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    US20130109602

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    Virender Kumar

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    U! cu») United States 2) Patent Application Publication — co) Pub. No.: US 2013/0109602 A1 oy ow ~ en @y (60) on Waynick CALCIUM CARBONATE BASED SULFONATE GREASE COMPOSITIONS AND METHOD OF MANUFACTURE Applicant: J. Andrew Waynick, Lantana, TX (US) Inventor: J. Andrew Waynick, Lantana, TX (US) Appl. No. 131664574 Filed: Oct. 31,2012 Related US. Application Data Provisional application No, 61/583,674, fled on Oct 31,2011 Publication Classification Intl. c10M 16904 (2006.01) S 2013 0960241 (43) Pub, Date May 2, 2013 (52) US. usp sows on An overbased calcium sulfonate grease compesition co Prising a reduced amount of overbased cali sulfonat fade calcium easbonste, base oil, one or more converting ‘agents, and one or morecomplexing acids if complex grease js desired, The calcium sulfonate grease composition ‘improves thickener yield and expected high temperate util- dtyas demonstrated by dropping point. The caleium carbonate ‘may be used to react with complexing acids when making @ ‘complex grease, sch thatthe addition of ealeium oxide oF caleium hydroxide is not required, A method of making the ‘composition comprising the steps of mixing the overbased ‘alejum sulfonate andl base oil adding the caleium carbonate, ‘adding one or more converting agents, and adding one oF ‘more complexing acids, ll ora porion of oneor more the ‘complexing acids may be added with or peor to the one or ‘more converting agents ABSTRACT US 2013/0109602 Al CALCIUM CARBONATE BASED SULFONATE GREASE COMPOSITIONS AND METHOD OF MANUFACTURE (CROSS: REFERENCE TO RELATED "APPLICATION 10001) This application claims the benefit of U.S. provi- sional patent application No, 61/553,674 filed Oe, 31,2011 BACKGROUND OF THE INVENTION 0002] 1. Field ofthe Invention [0003] This invention relates to overbased calcium sul- nate greases made with added calcium earbonate as the basesource and themethod formanfacturing such greasest0 provide improvements in both thickener yield and expected high temperature utility as demonstrated by dropping point. {0004} 2. Description of Related Art 10005] | Overbased calcium sulfonate preases have been aa ‘established grease eaegory for many’ years, One known pro- ‘ess for making such greases isa two-step process imolving thesteps of “promotion” and “conversion.” Typically the fst step (“promotion”) ito react stoichiometric exeoss amonnt ‘ofealcium oxide (CO jorcalcium hydroxide (Ca(OH), asthe base source with an alkyl benzene sulfonic acid, carbon diox- ide (CO,), and with other componeats to produce an oie Soluble overbased calcium sulfonate with amorphous cal- ‘cium carbonate dispersed therein, These overbased oil. soluble calcium sulfonates are typically clear and bright and have Newtonian rheology. Insomecases, they may beslightly turbid, but such variations do not prevent their use in prepar- ing overbased calcium sulfonate greases. For the purposes of this disclosure, the terms “overbasedoiL-soluble calcium su- onate” and “cil-sluble overbased calcium sulfonate” and “overhased calcium sulfonate” refer to any overbased cal- cium sulfonate suitable for making caleium sulfonate sreases. Typically the second step conversion”) sto add 2 ‘converting agent or agents, such as propylene glyco, is0- propyl alcohol, water, fie acid or acete sei tothe prod- Uuctof the promotion step, along witha suitable Base oil (such 35 mineral oi), to convert the amorphous calcium carbonate to a very finely divided dispersion of crystalline caleinm ‘carbonate, Because an excess of caleium hydroxide or cal ‘cum oxides used to achieve overbasing, a saall anouat of residual calcium oxide or calcium hydroxide may also be present and will be dispersed. The crystalline form of the ‘calcium earbonate i preferably cali, Thisextremely finely ‘divided calcium carbonate, also known as a colloidal disper- ‘on, interacts with the calcium sulfonate to foem a grease- Tike consistency. Such overbased caleium sulfonate preases produced through the two-step process have come to be Known as “simple calcium sulfonate greases” and ae dis: ‘closed, for example, in U.S, Pa Nos. 3,242,079: 3,372,115 53,376,222, 3,377,288; and 3,492,231 10006] Its aso known in he prorat to combine these two steps, by carefully controlling the reaction, into singe te. Inthis one-step process, the simple calcium sulfonate grease prepared by reaction of an appropriate sulfonic acid with ther calcium hydroxide or calcium oxide inthe presence of ‘carbon dioxide an a system of reagents that simultaneously fact as both promoter (ereting the amorphous calcium