EP3400279A1 - Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux - Google Patents

Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux

Info

Publication number
EP3400279A1
EP3400279A1 EP16884166.6A EP16884166A EP3400279A1 EP 3400279 A1 EP3400279 A1 EP 3400279A1 EP 16884166 A EP16884166 A EP 16884166A EP 3400279 A1 EP3400279 A1 EP 3400279A1
Authority
EP
European Patent Office
Prior art keywords
added
grease
mixture
calcium
calcium sulfonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16884166.6A
Other languages
German (de)
English (en)
Other versions
EP3400279A4 (fr
Inventor
Andrew J. Waynick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NCH Corp
Original Assignee
NCH Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/990,473 external-priority patent/US9976101B2/en
Application filed by NCH Corp filed Critical NCH Corp
Publication of EP3400279A4 publication Critical patent/EP3400279A4/fr
Publication of EP3400279A1 publication Critical patent/EP3400279A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/10—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M121/00—Lubricating compositions characterised by the thickener being a compound of unknown or incompletely defined constitution
    • C10M121/04—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046—Hydroxy ethers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C10M2207/1245—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C10M2219/0466—Overbasedsulfonic acid salts used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • This invention relates to overbased calcium sulfonate greases made with delayed addition of non-aqueous converting agents and the method for manufacturing such greases to provide improvements in both thickener yield and expected high temperature utility as demonstrated by dropping point, even when the oil-soluble overbased calcium sulfonate used to make the grease is considered to be of poor quality.
  • Overbased calcium sulfonate greases have been an established grease category for many years.
  • One known process for making such greases is a two-step process involving the steps of "promotion” and “conversion.”
  • the first step is to react a stoichiometric excess amount of calcium oxide (CaO) or calcium hydroxide (Ca(OH) 2 ) as the base source with an alkyl benzene sulfonic acid, carbon dioxide (C0 2 ), and with other components to produce an oil-soluble overbased calcium sulfonate with amorphous calcium carbonate dispersed therein.
  • These overbased oil-soluble calcium sulfonates are typically clear and bright and have Newtonian rheology.
  • overbased oil-soluble calcium sulfonate and “oil- soluble overbased calcium sulfonate” and “overbased calcium sulfonate” refer to any overbased calcium sulfonate suitable for making calcium sulfonate greases.
  • the second step is to add a converting agent or agents, such as propylene glycol, iso-propyl alcohol, water, formic acid or acetic acid, to the product of the promotion step, along with a suitable base oil (such as mineral oil) if needed to keep the initial grease from being too hard, to convert the amorphous calcium carbonate to a very finely divided dispersion of crystalline calcium carbonate.
  • a converting agent or agents such as propylene glycol, iso-propyl alcohol, water, formic acid or acetic acid
  • a suitable base oil such as mineral oil
  • the crystalline form of the calcium carbonate is preferably calcite.
  • This extremely finely divided calcium carbonate also known as a colloidal dispersion, interacts with the calcium sulfonate to form a grease-like consistency.
  • Such overbased calcium sulfonate greases produced through the two-step process have come to be known as "simple calcium sulfonate greases" and are disclosed, for example, in U.S. Pat. Nos.
  • the simple calcium sulfonate grease is prepared by reaction of an appropriate sulfonic acid with either calcium hydroxide or calcium oxide in the presence of carbon dioxide and a system of reagents that simultaneously act as both promoter (creating the amorphous calcium carbonate overbasing by reaction of carbon dioxide with an excess amount of calcium oxide or calcium hydroxide) and converting agents (converting the amorphous calcium carbonate to very finely divided crystalline calcium carbonate).
  • the grease-like consistency is formed in a single step wherein the overbased, oil-soluble calcium sulfonate (the product of the first step in the two-step process) is never actually formed and isolated as a separate product.
  • This one-step process is disclosed, for example, in U.S. Patent Nos. 3,661 ,622; 3,671 ,012; 3,746,643; and 3,816,310.
  • calcium sulfonate complex greases are also known in the prior art. These complex greases are typically produced by adding a strong calcium-containing base, such as calcium hydroxide or calcium oxide, to the simple calcium sulfonate grease produced by either the two-step or one-step process and reacting with up to stoichiometrically equivalent amounts of complexing acids, such as 12- hydroxystearic acid, boric acid, acetic acid (which may also be a converting agent when added pre-conversion), or phosphoric acid.
  • complexing acids such as 12- hydroxystearic acid, boric acid, acetic acid (which may also be a converting agent when added pre-conversion), or phosphoric acid.
  • the claimed advantages of the calcium sulfonate complex grease over the simple grease include reduced tackiness, improved pumpability, and improved high temperature utility. Calcium sulfonate complex greases are disclosed, for example, in U.S. Patent Nos. 4,560,489; 5,126,062; 5,308,
  • the resulting grease contains greater than 38% overbased calcium sulfonate and the '489 patent points out that the ideal amount of overbased calcium sulfonate for the processes disclosed therein is around 41 -45%, since according to the '489 patent using less than 38% results in a soft grease.
  • the resulting grease of example 1 in the '489 patent has a dropping point of around only 570°F.
  • the '489 patent does not state the duration of delay between the addition of water and the addition of the non-aqueous converting agents, but indicates that the addition was immediate after a period of heating from 150 F to just 190 F.
  • the dropping point and thickener yield in the '489 patent are not desirable.
  • U.S. Patent Nos. 5,338,467 and 5,308,514 disclose the use of a fatty acid, such as 12-hydroxystearic acid, as a converting agent used along with acetic acid and methanol, where there is no delay for the addition of the fatty acid but some interval between the addition of water and the addition of acetic acid and methanol.
  • Example B in the '514 patent and example 1 in the '467 patent both describe a process where water and the fatty acid converting agent are added to other ingredients (including the overbased calcium sulfonate and base oil), then heated to around 140-145°F before adding acetic acid followed by methanol. The mixture is then heated to around 150-160°F until conversion is complete.
  • the amount of overbased calcium sulfonate in the final grease products in both examples is 32.2, which is higher than desirable.
  • These patents do not state the duration of delay between the addition of water and fatty acid and the addition of the acetic acid and methanol, but indicates that the addition was immediate after an unspecified period of heating. Similar processes are disclosed in example A of the '467 patent and example C of the '514 patent except all of the fatty acid was added post conversion, so the only non-aqueous converting agents used were the acetic acid and methanol added after the mixture with water was heated to 140- 145 F. The amount of overbased calcium sulfonate in these examples is even higher than the previous examples at 40%.
  • the known prior art always teaches the use of calcium oxide or calcium hydroxide as the sources of basic calcium for production of calcium sulfonate greases or as a required component for reacting with complexing acids to form calcium sulfonate complex greases.
  • the known prior art teaches that the addition of calcium hydroxide or calcium oxide needs to be in an amount sufficient (when added to the amount of calcium hydroxide or calcium oxide present in the overbased oil-soluble calcium sulfonate) to provide a total level of calcium hydroxide or calcium oxide sufficient to fully react with the complexing acids.
  • the known prior art generally teaches that the presence of calcium carbonate (as a separate ingredient or as an "impurity" in the calcium hydroxide or calcium oxide, other than that presence of the amorphous calcium carbonate dispersed in the calcium sulfonate after carbonation), should be avoided for at least two reasons.
  • the first being that calcium carbonate is generally considered to be a weak base, unsuitable for reacting with complexing acids to form optimum grease structures.
  • the second being that the presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion process, resulting in inferior greases if the unreacted solids are not removed prior to conversion or before conversion is completed.
  • nano-sized particles would add to the thickening of the grease to keep it firm, much like the fine dispersion of crystalline calcium carbonate formed by converting the amorphous calcium carbonate contained within the overbased calcium sulfonate (which can be around 20 A to 5000A or around 2 nm to 500 nm according to the '467 patent), but would also substantially increase the costs over larger sized particles of added calcium carbonate.
  • This Chinese patent application greatly emphasizes the absolute necessity of the added calcium carbonate having a true nano particle size.
  • superior greases may be formed by the addition of micron sized calcium carbonate without requiring the use of the very expensive nano-sized particles and when using added calcium carbonate as one of or the sole added calcium containing base for reacting with complexing acids.
  • tricalcium phosphate as an additive in lubricating greases.
  • U.S. Patent Nos. 4,787,992; 4,830,767; 4,902,435; 4,904,399; 4,929,371 all teach using tricalcium phosphate as an additive for lubricating greases.
  • hydroxyapatite is disclosed as a mixture of tricalcium phosphate and calcium hydroxide, which is not the same as the calcium hydroxyapatite disclosed and claimed in the '768 application and herein having the formula Ca 5 (P0 4 ) 3 OH or a mathematically equivalent formula with a melting point of around 1 100 C.
  • calcium hydroxyapatite, tricalcium phosphate, and calcium hydroxide are each distinct chemical compounds with different chemical formulae, structures, and melting points.
  • tricalcium phosphate (having the formula Ca 3 (P0 4 ) 2 )
  • calcium hydroxide (having the formula Ca 3 (P0 4 ) 2 )
  • the melting point of tricalcium phosphate is 1670 C.
  • Calcium hydroxide does not have a melting point, but instead loses a water molecule to form calcium oxide at 580 C.
  • the calcium oxide thus formed has a melting point of 2580 C.
  • Calcium hydroxyapatite (having the formula Ca 5 (P0 4 ) 3 OH or a mathematically equivalent formula) has a melting point of around 1 100 C. Therefore, regardless of how inaccurate the nomenclature may be, calcium hydroxyapatite is not the same chemical compound as tricalcium phosphate, and it is not a simple blend of tricalcium phosphate and calcium hydroxide. [0013] Additionally, it is desirable to have a calcium sulfonate complex grease composition and method of manufacture that results in both improved thickener yield and dropping point. Many of the known prior art compositions require an amount of overbased calcium sulfonate of least 36% (by weight of the final grease product) to achieve a suitable grease in the NGLI No.
  • the overbased oil-soluble calcium sulfonate is one of the most expensive ingredients in making calcium sulfonate grease, therefore it is desirable to reduce the amount of this ingredient while still maintaining a desirable level of firmness in the final grease (thereby improving thickener yield).
  • many prior art references utilize a pressure reactor. It is desirable to have an overbased calcium sulfonate grease wherein the percentage of overbased oil-soluble calcium sulfonate is less than 36% and the dropping point is consistently 575 F or higher when the consistency is within an NLGI No. 2 grade (or the worked 60 stroke penetration of the grease is between 265 and 295), without requiring a pressure reactor. Higher dropping points are considered desirable since the dropping point is the first and most easily determined guide as to the high temperature utility limitations of a lubricating grease.
  • This invention relates to overbased calcium sulfonate greases and methods for manufacturing such greases to provide improvements in both thickener yield (requiring less overbased calcium sulfonate while maintaining acceptable penetration measurements) and expected high temperature utility as demonstrated by dropping point.
  • a simple calcium sulfonate grease is produced by reacting and mixing certain compounds comprising: (a) a primary overbasing material comprising overbased oil-soluble calcium sulfonate having dispersed amorphous calcium carbonate; (b) optionally, a suitable base oil, if needed, so as to provide acceptable consistency to the product after conversion (any amount of added base oil may be added before conversion, after conversion, or both); (c) water as a converting agent; and (d) one or more other converting agents (non-aqueous converting agents), wherein there is one or more delay periods between the pre-conversion addition of the water and the pre- conversion addition of at least a portion of the one or more other non-aqueous converting agents.
  • non-aqueous converting agent means any converting agent other than water and includes converting agents that may contain some water as a diluent or an impurity.
  • complex calcium sulfonate grease is produced by reacting and mixing certain compounds comprising: (a) a primary overbasing material comprising overbased oil-soluble calcium sulfonate having dispersed amorphous calcium carbonate; (b) optionally, a suitable base oil, if needed, so as to provide acceptable consistency to the product after conversion (any amount of added base oil may be added before conversion, after conversion, or both); (c) water as a converting agent; (d) one or more other converting agents (non-aqueous converting agents); (d) one or more complexing acids; and (e) one or more added calcium containing bases for reacting with the complexing acid(s); wherein there is one or more delay periods between the pre-conversion addition of the water and the pre-conversion addition of at least a portion of the one or more other non-aqueous converting agents.
