxide and/or calcium oxide and calcium hydroxy apetite that add no more than 75% provides The amount for measuring basicity exists；(d) according to another implementation of the invention, the calcium carbonate of addition is mixed in post-conversion；Or (e) root According to the another embodiment of the present invention, calcium hydroxy apetite is mixed after conversion and is present in an amount at least sufficient to and is added with after conversion Any Compound-acid is reacted and is neutralized completely.According to another embodiment, the method for complex grease and above-mentioned phase are used to prepare Together, in addition to adding calcium carbonate fine crushing (before or during step 6) before conversion as oily insoluble solid calcic alkali, and Step (7) includes mixing calcium hydroxy apetite and calcium hydroxide and/or calcium oxide fine crushing, and amount is not enough in reacting simultaneously completely The Compound-acid being then added, wherein calcium hydroxide and/or calcium oxide are preferably with the calcium hydroxide no more than 75% by adding And/or the amount of the hydroxide equivalent basicity of the total amount of calcium oxide and calcium hydroxy apetite offer exists, wherein previously add The addition of calcium carbonate is enough and any is not added then by what calcium hydroxy apetite and calcium hydroxide and/or calcium oxide neutralized It fully reacts and neutralizes in the part of Compound-acid.

Another preferred method of complex grease constructed in accordance includes the following steps：In suitable lubricating grease system Make the height high alkalinity oil-soluble sulfonic acid calcium of amorphous calcium carbonate of the mixing containing dispersion and a certain amount of suitable base in container Plinth oil (if necessary), and start to mix.Then, one or more promotion acid are added and mix, preferably from about 20-30 minutes. Then, all calcium hydroxy apetites are added, then a part of calcium hydroxide, then in addition all calcium carbonate, is mixed 20-30 minutes.Next, the 12- hydroxy stearic acids of a part of acetic acid and a part are added and mix 20-30 minutes other (note It may be transforming agent to anticipate to these ingredients, but because they are added before water, therefore there is no period of delay).Then, water is added As transforming agent and while being heated to 190 °F to 230 °F of temperature (the first temperature adjusts period of delay and final delay phase) Mixing.Then, all hexylene glycols are added as non-aqueous transforming agent.By maintaining the temperature within the scope of conversion temperature (preferably 190F to 230F) continue to mix and carrys out transformation mixture, until completing amorphous calcium carbonate conversion contained in high alkaline calcium sulfonate For crystalline calcium carbonate very fine crushing.After conversion, remaining calcium hydroxide is added and mixes about 20-30 minutes.Then, it is added surplus Remaining acetic acid and remaining 12- hydroxy stearic acids simultaneously mix about 30 minutes.It is subsequently added into the boric acid being dispersed in water, then slowly It is gradually added into phosphoric acid.Then, heating mixture is cooling to remove water and volatile matter, and more base oils are added as needed, and And lubricating grease is ground as described below.Can it is last step is heated or cooled during additional additive is added.According to another kind It is identical as what is be outlined above to prepare the preferred method of complex grease, step and ingredient, in addition to being that water is being added as conversion After agent and before whole hexylene glycols are added as non-aqueous transforming agent, heating the mixture to about 160 °F, (the first temperature is adjusted Period of delay), and being kept before continuing to be heated to 190 °F to 230 °F (second temperature adjusts period of delay and final delay phase) should Temperature about 30 minutes (first is kept for period of delay).

For simple lubricating grease according to the present invention and complex grease embodiment, added in step 1,3 and/or 5 Non-aqueous transforming agent any part can be with the identical non-aqueous transforming agent that is added in another step or multiple steps, or Any non-aqueous transforming agent different from what is added in another step or multiple steps.Condition is after period of delay (in step 3 Or in step 5) at least part of at least one non-aqueous transforming agent is added, it can add in any combinations of step 1,3 and/or 5 Add another part identical and/or one or more non-aqueous transforming agents different at least partially.According to for simple lubricating grease or Another preferred embodiment of complex grease, will be all one or more non-after the final delay phase in steps of 5 Water transforming agent mixes, and without adding any non-aqueous transforming agent during step 1 or 3.According to for simple lubricating grease or compound Another preferred embodiment of lubricating grease is added at least one together with the first mixture in step 1 before any delay Partial one or more non-aqueous transforming agents, and addition at least part is identical or different in step 3 and/or step 5 Non-aqueous transforming agent.According to another preferred embodiment for simple lubricating grease or complex grease, not with the first mixture Non-aqueous transforming agent is added together, and at least part of one or more non-aqueous transforming agents are added in step 3 and step 5.Root According to another preferred embodiment for simple lubricating grease or complex grease, in step 3 after a period of delay or At least part of one or more non-aqueous transforming agents are added in period, and after or during the period another period of delay (in step 3 The final delay phase in second period of delay and/or step 5) at least part of identical or different non-aqueous transforming agent is added.According to For another preferred embodiment of simple lubricating grease or complex grease, add after one or more postpones in step 3 Enter at least part of one or more non-aqueous transforming agents, but does not add non-aqueous turn after last period of delay in steps of 5 Agent.

Most preferably, the method for manufacturing compound and simple lubricating grease is further comprising the steps of：(a) it is mixed and heated to enough High temperature is to ensure water removal and any volatile reaction by-product and optimize end product quality；(b) cooling as needed Additional base oil is added simultaneously in lubricating grease；(c) remaining required additive well known in the art is added；And if necessary Words (d) grind final lubricating grease to obtain final smooth homogeneous product as needed.Although sequence and the time of these steps It is not important, but rapidly remove water after preferably converting.In general, by lubricating grease heating (preferably under open condition, rather than Under pressure, although pressure can be used) 250F to 300F is arrived, preferably 300F to 380F, most preferably 380F to 400F is to remove The water being added initially as transforming agent is removed, and by chemically reacting any water formed during lubricating grease is formed.It is manufacturing There is the reduction that water may lead to thickener yield, dropping point or both for a long time in lubricating grease batch in the process, and can be with This adverse effect is avoided by rapidly removing water.If polymeric additive is added in lubricating grease, preferably not Them are added until grease temperature reaches 300F.If polymeric additive is added with enough concentration, water can be hindered Effectively volatilization.Therefore, polymeric additive should preferably only just be added in lubricating grease after all water have been removed.If making It can determine that water all before the temperature in lubricating grease reaches preferred 300F values has been removed during making, then preferably Any time thereafter adds any polymeric additive.

According to another preferred embodiment being used together with simple or complex grease method, one or more delay Phase (time before the conversion of water between addition and the addition of the non-aqueous transforming agent of at least part) is that temperature adjusts period of delay or guarantor Hold period of delay or both.Period of delay may include that multiple temperature adjust period of delay and multiple holding period of delays.For example, the first temperature tune Section period of delay is that the temperature adjusting after the water addition by mixture is spent to certain temperature or temperature range (the first temperature) Period.First heat preservation period of delay was the time quantum for holding the mixture in the first temperature.Second temperature adjust period of delay be It keeps heating the mixture to another temperature or temperature range (second temperature) the time it takes section after delay first.The Two heat preservation period of delays were the time quantums for holding the mixture in second temperature.Additional temperature adjusts period of delay or is kept for period of delay (that is, third temperature adjusts period of delay) follows identical pattern.First temperature can be that environment temperature (is not deposited in this case Period of delay is adjusted in the first temperature).Any following temperature could possibly be higher than or less than previous temperature.Temperature will before final conversion It is preferred that in about 190F to 220F or up to 230F, as the temperature usually converted in open kettle.

If adding non-aqueous transforming agent or part thereof immediately after reaching certain temperature or temperature range, for the spy Constant temperature degree does not keep period of delay.It can be added after any temperature adjusts period of delay or holding period of delay one or more non- Water transforming agent all or part of, and can another temperature adjust period of delay or keep period of delay after add another portion Split-phase with or all or part of different non-aqueous transforming agent.Most preferably, non-aqueous transforming agent is being added to mixture immediately It will adjust period of delay with the specific non-aqueous relevant end temperature of transforming agent (and last to prolong that temperature later, which adjusts period of delay, The slow phase), but another temperature or temperature range can be heated the mixture to, and add additional one or more non-aqueous transforming agents with It generates additional temperature and adjusts period of delay and possible additional holding period of delay.

In one preferred embodiment, at least one is added at the end of the last one of one or more period of delays The one or more non-aqueous transforming agents divided, and the identical of another part is added after the period of delay before one or more And/or different non-aqueous transforming agent.According to another preferred embodiment, in the last one knot of one or more period of delays All one or more non-aqueous transforming agents are added when beam.According to another preferred embodiment, roughly the same with addition water Time (non-delay phase) add at least part of one or more non-aqueous transforming agents, and in one or more previous delays The identical and/or different non-aqueous transforming agent of another part is added after phase.According to another preferred embodiment, in temperature tune During saving period of delay, holding period of delay or both, it is slowly added at least in a substantial continuous manner or with the amount of discrete increment A kind of non-aqueous transforming agent or part of it.

Although period of delay within the scope of the invention may relate to keep period of delay section, it is not related to heating (under The embodiment 15 in face, wherein by mixture in environment before being heated to conversion temperature range during second temperature adjusts period of delay At a temperature of keep first keep period of delay), addition water there is no the feelings of any heating as transforming agent and during the period The short time period added under condition between all one or more non-aqueous transforming agents less than 15 minutes is not " delay " used herein Or " period of delay ".For the purposes of the present invention, any or all of one kind is added during period of delay in the case where not heating Or the delay of a variety of non-aqueous transforming agents should be at least about 20 minutes and more preferably at least about 30 minutes.Add water and a part Interval between non-aqueous transforming agent is less than 20 minutes, is not heated during 20 minutes, but in the identical of addition another part or Subsequent longer holding period of delay before some or all of different one or more non-aqueous transforming agents or it is subsequent plus Hot " period of delay " being related to really in the scope of the present invention.In this case, initial short time interval is not " period of delay ", but It is to keep for the purposes of the present invention that subsequent longer holding delay or temperature before adding non-aqueous transforming agent, which adjust delay, Period of delay or temperature adjust period of delay.In addition, adjusting period of delay section in one or more temperature or being kept for period of delay or both the phase Between, all or some part of one or more non-aqueous transforming agents can be slowly added.This be slowly added may include one During a or multiple period of delays the non-aqueous transforming agent of substantially continuous addition or repeated during one or more period of delays, increment adds Add.

In addition, when adding acetic acid before conversion or when 12- hydroxy stearic acids, these acidic acids will have as transforming agent and The double action of Compound-acid.When these acid are added together with another more active non-aqueous transforming agent (e.g., glycol), can recognize Mainly play Compound-acid for the acid, more active reagent undertakes the main function of transforming agent.Therefore, when before conversion by second When acid or 12- hydroxy stearic acids are added together with more active transforming agent, add water and any portion of acetic acid or 12- hydroxyls are hard Any between resin acid is not considered as the delay of terms used herein by the time.It that case, only in water Temperature between being added before the preceding addition of conversion and any portion of conversion of other non-aqueous transforming agents adjusts period of delay or keeps prolonging The slow phase is considered as delay for the purposes of the present invention.If acetic acid or 12- hydroxy stearic acids or combinations thereof are uniquely to use One or more non-aqueous transforming agents, then it is hard that any portion of acetic acid of addition or 12- hydroxyls before water and conversion are added before conversion It is delay for the purposes of the present invention that temperature between resin acid, which adjusts period of delay or kept for period of delay,.