car- bonate overbasing by reaction of carbon dioxide with nn ‘excess amount of caleiam oxide or ealeivin hydroxide) and ‘converting agents (converting the amorphous calcium ear May 2, 2013 Donate 10 very finely divided crystalline calcium carbonate). Thus, the rease-like consistency is formed in a single step wherein the overbased, oilsoluble calcium sulfonate (the product of the fist step in the two-step process) is never actualy formed and isolated as.a separate pret, This one- step process is disclosed, for example, in U.S. Put. Nos. 3,661,622; 3,671,012; 3,746,645; and 3,816,310, 0007} Inadditiono simple calcium sulfonate greases, cal- in sulfonate complex grease compounds are also known in thepriorart. These complex greases are typically produced by adding a strong ealcium-containing base, such as calcium lhydroxide or calcium oxide, to the simple eaeium sulfonate grease produced by either the two-step or one-step process land reacting with soichiomeirically equivalent amounts of complexing acids, such as 12-hydroxystearic acd, boric acid, aeeticneid or phosphoric avid. Theclaimedadvantages of the calcium sulfonate complex grease over the simple grease include reduced teekiness, improved pumpability, and ‘improved high temperature uiity. Caleium sulfonate com- plex greases are disclosed, for example, in U.S. Pat. Nos. 4,560,489; $126,062; 5,308,514 and 5,398,467. [0008] _Alfoftheknown priorart teaches the use of calcium ‘oxide or ealeum hydroxide as the sources of basic ealeinm {or production of caleium sulfonate greases or a6 required ‘component for reacting with complexing aeids to form cal- cium sulfonate complex greases. The known prior art gener- ally teaches that the presence of caleium carbonate (as a separate ingredientorasan “impurity” inthe eam hycrox- ‘de o caleiuo oxide, ether than that presence of the amor. phous caleium earbonate dispersed inthe ealcium sulfonate after carbonation), should be aided forat leas wo reasons. ‘The rstheing tha calcium carbonate is generally cotsidered to bea weak base, unsuitable for reacting with complexing acids. The second boing thatthe presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion process, resulting in inferior prease compounds ifthe unre- Acted solids are not removed prior to conversion or before ‘conversion is completed [0009] Additionally, the prior art does not provide a eal- ium sufonate complex grease with both improved thickener yield and dropping point. The known prior art requires an Amount of overbased calcium sulfonate of least 36% (by ‘weight ofthe final grease procuet) to achieve suitable grease in the NGLI No, 2 eategony with a demonstrated dropping point of at least $75 F. The overbased cil-soluble cleinm ulfonate is one ofthe most expensive ingredients in making calcium sulfonate urease, therefore itis desirable to reduce the amount ofthis ingredient while still maintaining a desir able level of firmness in the final grease (thereby improving {hickener yield). Specifically, ts desirable to have an over- based calcium sulfonate grease wherein the percentage of ‘overbasedoisolublecaleium sulfonates les 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). Higher dropping points are considered desirable since the dropping points the stand most easily determined guide as to the high temperature uit limitaions of a lubricating arease SUMMARY OF THE INVENTION [0010] Tis invention relates to overbased calcium sul- Tonate greases made with the addition of solid eaeium care US 2013/0109602 Al bonate and the method for manufacturing such greases 10 provide impeovements in both thickener yield (requiring less ‘overbased calcium sulfonate while maintaining acceptable Penetration measurements) and expected high temperature utility as demonstrated by dropping point. Alubough the known prior art consistently and wniformly teaches against ‘making a high quality calcium sulfonate-based grease hy having basic material, such asthe weak base calcium ear bona, present as an insoluble solid before conversion thas been found that a suitable simple calcium sulfonate grease may be produced according to the invention by adding cal- ‘cium carhonate before conversion, The knowa prior at also teaches against using the weak base calcium carbonste a the base material to reat with complexing acids when producing calcium sulfonate complex greases; however, it has been also ound that an improved calcium sulfonate complex grease ‘may'be produced according tothe invention by using calcium ‘earonate asthe added base, and as the sole added base, 10 react with complexing acids. Additionally, the known prioe art generally requires an amount of overbased oi-soluble ‘calcium sulfonate of 36% or preter (by weight ofthe final trcase product) Io