  • All of one or more the complexing acids may be added prior to conversion or after conversion. Alternatively, a portion of one of more of the complexing acids may be added prior to conversion of the complex calcium sulfonate grease, with the remainder of the one or more complexing acids added after conversion. All of the one or more calcium containing bases may be added prior to conversion or after conversion. Alternatively, a portion of one or more of the calcium containing bases may be added prior to conversion, with the remainder added after conversion. Calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, added calcium oxide, or a combination thereof may be used as the calcium containing bases for reacting with the complexing acids. It is preferred that an excess amount of calcium hydroxide relative to the total amount of complexing acids used not be added prior to conversion.
  • one or more of the delay periods is a temperature adjustment delay period or a holding delay period or both. If additional water is added pre-conversion to make up for evaporation losses during the manufacturing process, those additions are not used in re-starting or determining delay periods, and only the first addition of water is used as the starting point in determining delay periods.
  • the delay periods may involve multiple temperature adjustment delay periods and/or multiple holding delay periods. For example, a first temperature adjustment delay period is the amount of time after water is added that it takes to heat the mixture to a temperature or range of temperatures (the first temperature).
  • a first holding delay period is the amount of time the mixture is held at the first temperature before being heated or cooled to another temperature or before adding at least a portion of a non-aqueous converting agent.
  • a second temperature adjustment delay period is the amount of time after the first holding delay period that it takes to heat or cool the mixture to another temperature or temperature range (the second temperature).
  • a second holding delay period is the amount of time the mixture is held at the second temperature before being heated or cooled to another temperature or before adding at least a portion of a nonaqueous converting agent. Additional temperature adjustment delay periods or holding delay periods (i.e. a third temperature adjustment delay period) follow the same pattern.
  • a holding delay period will be followed or preceded by a temperature adjustment delay period and vice versa, but there may be two holding delay periods back to back or two temperature adjustment periods back to back.
  • the mixture may be held at ambient temperature for 30 minutes prior to adding one non-aqueous converting agent (a first holding delay period) and may continue to be held at ambient temperature for another hour prior to adding the same or a different nonaqueous converting agent (a second holding delay period).
  • the mixture may be heated or cooled to a first temperature after which a nonaqueous converting agent is added (a first temperature adjustment period) and then the mixture is heated or cooled to a second temperature after which the same or a different non-aqueous converting agent is added (a second temperature adjustment period, without any interim holding period).
  • a portion of a non-aqueous converting agent need not be added after every delay period, but may skip delay periods prior to addition or between additions.
  • the mixture may be heated to a temperature (first temperature adjustment delay period) and then held at that temperature for a period of time (a first holding delay period) before adding any non-aqueous converting agent.
  • the first temperature may be ambient temperature or another temperature. Any subsequent temperature may be higher or lower than the previous temperature.
  • the final pre-conversion temperature (for non-pressurized production) will be between about 190°F and 220°F or up to 230°F, as the temperature at which conversion in an open kettle typically occurs. Final pre-conversion temperatures can be below 190 F, however such process conditions will usually result in significantly longer conversion times, and thickener yields may also be diminished.
  • a portion of a non-aqueous converting agent is added immediately after reaching a temperature or range of temperatures, then there is no holding time delay for that particular temperature and that portion of the non-aqueous converting agent; but if another portion is added after holding at that temperature or range of temperatures for a period of time then there is a holding time delay for that temperature and that portion of the non-aqueous converting agent.
  • a portion of one or more non-aqueous converting agents may be added after any temperature adjustment delay period or holding delay period and another portion of the same or a different non-aqueous converting agent may be added after another temperature adjustment delay period or holding delay period.
  • At least a portion of a non-aqueous converting agent is added after the mixture is heated to the final pre-conversion temperature range between about 190 F and 230 F.
  • no amount of non-aqueous converting agent is added at substantially the same time as the water and there is at least one delay period prior to the addition of any non-aqueous converting agent.
  • at least one of the nonaqueous converting agents is a glycol (e.g. propylene glycol or hexylene glycol)
  • a portion of the glycol is added at substantially the same time as the water and another portion of glycol and all of any other non-aqueous converting agents are added after at least one delay period.
  • acetic acid when added pre-conversion, it is added at substantially the same time as the water, and another (different) non-aqueous converting agent is added after a delay period.
  • alcohols are not used as non-aqueous converting agents.
  • all or a portion of the non-aqueous converting agents are added in a batch manner (all at once, en masse, as opposed to a continuous addition over the course of a delay period, described below) after a delay period. It is noted, however, that in large or commercial scale operations, it will take some time to complete the batch addition of such non-aqueous converting agents to the grease batch because of the volume of materials involved. In batch addition, the amount of time it takes to add the non-aqueous converting agent to the grease mixture is not considered a delay period. In that case, any delay prior to the addition of that non-aqueous converting agent or portion thereof ends at the start time of the batch addition of the non-aqueous converting agent.
  • At least one or a portion of one non-aqueous converting agent is added in a continuous manner during the course of a delay period (either a temperature adjustment delay period or a holding delay period).
  • a delay period either a temperature adjustment delay period or a holding delay period.
  • Such continuous addition may be by slowly adding the non-aqueous converting agent at a substantially steady flow rate or by repeated, discrete, incremental additions during a temperature adjustment delay period, a holding delay period, or both. In that case, the time it takes to fully add the non-aqueous converting agent is included in the delay period, which ends when the addition of nonaqueous converting agent is complete.
  • At least a portion of one non-aqueous converting agent is added in a batch manner after a delay period and at least another portion of the same or a different non-aqueous converting agent is added in a continuous manner during a delay period.
  • improved thickener yield results are achieved using at least one delay period even when the overbased calcium sulfonate is considered to be of "poor quality.”
  • Certain overbased oil-soluble calcium sulfonates marketed and sold for the manufacture of calcium sulfonate-based greases can provide products with unacceptably low dropping points when prior art calcium sulfonate technologies are used. Such overbased oil-soluble calcium sulfonates are referred to as "poor quality" overbased oil-soluble calcium sulfonates throughout this application.
  • overbased oil-soluble calcium sulfonates producing greases having higher dropping points are considered to be "good” quality calcium sulfonates for purposes of this invention and those producing greases having lower dropping points are considered to be “poor” quality for purposes of this invention.
  • Several examples of this are provided in the 768 application, which is incorporated by reference. Although comparative chemical analyses of good quality and poor quality overbased oil-soluble calcium sulfonates has been performed, it is believed that the precise reason for this low dropping point problem has not been proven.
  • the non-aqueous converting agents is a glycol (e.g. propylene glycol or hexylene glycol)
  • all of the glycol is added after at least one delay period (none is added with the water) and a poor quality calcium sulfonate is used.
  • consistently high quality calcium sulfonate greases may be made with thickener yield and dropping point properties superior to those of prior art greases.
  • the overbased calcium sulfonate complex greases made according to preferred embodiments of the invention have an NLGI No. 2 grade consistency (or better, i.e. harder) and a dropping point of 575° F (or higher), with the percentage of overbased oil-soluble calcium sulfonate being between about 10% and 45% when made in an open vessel (without pressure).
  • the amount of overbased oil-soluble calcium sulfonate in greases made according to preferred embodiments of the invention is at least around 10% but around 36% or less, more preferably around 30% or less, and most preferably around 22% or less when made in an open vessel (without pressure).
  • These improved thickener yields are achievable with both good quality and poor quality overbased calcium sulfonates. Even greater thickener yield may be achieved with the methods of the invention when the grease is made in a pressurized vessel. Most preferably a dropping point in excess of 650 F is achieved.
  • the lower concentrations of the overbased oil-soluble calcium sulfonate achieved by the invention are desirable since the cost of the grease is reduced. Other properties such as mobility and pumpability, especially at lower temperatures, may also be favorably impacted by the improved thickener yield achieved according to the invention.
  • the overbased calcium sulfonate simple greases made according to preferred embodiments of the invention have an NLGI No. 2 grade consistency and a dropping point of 575° F (or higher), with the percentage of overbased oil-soluble calcium sulfonate being between about 30% and 70% and most preferably between about 45% and 54%. If a softer grease is desired, then a less percentage of overbased oil soluble calcium sulfonate will be needed, as well-understood by those of ordinary skill in the art. While this invention deals primarily with greases made in open vessels, it may also be used in closed vessels where heating under pressure is accomplished. The use of such pressurized vessels may result in even better thickener yields.
  • an open vessel is any vessel with or without a top cover or hatch as long as any such top cover or hatch is not vapor-tight so that significant pressure cannot be generated during heating.
  • Using such an open vessel with the top cover or hatch closed during the conversion process will help to retain the necessary level of water as a converting agent while generally allowing a conversion temperature at or even above the boiling point of water.
  • Such higher conversion temperatures can result in further thickener yield improvements for both simple and complex calcium sulfonate greases, as will be understood by those with ordinary skill in the art.
  • a simple calcium sulfonate grease is produced by reacting and mixing certain compounds comprising: (a) a primary overbasing material comprising overbased oil-soluble calcium sulfonate having dispersed amorphous calcium carbonate; (b) optionally, a suitable base oil, if needed, so as to provide acceptable consistency to the product after conversion (any amount of added base oil may be added before conversion, after conversion, or both); (c) water as a converting agent; and (d) one or more other converting agents (nonaqueous converting agents), with there being one or more delay periods between the pre-conversion addition of the water and the addition of at least a portion of the one or more other non-aqueous converting agents.
  • complex calcium sulfonate grease is produced by reacting and mixing certain compounds comprising: (a) a primary overbasing material comprising overbased oil-soluble calcium sulfonate having dispersed amorphous calcium carbonate; (b) optionally, a suitable base oil, if needed, so as to provide acceptable consistency to the product after conversion (any amount of added base oil may be added before conversion, after conversion, or both); (c) water as a converting agent; (d) one or more other converting agents (non-aqueous converting agents), with there being one or more delay periods between the pre-conversion addition of the water and the addition of at least a portion of the one or more other non-aqueous converting agents; (e) one or more complexing acids; and (f) one or more added calcium containing bases for reacting with the complexing acid(s).
  • a primary overbasing material comprising overbased oil-soluble calcium sulfonate having dispersed amorphous calcium carbonate
  • a suitable base oil if needed
  • a portion of one of more of the complexing acids may be added prior to conversion of the complex calcium sulfonate grease, with the remainder of the one or more complexing acids added after conversion.
  • Calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, added calcium oxide, or a combination thereof may be used as the calcium containing bases for reacting with the complexing acids.
  • some or all of the ingredients, including converting agents may not be in the final finished product due to evaporation and volatilization during manufacture.
  • a facilitating acid may be added prior to conversion according to another embodiment of the invention. Such facilitating acid aids in grease structure formation.
  • one or more delay periods between the pre-conversion addition of the water and the addition of at least a portion of the one or more other non-aqueous converting agents.
  • the mixture is also most preferably heated to a temperature or temperature range during at least one of the delay periods or during each delay period, as described below with respect to the preferred methods for making calcium sulfonate greases according to the invention.
  • one or more of the delay periods is a temperature adjustment delay period or a holding delay period or both.
  • the delay periods may involve multiple temperature adjustment delay periods and multiple holding delay periods.
  • a first temperature adjustment delay period is the period of time after water is added that it takes to change the temperature of the mixture (typically by heating) to a desired temperature or range of temperatures (the first temperature).