The sequence of the step of for both simple lubricating grease and complex grease (2)-(6), wherein relative to as conversion There are at least part of one or more non-aqueous transforming agents for the addition (being adjusted with or without medium temperature) of the water of agent Delay addition is the importance of the present invention.Other certain aspects of this method are for obtaining preferred sulfonic acid according to the present invention Grease of calcium composition is not critical.For example, the sequence that calcic alkali is added relative to each other is not important.Moreover, addition conduct The water of transforming agent and the temperature of calcic alkali are not critical, but they preferably are added before temperature reaches 190F to 200F.When When using more than one Compound-acid, it is generally also not crucial that their sequence is added before or after conversion.These processes may It appears in the open or close kettle commonly used in LUBRICATING GREASES.It can complete to turn under the pressure in normal pressure or closed kettle Change process.Manufacture is preferably as this grease manufacture equipment is typically in open kettle (not container under stress) It is available.For the purposes of the present invention, open container is any container with or without head cover or hatch, if it is any this Kind head cover or hatch are not airtight, to not will produce significant pressure during heating.This is used during conversion process The open container that kind head cover or hatch are closed will be helpful to keep the necessary water as transforming agent, while allow generally for converting The boiling point of temperature water under the boiling point of water or even higher than.As one of ordinary skill understood, this higher conversion Temperature can cause the further thickener yield of both simple and composite calcium sulfonate grease lubricants to improve.It can also use and pressurize It is manufactured in kettle, and the even greater improvement of thickener yield can be caused, but pressure process is possible more complicated and is difficult to Control.In addition, manufacturing grease of calcium sulfonic acid in autoclave may result in productivity issue.The use of compressive reaction is to Mr. Yu The lubricating grease (e.g., polyurea grease) of a little types is important, and most of grease plants only with limited quantity can Use autoclave.Dress may be limited (in the case where compressive reaction is less important) using autoclave manufacture grease of calcium sulfonic acid Set the ability that other lubricating grease are prepared in the case that those react critically important wherein.Open container avoids these problems.

The 1-29 in the applications of embodiment 1-18 and ' 768 in ' 574 applications is incorporated herein by reference.About following implementation Example further describes and explains high alkaline calcium sulfonate lubricant composition and is used to prepare this composition according to the present invention Method：

Embodiment 1：The sulfoacid calcium complex grease of composition according to the present invention is carried out as follows, but in addition water and non-aqueous turn There is no period of delay between agent：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.61g is added in open mixing vessel, Then the neutral 1st group of paraffin base oil of solvent that the viscosity being added at 100F is the 327.55g of about 600SUS (paraffinic base oil, paraffin base oil, paraffin hydrocarbon base oil), and 11.70g that viscosity at 100C is 4cSt PAO.Similar with used in above-mentioned and ' 768 applications embodiments 10 and 11,400TBN high alkalinity oil-soluble sulfonic acid calcium is bad Matter sulfoacid calcium.Start mixing without heating using planetary agitating paddle.Then, the predominantly C12 benzene sulfonamides of 23.94g are added Acid.Mixing after twenty minutes, calcium hydroxy apetite that the average particle size that 50.65g is added is about 1 to 5 micron and 3.63g's is averaged The food-grade purity calcium hydroxide that granularity is about 1 to 5 micron, and its mixing is made to continue 30 minutes.It is added as separate constituent The amount of calcium hydroxide is other than the amount of the remaining calcium hydroxide included in high alkaline calcium sulfonate.Then, the ice of 0.88g is added The 12- hydroxy stearic acids of acetic acid and 10.53g simultaneously make it mix 10 minutes.Then, the average particle size that 55.03g is added is about 1 to 5 The calcium carbonate fine crushing of micron simultaneously makes it mix 5 minutes.The amount of calcium carbonate as separate constituent addition is in addition to being included in high alkalinity Except the amount of the calcium carbonate of dispersion in sulfoacid calcium.Then, it is added 13.20g's in the substantially the same time (non-delay phase) The water of hexylene glycol (non-aqueous transforming agent) and 38.22g.Heating mixture reaches 190F until temperature.Keep the temperature at 190F extremely 200F continues 45 minutes, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline carbon Sour calcium (calcite).Due to the weight of the lubricating grease of conversion, the identical paraffin base oil of other 56.07g is added.Then, The identical calcium hydroxide of 7.36g is added and it is made to mix 10 minutes.Then, the glacial acetic acid of 1.52g is added, is then added 27.30g 12- hydroxy stearic acids.When these acid react and lubricating grease is made further to thicken, the paraffinic base of 111.07g is added Base oil.Then, the boric acid of 9.28g is mixed in the hot water of 50g, and added mixture in lubricating grease.It is added in addition Then the aqueous solution of 75% phosphoric acid of 17.92g is added in the paraffin base oil of 54.47g.Then, electricity consumption heating mantle heats are mixed Object is closed, while continuing to stir.When lubricating grease reaches 300F, the styrene-of 22.22g is added with the solid form that clast is formed Ethylene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer all melt and are dissolved completely in profit at this time In consistent lubricant mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When lubricating grease is cooled to 300F When, food-grade anhydrous calcium sulfate that average particle size that 33.01g is added is about 1 to 5 micron.When the temperature of lubricating grease is cooled to When 200F, the polyisobutylene polymer of 4.43g is added.Continue to mix until lubricating grease reaches the temperature of 170F.Then, from mixing Lubricating grease is taken out in device, and by three-roll mill three times to obtain final smooth even quality.The lubricating grease has 287 work Make 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 23.9%.Dropping point>650F. In the embodiment, according to the embodiment of ' 768 applications, calcium hydroxy apetite and calcium carbonate are added before conversion.In addition, Then the 12- of the glacial acetic acid of 35% total amount and 28% total amount is added in the calcium hydroxide of the total amount of addition 33% before conversion Hydroxy stearic acid.Calcium hydroxide, glacial acetic acid, the 12- hydroxy stearic acids of surplus are added after conversion.

Embodiment 2：Other than adding non-aqueous transforming agent (hexylene glycol) there are delay, the lubricating grease with embodiment 1 is used Identical equipment, raw material, amount and manufacturing method prepare another sulfoacid calcium complex grease.By other Initial Compositions (including Water) be mixed and heated to about 190 °F of temperature (the first temperature adjust period of delay) and before hexylene glycol is added at such a temperature Kept for 1 hour (the first heat preservation period of delay).When hexylene glycol is added, almost moment convert.By lubricating grease in 190F-200F It is lower to be kept for other 45 minutes.Then, remaining process is identical as the lubricating grease of embodiment 1 of front.The lubricating grease is with 261 Work 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 21.1%.Dropping point>650F. As can be seen that compared with the lubricating grease of preceding embodiment 1, the lubricating grease of the present embodiment has improved a thickener yield, such as with What the relatively low final percentage for the high alkaline calcium sulfonate that work needle penetration is compared was proved.In fact, using work needle penetration with The linear dilution relationship of the percentage of high alkaline calcium sulfonate in final lubricating grease, if diluted with enough base oils to obtain The identical work needle penetration of 1 lubricating grease of embodiment, the then percentage of the prediction of the high alkaline calcium sulfonate in 2 lubricating grease of embodiment To be 19.2%.

Embodiment 3：Other than adding non-aqueous transforming agent (hexylene glycol) there are delay, the lubricating grease with embodiment 1 is used Identical equipment, raw material, amount and manufacturing method prepare another calcium complex grease.Other Initial Compositions (including water) is mixed Merge the temperature for being heated to about 190 °F (the first temperature adjusts period of delay), but different from embodiment 2, reaches 190 °F of (no guarantors Hold period of delay) when hexylene glycol is added immediately.When hexylene glycol is added, convert rapidly.Lubricating grease is protected at 190F-200F It holds other 45 minutes.Then, remaining process is identical as the lubricating grease of embodiment 1 of front.The final lubricating grease is with 290 Work 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 21.4%.Dropping point>650F. As can be seen that compared with the lubricating grease of preceding embodiment 1, the lubricating grease of the present embodiment has improved a thickener yield, such as with What the relatively low final percentage for the high alkaline calcium sulfonate that work needle penetration is compared was proved.

Embodiment 4：Carry out another sulfoacid calcium complex grease of composition according to the present invention as follows, but in addition water and There is no period of delay between non-aqueous transforming agent：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 311.67g is added to open mixing In container, the neutral 1st group of paraffinic base basis of solvent of the 451.37g of the viscosity with about 600SUS at 100F is then added Oil, and at 100C with 4cSt viscosity 10.30g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and The similar high-quality sulfoacid calcium used in the embodiment 4 and 12 of ' 768 applications.Using planetary agitating paddle start mixing without Heating.Then, the predominantly C12 alkyl benzene sulphonates of 31.48g are added.It is mixing after twenty minutes, the average particle size of 7.56g is added The calcium carbonate (other than the amount of the calcium carbonate of the dispersion contained in high alkaline calcium sulfonate) fine crushing for being about 1-5 microns simultaneously makes it Mixing 20 minutes.Then, the 12- hydroxy stearic acids of 4.90g are added, then be added 15.50g hexylene glycol (non-aqueous transforming agent) and The water (be substantially added simultaneously with hexylene glycol-non-delay phase) of 40.75g.Heating mixture reaches 190F until temperature.Then plus Enter the calcium carbonate of other 67.60g.It keeps the temperature at 190F to 200F and continues 45 minutes, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).The water of other 5.00g is added, Then be added 19.60g 12- hydroxy stearic acids, the glacial acetic acid of 2.40g and the 75% of 16.64g phosphoric acid aqueous solution.Then, Electricity consumption heating mantle heats mixture, while continuing to stir.When lubricating grease reaches 300F, it is added with the solid form that clast is formed 27.85g styrene ethylene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer are all molten at this time Change and is dissolved completely in lubrication lipoprotein mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When When lubricating grease is cooled to 250F, the paraffin base oil of other 32.75g is added.Then, the polyisobutene that 5.05g is added is poly- Close object.Continue to mix until lubricating grease reaches the temperature of 170F.Then, lubricating grease is taken out from mixer, and passes through triple-roller mill Machine is three times to obtain final smooth even quality.The lubricating grease has 271 60 stroke needle penetration of work.In final lubricating grease High alkalinity oil-soluble sulfonic acid calcium percentage be 31.0%.Dropping point is 629F.In this embodiment, according to the reality of ' 574 applications Mode is applied, added calcium carbonate is added before conversion.Moreover, the 12- hydroxyls that 20% total amount is added before conversion are hard Resin acid.The 12- hydroxy stearic acids of surplus are added in post-conversion.

Embodiment 5：Other than adding non-aqueous transforming agent (hexylene glycol) there are delay, the lubricating grease with embodiment 4 is used Identical equipment, raw material, amount and manufacturing method prepare another calcium complex grease.Other Initial Compositions (including water) is mixed Merge and is heated to about 190 °F of temperature (the first temperature adjusts period of delay) and keeps 1 at such a temperature before hexylene glycol is added Hour (first is kept for period of delay).When hexylene glycol is added, almost moment visible conversion takes place.Seem to complete in conversion Later, lubricating grease is kept other 45 minutes at 190F-200F.Then, the lubrication of remaining process and the embodiment of front 4 Lipid phase is same.Final lubricating grease has 265 60 stroke needle penetration of work.High alkalinity oil-soluble sulfonic acid calcium in final lubricating grease Percentage is 29.2%.Dropping point>650F.As can be seen that compared with the lubricating grease of preceding embodiment 4, the lubricating grease of the present embodiment It is proved with improved thickener yield, such as relatively low final percentage of the high alkaline calcium sulfonate compared with the needle penetration that works 's.