achieve a finn enough grease while also having & dropping point of $75 F or higher. The overbesed cilsoluble caleiom sulfonate is one of the most expensive ingredients in making a calcinm sulfonate grease, s0 itis desirable to oduce the amount of this ingredient while still, providing excellent demonstrated dropping point properties Such a reduction has been achieved with te greases accord- ing to the invention without resulting in a grease that is 00 toll ora dropping point that is inferior. [0011] According 10 one preferred embodiment of the invention, a highly overbased ol-soluble calcium sulfonate _arease composition is provided having the follssing ingre= ‘ientshy weight perentof the inal grease product although, some ingredients, such as water, may not be in the final grease product or may not be in the concentrations indicated for dition: 20%-36%% overbased calcium sulfonate, ¥%15% ‘aed calcium carbonate, 265% water, 4% other vertingagents, suchas alcohols eters, alyeols glycol ethers, lyeo! polyethers, and carboxylic acids, an optional 196% alky! benzene sulfonic acid; and optionally 28%-11.0%% (o- tal) of one oF more complexing acids, sich as boric acid, aceticacid, 2hydroxystearic acid, or phosphoric acd (when ‘a complex prease is desire) The caeium sulfonate complex. grease according t this prefered embodiment is an NGLL No, 2grade grease havinga dropping pointof 575 F or higher. [0012] According to one embodiment of the invention, & simple calcium sulfonate grease is produced by combining @ highly overbased oi-soluble calm sulfonate comprising ‘amorphous caleinm earbonate as the primary averbasing ‘material with an appropriate initial amount ofa suitable base cil, such as mineral oil, which is then admixed with finely be added to either the simple or complex prease embodiments ofthe inveaton after conversion, and afterall waction with ‘complexing acids is complete in the case of « complex grease However, elerences to added calcium carbonate herein refer to the ealeiam carbonate that is added prior to conversion and as the sole added caleium-contuiing base for euction Wilh complexing acids when making complex grease according tothe invention [0027] ‘The compositions according to the invention are preferably made acconling to the method described herein. ‘This method comprises the stepso(I)admixing ina suitable arease manufocturing vessel a highly overbased oi-soluble ‘alcium sulfonate and an appropriate ammount of a suitable base oil ata temperature of between ambient air temperature and about 190 F; 2) admixing finely divided ealeium carbon- ate: G) optioually admixing «lailtating acid; (4) admixing converting agent or agents; (3) and continuing to mix while heating as roquiredto about 190 F-200F and remaining at that temperature range until eonversion ofthe ameorphots acim carbonate 1o very finely divided erystallinecaletum carbonate is complete, This procese results in prefered simple cal- in sulfonate gresse. To produce a calcium sulfonate com- plex grease composition according to the invention, the method preferably comprises previous steps (1)}(S) and the ‘addtional steps oF (6) adding aay complexing acids required ‘with all or part of them added before conversion and the remainder added after conversion; (7) mixing and heating to temperature sulicently high to insure removal of water and fany volatile reaction byproducts and optimize final product quality; (8) cooling the grease while adding adlitional base oil as needed; (9) adding remaining desired additives as are ‘well known in the art and if desired, (10) milling te final grease as required to obit a final smooth homogenous prod- [0028] This process may occur in either an open oF closed kettle a is commonly used for grease manufaetring. The conversion process can be achieved at normal atmospheric pressure or under pressure ina eloged ketle. Manufactoring in open kettles is prefered since sch grease manufacturing equipment is commonly available, [0029] Cenain aspects of the process ate not eritcal to ‘oblaining « preferred calcium sulfonate grease composition according 1 the invention. For instance, the order that the calcium carbonate, water, and otber converting agents are sade relative o each other isnot important. Also, the tem- perature at which the calcium carbonate, water, and other fonverting agents are added is not iia but itis prefered that they’ be added before the temperature reaches 190 F vo 200 F. However, forthe sake of eonvenienee, these compo- ‘ents are usually added atte beginning ofthe process, a Will be illustrated in the examples provided below. When more ‘than one complexing acids used, the onder in which they are added eiter before or ater conversion isnt generally impor tant [0030] According to one preferred method of m: calcium sulfonate grease according to the invention US 2013/0109602 Al removed fom the arease after conversion Preferably, the free ishestedalter everson is complete anda complex ingacids (if complex greases being ade have boenated toremove the water as quickly as possible This penerilly possible by eating and mixing the batch under open eon tions. Having water inte use batch for prolonged periods ‘oftime may esultin degradation of thickener yield dropping Point, oF Both, and such adverse effets many be avoid by Femoving the water quickly {0031} ‘The converte grease shoul be bested atempera- {ure sufiiel high wo remove the water dat Was nity added asa converting agent, as well any water Formed by ‘chemical rections during the formation af the pase, iene ‘nally, this temporaare will be hetween 250 F and 300 F, preferably 300 to 380 F. most preferably 380 F to 400 F. Polymeric additives are added to the areas, they should Preferably not be added uni Use reas emportur reaches 500 Polymeric adltives ean if addin suficienteoncen- tration hinder theeecve volatilization of ater Therefore polymeric addives shoul preferably be added othe grease ‘nly afer al water has been removed {0032} The overbased calcium sulfonate grease compesic tions and methods for making sch compositions according tothciaventionare far described snd explainedinrelation to the following examples Example 1 10033] A calcium sulfonate complex grease was prepared ‘acconting othe preset invention as follows: 36.00 pars by ‘weight of a 400 TAN overbased calcium sulfonate (having amorphous calcium carbonate dispersed therein) was added to an open mixing vessel fllowed by 33.38 parts ofa solvent neutral group 1 paralinc base il having a viscosity of about (600 SUS at 100 F and 1.00 part of PAO having a viscosity of 4 Stat 100, Mixing without heat began using a planetary mixing paddle. Then 3.60 parts ofa primarily C12 alkylben- zone sulfone acid was added asa felitating acid, Aer 20 rminntes, 7.58 parts of finely divided caleum carbonate with antean particle size below 5 mirons was added asa source of basic calcium and allowedto mixin for 10 minutes, Then 1.80 paris of hexylene glyeol and 4.5 parts water were add as ‘converting agents. The mixture ws heated uni the tempera ture reached 190 F. The temperature was held between 190 F ‘and 200 F for 45 minutes ntl Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystallin calcium carbon- ate (caleite) had occured. Immediately, 2.84 parts of 12-hy- “droxyslearic acid was added followed by 0.28 parts glacial seat acid. Then 1.90 parts of 75% solution of phosphoric in water was added, These three acids were the complex- ing acids for this batch. The mixture was then heated with an ‘electic heating mantle. When the prease reached 300 F, 2.78, pars of a styrene-isoprene copolymer were added as acrumb- ormed solid. The pease was further heated to about 390 Fat ‘hich time all the polymer was melted and fly dissolved in the grease mixture, The heating mantle was removed and the trease was allowod to cool by continuing to stir in open ai. ‘Whea the grease cooled to 250 F, another 8.34 parts of the same paraffinie group 1 base oil was added. When the tem- perature of the grease cooled to 200 F, 0.50 pars aa poly- ‘sobutylene polymer was added, Mixing contnucd until the rease reached a temperature of 170 F. The grease was then Femoved from the mixer and given three passes through & three-roll illo achieve the Final smooth homogenous tex- May 2, 2013 ture, The grease had an unworked penetration of 252 and a ‘worked60 strokes penetration of 283. Tae dropping point was 608 F. The percentage of overbased oil-soluble caleium sul- Tonate in the grease of this batch was 36.09%. Note that the ‘only ealeium-containing base ade to make this grease was calcium carbonate. No calcium hydroxide or calcium oxide was added during the making ofthis prease Example 2 [0034] Another batch of grease was made wsing the same ‘equipment, raw materials, amounts, and manufacturing pro- ‘cess the Example I grease, except that the calm carbon- ate was added immediately after conversion but before the ‘complexing acids (I2-hydroxystearie acid, acetic acid, and phosphor acd) were aided. The ingredieat composition of {his grease was identical to the previous Example I grease. ‘The final grease had an unworked penetration of 285 and 3 ‘worked 60 stoke penetration of 288. The dropping point was ‘555 F. The pereentage of overbased oil-soluble ealeium sul- onate in the grease ofthis batch was 36.0%. As ean be seen the grease ofthis example was both softer than the Example | grease by 35 points and had a dropping point that was janificantly lower. ince the only difference between