  • a first holding delay period is the amount of time the mixture is held at the first temperature.
  • a second temperature adjustment delay period is the period of time after the first holding delay that it takes to heat or cool the mixture to another temperature or temperature range (the second temperature).
  • a second holding delay period is the amount of time the mixture is held at the second temperature. Additional temperature adjustment delay periods and holding delay periods (i.e. a third temperature adjustment delay period) follow the same pattern.
  • the first temperature may be ambient temperature or an elevated temperature. Any subsequent temperature may be higher or lower than the previous temperature.
  • the final pre-conversion temperature will be between about 190°F and 220°F or up to 230°F, as the temperature at which conversion in an open kettle typically occurs. Any combination of temperature adjustment delay periods and/or holding delay periods may be used.
  • a non-aqueous converting agent or portion thereof is added immediately after reaching a temperature or range of temperatures, then there is no holding delay period for that particular temperature.
  • a portion of one or more non-aqueous converting agents may be added after any temperature adjustment delay period or holding delay period and another portion of the same or a different non-aqueous converting agent may be added after another temperature adjustment delay period or holding delay period.
  • the duration of each temperature adjustment delay period will be about 30 minutes to 24 hours, or more typically about 30 minutes to 5 hours.
  • the duration of any temperature adjustment delay period will vary depending on the size of the grease batch, the equipment used to mix and heat the batch, and the temperature differential between the starting temperature and final temperature, as will be understood by those of ordinary skill in the art. Preferred embodiments regarding the delay period(s) are further discussed below in relation to preferred methods for making greases according to the invention.
  • the highly overbased oil-soluble calcium sulfonate used according to these embodiments of the invention can be any typical to that documented in the prior art, such as U.S. Pat Nos. 4,560,489; 5, 126,062; 5,308,514; and 5,338,467.
  • the highly overbased oil-soluble calcium sulfonate may be produced in situ according to such known methods or may be purchased as a commercially available product.
  • Such highly overbased oil- soluble calcium sulfonates will have a Total Base Number (TBN) value not lower than 200, preferably not lower than 300, and most preferably about 400 or higher.
  • TBN Total Base Number
  • overbased calcium sulfonates of this type include, but are not limited to, the following: Hybase C401 as supplied by Chemtura USA Corporation; Syncal OB 400 and Syncal OB405-WO as supplied by Kimes Technologies International Corporation; Lubrizol 75GR, Lubrizol 75NS, Lubrizol 75P, and Lubrizol 75WO as supplied by Lubrizol Corporation.
  • the overbased calcium sulfonate contains around 28% to 40% dispersed amorphous calcium carbonate by weight of the overbased calcium sulfonate, which is converted to crystalline calcium carbonate during the process of making the calcium sulfonate grease.
  • the overbased calcium sulfonate also contains around 0% to 8% residual calcium oxide or calcium hydroxide by weight of the overbased calcium sulfonate. Most commercial overbased calcium sulfonates will also contain around 40% base oil as a diluent, to keep the overbased calcium sulfonate from being so thick that it is difficult to handle and process. The amount of base oil in the overbased calcium sulfonate may make it unnecessary to add additional base oil (as a separate ingredient) prior to conversion to achieve an acceptable grease.
  • the overbased calcium sulfonate used may be of a good quality or a poor quality as defined herein and in the 768 application.
  • the amount of the highly overbased oil-soluble calcium sulfonate in the final complex grease according to an embodiment of the invention can vary, but is generally between 10 and 45%.
  • the amount of the highly overbased oil-soluble calcium sulfonate in the final complex grease according to an embodiment of the invention is around 36% or less, more preferably around 30% or less, and most preferably around 22% or less when made in an open vessel (without pressure), with even smaller percentages achievable when made in pressurized vessels.
  • the amount of the highly overbased oil-soluble calcium sulfonate in the final simple grease according to an embodiment of the invention can vary, but is generally between 30 and 70%, more preferably less than 60% and most preferably less than 55%.
  • any petroleum -based naphthenic or paraffinic mineral oils commonly used and well known in the grease making art may be used as the base oil according to the invention.
  • Base oil is added as needed, since most commercial overbased calcium sulfonates will already contain about 40% base oil as a diluent so as to prevent the overbased sulfonate from being so thick that it cannot be easily handled, it may be unnecessary to add additional base oil depending on the desired consistency of the grease immediately after conversion as well as the desired consistency of the final grease.
  • Synthetic base oils may also be used in the greases of the present invention.
  • Such synthetic base oils include polyalphaolefins (PAO), diesters, polyol esters, polyethers, alkylated benzenes, alkylated naphthalenes, and silicone fluids.
  • PAO polyalphaolefins
  • synthetic base oils may have an adverse effect if present during the conversion process as will be understood by those of ordinary skill in the art.
  • those synthetic base oils should not be initially added, but added to the grease making process at a stage when the adverse effects will be eliminated or minimized, such as after conversion.
  • Naphthenic and paraffinic mineral base oils are preferred due to their lower cost and availability.
  • the total amount of base oil added (including that initially added and any that may be added later in the grease process to achieve the desired consistency) will typically be between 30% and 70%, preferably 45% and 70%, most preferably 50% and 70%, based on the final weight of the grease.
  • the amount of base oil added as a separate ingredient will increase as the amount of overbased calcium sulfonate decreases.
  • Nonaqueous converting agents include any converting agent other than water, such as alcohols, ethers, glycols, glycol ethers, glycol polyethers, carboxylic acids, inorganic acids, organic nitrates, and any other compounds that contain either active or tautomeric hydrogen.
  • Non-aqueous converting agents also include those agents that contain some water as a diluent or impurity.
  • alcohols such as methanol or isopropyl alcohol or other low molecular weight (i.e. more volatile) alcohols, because of environmental concerns and restrictions related to venting gases during the grease manufacturing process or hazardous waste disposal of scrubbed alcohols.
  • the total amount of water added as a converting agent, based on the final weight of the grease, is between 1 .5% and 10%, preferably between 2.0% and 5.0%, most preferably between 2.2% and 4.5%. Additional water may be added after conversion. Also, if the conversion takes place in an open vessel at a sufficiently high temperature so as to volatilize a significant portion of the water during conversion, additional water may be added to replace the water that was lost.
  • the total amount of one or more non-aqueous converting agents added, based on the final weight of the grease, is between 0.1 % and 5%, preferably 0.5 % and 4%, most preferably 1 .0% and 3.0%.
  • the amount of nonaqueous converting agent used will decrease as the amount of overbased calcium sulfonate decreases.
  • some or all of them may be removed by volatilization during the manufacturing process.
  • the lower molecular weight glycols such as hexylene glycol and propylene glycol.
  • some converting agents may also serve as complexing acids, to produce a calcium sulfonate complex grease according to one embodiment of the invention, discussed below. Such materials will simultaneously provide both functions of converting and complexing.
  • a small amount of a facilitating acid may be added to the mixture prior to conversion according to another embodiment of the invention.
  • Suitable facilitating acids such as an alkyl benzene sulfonic acid, having an alkyl chain length typically between 8 to 16 carbons, may help to facilitate efficient grease structure formation.
  • this alkyl benzene sulfonic acid comprises a mixture of alkyl chain lengths that are mostly about 12 carbons in length.
  • Such benzene sulfonic acids are typically referred to as dodecylbenzene sulfonic acid ("DDBSA").
  • benzene sulfonic acids of this type include JemPak 1298 Sulfonic Acid as supplied by JemPak GK Inc., Calsoft LAS-99 as supplied by Pilot Chemical Company, and Biosoft S-101 as supplied by Stepan Chemical Company.
  • the alkyl benzene sulfonic acid is used in the present invention, it is added before conversion in an amount from about 0.50% to 5.0%, preferably 1.0% to 4.0%, most preferably 1 .3% to 3.6%, based on the final weight of the grease.
  • the calcium sulfonate is made in situ using alkyl benzene sulfonic acid, the facilitating acid added according to this embodiment is in addition to that required to produce the calcium sulfonate.
  • the calcium containing bases may include calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, added calcium oxide, or a combination of one or more of the foregoing.
  • the calcium hydroxyapatite used as a calcium containing base for reacting with complexing acids according to this embodiment may be added pre-conversion, post-conversion, or a portion added pre- and a portion added post-conversion.
  • the calcium hydroxyapatite is finely divided with a mean particle size of around 1 to 20 microns, preferably around 1 to 10 microns, most preferably around 1 to 5 microns.
  • the calcium hydroxyapatite will be of sufficient purity so as to have abrasive contaminants such as silica and alumina at a level low enough to not significantly impact the anti-wear properties of the resulting grease.
  • the calcium hydroxyapatite should be either food grade or U.S. Pharmacopeia grade.
  • the amount of calcium hydroxyapatite added will be between 2.0% and 20%, preferably 4% and 15%, most preferably 5% and 10%, based on the total weight of the grease, although more can be added, if desired, after conversion and all reaction with complexing acids is complete.
  • calcium hydroxyapatite may be added to the above ingredients in an amount that is insufficient to fully react with the complexing acids.
  • finely divided calcium carbonate as an oil-insoluble solid calcium-containing base may be added, preferably before conversion, in an amount sufficient to fully react with and neutralize the portion of any subsequently added complexing acids not neutralized by the calcium hydroxyapatite.
  • calcium hydroxyapatite may be added to the above ingredients in an amount that is insufficient to fully react with the complexing acids.
  • finely divided calcium hydroxide and/or calcium oxide as an oil-insoluble solid calcium-containing base may be added, preferably before conversion, in an amount sufficient to fully react with and neutralize the portion of any subsequently added complexing acids not neutralized by the co-added calcium hydroxyapatite.
  • the calcium hydroxide and/or calcium oxide preferably represents no more than 75% of the hydroxide equivalent basicity provided by the total of the added calcium hydroxyapatite, calcium hydroxide, and calcium oxide.
  • calcium carbonate may also be added with the calcium hydroxyapatite, calcium hydroxide and/or calcium oxide, with the calcium carbonate being added either before or after reacting with complexing acids.
  • calcium carbonate is preferably added in an amount that is more than sufficient to neutralize any remaining complexing acid or acids.
  • the added calcium carbonate used as a calcium containing base is finely divided with a mean particle size of around 1 to 20 microns, preferably around 1 to 10 microns, most preferably around 1 to 5 microns.
  • the added calcium carbonate is preferably crystalline calcium carbonate (most preferably calcite) of sufficient purity so as to have abrasive contaminants such as silica and alumina at a level low enough to not significantly impact the anti-wear properties of the resulting grease.
  • the calcium carbonate should be either food grade or U.S. Pharmacopeia grade.
  • the amount of added calcium carbonate added is between 2.0% and 20%, preferably 4% and 15%, most preferably 6% and 10%, based on the final weight of the grease. These amounts are added as a separate ingredient in addition to the amount of dispersed calcium carbonate contained in the overbased calcium sulfonate.
  • the added calcium carbonate is added prior to conversion as the sole added calcium-containing base ingredient for reacting with complexing acids. Additional calcium carbonate may be added to either the simple or complex grease embodiments of the invention after conversion, and after all reaction with complexing acids is complete in the case of a complex grease.
  • references to added calcium carbonate herein refer to the calcium carbonate that is added prior to conversion and as one of or the sole added calcium-containing base for reaction with complexing acids when making a complex grease according to the invention.
  • the added calcium hydroxide and/or added calcium oxide added pre-conversion shall be finely divided with a mean particle size of around 1 to 20 microns, preferably around 1 to 10 microns, most preferably around 1 to 5 microns.
  • the calcium hydroxide and calcium oxide will be of sufficient purity so as to have abrasive contaminants such as silica and alumina at a level low enough to not significantly impact the anti-wear properties of the resulting grease.
  • the calcium hydroxide and calcium oxide should be either food grade or U.S. Pharmacopeia grade.
  • the total amount of calcium hydroxide and/or calcium oxide will be between 0.07% and 1 .00%, preferably 0.15% and 0.85%, most preferably 0.18% and 0.40%, based on the total weight of the grease. These amounts are added as separate ingredients in addition to the amount of residual calcium hydroxide or calcium oxide contained in the overbased calcium sulfonate. Most preferably, an excess amount of calcium hydroxide relative to the total amount of complexing acids used is not added prior to conversion. According to yet another embodiment, it is not necessary to add any calcium hydroxide or calcium oxide for reacting with complexing acids and either added calcium carbonate or calcium hydroxyapatite may be used as the sole added calcium containing base for such reaction or may be used in combination for such reaction.