Embodiment 6：Using with United States Patent (USP) 5,308,514 and 5,338,467 (respectively on May 3rd, 1994 and 1994 August licenses to Witco companies on 16th) in similar component and method prepare another sulfoacid calcium complex grease, wherein turning It adds at least part of long chain fatty acids before changing and transforming agent can be served as.Specifically, it is added before conversion The 12- hydroxy stearic acids of 54.1% total amount and whole glacial acetic acids.The 12- hydroxy stearic acids of surplus are added in post-conversion, Then calcium hydroxide and boric acid aqueous mixtures are added.According to the range of ' 514 patents, the calcium hydroxide of addition be used as with it is compound The alkali of acid reaction uniquely added, and without using calcium hydroxy apetite or the calcium carbonate of addition.Do not postpone in embodiment 6 Non-aqueous transforming agent is added.

The following lubricating grease for preparing embodiment 6：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 380.26g is added to out It puts in mixing vessel, the neutral 1st group of paraffinic base of solvent of the 603.6g of the viscosity with about 600SUS at 100F is then added Base oil.Start mixing without heating using planetary agitating paddle.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned with And the similar high-quality sulfoacid calcium used in the embodiment 4 and 12 of ' 768 applications.Then, the predominantly C12 of 21.75g is added Alkyl benzene sulphonate.It is mixing after twenty minutes, the 12- hydroxy stearic acids of 21.56g is added, the hexylene glycol that 18.12g is then added is (non- Water transforming agent) and 38.45g water (being substantially added simultaneously with hexylene glycol).After 10 minutes of mixing, the ice second of 2.46g is added Acid.Then, which is heated in the case where continuing mixing until temperature reaches 190F.190F, which is kept the temperature at, to the 200F times is 45 minutes.Then, the acetic acid of other 2.03g is added, and the batch is mixed until Fourier transform infrared (FTIR) spectrum Show that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).The paraffinic base basis of other 248.29g is added Then the 12- hydroxy stearic acids of 18.29g are added in oil.So that it is kept mixing 15 minutes, while maintaining the temperature at 190F to 200F. Then, the calcium hydroxide of the addition of the food-grade purity fine crushing for the 38.23g for being about 1 to 5 micron by average particle size is (in addition to packet Except any remaining calcium hydroxide being contained in high alkaline calcium sulfonate) it is mixed with the water of 50g, and add mixture to lubricating grease In.Then, the boric acid of 23.12g is mixed with the hot water of 50ml, and added mixture in lubricating grease.Then, by lubricating grease It is heated to 390F.Then, heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.It is cooled to when by lubricating grease When 170F, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain final smooth even quality.

The lubricating grease of embodiment 6 has 320 60 stroke needle penetration of work.High alkalinity oil-soluble sulphur in final lubricating grease The percentage of sour calcium is 27.6%.In this embodiment, all hexylene glycol transforming agents are added together with water, then add any Heat before be added a part acetic acid, and be heated to 190 °F of times be 45 minutes after be added a part.The acetic acid added twice It is not related to " postponing ", because in the presence of the non-aqueous transforming agent (hexylene glycol) of another kind used, and 10 minutes not heated are mixed It is considered as delay to close interval not.It puts into practice according to prior art, by all hexylene glycols (it is main transforming agent) and conversion The hydroxy stearic acid of preceding addition is added together with water.Therefore, which is not related to any " delay " and results in higher than expectation hundred Divide the high alkaline calcium sulfonate of ratio.Based on the embodiment, when not postponing to other non-aqueous transforming agents, in addition at least part When acetic acid, time passage is helpless to the amount of high alkaline calcium sulfonate being reduced to aspiration level, here it is for the purposes of the present invention, The reason of this addition is not considered as " delay ".

Embodiment 6A：Another lubricating grease is almost identically prepared with 6 lubricating grease of embodiment of front.Unique area It is not, once reaching 190F in initial heating process, just not add other glacial acetic acid.The lubricating grease has 339 work Make 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 27.6%.These results and reality It is similar to apply example 6, and further demonstrates that, when using another non-aqueous transforming agent, adds water and adds the time between acetic acid Interval is not that thickener yield is caused to improve " delay ".

Embodiment 7：Other than adding non-aqueous transforming agent (hexylene glycol) there are delay, the lubricating grease with embodiment 6 is used Identical equipment, raw material, amount and manufacturing method prepare another calcium complex grease.By other Initial Compositions (including water and Acetic acid) it is mixed and heated to about 190 °F of temperature (the first temperature adjusts period of delay) and before hexylene glycol is added in the temperature It is lower to be kept for 1 hour (the first heat preservation period of delay).When hexylene glycol is added, lubricating grease is maintained at 190F-200F until conversion seems It completes.Then, remaining process is identical as the lubricating grease of embodiment 6 of front.Final lubricating grease has 281 60 stroke of work Needle penetration.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 27.6%.Dropping point>650F.As can be seen that with The lubricating grease of preceding embodiment 6 is compared, and the lubricating grease of the present embodiment has improved thickener yield, although as having substantially The high alkalinity oil-soluble sulfonic acid calcium of same percentage, but firmer needle penetration proof.In fact, using work needle penetration with The linear dilution relationship of the percentage of high alkaline calcium sulfonate in final lubricating grease, if diluted with enough base oils to obtain The identical work needle penetration of 6 lubricating grease of embodiment, the then percentage of the prediction of the high alkaline calcium sulfonate in 7 lubricating grease of embodiment To be 24.2%.The embodiment is shown than embodiment 6 and 6A preferably as a result, wherein unique variation is that delay is added non-aqueous turn Agent hexylene glycol.

The following table 1 summarizes the result and method used in embodiment hereof 1-7.High alkaline calcium sulfonate shown in bracket Amount is with dilute sample lubricating grease when the additional base oil of addition come after realization in dash and as described above shown Embodiment number the amount of the high alkaline calcium sulfonate estimated when identical needle penetration.These the first seven embodiments strong table together It is bright, improve thickener yield by postponing to add non-aqueous transforming agent.In addition, (1) poor quality and good height is added by delay Both alkaline sulfoacid calciums, and (2) using for being reacted with Compound-acid representative prior art calcic alkali (for example, calcium hydroxide) with And using for being reacted with Compound-acid addition calcium calcium carbonate or calcium hydroxy apetite improve thickener yield.Complex grease Also excellent dropping point is shown.

Table 1- high basicity composite mahogany grease of calcium sulfonic acid

Following embodiment further demonstrates the superior function of the high alkaline calcium sulfonate lubricating grease of the present invention, can pass through Delay adds non-aqueous transforming agent and realizes and have different period of delays and temperature range for the duration of each period of delay.

Embodiment 8：According to ' 768 application an embodiment, using calcium hydroxy apetite, addition calcium carbonate and The calcium hydroxide of addition prepares another sulfoacid calcium complex grease as calcic alkali to be reacted with Compound-acid.The embodiment is to use In the baseline compared with embodiment 9-17, do not postpone because non-aqueous transforming agent (hexylene glycol) is added in this embodiment.

The following lubricating grease for preparing embodiment 8：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.98g is added to out It puts in mixing vessel, the neutral 1st group of paraffinic base of solvent of the 378.68g of the viscosity with about 600SUS at 100F is then added Base oil, and at 100C with 4cSt viscosity 11.10g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is upper The similar sulfoacid calcium inferior stated and used in the embodiment 10 and 11 of ' 768 applications.Start to mix using planetary agitating paddle It closes without heating.Then, the predominantly C12 alkyl benzene sulphonates of 23.96g are added.It is mixing after twenty minutes, the flat of 50.62g is added The food-grade purity addition that the average particle size for the calcium hydroxy apetite and 3.68g that equal granularity is about 1 to 5 micron is about 1 to 5 micron Calcium hydroxide, and its mixing is made to continue 30 minutes.Then, the glacial acetic acid of 0.84g and the 12- hydroxy stearic acids of 10.56g is added And it is made to mix 10 minutes.Then, the calcium carbonate for the addition fine crushing that the average particle size that 55.05g is added is about 1 to 5 micron simultaneously makes It is mixed 5 minutes.Then, the hexylene glycol of 13.34g and the water (not postponing) of 39.27g is added.Heating mixture is reached until temperature To 190F.It keeps the temperature at 190F to 200F and continues 45 minutes, until Fourier transform infrared (FTIR) spectrum shows to have sent out Raw amorphous calcium carbonate is converted into crystalline calcium carbonate (calcite).Then, the calcium hydroxide of the identical addition of 7.34g is added and makes It is mixed 10 minutes.Then, the glacial acetic acid of 1.59g is added, the 12- hydroxy stearic acids of 27.22g are then added.It is hard in 12- hydroxyls After resin acid is melted and is mixed into lubricating grease, then, the boric acid of 9.37g is mixed in the hot water of 50g, and mixture is added Enter into lubricating grease.Due to the weight of lubricating grease, the identical paraffin base oil of other 62.29g is added.Then, it is added 75% phosphate aqueous solution of 17.99g simultaneously makes it mix and react.The paraffin base oil of other 46.90g is added.Then, it uses Electric heating cover heats mixture, while continuing to stir.When lubricating grease reaches 300F, it is added with the solid form that clast is formed 22.17g styrene ethylene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer are all molten at this time Change and is dissolved completely in lubrication lipoprotein mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When When lubricating grease is cooled to 300F, food-grade anhydrous calcium sulfate that average particle size that 33.30g is added is about 1 to 5 micron.Work as lubrication When the temperature of fat is cooled to 200F, the arylamine antioxidant of 2.27g and the polyisobutylene polymer of 4.46g is added.Addition is another The identical paraffin base oil of outer 55.77g.Continue to mix until lubricating grease reaches the temperature of 170F.Then, from mixer Lubricating grease is taken out, and by three-roll mill three times to obtain final smooth even quality.The lubricating grease has 281 work 60 Stroke needle penetration.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 24.01%.Dropping point is>650F.