these tho greases wis the timing of adding the calcium carbone relative to conversion, the softer conssteney lower thickener yield) and lower dropping point must be due to that differ- fence, Thus, adling calcium carbonate before coaversion fceording t9 8 preferred embodiment of the invention pro- vides a superior produet tothe same composition if the cal cium carbonate i added after conversion, [0035] A comparison of the greases of Examples 1 and 2 ‘demonstrate yet another important point. When tae complen- ing acids are aclded in Example 1, the grease at that pont is simple caleium sulfonate grease tat was formed with added calcium carbonate (in addition to the amorphous caleinm carbonate dispersed in he overbased calcium sulfonate thats converted to a erystaline dispersion during the conversion process) present during eonversion. Whea the complexing acids are added in Example 2, the grease at that point is & imple caleium sulfonate grease that was formed without alec calcium carbonate present during conversion, but 10 ‘whieh the caleium carbonate was added aller conversion, At the point that the complexing acids are added, the simple calcium sulfonate greases in Examples | and 2are identical in ‘composition, The same complexing acids in the same amounts were used in both Examples. The only difference is ‘whether or not the simple calcium sulfonate grease was Tormed with added calcium carbonate present during conver sion or added later, after grease formation. Therefore, any rence in the properties of the final calcium sulfonate ‘complex grease must correspond to the difference in the simple caleium sulfonate greases from which they were ‘made, This demonstrates that forming simple ealeium sul- Tonate grease With added calm earhonate present before conversion provides a superior simple grease composition to ‘one where calcium carbonate is added aftereonversioa, Add tional examples 3-7 prove farther confimmation ofthis fct as well asthe advantageous properties ofthe preset inven- ‘ion compared lo prior art greases where strong bases such as caleium hydroxide are used, Example 3 [0036] Another batch of grease was made using the same ‘equipment, raw materials, amounts, and manufacturing pro- US 2013/0109602 Al ‘ess as the Example 1 grease except for the following ‘changes (1) the soetic acid was added just before adding the hexylene glycol and water while the batch was at ambient temperature; 2) the 12-hydroxystearic acid wasadded before ‘conversion at 170 F while heating the batch to 190 F; and @) no calcium carbonate was added. The percentage of over based ol-soluble calcium sulfonate in this batch as 36.0%. “This batch did not convert to a grease stricture even alter several hours of heating and was abandoned, Example 4 [0037] Another batch of grease was made similar ro the Example 1 grease except forthe following change: the cal- ‘ium carbonate was not added until aie the conversion and aller the complexing acids (I2-hydroxystearic acid, acetic ‘acid, and phosphoric acid) were added, The final prease had fn unworked penetration of 308 and a worked 60 stroke penetration of 305. The repping point was 567. The percent- tage of overbascd oil-soluble calcium sulfonate inthe grease ‘of this bateh was 36.0%. 10038] Examples 3 and 4 continue to demonstrate the importance of adding thecalcium carbonate as the sole added calcium-contsining base before coaversion as opposed {0 aller conversion or not adding it at all. Inthe Example 3 trease, wen no caleium carbonate was added and the acetic id and 12-hydroxystearie acid were added before eonver- sion as converting agents, conversion did not occur, and no _srease structure was obtained. In the Example grease, when, the calcium carbonate Was alded after coaversion and ater the addition of the three complexing acid, the grease was softer than the Example | grease by $2 points, and the drop- Ping point was also significantly lowered. Example S [0039] A calcium sulfonate complex grease was prepared ‘aeconting toa peoferod embodiment ofthe present invention fs follows: 36.00 parts by weight of a 400 TBN overbssed ‘calcium sulfonate (with amorphous caleium carbonate diss therein) was added to an open mixing vessel followed by 33.15 parts ofa solvent neutral group 1 parafinie base oil having viscosity of about 600SUS at 100 Fand 1.00 part of PAO huvinga viseosity of4eStat 100C. Mixing without heat began using aplanctary mixing paddle. Then 3.60 pans of a primarily C12 alkylbenzene sulfonic acid was added as 2 Facilitating acid ARer 20 minutes, 7.58 pars finely divided ‘aleium carbonate witha mean patel size below 5 microns ‘was added and allowed to mix infor 10 minutes. Then 1.80 parts of hexylene glycol and 2.2 parts water were added as ‘converting