  • Complexing acids used in these embodiments will comprise at least one and preferably two or more of the following: long chain carboxylic acids, short chain carboxylic acids, boric acid, and phosphoric acid.
  • Acetic acid and other carboxylic acids may be used as a converting agent or complexing acid or both, depending on when it is added.
  • some complexing acids (such as the 12-hydroxystearic acid in the '514 and '467 patents) may be used as converting agents.
  • the total amount of complexing acids added is preferably between 2.8% and 1 1 % by weight of the final grease.
  • the long chain carboxylic acids suitable for use in accordance with the invention comprise aliphatic carboxylic acids with at least 12 carbon atoms.
  • the long chain carboxylic acids comprise aliphatic carboxylic acids with at least 16 carbon atoms.
  • the long chain carboxylic acid is 12- hydroxystearic acid.
  • the amount of long chain carboxylic acid is between 0.5% and 5.0%, preferably 1 .0% to 4.0%, most preferably 2.0% to 3.0%, based on the final weight of the grease.
  • Short chain carboxylic acids suitable for use in accordance with the invention comprise aliphatic carboxylic acids with no more than 8 carbon atoms, and preferably no more than 4 atoms. Most preferably, the short chain carboxylic acid is acetic acid. The amount of short chain carboxylic acids is between 0.05% and 2.0%, preferably 0.1 % to 1 .0%, most preferably 0.2% to 0.5%, based on the final weight of the grease. Any compound that can be expected to react with water or other components used in producing a grease in accordance with this invention with such reaction generating a long chain or short chain carboxylic acid are also suitable for use.
  • acetic anhydride would, by reaction with water present in the mixture, form the acetic acid to be used as a complexing acid.
  • methyl 12- hydroxystearate would, by reaction with water present in the mixture, form the 12-hydroxystearic acid to be used as a complexing acid.
  • additional water may be added to the mixture for reaction with such components to form the necessary complexing acid if sufficient water is not already present in the mixture.
  • boric acid is used as a complexing acid according to this embodiment, an amount between 0.4% to about 4.0%, preferably 0.7% to 3.0%, and most preferably 1 .0% and 2.5%, based on the final weight of the grease, is added.
  • the boric acid may be added after first being dissolved or slurried in water, or it can be added without water. Preferably, the boric acid will be added during the manufacturing process such that water is still present.
  • any of the well-known inorganic boric acid salts may be used instead of boric acid.
  • any of the established borated organic compounds such as borated amines, borated amides, borated esters, borated alcohols, borated glycols, borated ethers, borated epoxides, borated ureas, borated carboxylic acids, borated sulfonic acids, borated epoxides, borated peroxides and the like may be used instead of boric acid.
  • phosphoric acid is used as a complexing acid, an amount between 0.4% to 4.0%, preferably 1 .0% and 3.0%, most preferably 1 .4% and 2.0%, based on the final weight of the grease, is added.
  • the percentages of various complexing acids described herein refer to pure, active compounds.
  • any of these complexing acids are available in a diluted form, they may still be suitable for use in the present invention. However, the percentages of such diluted complexing acids will need to be adjusted so as to take into account the dilution factor and bring the actual active material into the specified percentage ranges.
  • additives commonly recognized within the grease making art may also be added to either the simple grease embodiment or the complex grease embodiment of the invention.
  • Such additives can include rust and corrosion inhibitors, metal deactivators, metal passivators, antioxidants, extreme pressure additives, antiwear additives, chelating agents, polymers, tackifiers, dyes, chemical markers, fragrance imparters, and evaporative solvents.
  • the latter category can be particularly useful when making open gear lubricants and braided wire rope lubricants.
  • the inclusion of any such additives is to be understood as still within the scope of the present invention.
  • the calcium sulfonate grease compositions are preferably made according to the methods of the invention described herein. All percentages are based on the final weight of the finished grease unless otherwise indicated.
  • One preferred method of making a simple grease or a complex grease comprises mixing water, less than 30% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a complex grease or between 30% and 70% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a simple grease, and optionally base oil to form a first mixture; adding at least a portion of one or more non-aqueous converting agents to the first mixture after one or more delay periods to form a pre- conversion mixture; and converting the pre-conversion mixture to a converted mixture by heating until conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate has occurred.
  • Another preferred method of making a simple grease or a complex grease comprises mixing water, less than 45% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a complex grease or between 30% and 70% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a simple grease, and optionally base oil to form a first mixture; adding at least a portion of one or more nonaqueous converting agents to the first mixture after or during one or more delay periods to form a pre-conversion mixture; converting the pre-conversion mixture to a converted mixture by heating until conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate has occurred, with at least one of the delay periods being a holding delay period where the first mixture or pre-conversion mixture is maintained at a temperature or within a range of temperatures for a period of time.
  • Another preferred method of making a simple grease or a complex grease comprises mixing water, less than 22% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a complex grease or between 30% and 70% overbased calcium sulfonate containing dispersed amorphous calcium carbonate for a simple grease, and optionally base oil to form a first mixture; adding at least a portion of one or more nonaqueous converting agents to the first mixture after or during one or more delay periods to form a pre-conversion mixture; converting the pre-conversion mixture to a converted mixture by heating until conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate has occurred.
  • Another preferred method of making a simple grease comprises the steps of: (1 ) admixing in a suitable grease manufacturing vessel the following ingredients: water as a converting agent, a highly overbased oil- soluble calcium sulfonate containing dispersed amorphous calcium carbonate, optionally an appropriate amount of a suitable base oil (if needed), and optionally at least a portion of one or more non-aqueous converting agents to form a first mixture; (2) mixing or stirring the first mixture while maintaining it at a temperature or within a range of temperatures and/or adjusting the temperature of the first mixture to heat or cool it to another temperature(s) or range of temperatures during one or more delay periods; (3) optionally admixing at least a portion of one or more non-aqueous converting agents with the first mixture after or during one or more delay periods to form a second mixture; (4) heating the first mixture (or second mixture if non-aqueous converting agents are added in step 3) to a conversion temperature (preferably in the range of 190 F to 230
  • This process results in a preferred simple calcium sulfonate grease.
  • This preferred method also optionally includes the steps of (7) admixing added calcium carbonate and/or (8) admixing a facilitating acid.
  • Step (7) may be carried out at any time prior to conversion, after conversion or a portion may be added prior to conversion and another portion added after conversion.
  • Step (8) may be carried out at any time prior to conversion. Most preferably, this method is carried out in an open vessel, but may also be carried out in a pressurized vessel.
  • One preferred method of making a complex grease according to the invention comprises steps of: (1 ) admixing in a suitable grease manufacturing vessel the following ingredients: water as a converting agent, a highly overbased oil-soluble calcium sulfonate containing dispersed amorphous calcium carbonate, optionally an appropriate amount of a suitable base oil (if needed), and optionally at least a portion of one or more non-aqueous converting agents to form a first mixture; (2) mixing or stirring the first mixture while maintaining it at a temperature or within a range of temperatures and/or adjusting the temperature of the first mixture to heat or cool it to another temperature(s) or range of temperatures during one or more delay periods; (3) optionally admixing at least a portion of one or more non-aqueous converting agents with the first mixture after or during one or more delay periods to form a second mixture; (4) heating the first mixture (or second mixture if non-aqueous converting agents are added in step 3) to a conversion temperature (preferably in the range of 190 F to
  • Step (7) may be carried out prior to conversion or after conversion, or some portion or all of one or more calcium containing bases may be added prior to conversion and some portion or all of one or more calcium containing bases may be added after conversion.
  • Step (8) may be carried out at any time prior to conversion.
  • Step (9) may be carried out prior to conversion or after conversion, or some portion or all of one or more of the complexing acids may be added prior to conversion and some portion or all of one or more of the complexing acids added after conversion. Most preferably, this method is carried out in an open vessel, but may also be carried out in a pressurized vessel.
  • step (7) involves one of the following: (a) admixing finely divides calcium hydroxyapatite prior to conversion as the only calcium containing base added; (b) admixing finely divided calcium hydroxyapatite and calcium carbonate in an amount sufficient to fully react with and neutralize subsequently added complexing acids, according to one embodiment; (c) admixing finely divided calcium hydroxyapatite and calcium hydroxide and/or calcium oxide in an amount sufficient to fully react with and neutralize subsequently added complexing acids, with the calcium hydroxide and/or calcium oxide preferably being present in an amount not more than 75% of the hydroxide equivalent basicity provided by the total of the added calcium hydroxide and/or calcium oxide and the calcium hydroxyapatite, according to another embodiment of the invention; (d) admixing added calcium carbonate after conversion, according to another embodiment of the invention; or (e) admixing calcium hydroxyapatit
  • the method for making a complex grease is the same as above except that finely divided calcium carbonate as an oil-insoluble solid calcium-containing base is added prior to conversion (before or during step 6) and step (7) involves admixing finely divided calcium hydroxyapatite and calcium hydroxide and/or calcium oxide in an amount insufficient to fully react with and neutralize subsequently added complexing acids, with the calcium hydroxide and/or calcium oxide preferably being present in an amount not more than 75% of the hydroxide equivalent basicity provided by the total of the added calcium hydroxide and/or calcium oxide and the calcium hydroxyapatite, with the previously added calcium carbonate being added in an amount sufficient to fully react with and neutralize the portion of any subsequently added complexing acids not neutralized by the calcium hydroxyapatite and calcium hydroxide and/or calcium oxide.
  • Another preferred method of making a complex grease according to the invention comprises steps of: admixing in a suitable grease manufacturing vessel a highly overbased oil-soluble calcium sulfonate containing dispersed amorphous calcium carbonate and an amount of suitable base oil (if needed) and begin mixing. Then one or more facilitating acids are added and mixed, preferably for about 20-30 minutes. Then all of the calcium hydroxyapatite is added, followed by a portion of the calcium hydroxide, and then all of the calcium carbonate, which is mixed for another 20-30 minutes.
  • acetic acid and a portion of the 12-hydroxystearic acid are added and mixed for another 20-30 minutes (it is noted that these ingredients may be converting agents, but since they are added before the water there is no delay period).
  • water is added as a converting agent and mixed while heating to a temperature between 190°F and 230°F (a first temperature adjustment delay period and the final delay period).
  • all of the hexylene glycol is added as a non-aqueous converting agent.
  • the mixture is converted by continuing to mix while maintaining the temperature in the conversion temperature range (preferably 190 F to 230 F) until conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to very finely divided crystalline calcium carbonate is complete
  • the remaining calcium hydroxide is added and mixed for about 20-30 minutes.
  • the remaining acetic acid and remaining 12-hydroxystearic acid are added and mixed for around 30 minutes.
  • boric acid dispersed in water is added followed by the slow, gradual addition of phosphoric acid.
  • the mixture is then heated to remove water and volatiles, cooled, more base oil is added as needed, and the grease is milled as described below. Additional additives may be added during the final heating or cooling steps.
  • the steps and ingredients are the same as outlined above except that after adding the water as a converting agent and before adding all of the hexylene glycol as a non-aqueous converting agent, the mixture is heated to around 160°F (a first temperature adjustment delay period) and held at that temperature for around 30 minutes (a first holding delay period) before continuing to heat to between 190°F and 230°F (a second temperature adjustment delay period and the final delay period).
  • any portion of a non-aqueous converting agent added in steps 1 , 3, and/or 5 may be the same non-aqueous converting agent as that added in another step or steps or different from any non-aqueous converting agent added in another step or steps.
  • a delay period in step 3 or step 5
  • another portion of the same and/or at least a portion of a different non-aqueous converting agent or agents may be added in any combination of steps 1 , 3, and/or 5.