Embodiment 9：Another sulfoacid calcium complex grease is prepared in a manner of similar with previous 8 lubricating grease of embodiment. Unique significant difference is that delay addition hexylene glycol until lubricating grease has been heated to about 190F to 200F, (prolong by the adjusting of the first temperature The slow phase) and 30 minutes (first is kept for period of delay) is kept at such a temperature.Prepare lubricating grease as follows：By the 400TBN of 264.04g High alkalinity oil-soluble sulfonic acid calcium is added in open mixing vessel, and the viscosity with about 600SUS at 100F is then added The neutral 1st group of paraffin base oil of the solvent of 378.21g, and at 100C the 11.15g of the viscosity with 4cSt PAO. 400TBN high alkalinity oil-soluble sulfonic acid calcium be with it is above-mentioned and being used in the embodiment 10 and 11 of ' 768 applications similar bad Matter sulfoacid calcium.Start mixing without heating using planetary agitating paddle.Then, the predominantly C12 benzene sulfonamides of 23.91g are added Acid.Mixing after twenty minutes, calcium hydroxy apetite that the average particle size that 50.60g is added is about 1 to 5 micron and 3.61g's is averaged The calcium hydroxide for the food-grade purity addition that granularity is about 1 to 5 micron, and its mixing is made to continue 30 minutes.Then, it is added The glacial acetic acid of 0.83g and the 12- hydroxy stearic acids of 10.56g simultaneously make it mix 10 minutes.Then, the average grain of 55.05g is added The calcium carbonate for the addition fine crushing that degree is about 1 to 5 micron simultaneously makes it mix 5 minutes.Then, the water of 38.18g is added.Heating mixing Object is until temperature reaches 190F (the first temperature adjusts period of delay).Keep the temperature at 190F to the 200F times be 30 minutes (the One is kept for period of delay).Then, the hexylene glycol of 13.31g is added.It keeps the temperature at 190F to 200F and continues 45 minutes, until Fu In infrared (FTIR) spectrum of leaf transformation show that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).It is added in addition The water of 16ml is to replace the water lost by evaporation.Then, the calcium hydroxide of the identical addition of 7.39g is added and it is made to mix 10 Minute.Then, the glacial acetic acid of 1.65g is added, the 12- hydroxy stearic acids of 27.22g are then added.It is melted in 12- hydroxy stearic acids And after being mixed into lubricating grease, since lubricating grease becomes heavier, the identical paraffin base oil of other 54.58g is added.Then, The boric acid of 9.36g is mixed in the hot water of 50g, and is added mixture in lubricating grease.Due to the weight of lubricating grease, it is added In addition the identical paraffin base oil of 59.05g.Then, 18.50 75% phosphate aqueous solution is added and make its mix and it is anti- It answers.The paraffin base oil of other 52.79g is added.Then, electricity consumption heating mantle heats mixture, while continuing to stir.Work as lubrication When fat reaches 300F, the styrene ethylene-propylene copolymer of 22.25g is added with the solid form that clast is formed.By lubricating grease It is further heated to about 390F, all polymer are all melted and are dissolved completely in lubrication lipoprotein mixture at this time.Heating mantle is moved It removes and so that lubricating grease is cooled down by continuing stirring in outdoor.When lubricating grease is cooled to 300F, the average particle size of 33.15g is added The food-grade anhydrous calcium sulfate for being about 1 to 5 micron.When the temperature of lubricating grease is cooled to 200F, the arylamine that 2.29g is added is anti- The polyisobutylene polymer of oxidant and 4.79g.Add the identical paraffin base oil of other 108.11g.It is straight to continue mixing Reach the temperature of 170F to lubricating grease.Then, lubricating grease is taken out from mixer, and final to obtain three times by three-roll mill Smooth even quality.The lubricating grease has 272 60 stroke needle penetration of work.High alkalinity oil-soluble sulphur in final lubricating grease The percentage of sour calcium is 21.78%.Dropping point>650F.As can be seen that compared with the lubricating grease of embodiment 8, which, which has, carries High thickener yield.

Embodiment 10：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous embodiment 8 and 9 lubricating grease Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to about 190F to 200F (the first temperature tune Save period of delay) and 2 hours (first is kept for period of delay) is kept at such a temperature.Prepare lubricating grease as follows：By 264.35g's 400TBN high alkalinity oil-soluble sulfonic acid calcium is added in open mixing vessel, is then added at 100F viscous with about 600SUS The neutral 1st group of paraffin base oil of the solvent of the 377.10g of degree, and at 100C the 11.02g of the viscosity with 4cSt PAO. The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and being used in the embodiment 10 and 11 of ' 768 applications similar bad Matter sulfoacid calcium.Start mixing without heating using planetary agitating paddle.Then, the predominantly C12 benzene sulfonamides of 24.00g are added Acid.Mixing after twenty minutes, calcium hydroxy apetite that the average particle size that 50.66g is added is about 1 to 5 micron and 3.76g's is averaged The calcium hydroxide for the food-grade purity addition that granularity is about 1 to 5 micron, and its mixing is made to continue 30 minutes.Then, it is added The glacial acetic acid of 0.91g and the 12- hydroxy stearic acids of 10.60g simultaneously make it mix 10 minutes.Then, the average grain of 55.05g is added The calcium carbonate for the addition fine crushing that degree is about 1 to 5 micron simultaneously makes it mix 5 minutes.Then, the water of 38.50g is added.Heating mixing Object is until temperature reaches 190F (the first temperature adjusts period of delay).Keep the temperature at 190F to the 200F times be 2 hours (first Kept for period of delay).Then, the hexylene glycol of 13.57g is added.It is additionally added the water of other 15ml, because in the heating phase of two hours Between, some water initially added have evaporated.It is noted that in this embodiment, in order to make up evaporation loss (and in its hair In every other embodiment in the case of life), the water of this addition does not restart new period of delay, because it is Simply replace some water initially added.Once visible conversion has begun, just keeps the temperature at 190F to 200F and hold It is 45 minutes continuous, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).The water of other 35ml is added.Then, the identical calcium hydroxide of 7.27g is added and it is made to mix 15 minutes.So Afterwards, the glacial acetic acid of 1.59g is added, the 12- hydroxy stearic acids of 27.25g are then added.Then, by the boric acid of 9.36g 50g's It mixes, and is added mixture in lubricating grease in hot water.Due to the weight of lubricating grease, the identical stone of other 55.79g is added Cerul base oil.Then, 18.15 75% phosphate aqueous solution is added and it is made to mix and react.Then, with electric heating cover plus Hot mixt, while continuing to stir.When lubricating grease reaches 300F, the benzene second of 22.08g is added with the solid form that clast is formed Alkene-ethylene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer are all melted and are completely dissolved at this time In lubricating lipoprotein mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When lubricating grease is cooled to When 300F, food-grade anhydrous calcium sulfate that average particle size that 33.08g is added is about 1 to 5 micron.When the temperature of lubricating grease cools down When to 200F, the arylamine antioxidant of 2.44g and the polyisobutylene polymer of 4.52g is added.Add the phase of other 216.00g Same paraffin base oil.Continue to mix until lubricating grease reaches the temperature of 170F.Then, lubricating grease is taken out from mixer, And by three-roll mill three times to obtain final smooth even quality.The lubricating grease has 285 60 stroke needle penetration of work. The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 21.87%.Dropping point>650F.As can be seen that and embodiment 8 lubricating grease is compared, which has the thickener yield and similar to the lubricating grease of embodiment 9 improved.

Embodiment 11：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous embodiment 8-10 lubricating grease Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to about 190F to 200F (the first temperature tune Save period of delay) and keep at such a temperature 30 minutes (first is kept for period of delay), being subsequently cooled to 160F, (second temperature adjusting is prolonged The slow phase), and (second is kept for period of delay) is kept for two hours in 160F to 170F, it is then back to heating up to 190F (thirds Temperature adjusts period of delay), and hexylene glycol is added immediately when reaching 190F (being kept for period of delay without third).

The following lubricating grease for preparing embodiment 11：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.09g is added to In open mixing vessel, the neutral 1st group of paraffin of solvent of the 380.83g of the viscosity with about 600SUS at 100F is then added Base base oil, and at 100C with 4cSt viscosity 11.22g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with It is above-mentioned with the similar sulfoacid calcium inferior that uses in the embodiment 10 and 11 of ' 768 applications.Start to mix using planetary agitating paddle It closes without heating.Then, the predominantly C12 alkyl benzene sulphonates of 23.97g are added.It is mixing after twenty minutes, the flat of 50.59g is added The food-grade purity addition that the average particle size for the calcium hydroxy apetite and 3.73g that equal granularity is about 1 to 5 micron is about 1 to 5 micron Calcium hydroxide, and its mixing is made to continue 30 minutes.Then the 12- hydroxy stearic acids of the glacial acetic acid and 10.57g of 0.82g are added And it is made to mix 10 minutes.Then, the calcium carbonate for the addition fine crushing that the average particle size that 55.03g is added is about 1 to 5 micron simultaneously makes It is mixed 5 minutes.Then, the water of 38.11g is added.Until temperature reaches 190F, (the first temperature adjusts delay to heating mixture Phase).Keep the temperature at 190F to the 200F times be 30 minutes (first keep period of delay).Then, temperature is reduced to 160F (second temperature adjusts period of delay), and keep the temperature at two hours (the second heat preservation period of delay) of 160F to 170F.In this phase Between, since some water initially added have evaporated, the water of other 15ml is added.As already mentioned, in order to Evaporation loss is made up, the water added before subsequent transformation is not used in determining period of delay, only uses the water of addition for the first time.Then, will Temperature is increased to 190F (third temperature adjusts period of delay).The water of other 20ml is added.Immediately after be added 13.20g oneself two Alcohol (is kept for period of delay) without third.Once visible conversion has begun, just keeps the temperature at 190F to 200F and continue 45 Minute, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (side's solution Stone).Due to the thickening amount occurred, the identical paraffin base oil of other 54.53g is added and makes its mixing.Then, add Enter the identical calcium hydroxide of 7.27g and it is made to mix 15 minutes.Then, the glacial acetic acid of 1.60g is added, 27.23g is then added 12- hydroxy stearic acids.After 5 minutes, the boric acid of 9.38g is mixed in the hot water of 50g, and adds mixture to lubrication In fat.Due to the weight of lubricating grease, the identical paraffin base oil of other 55.41g is added.Then, it is added the 75% of 18.10 Phosphate aqueous solution and so that it is mixed and is reacted.Then, electricity consumption heating mantle heats mixture, while continuing to stir.Work as lubricating grease When reaching 300F, the styrene ethylene-propylene copolymer of 22.25g is added with the solid form that clast is formed.By lubricating grease into One step is heated to about 390F, and all polymer are all melted and are dissolved completely in lubrication lipoprotein mixture at this time.Heating mantle is removed And lubricating grease is set to cool down by continuing stirring in outdoor.When lubricating grease is cooled to 300F, the average particle size that 33.06g is added is About 1 to 5 micron of food-grade anhydrous calcium sulfate.When the temperature of lubricating grease is cooled to 200F, the arylamine antioxygen of 2.51g is added The polyisobutylene polymer of agent and 5.43g.Add the identical paraffin base oil of other 135.25g.Continue mixing until Lubricating grease reaches the temperature of 170F.Then, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain finally Smooth even quality.The lubricating grease has 278 60 stroke needle penetration of work.High alkalinity oil-soluble sulfonic acid in final lubricating grease The percentage of calcium is 22.27%.Dropping point>650F.As can be seen that compared with the lubricating grease of embodiment 8, which, which has, improves Thickener yield.

Embodiment 12：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous embodiment 8-11 lubricating grease Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to 160F (the first temperature adjusts period of delay) And be maintained at 160F to the 170F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (second Temperature adjusts period of delay), and hexylene glycol is added immediately when reaching 190F (without the second holding period of delay).