agents, The mixture was heated uni the tempera ture reached 190F. The temperature was held betwen 190 F ‘and 200 F foe 48 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate to crystallin calcium carbon- ate (calcite) had occured. Immediately, 284 parts of 12-hy- “droxystearie acid was added followed by 0.56 parts glacial tic acid. Then 1.90 parts of a 75% solution of phosphoric ‘eid in water was added, These three acids were the complex ing acids for this bateh. The mixture was then heated with an ‘leciic heating mantle while continuing to sti. When the _aease reached 300 F, 2.78 pansof a styrene isoprene copoly ‘mer were added as a crumb-formed solid, The grease was further heated to about 390 P at which time all the polymer was melted and fully dissolved in the grease mixture. The May 2, 2013 hating mantle was removed and the grease was allowed t0 cool by contining to stir in open sir, When the prewse cooled {0 250 F, another 829 parts of the sume paraffinic group 1 base oil was added. When the temperature of the grease onled to 200 F 0.0 pars of a polyisobutylene polymer was ‘added. Mixing comtined until the grease reaches a temper ture of 170 F, The grease was then removed from the mixer And given three passes through athrce-ol mil to achieve the final smooth homogenous texture. The grease had an ‘unworked penetration of 240 and a worked 60 strokes pen- tation of 239. The dropping point was 644 F. Thepereentage fof overbased oil-soluble calcium sulfonate in the grease of this atch was 36.0%. Note thatthe only ealium-containing base added to make this grease was calcium carbonate. No calcium hydroxide or caleium oxide was added during the making ofthis pease [040] It is seem thatthe greases of both Example $ and Example 1 ave dropping points much higher than the value ported for the calcium sulfonate complex grease of Example V of US, Pat, No, 4,560,489 wherein caleinm hydroxide was used as the caleium-containing base added after conversion to react wit the complexing acids AIS0, the ‘unwarke penetration af this prior art grease was reported to 'e271 andthe percent of the 400 TIN calcium sulfonate used was about 36.7%, based on the composition information provided by the inventors. By comparison, the worked pen- ‘tations of Examples 1 and § of the present invention Were sinificantly harder (smaller values) eventhough the percent- ‘age ofthe 400 TBN caleium sulfonate was 36%, Furthermore, in Example fof US, Pat, No, 4,560,489, the percent of the 400 TBN calcium sulfonate was about 41.7%, and the grease was reported to have a worked penetration within the NLGT No. 2 range, namely between 265 and 295. By comparison, the workod penetrations of Examples 1 and 5 of the present invention Were significanly harder (smaller yulues) even though the pereentage a the 400 TB calcium sulfonate was ‘36% Note that in both the Example {and 5 greases, more ol ‘would have heen needed soften thecansisteney to an NLGL No.2 grade. This would necessarily reduce the conceatration ofthe original il-sluble overbascd calcium sulfonate below 36%. This demonstrates thatthe present invention provides ‘both superior thickener yield and higher dropping point com- pared othe priorart fehinology ofaddingealeium hydroxide for reaction with the complexing acids. Additionally, the resent invention requies less overbased ol-soluble elcinm sulfonate compared to the prior art compositions, which reduces the costs involved [0041] An advantage of the preferred compositions of the resent invention aver te prior tis further demonsrated by ‘comparison with the example providedia US. Pat. No, 5126, (062. In the Example | grease ofthat prior art patent, the percentage ofthe 400 TBN caleium sulfonate was 45%, based ‘on compositional information provided by the inventor. The dropping point was not precisely disclosed, but was ony said to be above 600 F. The worked 60 stroke penetration was reported as 280, In this prior art urease, calcium carbonate ‘wasaadded before coaversion, but calcium hydroxide was also ‘added in suficient amount aler coaversion to flly react with all the complexing acids added thereafter, Punthermore, the ‘complexing acids used in this prior art patent are the ones ‘sed inthe Example I and Example 5 greases of the present invention. Ascan Be seen, the Examples land 5 eases ofthe present invention have dropping points that are at leat as ood as ifnot beter than the prior art Example I grease of US 2013/0109602 Al US. Pat. No. $126,062. Furthermore the thickener yield of the Examples I and 5 greases ofthe present invention preases far superior since their percentage ofthe 400 TBN cal- jum sulfonate is 36% and the worked penetrations are much harder. This comparison shows that even when adding