  • all of the one or more of the non-aqueous converting agents are admixed after the final delay period in step 5, with none being added during steps 1 or 3.
  • at least a portion of one or more non-aqueous converting agents is added with the first mixture in step 1 prior to any delay and at least a portion of the same or a different non-aqueous converting agent is added in step 3 and/or in step 5.
  • no non-aqueous converting agents are added with the first mixture and at least a portion of one or more non-aqueous converting agents is added is added in step 3 and in step 5.
  • at least a portion of one or more non-aqueous converting agents is added after or during one delay period in step 3 and at least a portion of the same or a different nonaqueous converting agent is added after or during another delay period (a second delay period in step 3 and/or a final delay period in step 5).
  • At least a portion of one or more non-aqueous converting agents is added after one or more delays in step 3, but no non-aqueous converting agents are added after the final delay period in step 5.
  • the method of making a complex and a simple grease also includes the steps of: (a) mixing and heating to a temperature sufficiently high to insure removal of water and any volatile reaction byproducts and optimize final product quality; (b) cooling the grease while adding additional base oil as needed; (c) adding remaining desired additives as are well known in the art; and, if desired, (d) milling the final grease as required to obtain a final smooth homogenous product.
  • the grease is heated (preferably under open conditions, not under pressure, although pressure may be used) to between 250 F and 300 F, preferably 300 F to 380 F, most preferably 380 F to 400 F, to remove the water that was initially added as a converting agent, as well as any water formed by chemical reactions during the formation of the grease. Having water in the grease batch for prolonged periods of time during manufacture may result in degradation of thickener yield, dropping point, or both, and such adverse effects may be avoided by removing the water quickly. If polymeric additives are added to the grease, they should preferably not be added until the grease temperature reaches 300 F. Polymeric additives can, if added in sufficient concentration, hinder the effective volatilization of water.
  • polymeric additives should preferably be added to the grease only after all water has been removed. If during manufacture it can be determined that all water has been removed before the temperature of the grease reaches the preferred 300 F value, then any polymer additives may preferably be added at any time thereafter.
  • one or more of the delay periods is a temperature adjustment delay period or a holding delay period or both.
  • the delay periods may involve multiple temperature adjustment delay periods and multiple holding delay periods.
  • a first temperature adjustment delay period is the period of time after water is added that it takes to adjust the temperature of the mixture (typically by heating) to a temperature or range of temperatures (the first temperature).
  • a first holding delay period is the amount of time the mixture is held at the first temperature.
  • a second temperature adjustment delay period is the period of time after the first holding delay that it takes to heat the mixture to another temperature or temperature range (the second temperature).
  • a second holding delay period is the amount of time the mixture is held at the second temperature. Additional temperature adjustment delay periods or holding delay periods (i.e. a third temperature adjustment delay period) follow the same pattern.
  • the first temperature may be ambient temperature (in which case there is no first temperature adjustment delay period). Any subsequent temperature may be higher or lower than the previous temperature.
  • the final pre-conversion temperature will preferably be between about 190 F and 220 F or up to 230 F, as the temperature at which conversion in an open kettle typically occurs.
  • non-aqueous converting agent or portion thereof is added immediately after reaching a temperature or range of temperatures, then there is no holding delay period for that particular temperature. All of or a portion of one or more non-aqueous converting agents may be added after any temperature adjustment delay period or holding delay period and another portion of the same, or all of or a portion of a different, non-aqueous converting agent may be added after another temperature adjustment delay period or holding delay period.
  • the temperature adjustment delay period after which a non-aqueous converting agent is immediately added to the mixture will be the last temperature adjustment delay period (and last delay period) associated with that specific non-aqueous converting agent, but the mixture may be heated to another temperature or temperature range and additional non-aqueous converting agent(s) added to result in additional temperature adjustment delay periods and possibly additional holding delay periods.
  • At least a portion of one or more non-aqueous converting agents is added at the end of a final of the one or more delay periods and another portion of the same and/or a different nonaqueous converting agent is added after one or more prior delay periods.
  • all of the one or more nonaqueous converting agents are added at the end of a final of the one or more delay periods.
  • at least a portion of one or more non-aqueous converting agents are added at around the same time as the water is added (no delay period) and another portion of the same and/or a different non-aqueous converting agent is added after one or more prior delay periods.
  • at least one non-aqueous converting agent or a portion thereof is slowly added in a substantially continuous manner or in discrete, incremental amounts during a temperature adjustment delay period, a holding delay period, or both.
  • a delay period within the scope of this invention may involve a holding delay period that does not involve heating (see Example 15 below where the mixture was held at ambient temperature for a first holding delay period prior to heating to a conversion temperature range during a second temperature adjustment delay period), a short period of time of less than 15 minutes between the addition of water as a converting agent and the addition of all of the non-aqueous converting agent(s) without any heating during that time period is not a "delay" or “delay period” as used herein.
  • a delay for the addition of any or all of the non-aqueous converting agent(s) without heating during the delay period should be at least about 20 minutes and more preferably at least about 30 minutes.
  • An interval of less than 20 minutes between the addition of water and a portion of a non-aqueous converting agent, without heating during the 20 minutes, but with a subsequent longer holding delay period or subsequent heating prior to the addition of another portion of the same, or a portion or all of a different, nonaqueous converting agent(s) does involve a "delay period" within the scope of the invention.
  • the initial short interval is not a "delay period”
  • the subsequent longer holding delay or temperature adjustment delay prior to addition of a non-aqueous converting agent is a holding delay period or temperature adjustment delay period for purposes of this invention.
  • all or some portion of one or more of the non-aqueous converting agents may be slowly added during one or more temperature adjustment delay periods or holding delay periods or both. Such slow addition may include a substantially continuous addition of the non-aqueous converting agent during the delay period(s) or repeated, incremental additions during the delay period(s).
  • acetic acid or 12-hydroxystearic acid when added pre-conversion, these acids acid will have a dual role as both converting agent and complexing acid.
  • these acids When these acids are added along with another more active non-aqueous converting agent (such as a glycol), the acid may be considered to act primarily in the role of complexing acid, with the more active agent taking on the primary role of converting agent.
  • another more active non-aqueous converting agent such as a glycol
  • the acid may be considered to act primarily in the role of complexing acid, with the more active agent taking on the primary role of converting agent.
  • any elapsed time between the addition of water and any portion of the acetic acid or 12-hydroxystearic acid is not considered a delay as that term is used herein.
  • steps (2)-(6) for both the simple grease and complex grease, wherein there is a delayed addition of at least a portion of the non-aqueous converting agent(s) relative to the addition of the water as a converting agent (either with or without interim temperature adjustment), are important aspects of the invention. Certain other aspects of the process are not critical to obtaining a preferred calcium sulfonate grease compositions according to the invention. For instance, the order that the calcium containing bases are added relative to each other is not important. Also, the temperature at which the water as a converting agent and calcium containing bases are added is not critical, but it is preferred that they be added before the temperature reaches 190 F to 200 F.
  • an open vessel is any vessel with or without a top cover or hatch as long as any such top cover or hatch is not vapor-tight so that significant pressure cannot be generated during heating. Using such an open vessel with the top cover or hatch closed during the conversion process will help to retain the necessary level of water as a converting agent while generally allowing a conversion temperature at or even above the boiling point of water.
  • Example 1 A calcium sulfonate complex grease according to the composition of the invention, but without a delay period between the addition of water and the non-aqueous converting agent was made as follows: 264.61 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 327.55 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1 .70 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the '768 application.
  • the grease was then removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the grease had a worked 60 stroke penetration of 287.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 23.9%.
  • the dropping point was >650 F.
  • calcium hydroxyapatite and calcium carbonate were added before conversion, according to an embodiment of the 768 application.
  • 33% of the total amount of calcium hydroxide was added before conversion followed by 35% of the total amount glacial acetic acid and 28% of the total amount of 12- hydroxystearic acid.
  • the remaining amounts of calcium hydroxide, glacial acetic acid, 12-hydroxystearic acid were added after conversion
  • Example 2 Another calcium sulfonate complex grease was made using the same equipment, raw materials, amounts, and manufacturing process as the Example 1 grease, except that there was a delay in adding the non-aqueous converting agent (hexylene glycol).
  • the other initial ingredients including water
  • the grease was held at 190 F - 200 F for an additional 45 minutes. Then the remaining process was the same as the previous Example 1 grease.
  • the final grease had a worked 60 stroke penetration of 261.
  • the percent overbased oil- soluble calcium sulfonate in the final grease was 21 .1 %.
  • the dropping point was >650 F.
  • the grease of this example had an improved thickener yield compared to the grease of the previous Example 1 as evidenced by the lower final percentage of overbased calcium sulfonate as compared to the worked penetration.
  • the predicted percentage of overbased calcium sulfonate in the Example 2 grease would be 19.2% if it was diluted with sufficient base oil to obtain the same worked penetration of the Example 1 grease.
  • Example 3 Another calcium complex grease using the same equipment, raw materials, amounts, and manufacturing process as the Example 1 grease was made, except that there was a delay in adding the nonaqueous converting agent (hexylene glycol).
  • the other initial ingredients including water
  • the hexylene glycol was added immediately upon reaching 190°F (no holding delay period).
  • the grease was held at 190 F - 200 F for an additional 45 minutes. Then the remaining process was the same as the previous Example 1 grease.
  • the final grease had a worked 60 stroke penetration of 290.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 21 .4%.
  • the dropping point was >650 F.
  • the grease of this example had an improved thickener yield compared to the grease of the previous Example 1 as evidenced by the lower final percentage of overbased calcium sulfonate as compared to the worked penetration.
  • Example 4 Another calcium sulfonate complex grease according to the composition of the invention, but without a delay period between the addition of water and the non-aqueous converting agent was made as follows: 31 1.67 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 451.37 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 10.30 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of '768 application.
  • the grease was further heated to about 390 F at which time all the polymer was melted and fully dissolved in the grease mixture.
  • the heating mantle was removed and the grease was allowed to cool by continuing to stir in open air.
  • an additional 32.75 grams of the paraffinic base oil was added.
  • 5.05 grams of a polyisobutylene polymer were added.
  • Mixing continued until the grease reached a temperature of 170 F.
  • the grease was then removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the grease had a worked 60 stroke penetration of 271.
  • the percent overbased oil- soluble calcium sulfonate in the final grease was 31 .0%.
  • the dropping point was 629 F.
  • the added calcium carbonate was added before conversion in accordance with an embodiment of the '574 application.
  • 20% of the total amount of 12-hydroxystearic acid was added before conversion.
  • the remaining amount of 12-hydroxystearic acid was added after conversion.
  • Example 5 Another calcium complex grease using the same equipment, raw materials, amounts, and manufacturing process as the Example 4 grease was made, except that there was a delay in adding the nonaqueous converting agent (hexylene glycol).
  • the other initial ingredients including water
  • the other initial ingredients were mixed and heated to a temperature of about 190°F (a first temperature adjustment delay period) and held at that temperature for 1 hour (a first holding delay period) prior to adding the hexylene glycol.
  • a first temperature adjustment delay period a first temperature adjustment delay period
  • 1 hour a first holding delay period
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 29.2%.
  • the dropping point was >650 F.