The following lubricating grease for preparing embodiment 12：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.48g is added to In open mixing vessel, the neutral 1st group of paraffin of solvent of the 382.94g of the viscosity with about 600SUS at 100F is then added Base base oil, and at 100C with 4cSt viscosity 11.18g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with It is above-mentioned with the similar sulfoacid calcium inferior that uses in the embodiment 10 and 11 of ' 768 applications.Start to mix using planetary agitating paddle It closes without heating.Then, the predominantly C12 alkyl benzene sulphonates of 24.21g are added.It is mixing after twenty minutes, the flat of 50.68g is added The food-grade purity addition that the average particle size for the calcium hydroxy apetite and 3.64g that equal granularity is about 1 to 5 micron is about 1 to 5 micron Calcium hydroxide, and its mixing is made to continue 30 minutes.Then, the glacial acetic acid of 0.89g and the 12- hydroxy stearic acids of 10.61g is added And it is made to mix 10 minutes.Then, the calcium carbonate for the addition fine crushing that the average particle size that 55.06g is added is about 1 to 5 micron simultaneously makes It is mixed 5 minutes.Then, the water of 39.08g is added.Then, mixture is heated until temperature reaches 160F.Temperature is kept It it is 30 minutes two hours in 160F to 170F times.During this period, it since some water initially added have evaporated, is added The water of other 15ml.Then, temperature is risen into 190F, the hexylene glycol of 13.19g is added immediately after.In addition, being added in addition The water of 25ml.Once visible conversion has begun, just keeps the temperature at 190F to 200F and continue 45 minutes, until Fourier Transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).Then, it is added The identical calcium hydroxide of 7.36g simultaneously makes it mix 10 minutes.Then, the glacial acetic acid of 1.53g is added, is then added 27.15g's 12- hydroxy stearic acids.Due to the weight of lubricating grease, the identical paraffin base plinth oil of other 54.31g is added and makes its mixing. Then, the boric acid of 9.36g is mixed in the hot water of 50g, and added mixture in lubricating grease.Since lubricating grease becomes more Weight, therefore the identical paraffin base plinth oil of other 57.39g is added.Then, 75% phosphate aqueous solution of 17.61g is added And it is made to mix and react.The identical paraffin base oil of other 52.07g is added.Then, electricity consumption heating mantle heats mix Object, while continuing to stir.When lubricating grease reaches 300F, styrene-second of 22.14g is added with the solid form that clast is formed Alkene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer all melt and are dissolved completely in lubrication at this time In lipoprotein mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When lubricating grease is cooled to 300F, The food-grade anhydrous calcium sulfate that the average particle size of 33.00g is about 1 to 5 micron is added.When the temperature of lubricating grease is cooled to 200F When, the arylamine antioxidant of 2.42g and the polyisobutylene polymer of 5.62g is added.Add the identical stone of other 192.05g Cerul base oil.Continue to mix until lubricating grease reaches the temperature of 170F.Then, lubricating grease is taken out from mixer, and is passed through Three-roll mill is three times to obtain final smooth even quality.The lubricating grease has 287 60 stroke needle penetration of work.Final profit The percentage of high alkalinity oil-soluble sulfonic acid calcium in consistent lubricant is 20.36%.Dropping point is 639F.As can be seen that the profit with embodiment 8 Consistent lubricant is compared, which has the thickener yield improved.

Embodiment 13：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous 12 lubricating grease of embodiment Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to 140F (the first temperature adjusts period of delay) And be maintained at 140F to the 150F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (second Temperature adjusts period of delay) it is converted for hexylene glycol to be added immediately and (is kept for period of delay without second), then addition is as implemented The other components that example 12 is summarized.Final lubricating grease has 283 60 stroke needle penetration of work.High alkalinity oil in final lubricating grease The percentage of dissolubility sulfoacid calcium is 20.88%.Dropping point>650F.As can be seen that compared with the lubricating grease of embodiment 8, the lubricating grease Thickener yield with raising.

Embodiment 14：The compound profit of another sulfoacid calcium is prepared in a manner of similar with previous embodiment 12-13 lubricating grease Consistent lubricant.Unique significant difference is that until lubricating grease has been heated to 110F, (the first temperature adjusts delay to delay addition hexylene glycol Phase) and be maintained at 110F to the 120F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (the Two temperature adjust period of delay) it is converted for hexylene glycol to be added immediately and (is kept for period of delay without second), then addition is strictly according to the facts Apply the other components of the general introduction of example 12.Final lubricating grease has 287 60 stroke needle penetration of work.High alkalinity in final lubricating grease The percentage of oil-soluble sulfonic acid calcium is 21.63%.Dropping point>650F.As can be seen that compared with the lubricating grease of embodiment 8, the lubrication Fat has the thickener yield improved.

Embodiment 15：The compound profit of another sulfoacid calcium is prepared in a manner of similar with previous embodiment 12-14 lubricating grease Consistent lubricant.Unique significant difference is delay addition hexylene glycol until lubricating grease has been stirred and has been maintained at ambient lab temperature (about 25C) the lower time is 30 minutes two hours (first is kept for period of delay, and period of delay is adjusted without any temperature), is then heated to Up to 190F (second temperature adjusts period of delay) is converted for hexylene glycol to be added immediately and (is kept for period of delay without second), with The addition other components that such as embodiment 12 is summarized afterwards.Final lubricating grease has 279 60 stroke needle penetration of work.Final lubricating grease In high alkalinity oil-soluble sulfonic acid calcium percentage be 21.40%.Dropping point>650F.As can be seen that the lubricating grease with embodiment 8 It compares, which has the thickener yield improved.Note that even if the first delay (being kept for period of delay) is not related to adding completely Heat, in all embodiment 9-14 lubricating grease of hexylene glycol technology for wherein using delay, which shows in thickener Apparent thickener yield in the general range of yield improves.In addition, by comparing these embodiments, the first temperature range is simultaneously The percentage of the high alkaline calcium sulfonate in these lubricating grease is not significantly affected, although the first temperature range is in about 140-170 Between range produce best thickener yield results.

Embodiment 16：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous embodiment 8-15 lubricating grease Fat.Unique significant difference be delay addition hexylene glycol until lubricating grease mixed under ambient lab temperature 2 hours 30 points Clock (first is kept for period of delay, is adjusted without any temperature), is then heated to 160F (second temperature adjust period of delay), and 30 minutes 2 hours (second is kept for period of delay) is mixed under 160F to 170F, being then heated to up to 190F, (adjusting of third temperature is prolonged The slow phase), and hexylene glycol (being kept for period of delay without third) is added immediately.

The following lubricating grease for preparing embodiment 16：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.28g is added to In open mixing vessel, the neutral 1st group of paraffin of solvent of the 382.25g of the viscosity with about 600SUS at 100F is then added Base base oil, and at 100C with 4cSt viscosity 11.10g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with It is above-mentioned with the similar sulfoacid calcium inferior that uses in the embodiment 10 and 11 of ' 768 applications.Start to mix using planetary agitating paddle It closes without heating.Then, the predominantly C12 alkyl benzene sulphonates of 24.08g are added.It is mixing after twenty minutes, the flat of 50.59g is added The food-grade purity addition that the average particle size for the calcium hydroxy apetite and 3.84g that equal granularity is about 1 to 5 micron is about 1 to 5 micron Calcium hydroxide, and its mixing is made to continue 30 minutes.Then, the glacial acetic acid of 0.89g and the 12- hydroxy stearic acids of 10.56g is added And it is made to mix 10 minutes.Then, the calcium carbonate for the addition fine crushing that the average particle size that 55.56g is added is about 1 to 5 micron simultaneously makes It is mixed 5 minutes.Then, the water of 38.59g is added.Mixture is mixed 2 hours 30 under ambient lab temperature (about 25C) Minute.Then, it heats the mixture to 160F and is maintained at 160F to 30 minutes 2 hours between 170F.During this period, due to one A little water initially added have evaporated, therefore the water of other 20ml is added.Then, temperature is risen into 190F, added immediately after Enter the hexylene glycol of 13.68g.Once visible conversion has begun, just keeps the temperature at 190F to 200F and continue 45 minutes, directly Show that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite) to Fourier transform infrared (FTIR) spectrum.Due to Lubricating grease becomes weight, and the identical paraffinic mineral oil of other 57.09g is added.In addition, the water of other 15ml is added.Then, it is added The identical calcium hydroxide of 7.17g simultaneously makes it mix 10 minutes.Then, the glacial acetic acid of 1.56g is added, is then added 27.16g's 12- hydroxy stearic acids.Then, the boric acid of 9.37g is mixed in the hot water of 50g, and added mixture in lubricating grease.By Become heavier in lubricating grease, therefore the identical paraffin base oil of other 70.35g is added.Then, 18.20 are added 75% phosphate aqueous solution simultaneously makes it mix and react.The identical paraffin base oil of other 33.49g is added.Then, electricity consumption Heating mantle heats mixture, while continuing to stir.When lubricating grease reaches 300F, it is added with the solid form that clast is formed 22.59g styrene ethylene-propylene copolymer.Lubricating grease is further heated to about 390F, all polymer are all molten at this time Change and is dissolved completely in lubrication lipoprotein mixture.Heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When When lubricating grease is cooled to 300F, food-grade anhydrous calcium sulfate that average particle size that 33.19g is added is about 1 to 5 micron.Work as lubrication When the temperature of fat is cooled to 200F, the arylamine antioxidant of 2.27g and the polyisobutylene polymer of 5.77g is added.Addition is another The identical paraffin base oil of outer 167.19g.Continue to mix until lubricating grease reaches the temperature of 170F.Then, from mixer Middle taking-up lubricating grease, and by three-roll mill three times to obtain final smooth even quality.Lubricating grease has 274 work 60 Stroke needle penetration.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 20.77%.Dropping point>650F.It can see Go out, compared with the lubricating grease of embodiment 8, which has the thickener yield improved.

Embodiment 17：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous 12 lubricating grease of embodiment Fat.Unique significant difference (is not postponed) before any heating, and 25% total amount oneself is added together with water when starting Glycol.It is first heated to 160F (the first temperature adjusts period of delay) in mixture and is maintained at 160F to 2 hours between 170F After 30 minutes (first is kept for period of delay), remaining hexylene glycol is added.Then, mixture is immediately heated to 190F-200F Carry out routine transformation.

The following lubricating grease for preparing embodiment 17：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 264.39g is added to In open mixing vessel, the neutral 1st group of paraffin of solvent of the 383.09g of the viscosity with about 600SUS at 100F is then added Base base oil, and at 100C with 4cSt viscosity 10.56g PAO.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with It is above-mentioned with the similar sulfoacid calcium inferior that uses in the embodiment 9 and 10 of ' 768 applications.Start to mix using planetary agitating paddle It closes without heating.Then, the predominantly C12 alkyl benzene sulphonates of 24.02g are added.It is mixing after twenty minutes, the flat of 51.55g is added The food-grade purity addition that the average particle size for the calcium hydroxy apetite and 3.64g that equal granularity is about 1 to 5 micron is about 1 to 5 micron Calcium hydroxide, and its mixing is made to continue 30 minutes.Then, the glacial acetic acid of 0.90g and the 12- hydroxy stearic acids of 10.61g is added And it is made to mix 10 minutes.Then, the calcium carbonate for the addition fine crushing that the average particle size that 55.26g is added is about 1 to 5 micron simultaneously makes It is mixed 5 minutes.Then, the water of 38.46g and the hexylene glycol (the addition hexylene glycol of about 25% total amount) of 3.62g is added.So Afterwards, mixture is heated until temperature reaches 160F.Keep the temperature at 160F to the 170F times be 30 minutes two hours.Herein The water of other 15ml is added since some water initially added have evaporated in period.Then be added 10.46g oneself two The water of alcohol and 10ml, and temperature is risen into 190F.Once visible conversion has begun, 190F is just kept the temperature to 200F Continue 45 minutes, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).Then, the calcium hydroxide of the identical addition of 7.55g is added and it is made to mix 10 minutes.Then, by the ice of 1.54g The 12- hydroxy stearic acids of acetic acid and 27.13g are added to lubricating grease.Due to the weight of lubricating grease, the identical of other 57.31g is added Paraffinic base meter plinth oil and make its mixing.Then, the boric acid of 9.36g is mixed in the hot water of 50g, and added mixture to In lubricating grease.Then, 75% phosphate aqueous solution of 17.78g is added and it is made to mix and react.The phase of other 54.03g is added Same paraffin base oil.Then, electricity consumption heating mantle heats mixture, while continuing to stir.When lubricating grease reaches 300F, with The styrene ethylene-propylene copolymer of 22.48g is added in the solid form that clast is formed.Lubricating grease is further heated to about 390F, at this time all polymer all melt and be dissolved completely in lubrication lipoprotein mixture in.Heating mantle is removed and by outdoor Continuing stirring makes lubricating grease cool down.When lubricating grease is cooled to 300F, the average particle size that 33.16g is added is about 1 to 5 micron Food-grade anhydrous calcium sulfate.When the temperature of lubricating grease is cooled to 200F, the arylamine antioxidant and 4.41g of 2.41g is added Polyisobutylene polymer.Add the identical paraffin base oil of other 232.52g.Continue mixing until lubricating grease reaches The temperature of 170F.Then, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain final smooth even matter Ground.The lubricating grease has 296 60 stroke needle penetration of work.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease It is 20.59%.Dropping point>650F.As can be seen that compared with the lubricating grease of embodiment 8, which has the thickener production improved Rate.