eal- ‘cium carbonate before conversion, itis Beller To use tat ‘calcium carbonate s the sole aided hase for reaction with ‘complexing acids rather than adding calcinm hydroxide alte Example 6 [0042] Another batch of grease was made using the same ‘equipment, raw materials, amounts, and manufacturing pro- ssa the Fxample 5 grease, excep that the calcium carbon fate Was added immediately afler conversion but before the 12-hydroxystearic acid, acti acid, and phosphoric acid were ‘added, The ingredient composition of this urease was identi ‘alto the eomposition of the previous Example 5 grease, The final grease had an unworked penetration of 236 anda worked 60 stroke penetration of 240. The dropping point was 416 F “The percentage of overbased ol-soluble calcium sulfonate in the grease ofthis hatch was 36.0%%. Once again, the clear ‘advantage of adding the calcium carbonate pre-conversion instead of postconversionisoserved. Although the penetn- tions ofthe Example 5 and 6 greases were comparable, the ‘dropping point of the Example 6 grease where the caleium ‘carbonate was added after conversion was nearly 200 Flower than the Pxample $ grease where the caleium carbonate was ‘added pre-coverson, Example 7 [0043] To demonstrate that adding calcium carbonate pre- ‘conversion asthe sole added ase is superior to adding cal- ‘ium hydroxide pre-conversion and to adding calcium car- bonate both post conversion and afterall reaction with ‘complexing ack, a grease was prepared as follows: 37.87 parts by weight of a 400 TBN overhased calcium sulfonate was added to an open mixing vessel followed by 30.13 parts ‘of a solvent neutral group 1 parallinie base oil having 3 viscosity of about 600 SUS at 100 . Mixing without heat began uting planetary mixing paddle, Then 3.19 parts of @ Primarily C12 alkylbenzene sullonic acid was added. Alter 20 minutes, 3.19 parts of finely divided food prade purity cal- ium hydroxide with a mean partiele size of about 4 mierons ‘at added and allowed to mixin for 10 minutes. Then 2.13, parts ofhexylene plyeol and 4.5 parts water were added, The mixture was heated nti the temperature reached 190 F.The temperature was held between 190 F and 200 F until Fourier ‘Transform Infrared (PTIR) spectroscopy indicated thatthe ‘conversion ofthe amorphous ealeium carbonate to crystalline ‘calcium carbonate (calete) had ovcured. Immediately, 3.19, paris of 12-hydroxystearie acid was added followed by 032 Pars glacial acetic aid. Then 2.02 pars of 875% solution oF Phosphoric acid in water was added. These three acids were the complexing acide for this hatch, The mixture was then heated with an cloctic heating mantle while continsing to heat. When the prease reehed 250 F and it appeared that ll the water had volatlized, 745 parts of the same caleinm ‘carbonate used in the previous examples herein was added, When the grease reached 300 F, 2.13 pars of a styrene- isoprene copolymer was addedas a eramb-formed solid. The _srease vas further heated to about 390 F at which tmeall the polymer was melted and fully dissolved in the grease mixture ‘Thehcating mantle was removed and the grease was allowed to cool by continuing to stir in open air. When the grease ‘cooled (0 250 F, another 7.53 parts of the same paraffinic May 2, 2013 aroup 1 base oil was added. When the temperature of the _rease cooled t0 200 F, 0.50 parts of a polyisabutylene poly- mer was added, Because the grease appeared heavy, another 2083 partsofthesame parafinie group 1 baseoil wereadde. ‘Mixing continued until the grease reached! a tempers of TOF. The grease was then remove rom the mixer and given thee passes through a three-roll mill wo achieve the final smooth homogenous texture. The prease had an unworked penetration of 278, The percentage of overbased oil-soluble calcium sulfonate in the prease of this batch was 31.39%, ‘whieh isnot significantly Beer than the percentage of over- based ol-souble cleium sulfonatein Examples land S once ‘addtional oil is added to achieve NGL No.2 grade greases, particularly when the dropping point for this Example 7 ‘grease was only $23 Fz which isc lower than the dropping points of Examples I and 5 0044) Summarizing thus far, these frst seven examples taken together sronaly demonstrate the following: (1) over ‘based calcium sulfonate-based eases can be prepared using caleium carbonates the only aided caleium-containing base Tor reaction with complesing acids: 2) use of calcium car ‘bonate ade pre-conversion provides superior greases com- pared to when the caleium carbonate is added post-conver sion, even when this i the only difference between the (wo greases; (3) adding calcium carbonate before conversion as the sole added calcinm-

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