  • the grease of this example had an improved thickener yield compared to the grease of the previous Example 4 as evidenced by the lower final percentage of overbased calcium sulfonate as compared to the worked penetration.
  • Example 6 Another calcium sulfonate complex grease was made using similar ingredients and methods as examples in U.S. Patents 5,308,514 and 5,338,467 (issued to Witco Corporation on May 3, 1994 and August 16, 1994, respectively), where at least a portion of the long chain fatty acid is added prior to conversion and may act as a converting agent. Specifically, 54.1 % of the total amount of 12-hydroxystearic acid and all of the glacial acetic acid were added before conversion. The remaining amount of 12- hydroxystearic acid was added after conversion followed by calcium hydroxide and a boric acid water mixture.
  • Added calcium hydroxide is used as the sole added base for reacting with complexing acids, in accordance with the scope of the '514 patent, and no calcium hydroxyapatite or added calcium carbonate was used. There was no delayed addition of non-aqueous converting agent in Example 6.
  • the grease of Example 6 was made as follows: 380.26 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 603.6 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of 768 application. Then 21 .75 grams of a primarily C12 alkylbenzene sulfonic acid were added.
  • the grease of Example 6 had a worked 60 stroke penetration of 320.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 27.6%.
  • all of the hexylene glycol converting agent was added with the water, a portion of the acetic acid was then added prior to any heating, and a portion added after heating to 190°F for 45 minutes.
  • Neither of the two additions of acetic acid involved a "delay," because there is another non-aqueous converting agent used (hexylene glycol) and the 10 minute mixing interval without heating is not considered a delay.
  • Example 6A Another grease was made almost exactly the same as the previous Example 6 grease. The only difference was that once 190 F was reached during the initial heating, no additional glacial acetic acid was added. The grease had a worked 60 stroke penetration of 339. The percent overbased oil-soluble calcium sulfonate in the final grease was 27.6%. These results are similar to Example 6, and further show that a time interval between the addition of water and addition of acetic acid, when there is another non-aqueous converting agent used, is not a "delay" that results in improved thickener yield.
  • Example 7 Another calcium complex grease using the same equipment, raw materials, amounts, and manufacturing process as the Example 6 grease was made, except that there was a delay in adding the nonaqueous converting agent (hexylene glycol).
  • the other initial ingredients including water and acetic acid
  • the other initial ingredients were mixed and heated to a temperature of about 190°F (a first temperature adjustment delay period) and held at that temperature for 1 hour (a first holding delay period) prior to adding the hexylene glycol.
  • the hexylene glycol was added, the grease was held at 190 F - 200 F until conversion appeared to be complete. Then the remaining process was the same as the previous Example 6 grease.
  • the final grease had a worked 60 stroke penetration of 281 .
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 27.6%.
  • the dropping point was >650 F.
  • the grease of this example had an improved thickener yield compared to the grease of the previous Example 6 as evidenced by the much firmer penetration despite having essentially the same percentage overbased oil-soluble calcium sulfonate.
  • the predicted percentage of overbased calcium sulfonate in the Example 7 grease would be 24.2% if it was diluted with sufficient base oil to obtain the same worked penetration of the Example 6 grease.
  • This example shows improved results over examples 6 and 6A where the only change was the delayed addition of the non-aqueous converting agent hexylene glycol.
  • Example 8 Another calcium sulfonate complex grease was made using calcium hydroxyapatite, added calcium carbonate, and added calcium hydroxide as the calcium containing bases for reaction with complexing acids according to an embodiment of the 768 application.
  • This example is a baseline for comparison with Examples 9-17, as there was no delay in the addition of the non-aqueous converting agent (hexylene glycol) in this example.
  • the grease of Example 8 was made as follows: 264.98 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 378.68 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1.10 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the '768 application. Mixing without heat began using a planetary mixing paddle.
  • Example 9 Another calcium sulfonate complex grease was made in like manner with the previous Example 8 grease. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to about 190 F to 200 F (a first temperature adjustment delay period) and held at that temperature for 30 minutes (a first holding delay period).
  • the grease was made as follows: 264.04 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 378.21 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1 .15 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the '768 application.
  • Mixing without heat began using a planetary mixing paddle. Then 23.91 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 50.60 grams of calcium hydroxyapatite with a mean particle size around 1 to 5 microns and 3.61 grams of food grade purity added calcium hydroxide having a mean particle size around 1 to 5 microns were added and allowed to mix in for 30 minutes.
  • FTIR Fourier Transform Infrared
  • the heating mantle was removed and the grease was allowed to cool by continuing to stir in open air.
  • 33.15 grams of food grade anhydrous calcium sulfate having a mean particle size of around 1 to 5 microns were added.
  • 2.29 grams of an aryl amine antioxidant and 4.79 grams of a polyisobutylene polymer were added.
  • An additional 108.1 1 grams of the same paraffinic base oil were added.
  • Mixing continued until the grease reached a temperature of 170 F.
  • the grease was then removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the grease had a worked 60 stroke penetration of 272.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 21 .78%.
  • the dropping point was >650 F. As can be seen, this grease had an improved thickener yield compared to the grease of Example 8.
  • Example 10 Another calcium sulfonate complex grease was made in like manner with the previous Example 8 and 9 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to about 190 F to 200 F (first temperature adjustment delay period) and held at that temperature for 2 hours (first holding delay period).
  • the grease was made as follows: 264.35 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 377.10 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1 .02 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the 768 application.
  • Mixing without heat began using a planetary mixing paddle. Then 24.00 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 50.66 grams of calcium hydroxyapatite with a mean particle size of around 1 to 5 microns and 3.76 grams of food grade purity added calcium hydroxide having a mean particle size of around 1 to 5 microns were added and allowed to mix in for 30 minutes. Then 0.91 grams of glacial acetic acid and 10.60 grams of 12-hydroxystearic acid were added and allowed to mix in for 10 minutes.
  • Example 11 Another calcium sulfonate complex grease was made in like manner with the previous Examples 8 - 10 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to about 190 F to 200 F (a first temperature adjustment delay period) and held at that temperature for 30 minutes (a first holding delay period), then cooled to 160 F (a second temperature adjustment delay period) and held at 160 F to 170 F for two hours (a second holding delay period), then heated back up to 190 F (a third temperature adjustment delay period) with immediate addition of the hexylene glycol upon reaching 190 F (no third holding delay period).
  • Example 1 1 The grease of Example 1 1 was made as follows: 264.09 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 380.83 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1.22 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the 768 application. Mixing without heat began using a planetary mixing paddle. Then 23.97 grams of a primarily C12 alkylbenzene sulfonic acid were added.
  • the temperature was reduced to 160 F (a second temperature adjustment delay period), and the temperature was held between 160 F and 170 F for two hours (a second holding delay period). During this time, an additional 15 ml of water was added since some of the originally added water had evaporated. As already mentioned, subsequent pre- conversion additions of water to make up for evaporation losses are not used in determining delay periods, only the first addition of water is used. Then the temperature was increased to 190 F (a third temperature adjustment delay period). Another 20 ml of water was added. Immediately thereafter, 13.20 grams of hexylene glycol was added (no third holding delay period).
  • FTIR Fourier Transform Infrared
  • Example 12 Another calcium sulfonate complex grease was made in like manner with the previous Examples 8 - 1 1 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to 160 F (a first temperature adjustment delay period) and held at 160 F to 170 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period) with immediate addition of the hexylene glycol upon reaching 190 F (no second holding delay period).
  • the grease of Example 12 was made as follows: 264.48 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 382.94 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1.18 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the 768 application. Mixing without heat began using a planetary mixing paddle. Then 24.21 grams of a primarily C12 alkylbenzene sulfonic acid were added.
  • the grease was further heated to about 390 F at which time all the polymer was melted and fully dissolved in the grease mixture.
  • the heating mantle was removed and the grease was allowed to cool by continuing to stir in open air.
  • 33.00 grams of food grade anhydrous calcium sulfate having a mean particle size of around 1 to 5 microns were added.
  • 2.42 grams of an aryl amine antioxidant and 5.62 grams of a polyisobutylene polymer were added.
  • An additional 192.05 grams of the same paraffinic base oil were added. Mixing continued until the grease reached a temperature of 170 F.
  • the grease was then removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the grease had a worked 60 stroke penetration of 287.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 20.36%.
  • the dropping point was 639 F. As can be seen, this grease had an improved thickener yield compared to the grease of Example 8.
  • Example 13 Another calcium sulfonate complex grease was made in like manner with the previous Example 12 grease. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to 140 F (a first temperature adjustment delay period) and held at 140 F to 150 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period) for immediate addition of the hexylene glycol for conversion (no second holding delay period), followed by addition of the other components as outlined in Example 12. The final grease had a worked 60 stroke penetration of 283. The percent overbased oil-soluble calcium sulfonate in the final grease was 20.88%. The dropping point was >650 F. As can be seen, this grease had an improved thickener yield compared to the grease of Example 8.
  • Example 14 Another calcium sulfonate complex grease was made in like manner with the previous Example 12-13 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to 1 10 F (a first temperature adjustment delay period) and held at 1 10 F to 120 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period) for immediate addition of the hexylene glycol for conversion (no second holding delay period), followed by addition of the other components as outlined in Example 12. The final grease had a worked 60 stroke penetration of 287. The percent overbased oil-soluble calcium sulfonate in the final grease was 21 .63%. The dropping point was >650 F. As can be seen, this grease had an improved thickener yield compared to the grease of Example 8.
  • Example 15 Another calcium sulfonate complex grease was made in like manner with the previous Example 12-14 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been stirred and held at ambient laboratory temperature (about 25 C) for two hours and 30 minutes (a first holding delay period, without any temperature adjustment delay period), then heated up to 190 F (a second temperature adjustment delay period) for immediate addition of the hexylene glycol for conversion (no second holding delay period), followed by addition of the other components as outlined in Example 12. The final grease had a worked 60 stroke penetration of 279. The percent overbased oil-soluble calcium sulfonate in the final grease was 21 .40%. The dropping point was >650 F.
  • this grease had an improved thickener yield compared to the grease of Example 8.
  • this grease showed significant thickener yield improvement within the general range of thickener yields for all the Example 9 - 14 greases where the delayed hexylene glycol technique was used even though the first delay (holding delay period) involved no heating at all. Additionally, by comparison of these examples, the first temperature range did not significantly impact the percentage of overbased calcium sulfonate in these greases, although having a first temperature range in the mid-range of around 140-170 produced the best thickener yield results.
  • Example 16 Another calcium sulfonate complex grease was made in like manner with the previous Examples 8 - 15 greases. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been mixed at ambient laboratory temperature for 2 hours and 30 minutes (first holding delay period, without any temperature adjustment), followed by heating to 160 F (a second temperature adjustment delay period) and mixing at 160 F to 170 F for two hours and 30 minutes (second holding delay period), followed heating up to 190 F (a third temperature adjustment delay period) and immediate addition of hexylene glycol (no third holding delay period).
  • the grease of Example 16 was made as follows: 264.28 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 382.25 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 1 1.10 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 10 and 1 1 of the '768 application. Mixing without heat began using a planetary mixing paddle. Then 24.08 grams of a primarily C12 alkylbenzene sulfonic acid were added.