The following table 2 summarizes the result and method used in embodiment hereof 8-17.All these examples use hydroxyl phosphorus The calcium hydroxide of lime stone calcium, the calcium carbonate of addition and addition is as calcic alkali, for being reacted with Compound-acid and all using bad Matter high alkaline calcium sulfonate.These embodiments show strongly together when use high alkaline calcium sulfonate inferior, and even if work as When not heated before first is kept for period of delay (environment temperature is kept for period of delay), changed by postponing that non-aqueous transforming agent is added Kind thickener yield.Complex grease also shows excellent dropping point.

Table 2- high basicity composite mahogany grease of calcium sulfonic acid

Following two embodiments further demonstrate the superior function of the high alkaline calcium sulfonate lubricating grease of the present invention, can be with By postponing to add non-aqueous transforming agent realization and there is different period of delays and temperature for the duration of each period of delay Range.

Embodiment 18：Similar to the implementation of United States Patent (USP) 4,560,489 (on December 24th, 1985 licenses to Witco companies) Mode prepares another composite calcium sulfonate grease lubricant, and the non-aqueous transforming agent for not postponing addition is used as baseline comparative example).Following system The lubricating grease of standby embodiment 18：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 440.02g is added in open mixing vessel, The neutral 1st group of paraffin base oil of solvent of the 390.68g of the viscosity with about 600SUS at 100F is then added.Start to make Start mixing without heating with planetary agitating paddle.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and ' 768 application The embodiment 4 of the file high-quality sulfoacid calcium similar with what is used in 12.Then, the predominantly C12 benzene sulfonamides of 17.76g are added Acid.It is mixing after twenty minutes, the water of 44.41g is added, the hexylene glycol of 14.37g is then added.Then, which is being continued to mix Lower heating is closed until temperature reaches 190F.When temperature reaches 190F, the glacial acetic acid of 5.75g is added.Once observing lubricating grease When the visible conversion of structure, just keeps the temperature at 190F to 200F and continue 45 minutes, until Fourier transform infrared (FTIR) Spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).Then, the average particle size of 15.37g is added The calcium hydroxide of the addition for the food-grade purity for being about 1 to 5 micron simultaneously makes it mix 10 minutes.Then, the 12- of 28.59g is added Hydroxy stearic acid simultaneously makes it melt and react.Then, the boric acid of 25.33g is mixed with the hot water of 50ml, and fed the mixture into Into lubricating grease.Then, lubricating grease is heated to 330F.Then, heating mantle is removed and makes profit by continuing stirring in outdoor Consistent lubricant cools down.When lubricating grease is cooled to 170F, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain Final smooth even quality.The 60 stroke needle penetration of work of lubricating grease is 291, dropping point>650F.It is high-alkali in final lubricating grease Property oil-soluble sulfonic acid calcium percentage be 46.92%.

Embodiment 19：It is composite lubricated that another sulfoacid calcium is prepared in a manner of similar with previous 18 lubricating grease of embodiment Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to 160F (the first temperature adjusts period of delay) And be maintained at 160F to the 170F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (second Temperature adjusts period of delay), and hexylene glycol (being kept for period of delay without second) is added immediately.The following lubrication for preparing embodiment 19 Fat：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 440.46g is added in open mixing vessel, is then added at 100F The neutral 1st group of paraffin base oil of the solvent of the 387.69g of viscosity with about 600SUS.Start to mix using planetary agitating paddle It closes without heating.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and in the embodiment 4 and 12 of ' 768 application documents The similar high-quality sulfoacid calcium used.Then, the predominantly C12 alkyl benzene sulphonates of 17.64g are added.It is mixing after twenty minutes, is adding Enter the water of 44.0g.Then, which is heated to 160F and be maintained at 160F to 30 minutes 2 hours between 170F.In this phase Between, since most of water initially added have evaporated, the water of other 43ml is added.Then, which is heated to The glacial acetic acid of the hexylene glycol and 5.73g of 14.49g is added in 190F immediately.When observing the visible conversion of grease structure, It just keeps the temperature at 190F to 200F and continues 45 minutes, until Fourier transform infrared (FTIR) spectrum shows to have occurred without fixed Shape calcium carbonate is converted into crystalline calcium carbonate (calcite).During this period, the water of other 20ml is added, because what some were more early added Water has evaporated.The identical paraffin base oil of other 3.73g is added, the average particle size that 15.37g is then added is about 1 to 5 micro- The food-grade purity calcium hydroxide of rice.It is allowed to mix 10 minutes.Then, the 12- hydroxy stearic acids of 28.59g are added and make it It melts and reacts.Then, the boric acid of 25.31g is mixed with the hot water of 50ml, and added mixture in lubricating grease.Then, Lubricating grease is heated to 330F.Then, heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When will lubricate When fat is cooled to 170F, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain final smooth even matter Ground.The lubricating grease has 260 60 stroke needle penetration of work.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease It is 46.90%.Dropping point>650F.Notice that 18 lubricating grease of embodiment of this lubricating grease and front has substantially the same percentage The high alkaline calcium sulfonate of ratio.However, harder 31 points of the work needle penetration of this lubricating grease.Therefore, it is used in the lubricating grease The glycol process of delay causes thickener yield to improve.In fact, using the high alkalinity in work needle penetration and final lubricating grease The linear dilution relationship of the percentage of sulfoacid calcium, if diluted with enough base oils to obtain the identical of 18 lubricating grease of embodiment Work needle penetration, then the percentage of the prediction of the high alkaline calcium sulfonate in 19 lubricating grease of embodiment will be 41.9%.In addition, Very high dropping point is kept in the lubricating grease of embodiment 19.These embodiments further demonstrate that, high-quality high alkalinity sulphur is used with working as It is compared (such as in embodiment 18-19) when sour calcium, it is non-aqueous when using high alkaline calcium sulfonate inferior (such as in embodiment 9-17) The delay addition of transforming agent improves thickener yield, and obtains higher result.The result of these embodiments is summarized in In the following table 3.

Table 3

Embodiment is numbered	18	19
			% high alkaline calcium sulfonates	46.92	46.9(41.9)
The quality of sulfoacid calcium	Well	Well
			The calcium alkali of addition	Calcium hydroxide	Calcium hydroxide
Work 60 needle penetrations	291	260
			Dropping point, F	>650	>650
The addition of non-aqueous transforming agent postpones	It is no	It is
			First temperature range, F	N/A	160-170
First is kept for period of delay, hour	N/A	2.5
			Second delay temperature adjusts the phase	N/A	It is
Second temperature range, F	N/A	190
			Second is kept for period of delay, hour	N/A	Without-add immediately

The additional embodiment of the result of the non-aqueous transforming agent of the delay addition in simple grease of calcium sulfonic acid is shown in reality It applies and is learned in a 20-23.When these embodiments are also shown that the addition delay before addition is relative to the conversion of water, hexylene glycol is used Or propylene glycol can get the thickener yield improved as non-aqueous transforming agent.For wherein adding the addition delay relative to water Other non-aqueous transforming agents, it is contemplated that similar result.

Embodiment 20：Similar to United States Patent (USP) 3,377,283 and 3,492,231 (respectively at April 9 nineteen sixty-eight and 1970 Authorize Lubrizol companies on January 27) in the range of embodiment prepare simple grease of calcium sulfonic acid, without any delay As baseline comparative example.The following lubricating grease for preparing embodiment 20：By the high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 496.49g It is added in open mixing vessel, the solvent neutrality the 1st of the 394.45g of the viscosity with about 600SUS at 100F is then added Group paraffin base oil.Start mixing without heating using planetary agitating paddle.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN is With similar high-quality sulfoacid calcium that is above-mentioned and being used in the embodiment 4 and 12 of ' 768 application documents.Then, it is added 20.23g's Predominantly C12 alkyl benzene sulphonates.It is mixing after twenty minutes, the water of 44.23g is added, the hexylene glycol of 16.57g is then added.So Afterwards, which is heated in the case where continuing mixing until temperature reaches 190F.When temperature reaches 190F, the ice second of 6.20g is added Acid.When observing the visible conversion of grease structure, just keeps the temperature at 190F to 200F and continue 45 minutes, until Fu In infrared (FTIR) spectrum of leaf transformation show that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).In this phase Between, the water of other 10ml is added.Then, gained lubricating grease is heated to 330F.Then, by heating mantle removal and by outdoor Continuing stirring makes lubricating grease cool down.When temperature reaches 200F, the arylamine antioxidant of 2.34g is added.When lubricating grease is cold When but arriving 170F, lubricating grease is taken out from mixer, and by three-roll mill three times to obtain final smooth even quality.It should Lubricating grease has 331 60 stroke needle penetration of work.Finally the percentage of the high alkalinity oil-soluble sulfonic acid calcium in lubricating grease is 53.03%, and dropping point>650F.

Embodiment 21：Another simple sulfoacid calcium lubrication is prepared in a manner of similar with previous 20 lubricating grease of embodiment Fat.Unique significant difference is delay addition hexylene glycol until lubricating grease has been heated to 160F (the first temperature adjusts period of delay) And be maintained at 160F to the 170F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (second Temperature adjusts period of delay), and hexylene glycol (being kept for period of delay without second) is added immediately.Prepare lubricating grease as follows：By 495.41g The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be added in open mixing vessel, being then added at 100F has about 600SUS Viscosity 391.96g the neutral 1st group of paraffin base oil of solvent.Start mixing without heating using planetary agitating paddle. The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and use in the embodiment 4 and 12 of ' 768 application documents similar High-quality sulfoacid calcium.Then, the predominantly C12 alkyl benzene sulphonates of 19.65g are added.It is mixing after twenty minutes, is being added 44.42g's Water.Then, which is heated to 160F and be maintained at 160F to 30 minutes 2 hours between 170F.During this period, due to big The water that majority initially adds has evaporated, therefore the water of other 50ml is added.Then, which is heated to 190F, be added The hexylene glycol of 16.53g, the glacial acetic acid of subsequent 6.34g.When observing the visible conversion of grease structure, just temperature is protected It holds and continues 45 minutes in 190F to 200F, until Fourier transform infrared (FTIR) spectrum shows that amorphous calcium carbonate, which has occurred, to be turned Turn to crystalline calcium carbonate (calcite).During this period, the water of other 10ml is added.Then, gained lubricating grease is heated to 330F.Then, heating mantle is removed and so that lubricating grease is cooled down by continuing stirring in outdoor.When temperature reaches 200F, it is added The arylamine antioxidant of 2.32g.When lubricating grease is cooled to 170F, lubricating grease is taken out from mixer, and pass through three rollers Grinding machine is three times to obtain final smooth even quality.The dropping point of 21 lubricating grease of embodiment>650F.60 stroke of work of lubricating grease Needle penetration is 290.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 53.14%.

It is noted that the lubricating grease of embodiment 21 and the lubricating grease of preceding embodiment 20 have the height of substantially the same percentage Alkaline sulfoacid calcium.However, harder 41 points of the work needle penetration of this lubricating grease.Therefore, the delay used in the lubricating grease Glycol process causes thickener yield to improve.In fact, using the high alkaline calcium sulfonate in work needle penetration and final lubricating grease Percentage linear dilution relationship, if diluted with enough base oil to obtain the identical work of 20 lubricating grease of embodiment Needle penetration, then the percentage of the prediction of the high alkaline calcium sulfonate in 21 lubricating grease of embodiment will be 46.6%.In addition, keeping very High dropping point.

Embodiment 22：Another simple sulfoacid calcium lubrication is prepared in a manner of similar with previous 20 lubricating grease of embodiment Fat.However, replacing hexylene glycol using propylene glycol as non-aqueous transforming agent.This is done to prove to see in embodiment previous The raising of the thickener yield observed is not only specifically directed to a kind of non-aqueous transforming agent.Embodiment 22 is not use delay wherein Baseline embodiment.Prepare lubricating grease as follows：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 550.60g is added to open mixing In container, the neutral 1st group of paraffinic base basis of solvent of the 354.69g of the viscosity with about 600SUS at 100F is then added Oil.Planetary agitating paddle is begun to use to start mixing without heating.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and The similar high-quality sulfoacid calcium used in the embodiment 4 and 11 of ' 768 application documents.Then, be added 22.23g predominantly C12 alkyl benzene sulphonates.It is mixing after twenty minutes, the water of 49.59g is added, the propylene glycol of 12.35g is then added.Then, by this Batch is heated in the case where continuing mixing until temperature reaches 190F.The glacial acetic acid of the part of 6.87g is added.Once observing lubricating grease When the visible conversion of structure, just keeps the temperature at 190F to 200F and continue 45 minutes, until Fourier transform infrared (FTIR) Spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).During this period, it is added other 20ml's Water.Then, gained lubricating grease is heated to 330F.Then, heating mantle is removed and makes lubricating grease by continuing stirring in outdoor It is cooling.When temperature reaches 200F, the arylamine antioxidant of 2.41g is added.When lubricating grease is cooled to 170F, from mixing Lubricating grease is taken out in device, and by three-roll mill three times to obtain final smooth even quality.The lubricating grease has 258 work Make 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 58.01%.Dropping point is 600F.

Embodiment 23：Another simple sulfoacid calcium lubrication is prepared in a manner of similar with previous 22 lubricating grease of embodiment Fat.Unique significant difference is delay addition propylene glycol until lubricating grease has been heated to 160F (the first temperature adjusts period of delay) And be maintained at 160F to the 170F times be 30 minutes two hours (first keep period of delay), be then heated to up to 190F (second Temperature adjusts period of delay).Prepare lubricating grease as follows：The high alkalinity oil-soluble sulfonic acid calcium of the 400TBN of 550.71g is added to out It puts in mixing vessel, the neutral 1st group of paraffinic base of solvent of the 354.74g of the viscosity with about 600SUS at 100F is then added Base oil.Start mixing without heating using planetary agitating paddle.The high alkalinity oil-soluble sulfonic acid calcium of 400TBN be with it is above-mentioned and The similar high-quality sulfoacid calcium used in the embodiment 4 and 11 of ' 768 application documents.Then, be added 22.92g predominantly C12 alkyl benzene sulphonates.It is mixing after twenty minutes, the water of 49.23g is added.Then, which is heated to 160F and be maintained at 160F to 30 minutes 2 hours between 170F.During this period, it since most of water initially added have evaporated, is added another The water of outer 35ml.Then, which is heated in the case where continuing mixing until temperature reaches 190F.When batch reaches 190F, The propylene glycol of 12.27g and the glacial acetic acid (being kept for period of delay without second) of 6.89g are added immediately.Once observing lubricating grease knot It when the visible conversion of structure, just keeps the temperature at 190F to 200F and continues 45 minutes, until Fourier transform infrared (FTIR) light Spectrum shows that amorphous calcium carbonate, which has occurred, is converted into crystalline calcium carbonate (calcite).During this period, the water of other 15ml is added. Then, gained lubricating grease is heated to 330F.Then, heating mantle is removed and keeps lubricating grease cold by continuing stirring in outdoor But.When temperature reaches 200F, the arylamine antioxidant of 2.38g is added.When lubricating grease is cooled to 170F, from mixer Middle taking-up lubricating grease, and by three-roll mill three times to obtain final smooth even quality.The lubricating grease has 239 work 60 stroke needle penetrations.The percentage of high alkalinity oil-soluble sulfonic acid calcium in final lubricating grease is 57.97%.Dropping point is 591F.

Again by comparing the lubricating grease and previous 22 lubricating grease of embodiment, it can be seen that by non-aqueous turn of delay addition The raising of thickener yield caused by agent.High alkaline calcium sulfonate percentage in 23 lubricating grease of embodiment is actually slightly below The percentage of 22 lubricating grease of preceding embodiment.Even so, the work needle penetration of 23 lubricating grease of embodiment is about 20 points more firmly. In fact, the linear dilution relationship of the percentage using the high alkaline calcium sulfonate in work needle penetration and final lubricating grease, if It is diluted to obtain the identical work needle penetration of 22 lubricating grease of embodiment, then in 23 lubricating grease of embodiment with enough base oils The percentage of the prediction of high alkaline calcium sulfonate will be 53.6%.The dropping point of embodiment 22 and 23 lubricating grease is less than the profit before other Consistent lubricant shows that propylene glycol is effective transforming agent unlike hexylene glycol, at least under conditions of using each.Nevertheless, The propylene glycol for postponing addition improves thickener yield compared with wherein its undelayed lubricating grease of addition.The knot of these embodiments Fruit is summarized in the following table 4.

The simple high alkaline calcium sulfonate lubricating grease of table 4-

Embodiment is numbered	20	21	22	23
					% high alkaline calcium sulfonates	53.03	53.14(46.6)	58.01	57.97(53.6)
Work 60 needle penetrations	331	290	258	239
					Dropping point, F	>650	>650	600	591
Non-aqueous transforming agent	Hexylene glycol	Hexylene glycol	Propylene glycol	Propylene glycol
					The addition of non-aqueous transforming agent postpones	It is no	It is	It is no	It is
First temperature range, F	N/A	160-170	N/A	160-170
					First is kept for duration, hour	N/A	2.5	N/A	2.5
Second delay temperature range, F	N/A	190	N/A	190
					Second is kept for duration, hour	N/A	Without-add immediately	N/A	Without-add immediately

These embodiments show that delay adds non-aqueous transforming agent and improves thickener yield always, but regardless of art heretofore taught Use the lubricating grease technology based on sulfoacid calcium.In addition, as defined in ' 768 applications, no matter high alkaline calcium sulfonate used is It is high-quality or inferior, it can observe that thickener yield improves, although being used in the exemplary compositing range for including herein Sulfoacid calcium inferior realizes the raising of bigger (with expected opposite).

According to the exemplary lubricating grease of the delay adding method preparation of aforementioned present invention and wherein all or some non-aqueous turn The exemplary lubricating grease that the addition of agent is not delayed by is used in each of embodiment compared to different physical properties is also showed that Its various composition and amount of a comparative group are identical or substantially similar.Use Fourier transform infrared spectroscopy (FTIR) and scanning electron Microscope (SEM) carries out test to the sample of exemplary lubricating grease and shows to postpone the lubricating grease that addition manufactures according to the present invention It can be distinguished with the analogous composition not manufactured lingeringly.For example, there are the difference of adsorption curve distribution and grain sizes and structure The difference of type.

Although embodiment provided herein is mainly fallen in No. 1, No. 2 or No. 3 grade of NLGI, wherein No. 2 grades are optimal Choosing, but it is to be further understood that the scope of the present invention includes the harder and softer all NLGI consistency grades of than No. 2 grades.So And for it is according to the present invention be not No. 2 grades of NLGI this lubricating grease, if their performance should with used More or less base oil obtains consistent, to provide No. 2 grade products, as one of ordinary skill will be understood.

As used herein, term " thickener yield " should be conventional sense when applied to the present invention, that is, providing has spy It periodically hopes the concentration of the height high alkalinity oil-soluble sulfonic acid calcium needed for the lubricating grease of consistency, is such as commonly marked in lubricating grease manufacture Measured by quasi- penetration test ASTM D217 or D1403.In a similar way, as used herein, " dropping point " of lubricating grease is answered Refer to by using the value that common standard dropping point test ASTM D2265 are obtained in being manufactured in lubricating grease.As used herein, to The reference of adding ingredient immediately means that the ingredient is added immediately after reaching that temperature after reaching temperature, because physically may be used The equipment that amount to be added can be given and used, but if preferably in a short time, being less than 10 minutes, more preferably less than 5 points Clock, after the temperature that mixture reaches about indicated.As used herein：(1) disperse carbonic acid contained in high alkaline calcium sulfonate Calcium or the amount of residual oxygen calcium or calcium hydroxide are based on the weight of high alkaline calcium sulfonate；(2) with two or more individual parts Some ingredients are added, and each section can be described as the percentage of the total amount of the ingredient；(3) with percentage or number table The every other amount (including total amount) of the ingredient shown is in terms of the weight of final grease product, even if special component (such as water) can Can be not present in final lubricating grease or may not be using as ingredient addition be quantitatively present in final lubricating grease really.Such as this For describing the present invention (how opposite using the term in certain prior art references), calcium hydroxy apetite in text Referring to (1) has formula Ca₅(PO₄)₃Mathematically Equivalent Form (a) has the fusing point of about 1100C or (b) passes through for the compound of OH or (2) Such equivalent expression particularly excludes the mixture of tricalcium phosphate and calcium hydroxide.Those skilled in the art are reading this Specification (including the embodiment being contained herein) will be understood that afterwards, can be somebody's turn to do within the scope of the invention to composition and preparation The method of composition is modified and is changed, and is intended to the range in invention disclosed herein only by inventor's legal authorization The broadest interpretation of appended claims limits.

Claims (according to the 19th article of modification of treaty)

1. a kind of method being used to prepare grease of calcium sulfonic acid, includes the following steps：

It adds and mixing water, the high alkaline calcium sulfonate of amorphous calcium carbonate containing dispersion and optional base oil is to form First mixture；

After at least one period of delay, at least part of one or more non-aqueous transforming agents is added to first mixing Object is to form mixture before conversion；

By heating until the amorphous calcium carbonate contained in the high alkaline calcium sulfonate has occurred to crystalline calcium carbonate Conversion, converts mixture before the conversion in the mixture of conversion；Wherein, the lubricating grease is comprising 30% or less height The composite calcium sulfonate grease lubricant of alkaline sulfoacid calcium or the lubricating grease are the high alkaline calcium sulfonates for including about 30% to 70% Simple grease of calcium sulfonic acid, and

Wherein, the period of delay is that water and addition one or more non-aqueous transforming agents are added in first mixture Period between at least part.

2. according to the method described in claim 1, further comprising at least one of one or more non-aqueous transforming agents Point be added to it is following in it is one or more：First mixture before any period of delay, the institute during period of delay State mixture before the first mixture or the conversion during one or more period of delays.