  • the mixture was heated to 160 F and held between 160 F and 170 F for two hours and 30 minutes. During this time, an additional 20 ml of water was added since some of the originally added water had evaporated. Then the temperature was increased to 190 F and immediately thereafter, 13.68 grams of hexylene glycol was added. Once visible conversion had begun, the temperature was held between 190 F and 200 F for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. Due to the grease becoming heavy, another 57.09 grams of the same paraffinic mineral oil was added. Another 15 ml of water was also added.
  • FTIR Fourier Transform Infrared
  • Example 17 Another calcium sulfonate complex grease was made in like manner with the previous Example 12 grease. The only significant difference was that 25% of the total amount of the hexylene glycol was added at the beginning with the water, prior to any heating (no delay). The remaining hexylene glycol was added after the mixture had first been heated to 160 F (a first temperature adjustment delay period) and held between 160 F and 170 F for two hours and 30 minutes (a first holding delay period). Then the mixture was immediately heated to 190 F - 200 F for conversion as usual.
  • the grease of Example 17 was made as follows: 264.39 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 383.09 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F, and 10.56 grams of PAO having a viscosity of 4 cSt at 100 C.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to the one previously described and used in Examples 9 and 10 of the '768 application. Mixing without heat began using a planetary mixing paddle. Then 24.02 grams of a primarily C12 alkylbenzene sulfonic acid were added.
  • the mixture was heated until the temperature reached 160 F.
  • the temperature was held between 160 F and 170 F for two hours and 30 minutes. During this time, an additional 15 ml of water was added since some of the originally added water had evaporated.
  • 10.46 grams of hexylene glycol and 10 ml of water were added, and the temperature was increased to 190 F. Once visible conversion had begun, the temperature was held between 190 F and 200 F for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. Then 7.55 grams of the same added calcium hydroxide were added and allowed to mix in for 10 minutes.
  • FTIR Fourier Transform Infrared
  • Example 18 Another complex calcium sulfonate grease was made similar to an embodiment of U.S. Patent 4,560,489 (issued to Witco Corporation on December 24, 1985), without delayed addition of the nonaqueous converting agent for use as a baseline comparison example).
  • the grease of Example 18 was made as follows: 440.02 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 390.68 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of the 768 application document. Then 17.76 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 44.41 grams water was added followed by 14.37 grams of hexylene glycol. Then the batch was heated with continued mixing until the temperature reached 190 F. When the temperature reached 190 F, 5.75 grams of glacial acetic acid were added.
  • FTIR Fourier Transform Infrared
  • Example 19 Another calcium sulfonate complex grease was made in like manner with the previous Example 18 grease. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to 160 F (a first temperature adjustment delay period) and held at 160 F to 170 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period) with immediate addition of the hexylene glycol (no second holding delay period).
  • the grease of Example 19 was made as follows: 440.46 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 387.69 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of the '768 application document. Then 17.64 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 44.0 grams water was added.
  • the mixture was heated to 160 F and held between 160 F and 170 F for two hours and 30 minutes. During this time, an additional 43 ml of water was added since most of the originally added water had evaporated.
  • the batch was then heated to 190 F, and 14.49 grams of hexylene glycol and 5.73 grams of glacial acetic acid were immediately added. Once visible conversion to a grease structure was observed, the temperature was held between 190 F and 200 F for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. An additional 20 ml of water was added during this time since some of the earlier added water had evaporated.
  • FTIR Fourier Transform Infrared
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 46.90%.
  • the dropping point was >650 F. It is noted that this grease and the previous Example 18 grease had essentially the same percent overbased calcium sulfonate. However, the worked penetration of this grease was 31 points harder. Therefore, the delayed glycol procedure used in this grease resulted in an improved thickener yield. In fact, using a linear dilution relation of worked penetration to the percentage of overbased calcium sulfonate in the final grease, the predicted percentage of overbased calcium sulfonate in the Example 19 grease would be 41 .9% if it was diluted with sufficient base oil to obtain the same worked penetration of the Example 18 grease. Additionally, a very high dropping point was maintained in the Example 19 grease.
  • Example 20 A simple calcium sulfonate grease was made similar to an embodiment within the scope of U.S. Patents 3,377,283 and 3,492,231 (issued to Lubrizol Corporation on April 9, 1968 and January 27, 1970, respectively), without any delay for use as a baseline comparison example.
  • the grease of Example 20 was made as follows: 496.49 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 394.45 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of the '768 application document. Then 20.23 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 44.23 grams water was added followed by 16.57 grams of hexylene glycol. Then the batch was heated with continued mixing until the temperature reached 190 F. When the temperature reached 190 F, 6.20 grams of glacial acetic acid were added.
  • Example 21 Another simple calcium sulfonate grease was made in like manner with the previous Example 20 grease. The only significant difference was that the addition of the hexylene glycol was delayed until the grease had been heated to 160 F (a first temperature adjustment delay period) and held at 160 F to 170 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period) with immediate addition of the hexylene glycol (no second holding delay period).
  • the grease was made as follows: 495.41 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 391 .96 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 12 of the 768 application document. Then 19.65 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 44.42 grams water was added.
  • the mixture was heated to 160 F and held between 160 F and 170 F for two hours and 30 minutes. During this time, an additional 50 ml of water was added since most of the originally added water had evaporated.
  • the batch was then heated to 190 F, and 16.53 grams of hexylene glycol followed by 6.34 grams of glacial acetic acid were added. Once visible conversion to a grease structure was observed, the temperature was held between 190 F and 200 F for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. During this time, an additional 10 ml of water was added. The resulting grease was then heated to 330 F.
  • FTIR Fourier Transform Infrared
  • the heating mantle was then removed and the grease was allowed to cool by continuing to stir in open air.
  • the temperature reached 200 F
  • 2.32 grams of an aryl amine antioxidant was added.
  • the grease cooled to 170 F it was removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the dropping point of the Example 21 grease was >650 F.
  • the grease had a worked 60 stroke penetration of 290.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 53.14%.
  • Example 21 Another simple calcium sulfonate grease was made in like manner to the previous Example 20 grease.
  • Example 22 is a baseline example where no delay was used.
  • the grease was made as follows: 550.60 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 354.69 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 1 1 of the 768 application document. Then 22.23 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 49.59 grams water was added followed by 12.35 grams of propylene glycol. Then the batch was heated with continued mixing until the temperature reached 190 F. A 6.87 gram portion of glacial acetic acid was added.
  • Example 23 Another simple calcium sulfonate grease was made in like manner with the previous Example 22 grease. The only significant difference was that the addition of the propylene glycol was delayed until the grease had been heated to 160 F (a first temperature adjustment delay period) and held at 160 F to 170 F for two hours and 30 minutes (first holding delay period), then heated up to 190 F (a second temperature adjustment delay period).
  • the grease was made as follows: 550.71 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to an open mixing vessel followed by 354.74 grams of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F. Mixing without heat began using a planetary mixing paddle.
  • the 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to the one previously described and used in Examples 4 and 1 1 of the 768 application document. Then 22.92 grams of a primarily C12 alkylbenzene sulfonic acid were added. After mixing for 20 minutes, 49.23 grams water was added.
  • the mixture was heated to 160 F and held between 160 F and 170 F for two hours and 30 minutes. During this time, an additional 35 ml of water was added since most of the originally added water had evaporated. Then the batch was heated with continued mixing until the temperature reached 190 F. When the batch reached 190 F, 12.27 grams propylene glycol and 6.89 grams of glacial acetic acid were immediately added (no second holding delay period). Once visible conversion to a grease structure was observed, the temperature was held between 190 F and 200 F for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. During this time, an additional 15 ml of water was added.
  • FTIR Fourier Transform Infrared
  • the resulting grease was then heated to 330 F.
  • the heating mantle was then removed and the grease was allowed to cool by continuing to stir in open air.
  • the temperature reached 200 F, 2.38 grams of an aryl amine antioxidant was added.
  • the grease cooled to 170 F, it was removed from the mixer and given three passes through a three-roll mill to achieve a final smooth homogenous texture.
  • the grease had a worked 60 stroke penetration of 239.
  • the percent overbased oil-soluble calcium sulfonate in the final grease was 57.97%.
  • the dropping point was 591 F.
  • Example 22 and 23 greases were lower than other previous greases, indicating that propylene glycol was not as effective a converting agent as hexylene glycol, at least under the conditions that each were used. Nonetheless, the delayed addition of propylene glycol improved the thickener yield compared to the grease where its addition was not delayed.
  • Table 4 The results of these examples are summarized in Table 4 below.
  • Example greases made according to the delayed addition methodology of the invention described above also show different physical properties compared to example greases where addition of all or some of a non-aqueous converting agent was not delayed, even though the ingredients and quantities thereof used in various comparison sets of the examples were the same or substantially similar.
  • FTIR Fourier Transform Infrared Spectroscopy
  • SEM Scanning Electron Microscopy
  • thickener yield shall be the conventional meaning, namely, the concentration of the highly overbased oil-soluble calcium sulfonate required to provide a grease with a specific desired consistency as measured by the standard penetration tests ASTM D217 or D1403 commonly used in lubricating grease manufacturing.
  • the "dropping point” of a grease shall refer to the value obtained by using the standard dropping point test ASTM D2265 as commonly used in lubricating grease manufacturing.
  • reference to the immediate addition of an ingredient after a temperature has been reached means that the ingredient is added as soon after reaching that temperature as is physically possible given the amount to be added and equipment being used, but if preferably within a short time, less than 10 minutes and more preferably less than 5 minutes, after the mixture reaches approximately the temperature indicated.
  • quantities of dispersed calcium carbonate or residual calcium oxide or calcium hydroxide contained in the overbased calcium sulfonate are by weight of the overbased calcium sulfonate; (2) some ingredients are added in two or more separate portions and each portion may be described as a percentage of the total amount for that ingredient; and (3) all other amounts (including total amounts) of ingredients identified by percentages or parts are by weight of the final grease product, even though the particular ingredient (such as water) may not be present in the final grease or may not be present in the final grease in the quantity identified for addition as an ingredient.
  • calcium hydroxyapatite means (1 ) the compound having the formula Ca 5 (P0 4 ) 3 0H or (2) a mathematically equivalent formula (a) having a melting point of around 1 100 C or (b) specifically excluding mixtures of tricalcium phosphate and calcium hydroxide by such equivalent formula.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une graisse de sulfonate de calcium surbasique comprenant une quantité réduite de sulfonate de calcium surbasique, de l'eau et au moins un agent de conversion non aqueux, au moins une partie de l'agent de conversion non aqueux étant ajoutée de façon différée par rapport à l'addition de l'eau. Le délai peut correspondre au laps de temps nécessaire pour ajuster la température du mélange, à un laps de temps pendant lequel le mélange est maintenu à une certaine température ou dans une plage de températures donnée et à des multiples et à une quelconque combinaison de ces divers laps de temps. Ces graisses de sulfonate de calcium présentent un rendement épaississant amélioré et des points de goutte élevés par rapport aux graisses de composition sensiblement similaire fabriquées sans délai entre l'addition d'eau et celle d'un agent de conversion non aqueux, notamment en cas d'utilisation de sulfonate de calcium surbasique de piètre qualité.
EP16884166.6A 2016-01-07 2016-12-14 Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux Pending EP3400279A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/990,473 US9976101B2 (en) 2011-10-31 2016-01-07 Method of manufacturing calcium sulfonate greases using delayed addition of non-aqueous converting agents
PCT/US2016/066547 WO2017119999A1 (fr) 2016-01-07 2016-12-14 Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux

Publications (2)

Publication Number Publication Date
EP3400279A4 EP3400279A4 (fr) 2018-11-14
EP3400279A1 true EP3400279A1 (fr) 2018-11-14

Family

ID=59273894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16884166.6A Pending EP3400279A1 (fr) 2016-01-07 2016-12-14 Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux

Country Status (3)

Country Link
EP (1) EP3400279A1 (fr)
CN (1) CN108463542B (fr)
WO (1) WO2017119999A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3071149A1 (fr) * 2017-07-24 2019-01-31 Chemtool Incorporated Graisse de sulfonate metallique pour pressions extremes
CN110437925A (zh) * 2019-08-19 2019-11-12 新乡市恒星科技有限责任公司 一种复合碳酸钙基润滑脂的制备方法
WO2024047447A1 (fr) * 2022-09-01 2024-03-07 The Lubrizol Corporation Gélifiant pour graisses au sulfonate de calcium

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US61721A (en) * 1867-02-05 Improvement in children s building-blocks
US4560489A (en) * 1983-09-14 1985-12-24 Witco Chemical Corporation High performance calcium borate modified overbased calcium sulfonate complex greases
US5308514A (en) * 1993-03-03 1994-05-03 Witco Corporation Sulfonate greases
US7294608B2 (en) * 2003-04-28 2007-11-13 Jet-Lube, Inc. Use of calcium sulfonate based threaded compounds in drilling operations and other severe industrial applications
US7517837B2 (en) * 2003-05-22 2009-04-14 Anderol, Inc. Biodegradable lubricants
US7241723B2 (en) * 2003-09-05 2007-07-10 Nch Corporation Bearing cleaning composition and method of use
US8563488B2 (en) * 2004-03-23 2013-10-22 The Lubrizol Corporation Functionalized polymer composition for grease
CN101705143B (zh) * 2009-11-09 2012-12-19 鞍山海华油脂化学有限公司 一种高极压抗水防锈润滑脂及其制备方法
EP2773590B1 (fr) * 2011-10-31 2020-09-09 NCH Corporation Procédé de fabrication d'une composition de graisse de sulfonate de calcium à base de carbonate de calcium
US9976102B2 (en) * 2011-10-31 2018-05-22 Nch Corporation Composition and method of manufacturing calcium sulfonate greases using alkali metal hydroxide and delayed addition of non-aqueous converting agents
FR3013056B1 (fr) * 2013-11-13 2018-01-19 Total Marketing Services Procede de preparation d'une graisse sulfonate de calcium complexe
CN103740435B (zh) * 2014-02-11 2015-06-17 上海禾泰特种润滑科技股份有限公司 一种复合磺酸钙润滑脂组合物及其制备方法
CN103952215A (zh) * 2014-04-24 2014-07-30 青州市东能润滑油脂有限公司 一种高性能复合磺酸钙基润滑脂及其制备方法

Also Published As

Publication number Publication date
EP3400279A4 (fr) 2018-11-14
CN108463542A (zh) 2018-08-28
WO2017119999A1 (fr) 2017-07-13
CN108463542B (zh) 2020-03-17

Similar Documents

Publication Publication Date Title
AU2012332673B2 (en) Calcium hydroxyapatite based calcium sulfonate grease compositions and method of manufacture
US9976101B2 (en) Method of manufacturing calcium sulfonate greases using delayed addition of non-aqueous converting agents
US10316266B2 (en) Calcium hydroxyapatite based calcium sulfonate grease compositions and method of manufacture
US9976102B2 (en) Composition and method of manufacturing calcium sulfonate greases using alkali metal hydroxide and delayed addition of non-aqueous converting agents
AU2016385438B2 (en) Manufacturing calcium sulfonate greases using alkali metal hydroxide and delayed addition of non-aqueous converting agents
EP3400279A1 (fr) Procédé de fabrication de graisses de sulfonate de calcium par addition différée d'agents de conversion non aqueux
WO2017200928A1 (fr) Composition et procédé de fabrication de graisses de sulfonate de magnésium et de calcium sans agent de conversion non aqueux classique
US10087387B2 (en) Composition and method of manufacturing calcium magnesium sulfonate greases
CA3022069C (fr) Composition et procede de fabrication de graisses de sulfonate de calcium et de sulfonate de magnesium-calcium au moyen d'un temps d'attente apres l'addition d'acide facilitant
US10519393B2 (en) Composition and method of manufacturing calcium magnesium sulfonate greases

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180706

A4 Supplementary search report drawn up and despatched

Effective date: 20180907

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20211215