3. according to the method described in claim 2, wherein, acetic acid is not added during any period of delay.

4. according to the method described in claim 1, wherein, the lubricating grease is complex grease, and further comprising following Step：

By mixture before one or more Compound-acids and first mixture, the conversion, the conversion mixture or it Combined hybrid；

By mixture before at least one calcic alkali and first mixture, the conversion, the conversion mixture or they Combined hybrid, wherein the calcic alkali include calcium hydroxy apetite, addition calcium carbonate or their mixture；And

Wherein, the high alkaline calcium sulfonate includes about 0% to 8% residual oxygen calcium or calcium hydroxide.

5. according to the method described in claim 1, wherein, at least one of described non-aqueous transforming agent be glycol, glycol ethers or Glycol polyethers.

6. according to the method described in claim 5, wherein, the glycol is hexylene glycol.

7. according to the method described in claim 6, wherein, before any period of delay by a part for the hexylene glycol with it is described First mixture adds together, and adds another part of the hexylene glycol after or during the period one or more period of delays Mixture before to first mixture or the conversion.

8. according to the method described in claim 1, wherein, the mixing and the conversion carry out in open container.

9. according to the method described in claim 1, wherein, the conversion carries out in pressurizing vessel.

10. according to the method described in claim 8, wherein, step of converting includes being maintained at mixture before the conversion about At a temperature of between 190F and 230F.

11. according to the method described in claim 2, wherein, during a period of delay, by the period of delay it is lasting when In with substantially stable flow velocity come it is continuous add or by with substantially uniform increment come discrete addition, will be described non-aqueous A kind of at least part in transforming agent is added to mixture before first mixture or the conversion.

12. according to the method for claim 11, wherein after a period of delay, by identical or different non-aqueous transforming agent At least part mixture before first mixture or the conversion is added batch-wise.

13. the grease of calcium sulfonic acid product prepared by method described in claim 1.

14. the grease of calcium sulfonic acid product prepared by method of claim 6.

15. a kind of method being used to prepare grease of calcium sulfonic acid, includes the following steps：

After or during the period at least one period of delay, at least part of one or more non-aqueous transforming agents is added to described One mixture is to form mixture before conversion；

By heating until the amorphous calcium carbonate contained in the high alkaline calcium sulfonate has occurred to crystalline calcium carbonate Conversion, converts mixture before the conversion in the mixture of conversion；

Wherein, the lubricating grease is the composite calcium sulfonate grease lubricant comprising 45% or less high alkaline calcium sulfonate or the profit Consistent lubricant is the simple grease of calcium sulfonic acid for including about 30% to 70% high alkaline calcium sulfonate；

Wherein, at least one of described period of delay is to maintain period of delay, wherein before first mixture or the conversion Mixture is maintained in certain temperature or certain temperature range and continues for some time, and

16. according to the method for claim 15, wherein the high alkaline calcium sulfonate is high alkaline calcium sulfonate inferior.

17. according to the method for claim 15, wherein the high alkaline calcium sulfonate is high-quality high alkaline calcium sulfonate.

18. according to the method for claim 15, wherein the lubricating grease is complex grease, and further comprise with Lower step：

19. according to the method for claim 18, wherein do not add other calcium oxide or calcium hydroxide be used as with it is multiple Close the calcic alkali of acid reaction.

20. according to the method for claim 18, wherein the calcic alkali include calcium hydroxy apetite and be following in one kind Or it is a variety of：The calcium carbonate of the calcium oxide of addition, the calcium hydroxide of addition and addition.

21. according to the method for claim 15, wherein temperature or temperature range are between environment temperature and about 190F.

22. according to the method for claim 15, wherein the period for the holding period of delay is at least 30 minutes.

23. according to the method for claim 15, wherein there are at least two period of delays.

24. according to the method for claim 23, wherein one in the period of delay is first mixture or described The temperature that mixture is heated or cooled before conversion adjusts period of delay.

25. according to the method for claim 23, wherein add institute during or after the second or any subsequent period of delay State a kind of at least part in non-aqueous transforming agent.

26. according to the method for claim 23, wherein do not add non-aqueous conversion immediately during or after the first period of delay Agent.

27. according to the method for claim 23, wherein be added batch-wise after a period of delay in the non-aqueous transforming agent A kind of at least part, and at least the one of identical or different non-aqueous transforming agent is continuously added during other period of delay Part.

28. according to the method for claim 23, wherein add the non-aqueous transforming agent after or during the period period of delay In a kind of at least part, and add identical or different non-aqueous transforming agent extremely after or during the period other period of delay A few part.

29. according to the method for claim 23, wherein by one kind in the non-aqueous transforming agent before any period of delay At least part added together with first mixture, and after or during the period one or two period of delay by identical or At least part of different non-aqueous transforming agents is added to mixture before first mixture or the conversion.

30. according to the method for claim 15, wherein at least one of described non-aqueous transforming agent is glycol, glycol ethers Or glycol polyethers.

31. according to the method for claim 30, wherein the glycol is hexylene glycol.

32. according to the method for claim 31, wherein by a part for the hexylene glycol and institute before any period of delay It states the first mixture to add together, and adds another part of the hexylene glycol after or during the period one or more period of delays It is added to mixture before first mixture or the conversion.

33. according to the method for claim 15, wherein there are at least three period of delays.

34. according to the method for claim 33, wherein the first period of delay was that first mixture is heated or cooled to The temperature of first temperature or the first temperature range adjusts period of delay, and the second period of delay was by first mixture or the conversion Preceding mixture is kept the holding period of delay of a period of time in first temperature or the first temperature range, and third postpones Phase is that mixture is heated or cooled the temperature to second temperature or second temperature range before first mixture or the conversion Spend the adjusting phase.

35. according to the method for claim 33, wherein the first period of delay was that first mixture is maintained at about environment The holding period of delay of temperature for a period of time；Second period of delay was that mixture is added before first mixture or the conversion Heat or the temperature adjusting period of delay for being cooled to the first temperature or the first temperature range, and third period of delay is mixed described first Mixture is maintained at another holding delay of first temperature or the first temperature range for a period of time before closing object or the conversion Phase.

36. according to the method for claim 15, wherein the mixing and the conversion carry out in open container.

37. according to the method for claim 15, wherein the conversion carries out in pressurizing vessel.

38. according to the method for claim 15, wherein step of converting includes being maintained at mixture before the conversion about At a temperature of between 190F and 230F.

39. according to the method for claim 15, wherein at least one of described period of delay is about one hour or longer.

40. according to the method for claim 15, wherein each period of delay is at least 20 minutes.

41. according to the method for claim 15, wherein each period of delay is at least 30 minutes.

42. according to the method for claim 15, wherein at least one of described non-aqueous transforming agent is methanol, isopropanol Or another low-molecular-weight alcohol.

43. according to the method for claim 15, wherein without using methanol, isopropanol or another low-molecular-weight alcohol conduct Non-aqueous transforming agent.

44. the grease of calcium sulfonic acid product prepared by method of claim 15.

45. the grease of calcium sulfonic acid product prepared by method of claim 18.

46. the grease of calcium sulfonic acid product prepared by method of claim 20.

47. the grease of calcium sulfonic acid product prepared by the method described in claim 22.

48. the grease of calcium sulfonic acid product prepared by method of claim 29.

49. the grease of calcium sulfonic acid product prepared by the method described in claim 32.

50. a kind of method being used to prepare grease of calcium sulfonic acid, includes the following steps：

By heating until the amorphous calcium carbonate contained in the high alkaline calcium sulfonate has occurred to crystalline calcium carbonate Conversion, converts mixture before the conversion in the mixture of conversion；Wherein, the lubricating grease is comprising 22% or less height The composite calcium sulfonate grease lubricant of alkaline sulfoacid calcium or the lubricating grease are the letters for including about 30% to 70% high alkaline calcium sulfonate Single grease of calcium sulfonic acid, and

51. according to the method for claim 50, wherein the high alkaline calcium sulfonate is high alkaline calcium sulfonate inferior.

52. according to the method for claim 50, wherein the lubricating grease is complex grease, and further comprise with Lower step：

53. method according to claim 52, wherein the calcic alkali include it is following in it is one or more：Hydroxyl phosphorus Lime stone calcium, the calcium carbonate of addition, the calcium hydroxide of addition or the calcium oxide of addition.

54. according to the method for claim 50, wherein by a kind of of the non-aqueous transforming agent before any period of delay At least part is added together with first mixture, and add after or during the period one or more period of delays it is identical or At least part of different non-aqueous transforming agents.

55. according to the method for claim 50, wherein at least one of described non-aqueous transforming agent is glycol.

56. method according to claim 55, wherein the glycol is hexylene glycol.

57. method according to claim 56, wherein by a part for the hexylene glycol and institute before any period of delay It states the first mixture to add together, and adds another portion of the hexylene glycol after or during the period one or more period of delays Point.

58. according to the method for claim 50, wherein add one in the non-aqueous transforming agent after a period of delay At least part of kind.

59. according to the method for claim 50, wherein at least one of described period of delay is about one hour or longer.

60. according to the method for claim 50, wherein each period of delay is at least 20 minutes.

61. according to the method for claim 50, wherein the high alkaline calcium sulfonate is high-quality high alkaline calcium sulfonate.

62. the grease of calcium sulfonic acid product prepared by the method described in claim 46.

63. the grease of calcium sulfonic acid product prepared by the method described in claim 52.

64. the grease of calcium sulfonic acid product prepared by the method described in claim 54.

65. the grease of calcium sulfonic acid product prepared by the method described in claim 57.

Claims

Water, the high alkaline calcium sulfonate of amorphous calcium carbonate containing dispersion and optional base oil are mixed to form first Mixture；

After one or more period of delays, at least part of one or more non-aqueous transforming agents is added to described first and is mixed Object is closed to form mixture before conversion；

By heating until the amorphous calcium carbonate contained in the high alkaline calcium sulfonate has occurred to crystalline calcium carbonate Conversion, converts mixture before the conversion in the mixture of conversion；And

Wherein, the lubricating grease is the composite calcium sulfonate grease lubricant or described for including 30% or less high alkaline calcium sulfonate Lubricating grease is the simple grease of calcium sulfonic acid for including about 30% to 70% high alkaline calcium sulfonate.

14. the grease of calcium sulfonic acid product prepared by method of claim 6.

After or during the period one or more period of delays, at least part of one or more non-aqueous transforming agents is added to described First mixture is to form mixture before conversion；

Wherein, the lubricating grease is the composite calcium sulfonate grease lubricant comprising 45% or less high alkaline calcium sulfonate or the profit Consistent lubricant is the simple grease of calcium sulfonic acid for including about 30% to 70% high alkaline calcium sulfonate；And

Wherein, at least one of described period of delay is to maintain period of delay, wherein before first mixture or the conversion Mixture is maintained in certain temperature or certain temperature range and continues for some time.

44. the grease of calcium sulfonic acid product prepared by method of claim 15.

45. the grease of calcium sulfonic acid product prepared by method of claim 18.

46. the grease of calcium sulfonic acid product prepared by method of claim 20.

48. the grease of calcium sulfonic acid product prepared by method of claim 29.

Wherein, the lubricating grease is the composite calcium sulfonate grease lubricant comprising 22% or less high alkaline calcium sulfonate or the profit Consistent lubricant is the simple grease of calcium sulfonic acid for including about 30% to 70% high alkaline calcium sulfonate.

56. method according to claim 55, wherein the glycol is hexylene glycol.